(ACS Symposium Volume 315) Willa Y. Garner, Richard C. Honeycutt, and Herbert N. Nigg (Eds.) - Evaluation of Pesticides in Ground Water-American Chemical Society (1986)

ACS SYMPOSIUM SERIES 315
Evaluation of Pesticides
in Ground Water
Willa Y. Garner, EDITOR
U.S. Environmental Protection Agency
Publication Date: July 17, 1986 | doi: 10.1021/bk-1986-0315.fw001
Richard C. Honeycutt, EDITOR

CIBA-GEIGY Corporation
Herbert N. Nigg, EDITOR

Citrus Research and Education Center
University of Florida
Developed from a symposium sponsored by

the Division of Pesticide Chemistry
at the 189th Meeting
of the American Chemical Society,
Miami Beach, Florida,
April 28-May 3, 1985
American Chemical Society, Washington, DC 1986

Library of Congress Cataloging-in-Publication Data
Evaluation of pesticides in ground water.
(ACS symposium series; 315)
Includes indexes.
1. Water, UndergroundPollutionCongresses.
2. Agricultural pollutionEnvironmental aspects-
Congresses. 3. PesticidesEnvironmental aspects-
Congresses.
I. Garner, Willa Y., 1936- . II. Honeycutt,
Richard C., 1945- . III. Nigg, Herbert N.,

1941- . IV. American Chemical Society. Division of
Pesticide Chemistry. V. American Chemical Society.
Meeting (189th: 1985: Miami Beach, Fla.) VI. Series.
TD426.E96 1986 628.6842 86-14153
ISBN 0-8412-0979-0
Copyright 1986
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA
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Advisory Board
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University o f CaliforniaBerkeley USDA, A g r i c u l t u r a l Research Service
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N a b i s c o B r a n d s , Inc. Exxon Chemical Company
Marye Anne Fox W. D . Shults

The University o f T e x a s A u s t i n Oak Ridge National Laboratory
M a r t i n L . Gorbaty Geoffrey K . S m i t h
Exxon Research and Engineering C o . R o h m & Haas C o .
R o l a n d F. H i r s c h Charles S.Tuesday
U . S . Department o f Energy G e n e r a l M o t o r s Research Laboratory
Rudolph J . Marcus Douglas B. Walters

Consultant, Computers & N a t i o n a l Institute o f
Chemistry Research Environmental Health
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Battelle C o l u m b u s Laboratories IBM Research Department
FOREWORD
T h e A C S SYMPOSIUM SERIES was founded i n 1974 to provide a
m e d i u m for p u b l i s h i n g s y m p o s i a q u i c k l y i n b o o k form. The
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IN C H E M I S T R Y SERIES except that, i n order to save time, the
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PREFACE
THE INTENSE PUBLIC INTEREST IN C H E M I C A L CONTAMINATION of O u r

nation's g r o u n d water has been well d o c u m e n t e d by the m e d i a . Pesticide
c o n t a m i n a t i o n of g r o u n d water t h r o u g h agricultural use is a unique situation
in c o m p a r i s o n to c o n t a m i n a t i o n by point source leaching f r o m dumps,
landfills, a n d spills. C o n s e q u e n t l y , data bases for a g r i c u l t u r a l pesticide
c o n t a m i n a t i o n are s m a l l , a n d published research a n d textbooks are limited.
Publication Date: July 17, 1986 | doi: 10.1021/bk-1986-0315.pr001
T h i s v o l u m e explores a l l aspects of the factors that impinge o n g r o u n d

water c o n t a m i n a t i o n f r o m a g r i c u l t u r a l l y a p p l i e d pesticides. A l t h o u g h o n l y
pesticide c o n t a m i n a t i o n is dealt w i t h i n this v o l u m e , the principles examined
a p p l y to a l l xenobiotics a n d natural substances that c a n reach o u r g r o u n d
waters.
A s organizers of the s y m p o s i u m a n d editors of this v o l u m e , we thank
the c o n t r i b u t o r s , whose generous time a n d c o m b i n e d expertise have made
this b o o k a valuable reference for those w o r k i n g i n the g r o u n d water area.
We also t h a n k o u r s y m p o s i u m session chairpersons, Jeff Wagenet ( C o r n e l l
University), S a m Creeger (U.S. Environmental Protection Agency), and
C h r i s W i l k i n s o n ( C o r n e l l University), for their special c o n t r i b u t i o n s that
made the s y m p o s i u m f r o m w h i c h this b o o k was developed a success.
W I L L A Y. G A R N E R
U . S . E n v i r o n m e n t a l Protection A g e n c y
Washington, DC 20460
RICHARD C. HONEYCUTT
CIBA-GEIGY Corporation
Greensboro, NC 27409
HERBERT N . NIGG
C i t r u s Research a n d E d u c a t i o n Center
700 E x p . S t a t i o n R o a d
L a k e A l f r e d , FL 33850
O c t o b e r 1985
ix
1
Processes and Factors Affecting Transport of Pesticides
to Ground Water
1 2
H . H . Cheng and W. C. Koskinen
1
Department of Agronomy and Soils, Washington State University, Pullman, WA 99164
2
Southern Weed Science Laboratory, Agricultural Research Service, U.S. Department of
Agriculture, Stoneville, MS 38776
Publication Date: July 17, 1986 | doi: 10.1021/bk-1986-0315.ch001
The process of transporting pesticides down through the

soil horizons and the vadose zone into the ground water
is affected by a number of other processes taking place
in the soil profile. The sorption process can retard
or retain the chemicals from moving with leaching
water. The commonly used pesticides, mostly being
organic chemicals, can be degraded partially or
completely to inorganic end products by chemical,
photochemical, or biochemical means. The degradation
process reduces or eliminates the presence of pesti-
cides in the environment. Pesticides can also be
transported to the atmosphere by volatilization or to
surface water by runoff from soil, or be removed from
soil by plant uptake. Whether circumstances for trans-
port of pesticides to groundwater exist will depend
upon a combination of factors including the nature of
the pesticide chemical, the properties and conditions
of the soil, and climatic and environmental variables.
Realistic assessment of the potential for transport of
pesticides to groundwater must include simultaneous
evaluation of all the processes and factors that may
impact the transport process.
The t o p i c o f t h i s symposium i s b o t h t i m e l y and o f s p e c i a l c o n c e r n t o

many s e c t o r s o f t h e p u b l i c as i t combines two c o n t r a s t i n g s u b j e c t
matters. Groundwater, b e i n g an e s s e n t i a l n a t u r a l r e s o u r c e , has been
assumed t o be p r i s t i n e i n q u a l i t y and must n o t be v i o l a t e d by
contamination. A f t e r a l l , 86% o f t h e water i n t h e U n i t e d S t a t e s i s
s t o r e d i n a q u i f e r s ; over 50% o f t h e U. S. p o p u l a t i o n and 95% o f r u r a l
U. S. u s e groundwater as d r i n k i n g w a t e r . On t h e o t h e r hand, any
m e n t i o n o f p e s t i c i d e s o f t e n connotes s u b s t a n c e s t h a t a r e t o x i c ,
hazardous, and even life-threatening. A tremendous amount o f
p e s t i c i d e s i s produced and used i n t h e U. S. each y e a r . I n 1984, 1.1
b i l l i o n pounds was s y n t h e s i z e d ; even t h i s amount was down from t h e
I. 5 b i l l i o n pounds produced i n 1975 ( 1 ) .
0097-6156/ 86/ 0315-O002$06.00/ 0

1986 A m e r i c a n C h e m i c a l Society
1. C H E N G A N D KOSKINEN Affecting Transport of Pesticides to Ground Water 3
Some 68% o f the p e s t i c i d e s was used f o r a g r i c u l t u r a l p u r p o s e s ,

17% by i n d u s t r i e s and commercial c o n c e r n s , 8% by homes and gardens,
and 7% by governmental u s e s . Over 60% o f the p e s t i c i d e s produced a r e
h e r b i c i d e s , the o t h e r s b e i n g m o s t l y i n s e c t i c i d e s and f u n g i c i d e s .
There i s i n c r e a s i n g e v i d e n c e f o r the p r e s e n c e of a v a r i e t y of
p e s t i c i d e s i n groundwater a t c e r t a i n l o c a t i o n s , such as i n s h a l l o w ,
unprotected a q u i f e r s or i n k a r s t formations. A r e p o r t by the U. S.
Environmental P r o t e c t i o n Agency (EPA) i n 1984 (2) l i s t e d some 12
pesticides t h a t have been d e t e c t e d i n d r i n k i n g water w e l l s i n
Florida, New York, California, Hawaii, and other locations.
R e c e n t l y , the EPA announced i t s i n t e n t i o n t o i n c l u d e 60 p e s t i c i d e s i n
its d r i n k i n g water survey (3), more than half of which are
herbicides. The seriousness of the potential contamination of
groundwater by p e s t i c i d e s c e r t a i n l y cannot be m i n i m i z e d .
A l t h o u g h the c o n c e r n s by EPA f o r groundwater q u a l i t y a r e t o be
l a u d e d , the p l a n n e d program on groundwater m o n i t o r i n g , p a r t i c u l a r l y
the d r i n k i n g w a t e r w e l l s s u r v e y , i s o f l i m i t e d v a l u e . The m o n i t o r i n g
program c o u l d a t b e s t a l e r t the p e o p l e o f e x i s t i n g h a z a r d . I t would
not be u s e f u l i n a s s e s s i n g the magnitude o f the p o t e n t i a l danger n o r
i n d e d u c i n g the s o u r c e s o f c o n t a m i n a t i o n . An e f f e c t i v e management
program must not o n l y i n c l u d e a groundwater m o n i t o r i n g e f f o r t but
a l s o s u p p o r t a p l a n n e d program of r e s e a r c h t h a t can i s o l a t e and
i d e n t i f y the p o t e n t i a l causes o f c o n t a m i n a t i o n by p e s t i c i d e s and
d e v i s e ways t o m i n i m i z e o r e l i m i n a t e the s o u r c e s o f c o n t a m i n a t i o n .
The h e a r t of such a program must be t h e s e a r c h f o r a b a s i c u n d e r -
s t a n d i n g of the p r o c e s s e s and f a c t o r s t h a t a f f e c t the t r a n s p o r t of
p e s t i c i d e s t o groundwater.
The Setting
It i s not always o b v i o u s t h a t groundwater i n most c a s e s is a

renewable r e s o u r c e . Few o f the a q u i f e r s t h a t s u p p l y d r i n k i n g water
a r e of a n c i e n t o r i g i n . Most o f them a r e dynamic i n n a t u r e , and a r e
r e c h a r g e d r e p e a t e d l y by water moving s l o w l y o r r a p i d l y downward from
the s u r f a c e o f the e a r t h through the s o i l p r o f i l e t o a l e v e l t h a t
accumulates the w a t e r . In the p r o c e s s , d i s s o l v e d c h e m i c a l s i n c l u d i n g
p e s t i c i d e s can a l s o be c a r r i e d downward i n t o the s o i l p r o f i l e and
e v e n t u a l l y r e a c h the groundwater. Thus, t h e c o n c e r n f o r c o n t a m i n a -
t i o n of groundwater i s l e g i t i m a t e and j u s t i f i e d . A number o f papers
of t h i s symposium a r e d e a l i n g w i t h the s p e c i f i c p r o c e s s o f t r a n s p o r t
of p e s t i c i d e s t o the groundwater. The o b j e c t i v e o f t h i s paper i s to
s e t the s t a g e f o r t h i s symposium by r e l a t i n g the t r a n s p o r t p r o c e s s t o
other processes occurring simultaneously i n s o i l that a f f e c t the
transport process. We w i l l attempt t o v i e w the t r a n s p o r t p r o c e s s i n
p e r s p e c t i v e o f the f a t e o f p e s t i c i d e s i n the t o t a l environment, and
to s h a r e some c a u t i o n s needed i n a s s e s s i n g these p r o c e s s e s .
The n a t u r a l environment can be viewed as c o n s i s t i n g of s e v e r a l
e n v i r o n m e n t a l zones ( F i g u r e 1 ) , e x t e n d i n g from the atmosphere and the
above-ground c r o p zone i n t o the s o i l from the s u r f a c e down, through
the r o o t zone, the u n s a t u r a t e d s o i l o r vadose zone below, e v e n t u a l l y
down t o the s a t u r a t e d zone where ground water i s s i t u a t e d . For a
p e s t i c i d e t o contaminate groundwater, the c h e m i c a l must f i r s t r e a c h
the s o i l , e i t h e r d i r e c t l y by a p p l i c a t i o n o r i n d i r e c t l y such as by
drift. F o l i a r - a p p l i e d chemicals are s u b j e c t to photodecomposition,
p l a n t a b s o r p t i o n , d r i p p i n g t o s o i l , o r f a l l i n g on s o i l when p l a n t s
4^
ENVIRONMENTAL ZONES WATER PROCESSES PESTICIDE PROCESSES
Addition Loss
Atmosphere Evaporation Precipitation A p p | i c a t i o n Photodecomposition
^ * '^' Drift Condensation
Foliar Plant a b s o r p t i o n
application Photodecomposition
Evaporation Precipitation
Above-ground Volatilization Drift
crop zone from soil Wash-off
Drift Condensation on soil
Irrigation Runoff
Soil s u r f a c e -
Surface- Degradation
Evaporation Leaching Subsurface (chemical/biological)
Unsaturated soil application Soil Retention
to r o o t d e p t h Washoff Root uptake
Root Uptake
Transport Transport .
0
Movement Transport Degradation
Unsaturated soil zone t (chemical/biological)
below root depth Upward
Soil Retention
(vadose zone) {Lateral)
Transport.
Downward
Movement Transport Degradation

1 ^ 1 (chemical/biological)
Saturated-zone Upward
Soil Retention
(groundwater) {Lateral) W
Transport .
Downward
F i g u r e 1. P r o c e s s e s a f f e c t i n g water movement and p e s t i c i d e

t r a n s p o r t i n v a r i o u s e n v i r o n m e n t a l zones.
die. Once i n t h e s o i l , t h e c h e m i c a l must be t r a n s p o r t e d , u s u a l l y by

w a t e r , t h r o u g h t h e v a r i o u s e n v i r o n m e n t a l zones down t o t h e ground
water. F a c t o r s t h a t a f f e c t water i n f i l t r a t i o n and movement w i t h i n a
zone o r from one zone t o a n o t h e r w i l l a l s o a f f e c t t h e l o c a t i o n o f t h e
chemical. In a d d i t i o n t o moving downward, water c a n a l s o be t r a n s
p o r t e d upward t o t h e s o i l s u r f a c e and e v a p o r a t e d i n t o t h e atmosphere,
t a k e n up by p l a n t s and t r a n s p i r e d , o r d i s c h a r g e d o v e r s o i l s u r f a c e
i n t o s u r f a c e water b o d i e s . P e s t i c i d e s c a n be t r a n s p o r t e d by water i n
s i m i l a r manners. B e f o r e t h e s e t r a n s p o r t p r o c e s s e s c a n be p r o p e r l y
characterized a t any p a r t i c u l a r setting, a l l t h e p r o c e s s e s and
f a c t o r s t h a t impact p e s t i c i d e t r a n s p o r t must be c h a r a c t e r i z e d .
Two major t y p e s o f p r o c e s s e s t h a t c a n a f f e c t t h e amount o f
p e s t i c i d e s present and a v a i l a b l e f o r t r a n s p o r t t h r o u g h t h e s o i l
p r o f i l e a r e r e t e n t i o n and t r a n s f o r m a t i o n . The r e t e n t i o n p r o c e s s e s do
not a f f e c t t h e t o t a l amount o f p e s t i c i d e p r e s e n t i n t h e s o i l b u t c a n
d e c r e a s e o r e l i m i n a t e t h e amount a v a i l a b l e f o r t r a n s p o r t . On t h e
o t h e r hand, t h e t r a n s f o r m a t i o n p r o c e s s e s a c t u a l l y r e d u c e o r t o t a l l y
eliminate t h e amount of p e s t i c i d e present and a v a i l a b l e f o r
transport.
Retention Processes
The l i t e r a t u r e abounds w i t h r e f e r e n c e s on t h e r e t e n t i o n o f p e s t i c i d e s
i n s o i l s ( e . g . , b_,5) . The term ' r e t e n t i o n ' i s used h e r e i n an a l l
encompassing s e n s e , b u t i t i s most f r e q u e n t l y equated w i t h a d s o r p t i o n
or s i m p l y s o r p t i o n . In a s t r i c t sense, a d s o r p t i o n i s a r e v e r s i b l e
process i n v o l v i n g n o n s p e c i f i c a t t r a c t i o n of a chemical to the s o i l
p a r t i c l e s u r f a c e and r e t e n t i o n o f t h e c h e m i c a l on t h e s u r f a c e f o r a
l o n g e r o r s h o r t e r p e r i o d o f time depending on t h e a f f i n i t y of the
chemical t o the surface. However, whether a c h e m i c a l i s a c t u a l l y
sorbed to a p a r t i c u l a r surface i s o f t e n not confirmed by t h e
technique used t o c h a r a c t e r i z e r e t e n t i o n . Few o f t h e t e c h n i q u e s
g e n e r a l l y used f o r r e t e n t i o n c h a r a c t e r i z a t i o n c a n d i f f e r e n t i a t e t h e
mechanisms i n v o l v e d i n a t t r a c t i n g t h e c h e m i c a l t o t h e s o i l s u r f a c e .
For i n s t a n c e , t h e commonly used b a t c h e q u i l i b r a t i o n method m e r e l y
d e t e r m i n e s t h e d e c r e a s e o r d i s a p p e a r a n c e o f a c h e m i c a l from s o l u t i o n
when s o i l i s added t o t h e s o l u t i o n , under t h e assumption t h a t what
does n o t remain i n t h e s o l u t i o n would be a d s o r b e d . T h i s method does
not p r o v i d e any i n f o r m a t i o n on t h e mechanism o f a d s o r p t i o n , o r t h e
strength of adsorption, o r whether the reduction i n solution
c o n c e n t r a t i o n was r e l a t e d t o a d s o r p t i o n a t a l l . S t u d i e s have shown
t h a t t h i s method c o u l d l e a d t o e r r o n e o u s e s t i m a t i o n o f a d s o r p t i o n i f
p r e c a u t i o n was n o t t a k e n i n e l i m i n a t i n g o r a c c o u n t i n g f o r d e g r a d a t i o n
of t h e c h e m i c a l d u r i n g t h e a d s o r p t i o n - d e s o r p t i o n p r o c e s s e s ( 6 , 7 ) .
A number o f q u i c k - t e s t t e c h n i q u e s have been used w i d e l y t o
e s t i m a t e t h e e x t e n t o f s o r p t i o n o f p e s t i c i d e s t o s o i l s , and t h e s e
e s t i m a t e s a r e o f t e n used i n p e s t i c i d e t r a n s p o r t models. The most
commonly used t e c h n i q u e i s t o d e t e r m i n e t h e r a t i o o f d i s t r i b u t i o n o f
a c h e m i c a l , o f t e n a t one c o n c e n t r a t i o n , between t h e s o l u t i o n and s o i l
s o l i d phases (K,) o r s i m p l y t h e d i s t r i b u t i o n between w a t e r and
o c t a n o l phases ?K ) . The u s e o f , as an i n d e x o f a d s o r p t i o n
assumes t h a t t h e R e t r i b u t i o n r a t i o i s c o n s t a n t o v e r a range o f
c o n c e n t r a t i o n s of t h e c h e m i c a l i n t h e s o i l . I n o t h e r words, t h e
amount o f c h e m i c a l adsorbed i n c r e a s e s l i n e a r l y w i t h t h a t r e m a i n i n g i n
the s o l u t i o n . The l i n e a r r e l a t i o n s h i p may be v a l i d o v e r a narrow
6 E V A L U A T I O N O F PESTICIDES IN G R O U N D WATER
range of c o n c e n t r a t i o n s . However, a p l o t t i n g o f v a l u e s t a k e n from

the l i t e r a t u r e v s . the e q u i l i b r i u m c o n c e n t r a t i o n of p e s t i c i d e i n
s o l u t i o n r e a d i l y d e m o n s t r a t e s the d i s p a r i t y o f t h e values (8).
Most literature values indicate that p e s t i c i d e adsorption data
o b t a i n e d by the b a t c h e q u i l i b r a t i o n method can be b e t t e r f i t t e d t o a
c u r v i l i n e a r e q u a t i o n , such as the F r e u n d l i c h e q u a t i o n . The wide
d i s p a r i t i e s i n the F r e u n d l i c h a d s o r p t i o n c o n s t a n t s (K^) r e p o r t e d i n
the literature should be critically evaluated, as the true
s i g n i f i c a n c e o f the d a t a o b t a i n e d by d i f f e r e n t s t u d i e s can be a
consequence of the parameters used i n the testing procedure.
K o s k i n e n and Cheng (9) have shown t h a t v a r i a t i o n s i n e x p e r i m e n t a l
p a r a m e t e r s c o u l d r e s u l t i n v a r i a t i o n s o f up t o s e v e r a l f o l d . As a
r e s u l t , m o b i l i t y o f the p e s t i c i d e 2,4,5-T ( 2 , 4 , 5 - t r i c h l o r o p h e n o x y -
a c e t i c a c i d ) i n t h e P a l o u s e s i l t loam s o i l , f o r i n s t a n c e , c o u l d be
c l a s s i f i e d as low o r h i g h depending on the e x p e r i m e n t a l p a r a m e t e r s
used.
Many s t u d i e s have shown t h a t p e s t i c i d e a d s o r p t i o n can be

c o r r e l a t e d t o t h e s o i l o r g a n i c m a t t e r c o n t e n t s , but not w i t h s o i l
m i n e r a l o r c l a y c o n t e n t s . Thus, a d s o r p t i o n c o n s t a n t s have o f t e n been
e x p r e s s e d i n terms o f the s o i l o r g a n i c m a t t e r o r o r g a n i c carbon
c o n t e n t s (K ) (4). Such c o r r e l a t i o n s have o f t e n been shown t o be
statisticalfy significant (8). Significant correlations between
sorption (K ) and estimates of sorption using water octanol
C
p a r t i t i o n (K ) (10), reverse-phase high-performance l i q u i d chroma
tographic reSiention (R )t ( 1 1 ) , and water solubility (S) o f the
c h e m i c a l (12) have l e d t o wide use o f t h e s e p a r a m e t e r s t o e s t i m a t e
. These e s t i m a t e s may be adequate as a f i r s t approximation,
e s p e c i a l l y f o r hydrophobic, nonionic chemicals. However, a rough
c o r r e l a t i o n between s o i l s o r p t i o n o f a c h e m i c a l and i t s , R , or S
t
ow t
does not a u t o m a t i c a l l y impart any t h e o r e t i c a l meaning t o the e m p i r i
cal measurement. Such f a c t o r s as s o i l s o l u t i o n composition and
temperature c a n a f f e c t t h e amount o f p e s t i c i d e s adsorbed but cannot
be a c c o u n t e d f o r by t h e s e i n d i r e c t methods. Thus, any measurement
w h i c h does n o t t a k e i n t o c o n s i d e r a t i o n the r o l e o f s o i l o r the
e n v i r o n m e n t a l v a r i a b l e s i n t h e a d s o r p t i o n p r o c e s s can a t b e s t be
s i m p l y an e s t i m a t i o n .
C e r t a i n c a u t i o n s s h o u l d a l s o be mentioned so t h a t the meaning of
t h e s e c o r r e l a t i o n s i s not extended beyond what the d a t a w a r r a n t . A
significant c o r r e l a t i o n between s o r p t i o n and soil organic carbon
c o n t e n t s does not i m p l y t h a t o n l y one mechanism o f s o r p t i o n i s
i n v o l v e d o r t h a t a l l p e s t i c i d e s i n t e r a c t w i t h a l l components o f s o i l
organic matter by the same mechanism. Furthermore, the l a c k o f
c o r r e l a t i o n between p e s t i c i d e s o r p t i o n and s o i l m i n e r a l or clay
c o n t e n t s s h o u l d n o t be t a k e n t o mean t h a t a d s o r p t i o n on s o i l m i n e r a l s
i s not i m p o r t a n t . A d s o r p t i o n of o r g a n i c c h e m i c a l s on s o i l m i n e r a l
s u r f a c e s i s a w e l l - e s t a b l i s h e d f a c t (13,14) The l a c k o f c o r r e l a t i o n
may o n l y i m p l y t h a t s o i l m i n e r a l c o n t e n t by w e i g h t i s not a good
index f o r the e x t e n t of m i n e r a l s u r f a c e a v a i l a b l e f o r a d s o r p t i o n .
The s i g n i f i c a n c e o f a d s o r p t i o n on m i n e r a l s u r f a c e s s h o u l d not be
i g n o r e d , e s p e c i a l l y i n m a t e r i a l s low i n o r g a n i c m a t t e r , such as the
g e o l o g i c a l m a t e r i a l s i n the vadose zone u n d e r n e a t h the s u r f a c e s o i l .
The c o m p l e x i t y o f the a d s o r p t i o n p r o c e s s s h o u l d be u n d e r s t o o d by
t h o s e i n t e r e s t e d i n a s s e s s i n g the impact o f s o r p t i o n on the t r a n s p o r t
of c h e m i c a l s t o the groundwater. Mechanisms o r f o r c e s i n v o l v e d i n
a d s o r p t i o n can range from v a n d e r Waals-London f o r c e s , hydrogen
bonding, l i g a n d and i o n exchange, charge t r a n s f e r , i o n - d i p o l e and

d i p o l e - d i p o l e f o r c e s , hydrophobic bonding, to chemisorption ( 5 ) . Any
s i m p l i s t i c r e p r e s e n t a t i o n o f a d s o r p t i o n such as d e p i c t i n g t h e p r o c e s s
as p a r t i t i o n i n g i n t o an o r g a n i c phase i s t o i g n o r e the t r u e n a t u r e of
the p r o c e s s e s i n v o l v e d as p o i n t e d out by M i n g l e g r i n and G e r s t l ( 1 5 ) .
Even c h a r a c t e r i z a t i o n of s o r p t i o n based s o l e l y on s o l u t e and s o l v e n t
f a c t o r s may not be adequate. The c o m p o s i t i o n o f t h e aqueous phase
can affect the pesticide-soil-solution equilibrium of certain
pesticides. F o r example, s o l u b l e o r g a n i c m a t t e r and m e t a l i o n s i n
soil solution can complex o r b i n d small organic molecules and
s t a b i l i z e them i n the aqueous phase ( 1 6 ) . K o s k i n e n and Cheng (9)
found t h a t l e a c h i n g s o i l d e c r e a s e d the amount of s o l u b l e o r g a n i c s i n
s o i l s o l u t i o n and i n c r e a s e d a d s o r p t i o n o f 2,4,5-T i n the s o i l s o l i d
phase.
C u r r e n t l y a number o f l a b o r a t o r i e s a r e d e v o t i n g c o n s i d e r a b l e
e f f o r t i n d e v e l o p i n g methodology to c h a r a c t e r i z e the v a r i o u s bonds
i n v o l v e d i n a d s o r p t i o n , many of which a r e not r e a d i l y r e v e r s i b l e by

simple e q u i l i b r a t i o n with water (e.g., 17). Thus r e t e n t i o n cannot be
viewed as p r o c e s s e s t h a t m e r e l y r e t a r d t r a n s p o r t o f p e s t i c i d e s i n
w a t e r , but can b i n d the c h e m i c a l s i r r e v e r s i b l y t o s o i l s u r f a c e s ( t h e
so-called 'bound r e s i d u e ' ) and t o t a l l y remove t h e c h e m i c a l s from
transport. Such p r o c e s s as c h e m i s o r p t i o n may not be e a s i l y d i s t i n -
g u i s h e d w i t h c h e m i c a l t r a n s f o r m a t i o n o f the compound i n the soil
media ( 1 8 ) .
Transformation Processes
The term ' t r a n s f o r m a t i o n ' i s used h e r e t o encompass a l l changes i n

the c h e m i c a l s t r u c t u r e o r c o m p o s i t i o n of the p e s t i c i d e compound. The
c h e m i c a l s t r u c t u r e may be m o d i f i e d by such r e a c t i o n s as o x i d a t i o n ,
r e d u c t i o n , h y d r o l y s i s , s u b s t i t u t i o n and removal o f f u n c t i o n a l groups,
complexation with metal i o n s , p o l y m e r i z a t i o n , and others. The
s t r u c t u r e may a l s o be b r o k e n down i n t o fragments o f the o r i g i n a l
m o l e c u l e and e v e n t u a l l y i n t o i n o r g a n i c e n d p r o d u c t s , such as HÔ, CO^,
h a l i d e , ammonium, p h o s p h a t e , and o t h e r s a l t s . The term d e g r a d a t i o n
s h o u l d o n l y be a s s o c i a t e d w i t h the breakdown p r o c e s s , a l t h o u g h i t i s
commonly used t o d e s c r i b e o t h e r t r a n s f o r m a t i o n p r o c e s s e s . One s h o u l d
be aware that while most transformation processes modify the
s t r u c t u r e t o d e t o x i f y the c h e m i c a l , o t h e r r e a c t i o n s may l e a d t o more
toxic products. A n o t a b l e example i s t h e f o r m a t i o n o f 3,3'4,4'-
t e t r a c h l o r o a z o b e n z e n e by c o n d e n s a t i o n o f 3 , 4 - d i c h l o r o a n i l i n e w h i c h i s
a d e g r a d a t i o n p r o d u c t o f many a n i l i d e h e r b i c i d e s ( 1 9 ) . Only by
degradation can a pesticide be totally eliminated from the
environment.
P e s t i c i d e s can be t r a n s f o r m e d by c h e m i c a l , p h o t o c h e m i c a l , and
b i o c h e m i c a l means. S o i l can p r o v i d e the c o n d i t i o n s o r s e r v e as the
c a t a l y s t o r component f o r c h e m i c a l r e a c t i o n s . C h e m i c a l r e a c t i o n s a r e
m e d i a t e d by such s o i l p r o p e r t i e s as pH o r c a t a l y z e d by s o i l m i n e r a l s
(20). P h o t o l y s i s of a c h e m i c a l can r e s u l t d i r e c t l y from a b s o r b i n g
r a d i a t i o n o r i n d i r e c t l y by r e a c t i o n w i t h a n o t h e r c h e m i c a l w h i c h i s
a c t i v a t e d by absorbed r a d i a t i o n . However, the predominant means of
transformation i s m i c r o b i a l or enzymatic. Mechanisms o f these
r e a c t i o n s have been e x t e n s i v e l y reviewed and summarized (21-23).
A t t e n t i o n s h o u l d be g i v e n t o e x p e r i m e n t a l methods b o t h f o r
characterizing the process and for assessing the kinetics of
degradation. C h a r a c t e r i z a t i o n o f d e g r a d a t i o n under f i e l d c o n d i t i o n s
is o f t e n complicated by other processes such as r e t e n t i o n and
t r a n s p o r t a c t i n g s i m u l t a n e o u s l y on t h e c h e m i c a l ( 2 4 ) . S t u d i e s on
p e r s i s t e n c e , d i s s i p a t i o n , d i s a p p e a r a n c e , o r l o s s o f e f f e c t i v e n e s s of
p e s t i c i d e s a r e u s u a l l y not a d i r e c t measure o f p e s t i c i d e d e g r a d a t i o n .
The i n f l u e n c e o f a l l p r o c e s s e s must be s o r t e d out b e f o r e t h a t
a t t r i b u t a b l e t o d e g r a d a t i o n can be e v a l u a t e d .
The k i n e t i c s o f p e s t i c i d e d e g r a d a t i o n i s a f f e c t e d by (a) the
quantity and availability of the pesticides, (b) presence of
m i c r o o r g a n i s m s o r enzyme systems c a p a b l e o f d e g r a d i n g the p e s t i c i d e ,
and (c) a c t i v i t y l e v e l o f t h e m i c r o o r g a n i s m s as a f f e c t e d by the
nutrients available to sustain the microbial population; by
environmental c o n d i t i o n s such as temperature, moisture, oxygen
s u p p l y , a e r a t i o n ; and by v a r i o u s s o i l p a r a m e t e r s . Many models f o r
e s t i m a t i n g t h e f a t e o f p e s t i c i d e s i n t h e environment assume t h a t
d e g r a d a t i o n can be s i m p l y e x p r e s s e d as a f i r s t o r d e r r e a c t i o n w i t h
r e s p e c t t o p e s t i c i d e c o n c e n t r a t i o n , a l t h o u g h the inadequacy o f t h i s
approach has been p o i n t e d out r e p e a t e d l y ( e . g . , 25-27). Expressions
for biodgradation rates should i n c l u d e c o n s i d e r a t i o n s of the
s u b s t r a t e c o n c e n t r a t i o n as w e l l as t h e a c t i v i t i e s o f microorganisms
or enzyme systems p r e s e n t , such as the Monod e q u a t i o n or the
analogous M i c h a e l i s - M e n t e n e q u a t i o n f o r enzyme k i n e t i c s . Lewis et
al. (27) have c a l l e d a t t e n t i o n t o t h e need t o have a m u l t i p h a s i c
approach in expressing the kinetics of pesticide degradation,
depending on the c o n c e n t r a t i o n o f the c h e m i c a l i n t h e environment. A
number o f s t u d i e s from A l e x a n d e r ' s l a b o r a t o r y (28) have shown t h a t
the k i n e t i c s o f d e g r a d a t i o n c a l c u l a t e d from the r a t e s n o r m a l l y used
f o r such s t u d i e s may not be a p p l i c a b l e f o r p e s t i c i d e s at e x t r e m e l y
low c o n c e n t r a t i o n s . The same c o u l d a l s o be s a i d f o r v e r y h i g h
c o n c e n t r a t i o n s of p e s t i c i d e s (e.g. 29).
In a d d i t i o n t o the amount of p e s t i c i d e p r e s e n t , the d e g r a d a t i o n
r a t e c o u l d be a f f e c t e d by t h e a v a i l a b i l i t y o f t h e c h e m i c a l f o r
degradation. Ogram e t a l . (30) have r e c e n t l y p r e s e n t e d evidence
s u g g e s t i n g t h a t o n l y the 2,4-D (2,4-dichloro phenoxyacetic acid) i n
s o i l s o l u t i o n , but not t h a t adsorbed on s o i l c o l l o i d s , c o u l d be
degraded by s o i l m i c r o b e s b o t h i n s o i l s o l u t i o n and sorbed on s o i l
colloids. Other c o n s i d e r a t i o n s s h o u l d a l s o be g i v e n t o the n a t u r e
and q u a n t i t y of soil m i c r o b i a l biomass p r e s e n t in relation to
n u t r i e n t a v a i l a b i l i t y (26,28,31) and the a d a p t a b i l i t y o f m i c r o b e s ,
e i t h e r by n a t u r a l s e l e c t i o n o r by g e n e t i c m a n i p u l a t i o n , t o a t t a c k and
u t i l i z e the p e s t i c i d e c h e m i c a l ( 3 2 ) .
Most of our knowledge on pesticide degradation has been
accumulated from s t u d i e s w i t h s u r f a c e s o i l s and under l a b o r a t o r y
incubation conditions. However, i t i s d i f f i c u l t to p r e d i c t the
b e h a v i o r o f p e s t i c i d e s under f i e l d c o n d i t i o n s from d a t a o b t a i n e d
under a c o n t r o l l e d l a b o r a t o r y c o n d i t i o n . The d e g r a d a t i o n i n s o i l
c o n t a i n i n g p l a n t s may be e n t i r e l y d i f f e r e n t . Root exudates and
decaying root fragments can provide energy and nutrients for
m i c r o b i a l growth (33) and l e a d t o an a c c e l e r a t e d m i n e r a l i z a t i o n o f
p e s t i c i d e s i n the r h i z o s p h e r e (34,35). The p r e s e n c e o f p l a n t s w i l l
also affect soil water potential, which i n turn affects soil
m i c r o b i a l a c t i v i t i e s and the d e g r a d a t i o n p r o c e s s e s . Furthermore,
i n d i c a t i o n s a r e t h a t o r g a n i c c h e m i c a l s do degrade i n the vadose zone
and i n groundwater ( e . g . , 36-38), but the mechanisms and k i n e t i c s of
d e g r a d a t i o n are m o s t l y unknown. More a t t e n t i o n i s needed t o b e t t e r
c h a r a c t e r i z e the mechanisms and k i n e t i c s of p e s t i c i d e d e g r a d a t i o n in

the vadose zone.
Transport Processes
A l t h o u g h the downward t r a n s p o r t of p e s t i c i d e s by water i s of u l t i m a t e

c o n c e r n i n e v a l u a t i n g the p o t e n t i a l of groundwater c o n t a m i n a t i o n ,
other modes o f pesticide transport should also be taken into
consideration. These p r o c e s s e s i n c l u d e the upward t r a n s p o r t by w a t e r
to s o i l s u r f a c e , evaporation o r v o l a t i l i z a t i o n from s o i l surface,
t r a n s p o r t by water i n s u r f a c e r u n o f f o r by s o i l p a r t i c l e s i n e r o s i o n ,
and uptake by plants. The volatilization process involves two
s t a g e s : the upward movement t o s o i l s u r f a c e and the escape from the
s o i l surface. V o l a t i l i z a t i o n i s a f u n c t i o n of the v a p o r p r e s s u r e of
the p e s t i c i d e and i s a f f e c t e d by p e s t i c i d e c o n c e n t r a t i o n , soil-water
content, adsorptivity of the soil, diffusion rate in soil,
t e m p e r a t u r e , and a i r movement (39-41). A model a c c o u n t i n g f o r most

of the p r o c e s s e s a f f e c t i n g v o l a t i l i z a t i o n has been t e s t e d by J u r y e t
al. (42). A l t h o u g h v o l a t i l i z a t i o n l o s s e s a r e u s u a l l y most r a p i d
i m m e d i a t e l y f o l l o w i n g p e s t i c i d e a p p l i c a t i o n , the c o n t i n u e d slow l o s s
over an extended p e r i o d i n a w a t e r - d e f i c i e n t environment such as i n
the a r i d west can a l s o be s i g n i f i c a n t .
P e s t i c i d e t r a n s p o r t by s u r f a c e r u n o f f and s o i l erosion i s a
f u n c t i o n of time l a g between r a i n f a l l and a p p l i c a t i o n ; the c h e m i c a l
n a t u r e and p e r s i s t e n c e of the p e s t i c i d e ; the h y d r o l o g i c a l , s o i l , and
v e g e t a t i v e c h a r a c t e r i s t i c s o f the f i e l d ; and the method and t a r g e t of
a p p l i c a t i o n (43). Wauchope (44) found t h a t u n l e s s s e v e r e r a i n f a l l
o c c u r r e d s h o r t l y a f t e r p e s t i c i d e a p p l i c a t i o n , t o t a l l o s s e s f o r the
m a j o r i t y o f p e s t i c i d e s due t o r u n o f f were l e s s t h a n 0.5% of the
amount a p p l i e d i n most c a s e s , a l t h o u g h s i n g l e - e v e n t l o s s e s from s m a l l
p l o t s o r watersheds can be much g r e a t e r .
In a s s e s s i n g the f a t e of p e s t i c i d e s i n the e n v i r o n m e n t , the
p r o c e s s o f p l a n t u p t a k e and i t s consequences have o f t e n been i g n o r e d ,
even though i t s importance i s r e a d i l y r e c o g n i z e d i n any s t u d y on the
e f f i c a c y of the c h e m i c a l (45,46). P l a n t s not o n l y degrade p e s t i c i d e s
and enhance t h e i r d e g r a d a t i o n , but t h e y can also participate i n
pesticide transport. I f the p e s t i c i d e i s not degraded a f t e r b e i n g
t a k e n up by p l a n t s , the p e s t i c i d e c o u l d be p a s s e d t h r o u g h the f o o d
c h a i n when the plants are harvested and consumed, o r c o u l d be
r e c y c l e d back t o s o i l i f the p l a n t p a r t s f a l l back on the ground and
are not removed.
Systems Approach
A number of m o d e l i n g approaches a t t e m p t i n g t o d e p i c t the p r o c e s s of

downward transport of pesticides to the groundwater have been
published (47) or presented at this symposium. A conceptual
framework f o r any such c o n s i d e r a t i o n s w i l l i n c l u d e not only the
r e t e n t i o n , t r a n s f o r m a t i o n , and t r a n s p o r t p r o c e s s e s i n v o l v e d , but a l s o
the f a c t o r s a f f e c t i n g a l l the p r o c e s s e s as i n p u t s t o the model,
before the outcome of a l l p r o c e s s e s a c t i n g s i m u l t a n e o u s l y on the
p e s t i c i d e s can be p r e d i c t e d ( F i g u r e 2 ) . Some o f the major f a c t o r s
can be b r o a d l y d i v i d e d as f o l l o w s :
I. P e s t i c i d e f a c t o r s :
Chemical p r o p e r t i e s : s t r u c t u r e , s o l u b i l i t y , v o l a t i l i t y
A p p l i c a t i o n methods: f o r m u l a t i o n , r a t e , mode
D e g r a d a t i o n p a t t e r n s : pathways, m e t a b o l i t e formation
II. Soil factors:
S o i l p r o p e r t i e s : type and amount of o r g a n i c m a t t e r , c l a y , and

amorphous m a t e r i a l s , pH, s t r u c t u r e ,
permeability
S o i l conditions: moisture, aeration, nutrient status, microbial
a c t i v i t y , h e t e r o g e n e i t y , d e p t h t o water t a b l e
Land forms: t o p o g r a p h y , s l o p e l e n g t h and s t e e p n e s s ,
drainage
I I I . Plant factors:
Species c h a r a c t e r i s t i c s
Stage of growth
Root system and rhizosphere
IV. Environmental f a c t o r s :
Temperature
Precipitation
A i r movement
Radiation
This l i s t i s by no means an e x h a u s t i v e one, but i t r e v e a l s the

m u l t i f a r i o u s i n t e r a c t i o n s o f the f a c t o r s i n v o l v e d t h a t a f f e c t a l l the
processes. What we have attempted i n t h i s p r e s e n t a t i o n was t o p o i n t
out some of the d i f f i c u l t i e s and p i t f a l l s one s h o u l d be aware of i n
any attempt t o model p e s t i c i d e t r a n s p o r t as w e l l as o t h e r f a c t o r s
a f f e c t i n g the f a t e of p e s t i c i d e i n the environment. While m o d e l i n g
can be an i m p o r t a n t t o o l f o r e s t i m a t i o n of p e s t i c i d e movement and
fate i n the environment, the current l a c k o f knowledge of the
mechanisms and i n t e r a c t i o n s of factors and processes a f f e c t i n g
p e s t i c i d e b e h a v i o r i n the environment has l e d t o assumptions and
simplifications i n the systems t o be modeled. Errors either i n
estimation s i m p l i f i c a t i o n s or inherent in the assumptions are
d i f f i c u l t to q u a n t i f y . Moreover, e r r o r s associated with inputs f o r
each f a c t o r or p r o c e s s i n the model can be compounded by e r r o r s i n
subsequent i n t e r a c t i o n s . Thus p r e d i c t i v e v a l u e s o b t a i n e d from many
c u r r e n t models must a l l be a c c e p t e d w i t h c a u t i o n i f they a r e to be
used f o r assessment p u r p o s e s .
As a f i n a l i t e m of f o o d f o r t h o u g h t , we would l i k e t o m e n t i o n
t h a t one sometimes has the i m p r e s s i o n t h a t p e s t i c i d e movement i n t o
groundwater i s an i n e v i t a b i l i t y , e s p e c i a l l y i f the c h e m i c a l moves
beyond the r o o t zone i n t o the s u b s o i l where m i c r o b i a l a c t i v i t i e s a r e
much lower and d e g r a d a t i o n would be l e s s e n e d . We a r e reminded of the
s o i l genesis process i n that a great d e a l of s o l u b l e organic matter
has been l e a c h e d from the s u r f a c e s o i l down i n t o the s u b s o i l o v e r
c e n t u r i e s and even m i l l e n n i a o f s o i l development. The q u e s t i o n i s
why have we not seen a m a s s i v e amount of n a t u r a l o r g a n i c m a t t e r i n
C H E N G A N D KOSKINEN Affecting Transport of Pesticides to Ground Water
Inputs Processes Output

Organisms
(plant, microbes)
F i g u r e 2 . I n t e r a c t i o n s o f t h e f a c t o r s and p r o c e s s e s affecting
the f a t e o f p e s t i c i d e s i n t h e s o i l environment.
12 EVALUATION OF PESTICIDES IN GROUND WATER
the groundwater? Perhaps we have n o t y e t a t t a i n e d n e a r l y t h e l e v e l

of u n d e r s t a n d i n g o f a l l t h e p r o c e s s e s i n v o l v e d i n the r e t e n t i o n ,
transformation, and t r a n s p o r t o f c h e m i c a l s i n t h e s o i l as we s h o u l d
have. The c h a l l e n g e i s s t i l l i n f r o n t o f u s .
Acknowledgments
J o i n t c o n t r i b u t i o n from Department o f Agronomy and S o i l s , Washington

State U n i v e r s i t y , P u l l m a n , and S o u t h e r n Weed S c i e n c e L a b o r a t o r y ,
USDA-ARS, S t o n e v i l l e , MS. S c i e n t i f i c Paper No. 7215. C o l l e g e o f
Agriculture and Home Economics R e s e a r c h C e n t e r , Washington State
U n i v e r s i t y , P u l l m a n , P r o j e c t 1858.
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11
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Guenzi, W. D., Ed.; Soil Science Society of America, Madison, WI,
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Weed Sci. 1985, (in press).
RECEIVED April 7, 1986
2
Soil Characteristics Affecting Pesticide Movement
into Ground Water
Charles S. Helling and Timothy J. Gish
Agricultural Research Service, U.S. Department of Agriculture, Beltsville, M D 20705
Processes that modify convective transport of pesti-

cides through soil and into groundwater include adsorp-
tion/desorption, degradation, volatilization, runoff,

and plant uptake. These processes, in turn, are
affected by soil characteristics, climate, pesticide
properties, and agricultural practices. A screening
model based on the convection-dispersion equation
(assuming 1st-order degradation) was used to rank sev-
eral soil properties that may affect atrazine leaching.
Transport was most retarded by low hydraulic conductiv-
ity and high soil organic matter content; increased
bulk density attenuated leaching to a lesser extent. A
literature survey, with emphasis on atrazine, aldicarb,
and DBCP (pesticides that have leached to groundwater),
tended to confirm that sandy soils (with high hydraulic
conductivity and low organic matter) were usually asso-
ciated with leaching. Restricted drainage has led to
lateral subsurface movement or occurrence of residues
in perched groundwater. At the other extreme, karst
topography allowed rapid recharge and high probability
of pesticide leaching.
Groundwater i s e s t i m a t e d t o s u p p l y 40-50% o f U.S. d r i n k i n g water
needs, and c o n s t i t u t e s at l e a s t p a r t o f t h e water s o u r c e f o r 75% o f
American c i t i e s ( 1 ) . About 95% o f t h e r u r a l p o p u l a t i o n depends on
groundwater f o r t h e i r d r i n k i n g water. R e l i a n c e on groundwater f o r
domestic consumption and a g r i c u l t u r a l uses becomes i n c r e a s i n g l y
important i n t h e more a r i d Western s t a t e s .
Groundwater c o n t a m i n a t i o n i n t h e U.S. was r e v i e w e d by Pye e t a l .
i n 1983 (1) The most common s o u r c e s o f such c o n t a m i n a t i o n i n c l u d e d
human and a n i m a l wastes, i n d u s t r i a l w a s t e s , p e t r o l e u m p r o d u c t s , l a n d -
f i l l l e a c h a t e , and ( a l o n g c o a s t a l r e g i o n s ) s a l t w a t e r i n t r u s i o n . Con-
t a m i n a t i o n from t h e a g r i c u l t u r a l use o f p e s t i c i d e s was a p p a r e n t l y f a r
l e s s common. N e v e r t h e l e s s , by 1984, Cohen e t a l . (2) r e p o r t e d t h a t
This chapter not subject to U.S. copyright.

Published 1986, American Chemical Society
2. H E L L I N G A N D GISH Soil Characteristics Affecting Pesticide Movement 15
12 p e s t i c i d e s were found i n groundwaters o f 18 s t a t e s as a c o n s e -

quence o f such u s e . T y p i c a l p o s i t i v e r e s i d u e l e v e l s v a r i e d w i d e l y ,
a l t h o u g h most commonly t h e y ranged from c a . 1-100 ppb.
The e x t e n t o f p e s t i c i d e l e a c h i n g depends on a c o m b i n a t i o n o f
f a c t o r s that include the physicochemical c h a r a c t e r i s t i c s o f the
pesticide (or i t s degradation products), s o i l properties, climate,
and agronomic f a c t o r s such as t h e t i m i n g , r a t e , and method o f
p e s t i c i d e a p p l i c a t i o n , t h e use o f i r r i g a t i o n , and t h e i n f l u e n c e o f
c r o p c o v e r . Whether a c t u a l c o n t a m i n a t i o n o f groundwater o c c u r s i s
a l s o i n f l u e n c e d by t h e depth t o groundwater and t h e p e r m e a b i l i t y o f
overlying s o i l .
In t h i s paper, we w i l l f i r s t f o c u s on s o i l f a c t o r s t h a t a f f e c t
p e s t i c i d e l e a c h i n g through t h e r o o t zone and i n t o t h e s u b s o i l . The
general c o n v e c t i o n - d i s p e r s i o n equation with f i r s t - o r d e r degradation
w i l l be used t o c h a r a c t e r i z e t h e e f f e c t s o f v a r i o u s s o i l p r o p e r t i e s
on a t r a z i n e movement. I n t h e remainder o f t h e paper, we w i l l d i s c u s s
l a b o r a t o r y and f i e l d experiments t h a t focus on a d s o r p t i o n and l e a c h -

ing. G e n e r a l i z a t i o n s from t h e s e s t u d i e s w i l l be compared w i t h s o i l
p r o p e r t i e s at s i t e s o f known groundwater c o n t a m i n a t i o n . F i n a l l y , the
r e s u l t s from t h e t r a n s p o r t model a n a l y s i s w i l l be used i n c o n j u n c t i o n
w i t h t h e l i t e r a t u r e r e v i e w t o propose a h i e r a r c h i c a l r a n k i n g o f
properties a f f e c t i n g leaching.
Background: Soil Properties
S o i l s c a n be c h a r a c t e r i z e d i n many ways, depending, f o r example, on

whether p r i m a r y c o n c e r n r e l a t e s t o agronomic a p p l i c a t i o n s , e n g i n e e r -
ing u t i l i t y , o r s o i l g e n e s i s . From t h e s t a n d p o i n t o f p r e d i c t i n g
p e s t i c i d e t r a n s p o r t , a s e r i e s o f p h y s i c a l , c h e m i c a l , and b i o l o g i c a l
properties some t r a n s i e n t c o u l d be c o n s i d e r e d . For convenience,
we have l i s t e d many such parameters i n o u t l i n e form w i t h i n T a b l e I .
Numerous r e f e r e n c e s d e s c r i b e them and t h e i r a n a l y s i s (3-7).
In a d d i t i o n t o t h e c l a s s i f i c a t i o n o f p r o p e r t i e s i n T a b l e I , t h e
s i t e c a n be c h a r a c t e r i z e d f u r t h e r as i n T a b l e I I . S u r f a c e o r
s u b s u r f a c e d r a i n a g e systems, i f p r e s e n t , would be important
additional descriptions.
Background: Other R e l a t e d Properties
M e t e r e o l o g i c a l c o n d i t i o n s a f f e c t t r a n s p o r t o f water and s o l u t e s
s i n c e , i n t h e absence o f i r r i g a t i o n , t h e y determine how much water
r e a c h e s t h e s o i l s u r f a c e , what t h e i n t e n s i t y and f r e q u e n c y o f t h a t
p r e c i p i t a t i o n i s , and how much water i s r e c y c l e d from t h e s o i l v i a
vapotranspiration l o s s e s . Temperature i n f l u e n c e s t h e r a t e o f p e s t i -
c i d e d e g r a d a t i o n and t h e r a t e s o f water and p e s t i c i d e v o l a t i l i z a t i o n .
P r o p e r t i e s o f t h e p e s t i c i d e s t r o n g l y a f f e c t the tendency t o l e a c h and
degrade, but a r e a d d r e s s e d elsewhere i n t h i s symposium. A g r i c u l t u r a l
f a c t o r s such as t h e manner and t i m i n g o f p e s t i c i d e a p p l i c a t i o n and
the c r o p p i n g t i l l a g e p r a c t i c e have p o t e n t i a l impact on t h e u l t i m a t e
fate of a chemical. These v a r i o u s n o n s o i l f a c t o r s a r e l i s t e d i n
Table I I I .
Table I. Classification o f Some S o i l Properties
A. P h y s i c a l composition
1. S o i l t e x t u r e (% Sand, s i l t , clay; gravel)
2. S o i l organic matter content (% OM)
B. Chemical c o m p o s i t i o n
1. Clay mineralogy
2. O r g a n i c m a t t e r type
C. Physical properties
1. Bulk d e n s i t y
2. F i e l d moisture capacity
3. Hydraulic conductivity
4. Pore s i z e d i s t r i b u t i o n , macropores; tendency t o c r a c k
on d r y i n g
D. Chemical p r o p e r t i e s
1. pH
2. Cation-exchange c a p a c i t y (CEC); anion-exchange capacity
3. % Base s a t u r a t i o n
4. Redox p o t e n t i a l , Eh
E. Transient s o i l properties
1. S o i l moisture content (volumetric)
2. S o i l temperature
F. Biological/biochemical properties
1. Number and type o f m i c r o o r g a n i s m s
2. A c t i v i t y o f s p e c i f i c enzymes
Table II. Classification o f Some Macro S o i l Properties
A. Surface
1. Relief
2. Slope
B. Subsurface
1. P r o f i l e changes ( t y p e , d e p t h , and a r e a l homogeneity)
2. Restricting layers
3. Depth t o groundwater ( p e r c h e d and u n c o n f i n e d aquifer)
2. HELLING AND GISH Soil Characteristics Affecting Pesticide Movement 17
Table I I I . C l a s s i f i c a t i o n of Nonsoil Factors P o t e n t i a l l y Affecting

T r a n s p o r t t o Groundwater
A. Climate
1. R a i n f a l l (temporal d i s t r i b u t i o n , intensity)
2. Temperature
3. E v a p o t r a n s p i r a t i o n
. Pesticide properties
1. S o i l a d s o r p t i o n c o e f f i c i e n t (K)
2. Water s o l u b i l i t y
3. O c t a n o l : water p a r t i t i o n c o e f f i c i e n t ( K ) o w
4. I o n i z a t i o n c o n s t a n t ( p K , pK^)
a
5. C h e m i c a l and b i o l o g i c a l s t a b i l i t y ( p e r s i s t e n c e i n s o i l s )
6. V o l a t i l i t y
C. Pesticide application
1. Formulation
2. Method o f a p p l i c a t i o n ( f o l i a r , s o i l s u r f a c e , s o i l
incorport ion)
3. Rate
4. Timing
5. H i s t o r y o f p e s t i c i d e use ( a c c e l e r a t e d d e g r a d a t i o n ;
buildup)
D. Agricultural practices
1. Cropland
a) Conventional t i l l a g e
b) Conservation t i l l a g e
c) Irrigation
2. Noncropland
a) Fallow
b) Rangeland, f o r e s t s , e t c .
3. S o i l amendments
Processes A f f e c t i n g Leaching
The d i s t r i b u t i o n o f p e s t i c i d e s throughout the s o i l p r o f i l e , as a

f u n c t i o n o f t i m e , r e p r e s e n t s the i n t e g r a t i o n o f p r o c e s s e s such as
mass flow, d i f f u s i o n , a d s o r p t i o n / d e s o r p t i o n , d e g r a d a t i o n , v o l a t i l i -
z a t i o n , r u n o f f , and p l a n t uptake ( t h e l a t t e r , m a i n l y as i t a f f e c t s
water movement i n the r o o t z o n e ) . These have been the s u b j e c t o f
many r e v i e w s ( 8 - 1 2 ) , and t h e r e f o r e o n l y l i m i t e d a t t e n t i o n w i l l be
g i v e n t o the s u b j e c t i n the f o l l o w i n g s e c t i o n s .
P e s t i c i d e Transport Model
M o d e l s f o r d e s c r i b i n g p e s t i c i d e t r a n s p o r t on a f i e l d s c a l e g e n e r a l l y
f a l l i n t o one o f two c a t e g o r i e s , d e t e r m i n i s t i c or s t o c h a s t i c . Deter-
m i n i s t i c models seek t o account f o r p e s t i c i d e l e a c h i n g by d e s c r i b i n g
the mechanisms g o v e r n i n g v o l a t i l i z a t i o n , a d s o r p t i o n , degradation,
c o n v e c t i o n and d i f f u s i o n , w h i l e at the same time a c c o u n t i n g f o r the

p h y s i c a l and c h e m i c a l c h a r a c t e r i s t i c s o f the s o i l medium. Due t o the
complex n a t u r e o f such an i n t e r a c t i o n , i t i s o f t e n n e c e s s a r y t o make
assumptions which are at b e s t a f i r s t a p p r o x i m a t i o n o f what o c c u r s
under f i e l d c o n d i t i o n s .
S t o c h a s t i c models assume t h a t a l t h o u g h p e s t i c i d e movement on a
s m a l l homogeneous s c a l e obeys c e r t a i n p h y s i c a l laws, the random
component a s s o c i a t e d w i t h those laws i n a heterogeneous system w i l l
override t h e i r deterministic behavior. Consequently, transport i s
a s c e r t a i n e d by e v a l u a t i n g t r a n s f e r f u n c t i o n models or by e v a l u a t i n g
the p r o b a b i l i t y d i s t r i b u t i o n o f some t r a n s p o r t p r o c e s s ( 1 3 ) . The
p r o b a b i l i t y d e n s i t y f u n c t i o n (PDF) f o r a s p e c i f i c t r a n s p o r t process,
on a f i e l d s i t e , can be combined w i t h d e t e r m i n i s t i c t h e o r y t o account
for s p a t i a l heterogeneity (14-18). However, a s o l e l y s t o c h a s t i c
model f o r s c r e e n i n g p e s t i c i d e s may be o f l i t t l e v a l u e f o r s e v e r a l
reasons. F i r s t , the PDF f o r a s p e c i f i c s o i l p r o p e r t y would r e q u i r e
the a n a l y s i s o f numerous s o i l samples. Second, a p u r e l y s t o c h a s t i c
model l a c k s the a b i l i t y o f p r e d i c t i n g the l o c a t i o n o f p o t e n t i a l l y
h a z a r d o u s areas w i t h i n a f i e l d . Third, i f large variations in s o i l
or s o i l water p r o p e r t i e s are p r e s e n t , t h e y may a f f e c t the r e l a t i v e
b e h a v i o r o f most p e s t i c i d e s i n a s i m i l a r manner.
Our t h e o r e t i c a l development o f a s c r e e n i n g model w i l l focus on
the d e t e r m i n i s t i c approach s i n c e i t may s t i l l be a p p l i e d i n a semi-
s t o c h a s t i c manner. T h i s model i s c o n d u c i v e to a n a l y z i n g the e f f e c t
of a s p e c i f i c s o i l property while holding others constant. Our
t h e o r e t i c a l c o n s i d e r a t i o n o f p e s t i c i d e t r a n s p o r t b e g i n s ( E q u a t i o n 1)
w i t h an e x p r e s s i o n o f the r a t e at which water moves through s o i l ,
where J w i s the water f l u x (volume o f water f l o w i n g through a c r o s s
s e c t i o n o f a r e a per t i m e ) , 1// i s the m a t r i c p o t e n t i a l , VH i s the
h y d r a u l i c g r a d i e n t , and K(y) i s the h y d r a u l i c c o n d u c t i v i t y .
J w = -KOf)VH (1)
F r e q u e n t l y termed the Buckingham-Darcy e q u a t i o n , E q u a t i o n 1 may

be used t o d e s c r i b e p e s t i c i d e movement through a s o i l volume by
employing mass b a l a n c e e q u a t i o n s f o r b o t h water and p e s t i c i d e
VJ W = 0 mass b a l a n c e f o r water (2a)

9t
+ =
V J S mass b a l a n c e f o r p e s t i c i d e (2b)
3t
where C i s t h e volume-averaged p e s t i c i d e c o n c e n t r a t i o n , J i s t h e
r s
s o l u t e f l u x , i s t h e v o l u m e t r i c water c o n t e n t , and i s a r e a c t i o n
term d e s c r i b i n g t h e s t a b i l i t y o r t h e r a t e o f p l a n t uptake f o r a
particular pesticide.
The s o l u t e f l u x o f t h e p e s t i c i d e c o n s i s t s o f two terms. The
f i r s t term c o r r e s p o n d s t o t h e c o n v e c t i v e o r b u l k t r a n s p o r t o f t h e
p e s t i c i d e w i t h t h e moving s o i l s o l u t i o n ; t h e second, a d i f f u s i o n -
d i s p e r s i o n term, a c c o u n t s f o r t h e random t h e r m a l m o t i o n o f t h e p e s
t i c i d e m o l e c u l e s (19) as w e l l as any hydrodynamic d i s p e r s i o n t h a t may
o c c u r due t o v a r i a t i o n s i n t h e pore water v e l o c i t y ( 2 0 ) . The mathe
matical representation of J i s g
D7C r (3)
where D i s t h e d i f f u s i o n - d i s p e r s i o n c o e f f i c i e n t . Combining E q u a t i o n s
2a, 2b, and 3, a s o l u t e t r a n s p o r t e q u a t i o n i n one d i m e n s i o n c a n be
w r i t t e n where
3 r
c
^ C2
r3C r
R = D ~ - V - ruC
r r (4a)
9t 32 3
where
R = l + ! ^ (4b)
and
S = KC r (4c)
Here, i s the s o i l bulk d e n s i t y , i s the f i r s t - o r d e r d e g r a d a t i o n

coefficient, i s the d i s t r i b u t i o n c o e f f i c i e n t f o r the s o i l / w a t e r
phases, V i s t h e average pore water v e l o c i t y (V = J / 8 ) , i s t h e w
s o i l d e p t h , S i s t h e adsorbed c o n c e n t r a t i o n p e r u n i t o f mass, and

R i s a dimensionless v a r i a b l e .
The assumption o f a l i n e a r a d s o r p t i o n i s o t h e r m , = in
E q u a t i o n 4b, may be v a l i d under low s o l u t i o n c o n c e n t r a t i o n s ( 2 1 ) .
However, Rao and D a v i d s o n (22) showed t h a t t h i s assumption c o u l d
produce e r r o r s w i t h i n a f a c t o r o f 2 o r 3. A d d i t i o n a l l y , c a n be
e s t i m a t e d from s o i l OM c o n t e n t ( 2 2 ) . C o n s e q u e n t l y , t h e s o l u t i o n
o f E q u a t i o n 4a, s u b j e c t e d t o a p p r o p r i a t e i n i t i a l and boundary c o n d i

t i o n s , can be used t o p e r f o r m a s e n s i t i v i t y a n a l y s i s on the e f f e c t o f
f^, OM and J w on p e s t i c i d e movement.
To s o l v e E q u a t i o n 4a, boundary c o n d i t i o n s are imposed t h a t
d e s c r i b e the i n i t i a l s o i l c o n d i t i o n s w i t h r e s p e c t t o the p e s t i c i d e
and the method o f c h e m i c a l a p p l i c a t i o n . I n i t i a l l y , t h e r e may be some
f i n i t e c o n c e n t r a t i o n i n the s o i l due t o the p r e v i o u s y e a r ( s ) o f pes
t i c i d e a p p l i c a t i o n . T h i s r e s i d u a l c o n c e n t r a t i o n w i l l be denoted i n
the s o l u t i o n as (see Appendix I ) . I f the p e s t i c i d e i s a p p l i e d
as a one-time a p p l i c a t i o n (per growing s e a s o n ) , a p u l s e boundary
c o n d i t i o n at the s u r f a c e and a f l u x bottom boundary c o n d i t i o n are
well s u i t e d (23). The s o l u t i o n o f E q u a t i o n 4a w i t h t h e s e r e s t r i c
t i o n s i s g i v e n by van Genuchten and A l v e s ( 2 4 ) .
A l t h o u g h the d e t e r m i n i s t i c model p r e s e n t e d assumes s t e a d y s t a t e
c o n d i t i o n s , l a b o r a t o r y s t u d i e s have shown t h a t s o l u t e t r a n s p o r t under
t r a n s i e n t f l o w c o n d i t i o n s may be approximated by assuming an
e q u i v a l e n t u n i f o r m water f l u x and water c o n t e n t ( 2 5 - 6 ) .
Model Assumptions
The model p r e s e n t e d can be used f o r s c r e e n i n g n o n v o l a t i l e p e s t i c i d e s

under v a r i o u s f i e l d c o n d i t i o n s . The assumptions b e h i n d i t s d e r i v a
t i o n should be c l e a r l y s t a t e d , as we attempt t o do f o r the f o l l o w i n g
a t t e n u a t i o n and t r a n s p o r t mechanisms.
A d s o r p t i o n . The s o l u t i o n used t o e v a l u a t e the p e s t i c i d e t r a n s p o r t

e q u a t i o n , E q u a t i o n 4a, assumes a l i n e a r a d s o r p t i o n i s o t h e r m t h a t i s
c o n s t a n t w i t h d e p t h . However, l i n e a r i t y may not be the case f o r some
p e s t i c i d e s and the a d s o r p t i o n c o e f f i c i e n t w i l l almost never be
constant with depth. The r a t i o n a l e f o r u s i n g a l i n e a r model i s
i n i t i a l l y based on the F r e u n d l i c h i s o t h e r m
1 11
S = KC / (5)
where i s the F r e u n d l i c h c o n s t a n t , and 1/n i s an exponent t h a t

g e n e r a l l y ranges between c a . 0.5 and 1.2. I f 1/n i s assumed t o be 1,
the r e s u l t i n g e q u a t i o n i s l i n e a r , i . e . , = i n E q u a t i o n 4c. Al
though the v a l i d i t y i s s t i l l under d i s c u s s i o n , K a r i c k h o f f (21) c o n s i
dered t h a t f o r the low s o l u t i o n c o n c e n t r a t i o n s t y p i c a l l y a s s o c i a t e d
w i t h p e s t i c i d e s , the l i n e a r model i s a p p r o p r i a t e . Rao and D a v i d s o n
(22) showed t h a t the assumption o f l i n e a r i t y c o u l d produce e r r o r s
w i t h i n a f a c t o r o f 2 or 3. The v a l u e o f i s c r i t i c a l s i n c e i t i n d i
c a t e s the p r o p o r t i o n o f p e s t i c i d e i n the m o b i l e water phase. has
o f t e n been used t o p r e d i c t the e x t e n t o f l e a c h i n g by assuming o n l y
c o n v e c t i v e movement and a d s o r p t i o n i n a r e t a r d a t i o n f a c t o r , R, as i n
E q u a t i o n 4b (14, 27-8).
S i n c e the a d s o r p t i o n c o e f f i c i e n t i s c r i t i c a l t o the t h e o r e t i c a l
development, c a u t i o n s h o u l d be e x e r c i s e d i n u s i n g a p a r t i c u l a r
v a l u e f o r a p a r t i c u l a r s o i l and p e s t i c i d e . The most common method
used t o measure a d s o r p t i o n i s by the b a t c h e q u i l i b r i u m t e c h n i q u e , i n
which s o i l samples are e q u i l i b r a t e d w i t h a s e r i e s o f p e s t i c i d e c o n
centrations. However, the e q u i l i b r i u m time i s c r i t i c a l , and may not
r e p r e s e n t a d s o r p t i o n under f i e l d c o n d i t i o n s where the p e s t i c i d e i s
moving i n the s o l u t i o n phase. C o n s e q u e n t l y , f l o w e q u i l i b r i u m methods
have a l s o been d e v e l o p e d ( 2 9 ) .
The a d s o r p t i o n c a n a l s o be e s t i m a t e d from t h e s o i l OM c o n t e n t .
O r g a n i c m a t t e r has been shown t o be a p r i m a r y s i t e f o r a d s o r p t i o n
( u n l e s s t h e p e s t i c i d e i s permanently c h a r g e d ) . As a r e s u l t , t h e
a d s o r p t i o n c o e f f i c i e n t may be approximated by t h e e q u a t i o n
= o c K o c (6)
where K o c i s t h e c o e f f i c i e n t o f l i n e a r a d s o r p t i o n n o r m a l i z e d on
o r g a n i c carbon and f Q Ci s the f r a c t i o n a l content o f organic
carbon ( 2 2 ) . K Q C c a n o f t e n be o b t a i n e d from p r e v i o u s l y p u b l i s h e d
v a l u e s o r e s t i m a t e d from t h e o c t a n o l : w a t e r p a r t i t i o n c o e f f i c i e n t
(30). One advantage o f employing E q u a t i o n 6 i s t h a t i t a l l o w s one
t o model t h e e f f e c t o f o r g a n i c m a t t e r on t r a n s p o r t . A d d i t i o n a l l y ,
the use o f E q u a t i o n 6 has o f t e n r e s u l t e d i n r e d u c i n g t h e c o e f f i c i e n t
o f v a r i a t i o n a s s o c i a t e d w i t h (22, 31-2). Thus, E q u a t i o n 6 w i l l be
employed i n s o l v i n g E q u a t i o n 4 a .
D i f fus ion-D i s p e r s i o n . A d i f f u s i o n - d i s p e r s i o n c o e f f i c i e n t was used i n

t r a n s p o r t E q u a t i o n 4. Depending upon t h e water v e l o c i t y , e i t h e r d i f
f u s i o n o r d i s p e r s i o n would be t h e d o m i n a t i n g mechanism. F o r r e l a
t i v e l y m o b i l e c h e m i c a l s , t h e v a r i a b i l i t y i n D may be l i n k e d d i r e c t l y
to t h e water v e l o c i t y ( 3 3 - 4 ) . C o n s e q u e n t l y , D would be dominated by
hydrodynamic d i s p e r s i o n w i t h D = SV, where d i s p e r s i v i t y ranges from
0.1-4 cm ( 3 5 ) . On t h e o t h e r hand, d i f f u s i o n may be t h e dominant mech
anism c o n t r o l l i n g t h e magnitude o f D, e s p e c i a l l y i f water movement i s
slow. I n a f i e l d s e t t i n g , t h e time between p r e c i p i t a t i o n e v e n t s w i l l
be much g r e a t e r than t h e d u r a t i o n o f p r e c i p i t a t i o n e v e n t s , a l l o w i n g
more time f o r d i f f u s i o n t h a n d i s p e r s i o n . T h i s being the case, the
d i f f u s i o n c o e f f i c i e n t c a n be e s t i m a t e d by u s i n g the M i l l i n g t o n and
Q u i r k t o r t u o s i t y model (36)
1 / 3 2
D = ( /0 ) D w a t e r (7)
where 0 i s t h e p o r o s i t y o f t h e b u l k s o i l and D w a t e r i s the d i f f u s i o n

c o e f f i c i e n t i n water; f o r most p e s t i c i d e s , D w a t e r c a n be a p p r o x i
5 2 1
mated as 4.3 X 1 0 ~ m day" .
Convection. Convection i s the bulk transport o f p e s t i c i d e with the

moving s o i l s o l u t i o n . C o n s e q u e n t l y , t h e water v e l o c i t y i s t h e major
mechanism g o v e r n i n g c o n v e c t i v e t r a n s p o r t . Numerous s t u d i e s have
shown t h a t a s t o c h a s t i c r e p r e s e n t a t i o n o f t h e water v e l o c i t y does a
b e t t e r job o f d e s c r i b i n g chemical t r a n s p o r t (14-8). However, f o r a
s c r e e n i n g mode, an a c c u r a t e d e p i c t i o n o f t h e water v e l o c i t y i s n o t
e s s e n t i a l s i n c e v e l o c i t y v a r i a t i o n s would a f f e c t t h e r e l a t i v e
b e h a v i o r o f most c h e m i c a l s i n a s i m i l a r manner once t h e p a r t i t i o n
c o e f f i c i e n t between t h e l i q u i d and adsorbed phases has been e s t a b
lished. P r e d i c t i o n s o f t h e average water v e l o c i t y ( e x p e c t e d o r mean
v a l u e ) have been made f o r f i e l d experiments by m o n i t o r i n g meteoro
l o g i c a l events and s u b t r a c t i n g e s t i m a t e s o f t h e vapotranspiration
from t h e water i n p u t s ( 3 3 ) .
Dgradt i o n . P e s t i c i d e d e g r a d a t i o n i s a complex phenomenon s i n c e the

p r o c e s s may be p u r e l y c h e m i c a l or dependent upon the p r e s e n c e o f
microorganisms. The assumption o f f i r s t - o r d e r k i n e t i c s may be m i s -
l e a d i n g s i n c e the d e g r a d a t i o n r a t e w i l l depend upon temperature as
w e l l as the p a r t i c u l a r phases i n which the p e s t i c i d e r e s i d e s . Thus,
a s p e c i f i c p e s t i c i d e may degrade by d i f f e r e n t mechanisms at d i f f e r e n t
rates. Assuming i s o t h e r m a l c o n d i t i o n s , the v o l u m e t r i c water c o n t e n t
w i l l d i c t a t e the o v e r a l l r a t e o f d e g r a d a t i o n ( 3 7 ) . The water c o n t e n t
a f f e c t s both a e r a t i o n as w e l l as the f r a c t i o n o f p e s t i c i d e u n d e r g o i n g
d e g r a d a t i o n i n the s o l u t i o n phase. In a d d i t i o n , the s o i l pH w i l l
a l s o a f f e c t the r a t e o f d e g r a d a t i o n f o r some p e s t i c i d e s ( 3 8 ) .
Assuming a f i r s t - o r d e r d e g r a d a t i o n p r o c e s s , the d e g r a d a t i o n r a t e
may be measured a c c o r d i n g t o
1
= In ( C / C ) t " 0 (8a)
t n e
or e s t i m a t e d from p u b l i s h e d v a l u e s o f t\/2> half-life of a
p a r t i c u l a r p e s t i c i d e , as i n E q u a t i o n 8b
1 1
In (1/2) t 1 / 9 ~ = 0.693 t ^ " (8b)
P e s t i c i d e Transport Simulations
The r e l a t i v e importance o f f^, 0M, and J on p e s t i c i d e movement was

w
a c c o m p l i s h e d by c o n d u c t i n g a s e r i e s o f computer s i m u l a t i o n s and sub

j e c t i n g the r e s u l t s t o a s e n s i t i v i t y a n a l y s i s . The s e n s i t i v i t y
a n a l y s i s compares the peak c o n c e n t r a t i o n s i n the l i q u i d phase, s i n c e
t h i s phase w i l l be the major v e h i c l e f o r p e s t i c i d e t r a n s p o r t t o
groundwater. The a t r a z i n e a p p l i c a t i o n r a t e used i n the s i m u l a t i o n s
was e q u i v a l e n t t o 2.8 kg/ha o f a c t i v e i n g r e d i e n t . The d i f f u s i o n -
2 1
d i s p e r s i o n c o e f f i c i e n t was assumed t o be c o n s t a n t , 1 cm day" . The
ranges chosen f o r 9^, 0M, J , and w i n the s i m u l a t i o n s were 0.8-

1
1.45 g m~3, 1-5%, 1-4 cm d a y " , and 0.15-0.35 m^ water/m^ s o i l , r e
spectively. These ranges c o r r e s p o n d t o t y p i c a l f i e l d v a l u e s . Since
a f a m i l y o f c u r v e s was g e n e r a t e d , o n l y a few r e p r e s e n t a t i v e c u r v e s
w i l l be shown, F i g u r e l a - c . So t h a t v i s u a l comparisons can be made
between d i f f e r e n t s i m u l a t i o n s , the a t r a z i n e p r o f i l e c o r r e s p o n d i n g t o
1
?b = 0.8, = 0.15, and J w = 1 cm d a y " was used i n F i g u r e l a - c .
A l l s i m u l a t i o n s assume t h a t 20 days have t r a n s p i r e d s i n c e a t r a z i n e
1
a p p l i c a t i o n and t h a t = 0.0098 d a y " (27, 39).
In F i g u r e l a the e f f e c t o f an i n c r e a s e d b u l k d e n s i t y on the
a t r a z i n e c o n c e n t r a t i o n p r o f i l e s i s shown, w h i l e h o l d i n g $ J , and v t w
0M c o n s t a n t . The s o i l b u l k d e n s i t y o f 0.8 g cm~3 c o r r e s p o n d s t o a

v e r y l i g h t s o i l a n d ( o r ) a s o i l t h a t has been r e c e n t l y plowed, w h i l e
=
?b 1.45 g cm~3 r e p r e s e n t s a s o i l t h a t has a n a t u r a l h i g h d e n s i t y
or a s o i l t h a t has been compacted by farm implements. As the s o i l
d e n s i t y i n c r e a s e s , the maximum p e s t i c i d e c o n c e n t r a t i o n i n the l i q u i d
phase d e c r e a s e s . A d d i t i o n a l l y , the maximum p e s t i c i d e c o n c e n t r a t i o n
w i l l o c c u r c l o s e r t o the s o i l s u r f a c e as 9^ i n c r e a s e s . S i n c e Pfc
i n c r e a s e s w i t h depth f o r most a g r i c u l t u r a l s o i l s , F i g u r e l a i n d i c a t e s
t h a t p e s t i c i d e movement would be more r e t a r d e d as i t moves t h r o u g h
the s o i l p r o f i l e , a l l o t h e r f a c t o r s h e l d c o n s t a n t . S i n c e the c o e f f i
c i e n t s o f v a r i a t i o n f o r ^ are g e n e r a l l y between 5-10%, assuming a
c o n s t a n t d e n s i t y c o u l d i n t r o d u c e e r r o r s w i t h i n a f a c t o r o f 2.
0.8 g cm-3
1.2 g cm" 3
1.45 g cm" 3
10h
<-
5% O M

2% O M
1% O M
20 h
< 30 V
1

1 cm d a y
1 /
4 cm day"
10h
L
0.1 0.2 0.3 0.4 0.5 . 0.7 0.8
SOIL D E P T H , m
F i g u r e 1. S i m u l a t e d e f f e c t o f s o i l p r o p e r t i e s on a t r a z i n e
leaching: ( a ) b u l k d e n s i t y [Pfc]; ( b ) o r g a n i c m a t t e r [0M] c o n t e n t ;
and ( c ) h y d r a u l i c c o n d u c t i v i t y [K(*^)]. Other symbols used i n c l u d e
( v o l u m e t r i c water c o n t e n t ) , V ( a v e r a g e pore water v e l o c i t y ) ,
and 3H/9z ( h y d r a u l i c g r a d i e n t ) . Assumptions a r e : F i g . l a 2 % OM
1 - 1
and J = 1 cm day"" ; F i g . l b =
w 0.8 and J = 1 cm d a y ;
w
F i g . l c - 2 % 0M and P = 0.8.b
The e f f e c t o f o r g a n i c m a t t e r c o n t e n t on a t r a z i n e movement i s
shown i n F i g u r e l b . L i k e the t r e n d f o r b the maximum p e s t i c i d e
c o n c e n t r a t i o n d e c r e a s e s as OM i n c r e a s e s . A l t h o u g h the s i m u l a t i o n s
assume a c o n s t a n t OM c o n t e n t w i t h d e p t h , most o f the peak c o n c e n t r a -
t i o n s were i n the t o p 0.3m where the o r g a n i c m a t t e r c o n t e n t s are
g e n e r a l l y l a r g e . S i n c e the o r g a n i c m a t t e r c o n t e n t g e n e r a l l y de-
c r e a s e s w i t h d e p t h , F i g u r e l b s u g g e s t s t h a t p e s t i c i d e movement w i l l
be more r e t a r d e d near the s o i l s u r f a c e . The r e l a t i v e change i n peak
c o n c e n t r a t i o n s between F i g u r e s l a and l b i n d i c a t e s t h a t the t y p i c a l
v a l u e s o f OM govern a t r a z i n e movement t o a g r e a t e r e x t e n t than does
e^. A l t h o u g h the c o e f f i c i e n t s o f v a r i a t i o n range between 20-50%, a
p r e d e t e r m i n e d mean v a l u e s h o u l d y i e l d r e s u l t s w i t h i n a f a c t o r o f 3.
K i n e t i c s may p l a y an important r o l e i n p e s t i c i d e a d s o r p t i o n (28,
39). Rapid t r a n s p o r t o f p e s t i c i d e i n l a r g e s o i l pores ( r o c k s , v o i d
r o o t c h a n n e l s , worm h o l e s , e t c . ) c o u l d take p l a c e , thus e x p o s i n g the
p e s t i c i d e t o o n l y a f r a c t i o n o f the a d s o r p t i o n s i t e s . S i n c e the
o r g a n i c m a t t e r c o n t e n t d e c r e a s e s w i t h d e p t h , the o c c u r r e n c e o f macro-
pore f l o w c o u l d r e s u l t i n p e s t i c i d e movement beyond the s u r f a c e
l a y e r s where most o f the OM r e s i d e s .
The e f f e c t o f the h y d r a u l i c c o n d u c t i v i t y on p e s t i c i d e t r a n s p o r t
can be s i m u l a t e d by assuming u n i t g r a d i e n t (VH = 1 ) ; t h u s , J w = ().
As a r e s u l t , J w can be a d j u s t e d i n such a way t h a t p o r e s o f d i f f e r e n t
r a d i i are s i m u l a t e d . For comparison, two h y p o t h e t i c a l s o i l s a r e
s i m u l a t e d i n F i g u r e l c . The pore r a d i i are 0.023 and 0.033 cm, which
1
c o r r e s p o n d t o h y d r a u l i c c o n d u c t i v i t i e s o f 1 and 4 cm d a y " .
Rawls e t a l . (40) e v a l u a t e d d a t a from 1,320 s o i l s and found t h a t mean
- 1
s a t u r a t e d c o n d u c t i v i t i e s ranged from 1.44 cm d a y i n clayey s o i l s to
1
504 cm d a y " i n sandy t e x t u r e d s o i l s . A l t h o u g h the c o n d u c t i v i t i e s
s i m u l a t e d i n F i g u r e l c d i f f e r by o n l y a f a c t o r o f 4, they r e f l e c t the
g r e a t e s t d i f f e r e n c e i n a t r a z i n e peak c o n c e n t r a t i o n s s i m u l a t e d w i t h i n
1
F i g u r e l a - c . The peak c o n c e n t r a t i o n c o r r e s p o n d i n g t o 4 cm d a y " is
s h a l l o w e r than one would expect under a c t u a l f i e l d c o n d i t i o n s s i n c e
the model i s assuming a c o n s t a n t OM c o n t e n t w i t h d e p t h . As a r e s u l t ,
the h y d r a u l i c c o n d u c t i v i t y i s the most important s o i l f a c t o r g o v e r n
ing p e s t i c i d e c o n t a m i n a t i o n o f groundwater.
Summary o f Model S i m u l a t i o n s . Using a one-dimensional convection-

d i s p e r s i o n t r a n s p o r t model w i t h f i r s t - o r d e r d e g r a d a t i o n , the r e l a t i v e
importance o f ? , OM, and Jb w was e v a l u a t e d . The h y d r a u l i c
c o n d u c t i v i t y was the most important s o i l parameter, f o l l o w e d by CM
and Both the o r g a n i c m a t t e r c o n t e n t and b can be e s t i m a t e d ,
r e s u l t i n g i n s o l u t i o n s t h a t are w i t h i n a f a c t o r o f 2 or 3. However,
p e s t i c i d e movement i s v e r y s e n s i t i v e t o the magnitude o f the
h y d r a u l i c c o n d u c t i v i t y . S o i l s with h y d r a u l i c c o n d u c t i v i t i e s w i t h i n a
f a c t o r o f 4 can y i e l d d r a m a t i c a l l y d i f f e r e n t c o n c e n t r a t i o n p r o f i l e s .
A d d i t i o n a l l y , s o i l s c o n t a i n i n g s o i l c r a c k s or l a r g e pores may be
prone to groundwater c o n t a m i n a t i o n .
Spatial Variability
To t h i s p o i n t , s e v e r a l assumptions have been b u i l t i n t o the t h e o r e t

i c a l development. The s o i l medium i s b e i n g c h a r a c t e r i z e d as a homo
geneous volume a l l o w i n g the o n e - d i m e n s i o n a l solute transport equation
(4a) t o be used. F i e l d s o i l s a r e n o t homogeneous, b u t c o n s i s t o f

h o r i z o n s , o r h o r i z o n t a l l a y e r s o f s o i l m a t e r i a l where each l a y e r
d i f f e r s w i t h r e s p e c t t o o r g a n i c and i n o r g a n i c c o m p o s i t i o n . Addi-
t i o n a l l y , t e x t u r a l d e p o s i t s may be randomly l o c a t e d below t h e s o i l
surface. These t e x t u r a l d e p o s i t s o r l e n s e s a l s o v a r y i n t h e i r com-
position. The l e n s e s may be composed o f f i n e p a r t i c l e s forming a
dense l a y e r , o r p o s s i b l y a v e r y c o a r s e sandy l e n s . The dense l e n s ,
as i s i n t u i t i v e , c a n r e s t r i c t downward water movement, t h e r e b y p r o -
d u c i n g a perched water t a b l e . However, t h e r e t a r d a t i o n o f f l o w by a
sand l e n s i s n o t so o b v i o u s . S o i l water w i l l n o t e n t e r a b u r i e d sand
l a y e r u n t i l t h e f i n e r t e x t u r e d s o i l o v e r l a y i n g t h e sand l e n s i s
e s s e n t i a l l y s a t u r a t e d , thus r e t a r d i n g v e r t i c a l t r a n s p o r t . This
mechanism was s u g g e s t e d f o r t h e l a t e r a l movemtent, f o r c a . 15 m, o f
s o l u t e s e l u t i n g from a l a n d f i l l ; i t i s d e p i c t e d i n F i g u r e 2 based
on G e r h a r d t ' s s t u d y ( 4 1 ) . I f o r when t h e f i n e r t e x t u r e d s o i l i s
s a t u r a t e d at t h e l e n s i n t e r f a c e , t h e s o i l water w i l l f l o w through
p r e f e r e n t i a l p o r e s , a p r o c e s s termed c h a n n e l i n g .
A h i e r a r c h y o f s o i l parameters was e s t a b l i s h e d i n t h e p r e v i o u s
section. I f t h e c o e f f i c i e n t s o f v a r i a t i o n a r e h i g h , on t h e o r d e r o f
100%, s e v e r a l hundred s o i l samples would need t o be t a k e n t o c h a r a c -
t e r i z e that s o i l property. Consequently, the v a r i a b i l i t y o f the
h y d r a u l i c c o n d u c t i v i t y d i c t a t e s t o what e x t e n t we c a n a c c u r a t e l y
predict pesticide transport. Even w i t h i n t h e same s o i l t e x t u r e
4 2 - 4 ) , c o e f f i c i e n t s o f v a r i a t i o n f o r t h e h y d r a u l i c c o n d u c t i v i t y were
found t o be w e l l i n e x c e s s o f 100%.
L a b o r a t o r y and F i e l d L e a c h i n g Tests
P e s t i c i d e r e g i s t r a t i o n r e q u i r e m e n t s have l o n g i n c l u d e d l e a c h i n g
t e s t s ; the r e p o r t s s u b m i t t e d i n r e g i s t r a t i o n p e t i t i o n s a r e c o n f i d e n -
t i a l , however, so such i n f o r m a t i o n o f t e n remains u n p u b l i s h e d .
D e s p i t e t h a t , a v a s t d a t a bank e x i s t s i n t h e l i t e r a t u r e on movement
o f p e s t i c i d e s i n s o i l s , a l t h o u g h no r e c e n t , comprehensive b i b l i o g -
raphy on l e a c h i n g i s t o our knowledge a v a i l a b l e . Methods o f
c o n d u c t i n g s o i l l e a c h i n g t e s t s f o r t o x i c o r g a n i c c h e m i c a l s have been
reviewed ( 4 5 ) .
T e x t u r a l d i f f e r e n c e s w i t h i n and among s o i l s were shown ( i n d i -
r e c t l y , v i a the hydraulic conductivity) to influence p e s t i c i d e
l e a c h i n g m a r k e d l y i n one t r a n s p o r t model. We a l s o d i s c u s s e d how they
c o n t r i b u t e t o s p a t i a l v a r i a b i l i t y , e s p e c i a l l y w i t h i n a p r o f i l e . In
lab and f i e l d e x p e r i m e n t s , t e x t u r a l d i f f e r e n c e s among s u r f a c e s o i l s
have o f t e n been a s s o c i a t e d w i t h l e a c h i n g . Thus, c h e m i c a l s a r e i n t u -
i t i v e l y e x p e c t e d t o move deeper i n t o c o a r s e - t e x t u r e d sandy s o i l s t h a n
i n medium-textured s i l t loams o r f i n e - t e x t u r e d c l a y s o i l s . T h i s was
i l l u s t r a t e d i n a l a b o r a t o r y s t u d y o f m e t r i b u z i n l e a c h i n g i n 16 s o i l s
( 4 6 ) ; c l a y and sand c o n t e n t s were h i g h l y c o r r e l a t e d ( n e g a t i v e l y and
p o s i t i v e l y , r e s p e c t i v e l y ) w i t h movement. A s t i l l b e t t e r p r e d i c t o r
was t h e 0.33-bar (0.033 MPa) s o i l m o i s t u r e c o n t e n t ( p r e v i o u s l y con-
s i d e r e d t o be f i e l d m o i s t u r e c a p a c i t y , FMC; FMC i s now g e n e r a l l y
a c c e p t e d as 0.01 MPa). T h i s p r o p e r t y i s l a r g e l y d e t e r m i n e d by s o i l
t e x t u r e and o r g a n i c m a t t e r c o n t e n t , so t h e PMC r e l a t i o n s h i p i s
expected. O r g a n i c m a t t e r c o n t e n t and pH were l e s s w e l l c o r r e l a t e d
with l e a c h i n g .
In an e a r l i e r i n v e s t i g a t i o n , H e l l i n g (47) s t u d i e d the i n f l u e n c e
of s o i l p r o p e r t i e s on l e a c h i n g by u s i n g 12 p e s t i c i d e s i n 14 s o i l s .
W i t h t h i s s o i l t h i n - l a y e r chromatography ( s o i l TLC) method, FMC gave
the b e s t p r e d i c t i o n o f m o b i l i t y f o r seven n o n i o n i c p e s t i c i d e s ,
whereas s o i l pH was b e s t c o r r e l a t e d ( p o s i t i v e l y ) t o movement o f f o u r
a c i d i c chemicals. C l a y and o r g a n i c m a t t e r c o n t e n t s were n e g a t i v e l y
c o r r e l a t e d with l e a c h i n g o f the nonionic p e s t i c i d e s .
F i g u r e 3 i l l u s t r a t e s t h e e f f e c t o f s o i l d i f f e r e n c e s on t h e h e r -
b i c i d e propham's movement i n s o i l TLC p l a t e s [ t h e summary d a t a were
p r e v i o u s l y published ( 4 8 ) ] . S o i l organic matter content increases
markedly g o i n g from N o r f o l k t h r o u g h C e l e r y v i l l e s o i l and i s thought
to be t h e dominant r e t a r d i n g f a c t o r . Based on s t u d i e s w i t h c h e m i c a l
homologue c h l o r p r o p h a m ( 4 7 ) , t h e b e s t p r e d i c t o r o f r e l a t i v e m o b i l i t y
would l i k e l y have been a c o m b i n a t i o n o f FMC ( n e g a t i v e ) p l u s water
flux (positive). The i n h e r e n t r i s k o f l e a c h i n g i n N o r f o l k sandy loam
i s c l e a r l y g r e a t e r than i n muck s o i l .
L e a c h i n g o f t h e nonfumigant n e m a t i c i d e oxamyl was r e c e n t l y

s t u d i e d i n u n s a t u r a t e d columns o f t h r e e s o i l s ( 4 9 ) . F i g u r e 4,
adapted from t h i s r e s e a r c h , shows t h a t oxamyl i s h i g h l y m o b i l e i n the
Arredondo sand, some o f t h e s o l u t e moving w i t h the water f r o n t (move-
ment i s h e r e e x p r e s s e d i n Rf u n i t s , i . e . , d i s t a n c e e l u t e d r e l a t i v e
to t h a t o f t h e water f r o n t , by analogy w i t h s o i l TLC p r e s e n t a t i o n ) .
Both Arrendondo and C e c i l p l o t s a r e n o t a b l y asymmetric, which t h e
authors a s c r i b e to n o n e q u i l i b r i u m a d s o r p t i o n . I t i s apparent from
F i g u r e 4 t h a t l e a c h i n g i n Webster s i l t y c l a y loam, w i t h 38% c l a y and
4% o r g a n i c c a r b o n c o n t e n t ( c a . 6.8% OM), i s much r e t a r d e d .
I t i s commonly r e c o g n i z e d t h a t an i n v e r s e r e l a t i o n s h i p e x i s t s
between a d s o r p t i o n o f p e s t i c i d e s and t h e i r tendency t o l e a c h i n s o i l s
(11, 50-1). A d s o r p t i o n i s u s u a l l y i n c o r p o r a t e d i n t o l e a c h i n g models
as the a d s o r p t i o n c o n s t a n t n o r m a l i z e d on t h e f r a c t i o n a l c o n t e n t o f
s o i l o r g a n i c c a r b o n ( s e e E q u a t i o n 6 ) , i . e . , K , s i n c e much
o c
r e s e a r c h has c o r r e l a t e d t h e a d s o r p t i o n o f n e u t r a l o r g a n i c compounds
with s o i l organic matter content. As i n d i c a t e d e a r l i e r , parameters
t h a t more d i r e c t l y i n d i c a t e t h e s o i l w a t e r - h o l d i n g c a p a c i t y and the
s i z e and range o f c o n d u c t i n g pores may a c t u a l l y c o r r e l a t e even b e t t e r
with transport of p e s t i c i d e s .
In a p r e v i o u s l y c i t e d l a b o r a t o r y study ( 4 7 ) , s o i l pH was p o s i -
t i v e l y c o r r e l a t e d w i t h movement o f a c i d i c p e s t i c i d e s . Figure 5 i s
p r e s e n t e d as a comparison i n which s o i l pH d i f f e r e n c e s may have
d i f f e r e n t i a l l y a f f e c t e d the m o b i l i t y o f two h e r b i c i d e s , s i m a z i n e and
terbacil. Based on t h e work o f Hogue et a l . ( 5 2 ) , who d i d not s u g -
g e s t t h i s h y p o t h e s i s , F i g u r e 5 shows the expected m i g r a t i o n o f r e s -
idues away from the s o i l s u r f a c e as water input i n c r e a s e s from 20 t o
80 cm, s i m u l a t i n g s e a s o n a l a p p l i c a t i o n o f i r r i g a t i o n water t o t h e
orchard s o i l s . T e r b a c i l was r e l a t i v e l y m o b i l e and s i m a z i n e , l e s s s o .
However, whereas, t e r b a c i l ' s m o b i l i t y was s i g n i f i c a n t l y g r e a t e r i n
R u t l a n d sandy loam than i n P e n t i c t o n loam, s i m a z i n e behaved s i m i l a r l y
i n both s o i l s . The loam had much h i g h e r c l a y and o r g a n i c m a t t e r
c o n t e n t s , so d i m i n i s h e d t e r b a c i l l e a c h i n g i n t h a t s o i l i s e x p e c t e d .
We suggest t h a t s i m a z i n e movement i n R u t l a n d sandy loam i s l e s s than
o t h e r w i s e a n t i c i p a t e d because at t h i s s o i l ' s low pH ( 4 . 6 ) , more o f
the s i m a z i n e i s p r o t o n a t e d , and t h e r e f o r e more s t r o n g l y adsorbed,
than i n P e n t i c t o n loam (pH 7.5).
F i g u r e 3. E f f e c t o f f o u r s o i l s on leaching o f propham, u s i n g soil

TLC p l a t e s ( a f t e r H e l l i n g , 4 8 ) .
Figure 4. E f f e c t o f t h r e e s o i l s on l e a c h i n g o f oxamyl, using

u n s a t u r a t e d s o i l columns. Adapted from r e f e r e n c e 4 9 .
SIMAZINE TERBACIL
DEPTH,
cm
C O N C E N T R A T I O N , ppm
F i g u r e 5. R e l a t i v e l e a c h i n g o f s i m a z i n e and t e r b a c i l , showing
e f f e c t s o f added water, s o i l t e x t u r e , and ( p o s s i b l y ) pH. Adapted
from r e f e r e n c e 52.
Groundwater C o n t a m i n a t i o n
Of the 700-800 U . S . - r e g i s t e r e d p e s t i c i d a l a c t i v e i n g r e d i e n t s , o n l y a
r e l a t i v e l y s m a l l number (2) have l e a c h e d t o groundwater. Unfortu-
n a t e l y , some o f these c h e m i c a l s are or were among the major p e s t i -
c i d e s used i n American a g r i c u l t u r e (2^). Three o f these w i l l be
d i s c u s s e d i n the f o l l o w i n g s e c t i o n , w i t h s p e c i a l a t t e n t i o n t o s o i l
c h a r a c t e r i s t i c s t h a t may have i n f l u e n c e d movement.
Atrazine. T h i s w i d e l y used h e r b i c i d e was d e t e c t e d i n the mid-1970s

i n a l l sampled Iowa m u n i c i p a l water s u p p l i e s i n which that water was
d e r i v e d from s h a l l o w w e l l s i n the a l l u v i a l p l a i n s o f r i v e r s c o n t a m i -
nated from a t r a z i n e r u n o f f ( 5 3 ) . L e v e l s ranged up t o 483 ppb.
An e x t e n s i v e s e r i e s o f s t u d i e s i n Nebraska (54-8) e s t a b l i s h e d
the common o c c u r r e n c e of s u b - p h y t o t o x i c (58) l e v e l s o f a t r a z i n e i n
groundwater. The s i t e s were a l l l o c a t e d i n i n t e n s i v e l y i r r i g a t e d
c o u n t i e s a d j a c e n t to the P l a t t e R i v e r . Where depth t o groundwater

ranged from 1-7 m ( 5 5 ) , s o i l s tended to be somewhat p o o r l y d r a i n e d ,
g r a d i n g to sand and g r a v e l at c a . 0.25-1 m; deeper groundwater s i t e s
had w e l l - d r a i n e d s i l t y s o i l s t h a t graded t o mixed sand and g r a v e l .
N e a r l y a l l a t r a z i n e l e v e l s were <1 ppb and r e s i d u e s tended to be
highest in shallow wells. Because o f v e r y h i g h p e r m e a b i l i t y o f
s u b s o i l i n the r i v e r bottomlands and the d i r e c t i o n o f groundwater
f l o w (away from the r i v e r , c a . 3 m/day), a t r a z i n e l e v e l s i n s h a l l o w
groundwater matched those i n the P l a t t e R i v e r by September ( 5 5 ) ,
c o n t r a s t i n g w i t h the a t t e n u a t i o n seen when s o i l s are p r e d o m i n a n t l y
f i n e r textured (54). Secondary a q u i f e r s , i . e . , groundwaters i s o l a t e d
by c l a y e y s i l t l a y e r s , c o n t a i n e d o n l y t r a c e amounts o f a t r a z i n e ( 5 5 ) .
The peak a t r a z i n e c o n c e n t r a t i o n s i n Nebraska were o b s e r v e d
down-gradient from i r r i g a t e d f i e l d s , at the end o f the i r r i g a t i o n
season ( 5 5 ) ; r e s i d u e l e v e l s d i m i n i s h e d w i t h l a t e r a l d i s t a n c e ( 5 8 ) .
There was some a r e a l and v e r t i c a l a s s o c i a t i o n w i t h n i t r a t e c o n c e n -
t r a t i o n , but no c o r r e l a t i o n c o u l d be drawn with d i s s o l v e d o r g a n i c
carbon ( o f which a t r a z i n e would c o n s t i t u t e 1 % ) .
Atrazine-contaminated water seeped from an i r r i g a t i o n t a i l w a t e r
p i t (54). Because r e s i d u e s would be h i g h e s t e a r l y i n the growing
season, seepage i n l a t e s p r i n g - e a r l y summer would i n c r e a s e a t r a z i n e
r e s i d u e s i n groundwater, whereas r e l a t i v e d i l u t i o n o f the a l r e a d y -
c o n t a m i n a t e d groundwater would o c c u r d u r i n g the b a l a n c e o f the y e a r .
In t h i s study ( 5 4 ) , w e l l water beneath somewhat p o o r l y d r a i n e d s u r -
f a c e s o i l s had l e s s a t r a z i n e ( a v e r a g e , 0.2 ppb) than d i d w e l l s under
moderate- and w e l l - d r a i n e d (1.5 ppb) s i t e s . The t h i c k n e s s o f the
vadose zone i n the t h r e e c l a s s e s was <1.5, 2.4-3.6, and 3.0-7.8 m,
respectively. P o o r l y d r a i n e d s o i l s g e n e r a l l y had h i g h e r 0M c o n t e n t s
i n the s u r f a c e h o r i z o n s . T h i s f a c t o r , t y p i c a l l y a s s o c i a t e d w i t h both
g r e a t e r a d s o r p t i o n and m i c r o b i a l a c t i v i t y , may have l i m i t e d a t r a z i n e
l e a c h i n g by the d i r e c t e f f e c t o f r e t a r d a t i o n and the i n d i r e c t e f f e c t
of l o n g e r r e s i d e n c e time l e a d i n g t o more complete d e g r a d a t i o n .
A l t h o u g h a t r a z i n e was r e g u l a r l y d e t e c t e d i n Nebraska ground-
water, 11 o t h e r p e s t i c i d e s were m o n i t o r e d , but not found ( 5 6 ) . These
i n c l u d e d h e r b i c i d e s 2,4-D, EPTC, and s i l v e x , and i n s e c t i c i d e s DDT,
DDE, d i e l d r i n , e n d r i n , h e p t a c h l o r , h e p t a c h l o r e p o x i d e , l i n d a n e , and
methoxychlor. In t h i s study, a l a c h l o r was found i n 2 o f 14 samples,
0.02 and 0.07 ppb; s i m i l a r l y low r e s i d u e s o f a l a c h l o r were found i n 2
o f 33 samples i n a n o t h e r Nebraska study ( 5 5 ) .
A t r a z i n e l e a c h i n g was f a r more l i m i t e d i n c o n v e n t i o n a l l y - t i l l e d
s i l t y c l a y loam and c l a y loam s o i l s i n P e n n s y l v a n i a ( 5 9 ) . These
T y p i c H a p l u d u l t s were deep, w e l l - d r a i n e d s o i l s o f moderate p e r m e a b i l -
i t y and h i g h a v a i l a b l e water c a p a c i t y . S u c t i o n l y s i m e t e r measure-
ments showed a t r a z i n e l e a c h i n g t o 122 cm, b u t g e n e r a l l y l e s s movement
o c c u r r e d , i n p a r t because d i s s i p a t i o n was f a i r l y r a p i d and t h e h i g h
vapotranspiration r a t e i n summer m i n i m i z e d downward f l o w o f water.
The g r e a t e s t l e a c h i n g o c c u r r e d at t h e h i g h e s t h e r b i c i d e r a t e s .
T y p i c a l s o i l s o l u t i o n c o n c e n t r a t i o n s o f a t r a z i n e were 10-40 ppb.
A t r a z i n e was shown t o l e a c h more r e a d i l y i n i r r i g a t e d , permeable
Nebraska s o i l s (54-8), b u t t o move much l e s s r e a d i l y below t h e plow
layer i n f i n e r textured, n o n i r r i g a t e d Pennsylvania s o i l s (59). A
d i f f e r e n t g e o l o g i c a l environment, t h e k a r s t - c a r b o n a t e a q u i f e r s o f
n o r t h e a s t Iowa, have been r e c o g n i z e d as b e i n g p o t e n t i a l l y f r a g i l e
with r e s p e c t t o groundwater q u a l i t y . A r e c e n t r e p o r t (60) documented
l e a c h i n g o f a t r a z i n e , a l a c h l o r , c y a n a z i n e , and m e t r i b u z i n i n t o
groundwater t h e r e .
Four g e o l o g i c a l r e g i o n s were d e f i n e d i n t h e study a r e a ( 6 0 ) , as
d e s c r i b e d i n T a b l e IV. The a r e a c h a r a c t e r i z e d by c o n s i d e r a b l e depth
t o c a r b o n a t e b e d r o c k had no contaminated w e l l water. In a d d i t i o n t o
t h e i r t h i c k n e s s , t h e o v e r l y i n g s o i l d e p o s i t s were s a i d t o be o f low
permeability, i n c r e a s i n g the p o t e n t i a l for surface l a t e r a l transport
o f water and s o l u t e s . I n t h e o t h e r t h r e e r e g i o n s , 67% o f sampled
w e l l s c o n t a i n e d p e s t i c i d e r e s i d u e s , u s u a l l y a t r a z i n e , d u r i n g at l e a s t
p a r t o f the y e a r . The h i g h e s t c o n c e n t r a t i o n s , i n mid-summer and
e a r l y f a l l , c o r r e s p o n d e d t o l e a c h i n g a f t e r the annual a p p l i c a t i o n o f
herb i c i d e .
T a b l e IV. A q u i f e r C h a r a c t e r i s t i c s and H e r b i c i d e C o n t a m i n a t i o n o f
Groundwater i n F l o y d and M i t c h e l l C o u n t i e s , Iowa ( a f t e r 60)
Pest i c ide r e s idues

Geological Depth t o Spec i a l Samples : Chemi-
region bedrock features posit ive/ cals*
(m) total
Deep Bedrock >15 0/12
Shallow <15 Few sinkholes 17/29 At

Bedrock
Karst Very Numerous open 12/23 At, A l ,

shallow sinkholes ; M
rolling terrain
Incip ient 1-3 Numerous i n c i p i e n t 7/20 At, A l ,

Karst sinkholes ; Cy, M
flat terrain
s
At = a t r a z i n e ; A l = a l a c h l o r ; Cy cyanazine; M = metribuzin.
S i g n i f i c a n t f e a t u r e s o f n o r t h e a s t e r n Iowa and southeastern

M i n n e s o t a i n c l u d e the p r e s e n c e of open and i n c i p i e n t s i n k h o l e s as
w e l l as l a r g e a r e a s where b e d r o c k i s exposed or w i t h i n 1-3 m of the
surface. S i n k h o l e s a l l o w v e r y r a p i d r e c h a r g e from s u r f a c e water and
thus d i r e c t i n t r o d u c t i o n o f s o l u t e s such as p e s t i c i d e s . The I n c i p e n t
S i n k h o l e r e g i o n s c o n t a i n e d hundreds o f s m a l l , s o i l - f i l l e d d e p r e s -
s i o n s ; p e s t i c i d e i n f i l t r a t i o n must, t h e r e f o r e , o c c u r through the s o i l
m a n t l e . Water movement through t h i s s o i l i s r a p i d . W i t h i n the
I n c i p i e n t K a r s t r e g i o n , one w e l l showed c o n s i s t e n t l y h i g h r e s i d u e s o f
a l a c h l o r , c y a n a z i n e , and m e t r i b u z i n . A n a l y s e s showed h i g h h e r b i c i d e
c o n c e n t r a t i o n i n the s o i l p r o f i l e and a v e r y s h a l l o w (3-5 m) water
t a b l e ; p r o b a b l e h i g h h e r b i c i d e a p p l i c a t i o n r a t e s were thought t o
c o n t r i b u t e to the c o n t a m i n a t i o n problem. L i b r a et a l . (60) found
t h a t r e s i d u e s i n t i l e d r a i n water were a good i n d i c a t o r o f the
q u a l i t y o f i n f i l t r a t i n g water.
Aldicarb. The i n s e c t i c i d e / n e m a t i c i d e a l d i c a r b and i t s m o b i l e d e g r a -

d a t i o n p r o d u c t s ( " a l d i c a r b r e s i d u e s " ) r e p o r t e d l y have been found i n
the groundwaters o f 13 s t a t e s ( 2 ) . In g e n e r a l , a l d i c a r b r e s i d u e s
were h i g h e s t f o r w e l l s sampled n e a r e s t the f i e l d a p p l i c a t i o n s i t e s .
The i n f l u e n c e o f s o i l d i f f e r e n c e s on the p a t t e r n o f a l d i c a r b movement
i s w e l l i l l u s t r a t e d i n a r e c e n t study ( 6 1 - 2 ) . Potato f i e l d s in
n o r t h e a s t e r n F l o r i d a were l o c a t e d on sandy s o i l u n d e r l a i n at 1-2 m by
an impervious c l a y l a y e r ( 6 1 ) . R e s i d u e s l e a c h e d downward, then
l a t e r a l l y , emerging i n t o d r a i n a g e d i t c h e s at c o n c e n t r a t i o n s o f c a .
1-7 ppb ( h i g h e s t was 190 ppb 49 days a f t e r a p p l i c a t i o n ) . Thus, under
r e s t r i c t e d p e r c o l a t i o n , the s u r f i c i a l water was c o n t a m i n a t e d whereas
the a q u i f e r beneath t h i s c l a y l a y e r a p p a r e n t l y was not.
I n v e s t i g a t i o n s i n c i t r u s f i e l d s elsewhere i n F l o r i d a (62) were
done i n two t y p e s o f s i t e s : (a) s h a l l o w , p o o r l y d r a i n e d " f l a t w o o d s "
s o i l s , and (b) deep, w e l l - d r a i n e d " r i d g e " s o i l s . Both had sandy
soils. At s i t e ( a ) , a l d i c a r b r e s i d u e s l e a c h e d o n l y t o 1.25 m i n 60
days, presumably a r e s p o n s e t o r e s t r i c t e d d r a i n a g e , h i g h e r FMC, and
s l i g h t l y h i g h e r a d s o r p t i o n i n the s u r f a c e 30 cm (OM c o n t e n t was
g r e a t e s t i n the f l a t w o o d s s o i l ) . L e a c h i n g i n the r i d g e s o i l s was
more e x t e n s i v e , w i t h r e s i d u e s d e t e c t e d to c a . 3 m by 45 days. Sub-
s o i l s [ i . e . , below 30-45 cm i n (a) and 60-90 cm i n ( b ) ] showed no
c a l c u l a t e d r e t a r d a t i o n o f l e a c h i n g due to a d s o r p t i o n .
S o i l p r o p e r t i e s were u n d o u b t e d l y a major f a c t o r i n the wide-
s p r e a d o c c u r r e n c e o f a l d i c a r b r e s i d u e s i n Long I s l a n d , New York
groundwater. S o i l s t h e r e are sandy and permeable. A c c o r d i n g to a
r e p o r t ( t h e i r r e f e r e n c e #39) c i t e d by Cohen et a l . ( 2 ) , " a t l e a s t
s e v e r a l p e r c e n t o f the a l d i c a r b a p p l i e d to c e r t a i n Long I s l a n d
f i e l d s " has l e a c h e d t o groundwater; generally, p e s t i c i d e residues
r e a c h i n g groundwater seem t o r e p r e s e n t 1 % of the agronomic dose.
Even under maximum assumed r a t e s of d e g r a d a t i o n and p l a n t uptake,
m o d e l i n g o f Pacenka and P o r t e r (63) p r e d i c t e d a s u b s t a n t i a l amount o f
a l d i c a r b to l e a c h below the r o o t zone. Such movement i s a c c e l e r a t e d
by a c o l d , wet s p r i n g , due to the c o m b i n a t i o n o f slower breakdown and
g r e a t e r net water i n f i l t r a t i o n .
The p o s s i b i l i t y of a l d i c a r b l e a c h i n g i s r e c o g n i z e d by the manu-
f a c t u r e r ' s (64) warning on the product l a b e l that "...a c o m b i n a t i o n
o f permeable and a c i d i c s o i l c o n d i t i o n s , moderate t o heavy i r r i g a t i o n
and/or r a i n f a l l , use of 20 or more pounds per a c r e , and s o i l tempera-
t u r e below 50F at a p p l i c a t i o n time, tend to reduce d e g r a d a t i o n and
1
promote movement o f r e s i d u e s t o groundwater." A l d i c a r b s use i s
p r o h i b i t e d i n S u f f o l k County, Long I s l a n d , New York.
DBCP. D u r i n g m o n i t o r i n g o f C a l i f o r n i a w e l l s i n 1979, t h e n e m a t i c i d e
DBCP was d e t e c t e d i n 59 o f 119 w e l l s t e s t e d ( 6 5 ) . Residues i n t h e
San J o a q u i n V a l l e y exceeded 10 ppb i n 11 c a s e s . Among t h e reasons
f o r f i n d i n g DBCP c o n t a m i n a t i o n i n c l u d e i t s long h i s t o r y o f use i n
C a l i f o r n i a (1960-1977), h i g h r e q u i r e d a p p l i c a t i o n r a t e s , d i r e c t i n -
j e c t i o n i n t o s o i l o r i n c o r p o r a t i o n v i a i r r i g a t i o n water, and moderate
m o b i l i t y i n l a b o r a t o r y or f i e l d l e a c h i n g t e s t s (66-8). DBCP i s
chemically hydrolyzed only very slowly (69); r e l i a b l e estimates o f
h a l f - l i f e from m i c r o b i a l d e g r a d a t i o n seem t o be l a c k i n g , perhaps
because o f d i f f i c u l t y i n d i s t i n g u i s h i n g breakdown from l o s s by v o l a -
tilization. One o f t h e major reasons f o r deep l e a c h i n g o f DBCP i n
C a l i f o r n i a i s probably that s o i l s i n the t r e a t e d area are t y p i c a l l y
v e r y sandy, w i t h low OM c o n t e n t and h i g h p e r c o l a t i o n ( 7 0 ) .
At about t h e same time t h a t DBCP was d i s c o v e r e d i n C a l i f o r n i a

water, i t was a l s o found i n 26 o f 93 A r i z o n a w e l l samples ( 7 1 ) ,
though v a r i o u s s h o r t - c i r c u i t i n g mechanisms were then c o n s i d e r e d as
a l t e r n a t i v e r o u t e s b e s i d e s normal p e r c o l a t i o n through t h e s o i l
profile. DBCP was absent i n 282 samples ( m o s t l y groundwater) from
F l o r i d a , G e o r g i a , and South C a r o l i n a ( 7 2 ) . A s l i g h t l y s m a l l e r s u r v e y
i n South C a r o l i n a showed DBCP t o o c c u r i n c a . 37% o f s u r f a c e waters
from a h i g h - u s e a r e a ; >1 ppb DBCP was found i n 10% o f w e l l waters
(73). I t was n o t d e t e c t e d i n areas where l i t t l e or no a p p l i c a t i o n
had been made. A f o l l o w u p s t u d y suggested t h a t t h e groundwater
c o n t a m i n a t i o n was due t o a s i n g l e p o i n t source ( 7 4 ) . In g e n e r a l , t h e
m o n i t o r i n g s t u d i e s i n t h e s o u t h e a s t e r n U.S. seemed t o i n d i c a t e t h a t
DBCP had not become a s e r i o u s c o n t a m i n a t i o n problem t h e r e .
Continued m o n i t o r i n g i n C a l i f o r n i a showed t h a t DBCP was p r e s e n t
i n s o i l s o f t h e San J o a q u i n V a l l e y at depths t o 15 m ( 7 5 ) , but more
1
r e c e n t c o r e s c o l l e c t e d 5 y e a r s f o l l o w i n g t e r m i n a t i o n o f DBCP s use i n
v i n e y a r d s d i d not c o n t a i n t h e n e m a t i c i d e ( 7 0 ) . I n t h e second c a s e ,
sampling was t o groundwater (7.5 and 10 m). Both s o i l s were h i g h l y
permeable, and t h e s h a l l o w e r groundwater had c o n t a i n e d DBCP, so
l e a c h i n g may have c o n t r i b u t e d s i g n i f i c a n t l y t o t h e c h e m i c a l ' s l o s s .
A C a l i f o r n i a groundwater s u r v e y i n 1982 showed no p e s t i c i d e s ( i . e . ,
DBCP, EDB, c a r b o f u r a n , o r s i m a z i n e ) i n t h e Santa M a r i a o r S a l i n a s
V a l l e y groundwater b a s i n s ( 7 6 ) . DBCP was p r e s e n t i n 6 o f 23 w e l l s i n
the Upper Santa Ana b a s i n (0.1-8 ppb), and i n 21 o f 166 w e l l s i n t h e
San J o a q u i n b a s i n (0.1-10 ppb). The a u t h o r s were unable t o c o r r e l a t e
w e l l c h a r a c t e r i s t i c s w i t h DBCP c o n c e n t r a t i o n i n water. Simazine was
a l s o found i n 5 w e l l s , c a r b o f u r a n i n 1 w e l l , and EDB i n 2 w e l l s .
A r e c e n t f i e l d experiment was r e p o r t e d (77) i n which DBCP was
c h i s e l - i n j e c t e d i n t o f a l l o w p l o t s , i n G e o r g i a , at normal and 3X
normal r a t e s . Under a c c e l e r a t e d i r r i g a t i o n , t r a c e s o f DBCP had
l e a c h e d t o at l e a s t 12 m by 8 months, though at normal r a t e s o f
p e s t i c i d e and water, l e a c h i n g below 4 m i n 6 months p r o b a b l y had not
occurred. The p e s t i c i d e was p r e s e n t i n perched groundwater and t h e r e
was e v i d e n c e , due t o t h e e x i s t e n c e o f r e s t r i c t i n g c l a y l a y e r s , t h a t
l a t e r a l movement i n t o c o n t r o l p l o t s u b s o i l was i m p o r t a n t .
Summary
The major emphasis o f t h i s d i s c u s s i o n c e n t e r e d on the importance

o f s u r f a c e and s u b s u r f a c e s o i l c h a r a c t e r i s t i c s i n i n f l u e n c i n g deep
pesticide leaching. Some f a c t o r s , such as the depth t o groundwater
and the amount o f i n c i p i e n t r a i n f a l l o r i r r i g a t i o n , a r e c l e a r l y
important f a c t o r s t h a t do a f f e c t t h e p r o b a b i l i t y o f p e s t i c i d e r e s i
dues r e a c h i n g groundwater. S i m i l a r l y , p r o p e r t i e s o f the p e s t i c i d e
i t s e l f ( e s p e c i a l l y i t s i n h e r e n t m o b i l i t y and c h e m i c a l / b i o l o g i c a l
s t a b i l i t y ) c o r r e l a t e c l o s e l y w i t h p o l l u t i o n p o t e n t i a l , but t h e i r
e v a l u a t i o n i s o u t s i d e t h e scope o f t h i s r e v i e w .
We attempted t o s e l e c t , from many s o i l p r o p e r t i e s , those c h a r a c
t e r i s t i c s best l i n k e d to p e s t i c i d e transport. Two approaches were
used: ( a ) s e n s i t i v i t y a n a l y s e s o f s e v e r a l p r o p e r t i e s through the use
of a o n e - d i m e n s i o n a l c o n v e c t i o n - d i s p e r s i o n t r a n s p o r t model and
(b) q u a l i t a t i v e r e v i e w o f l a b o r a t o r y and f i e l d s t u d i e s . The model
was thus i n t e n d e d t o s c r e e n s o i l s w i t h r e s p e c t t o t h e i r p o t e n t i a l f o r
permitting leaching. A moderately mobile, n o n v o l a t i l e pesticide
( a t r a z i n e ) was t e s t e d i n t h e d e t e r m i n i s t i c model.
The h i e r a r c h y o f s o i l c h a r a c t e r i s t i c s a f f e c t i n g l e a c h i n g , taking
i n t o c o n s i d e r a t i o n t h e i r t y p i c a l f i e l d v a r i a t i o n , was b u l k d e n s i t y <
s o i l organic matter < hydraulic c o n d u c t i v i t y . Lab and f i e l d r e s u l t s
support p a r t i c u l a r l y t h e l a s t two f a c t o r s , a l t h o u g h h y d r a u l i c conduc
t i v i t y i s u s u a l l y o n l y i n f e r r e d based on s o i l t e x t u r e ( i . e . , more
l e a c h i n g i n c o a r s e - t e x t u r e d , permeable s o i l s ) . The importance o f
macropore f l o w was r e c o g n i z e d as a p o t e n t i a l l y important r o u t e f o r
p e s t i c i d e m i g r a t i o n deep i n t o t h e vadose zone. I t i s not e a s i l y
q u a n t i f i e d , however, and so does not seem t o be amenable f o r c o n s i d
e r a t i o n i n s c r e e n i n g models. On a l o c a l s c a l e , s o i l s u r f a c e and
s u b s u r f a c e s p e c i a l c h a r a c t e r i s t i c s s h o u l d be i n c o r p o r a t e d a t l e a s t
q u a l i t a t i v e l y i n t o p r e d i c t i o n o f p e s t i c i d e movement.
APPENDIX
CjAtx.t) + CQ(B(x,t) < t < tQ

CT(x,t)
C.A(x,t) + CQB(x,t) - CQB(x,t-t0) t >tQ
where
(Rx - v t ) 2
- 4URt
e
+
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3
Determining Uncertainty in Physical Parameter
Measurements by Monte Carlo Simulation
1 2 1 1
David W. Coy , Gregory A. Kew , Michael E. Mullins , and Phillip V. Piserchia
1
Research Triangle Institute, Research Triangle Park, NC 27709
2
Office of Health and Environmental Assessment (RD-689), U.S. Environmental
Protection Agency, Washington, D C 20460
A statistical approach, often called Monte Carlo simu-

lation, has been used to examine propagation of error
and to better characterize the uncertainty associated
with measurement of several parameters important in
predicting environmental transport of chemicals. These
parameters are vapor pressure, water solubility, octanol-
water partition coefficient, and "volatilization from
water" (based on the ratio of laboratory-measured vola-
tilization rate constant to oxygen reaeration rate
constant for a specific system). Column chromatographic
and high pressure liquid chromatographic (HPLC) methods
are replacing more traditional equilibrium methods
(e.g. shake flask, isoteniscope) for measuring the
first three parameters. The newer methods tend to under-
predict aqueous solubility and vapor pressure and
overpredict octanol-water partition coefficient, although
deviations for both the equilibrium and dynamic systems
are similar. Measurement error proves not to be normally
distributed, with differing bias for each parameter.
For "volatilization from water", determinations of the
ratio of rate constants for compounds whose Henry's Law
constant equals or exceeds 1,000 torr/mole/liter typi-
cally report 95% percent confidence limits equal to 5
to 10 percent of the ratio. Analysis of a regression
approach often used to determine the ratio suggests
underestimation of both the ratio and its variance.
Monte Carlo simulation did not confirm underestimation
of the ratio but suggests variances may be underestimated
by a factor of 2.3. Using this statistical approach in
other cases might allow an investigator to choose levels
of a parameter (e.g. a drinking water standard) knowing the
uncertainty associated with the choice, or the converse.
0097-6156/ 86/ 0315-0039506.50/ 0
The purpose of t h i s study i s t o i l l u s t r a t e a s t a t i s t i c a l approach

f o r d e t e r m i n i n g o v e r a l l u n c e r t a i n t y i n a parameter c a l c u l a t e d
from more than one i n p u t , when d i s t r i b u t i o n of e r r o r f o r the
i n p u t s can be e s t i m a t e d . The approach i n c o r p o r a t e s t h i s i n f o r -
m a t i o n i n t o a c o n c i s e statement of o v e r a l l u n c e r t a i n t y . In
p a r t i c u l a r , i t p e r m i t s d e t e r m i n i n g the p r o b a b i l i t y of e x c e e d i n g
a specific level. The r e s u l t s then a r e compared w i t h e r r o r
e s t i m a t e s f o r s p e c i f i c e x p e r i m e n t a l procedures i n the l i t e r a t u r e .
T h i s approach seems a p p l i c a b l e t o b r o a d e r i n v e s t i g a t i o n s
than a r e e x p l o r e d h e r e , such as p r e d i c t i n g e n v i r o n m e n t a l t r a n s -
p o r t and f a t e of c h e m i c a l s where p r o p e r t i e s of v a r i o u s compounds
a r e used i n models. Even more g e n e r a l l y , i t might be a p p l i e d
t o exposure assessment where, u s u a l l y , too few d a t a a r e a v a i l a b l e
to c h a r a c t e r i z e d i s t r i b u t i o n s of exposure t o p a r t i c u l a r c h e m i c a l s .
G e n e r a l approaches f o r e x p r e s s i n g u n c e r t a i n t y most e v i d e n t
i n the l i t e r a t u r e may be viewed as v a r i o u s forms of " p r o p a g a t i o n
of e r r o r . " V a r i a n t s range from " s e n s i t i v i t y a n a l y s i s " where the

e f f e c t s of i n d i v i d u a l i n p u t v a r i a b l e s a r e examined by h o l d i n g
a l l o t h e r v a r i a b l e s a t midrange w h i l e the one under s t u d y i s
v a r i e d from minimum t o maximum, t o the use of f i x e d formulae
d e r i v e d f o r v a r i o u s mathematical r e l a t i o n s h i p s i n s p e c i f y i n g
a b s o l u t e maxima and minima f o r o u t p u t s . None of these methods
can s u p p l y a p r o b a b i l i t y of o c c u r r e n c e f o r a g i v e n v a l u e w i t h i n
the range of p o s s i b l e e r r o r .
What appears t o be y e t a n o t h e r v a r i a n t , a s t a t i s t i c a l
approach o f t e n c a l l e d Monte C a r l o s i m u l a t i o n , r e c e n t l y has been
demonstrated t o a p p l y by Walentowicz and F a l c o i f the d i s t r i b u -
t i o n of v a l u e s f o r each i n p u t v a r i a b l e i s known o r can be
approximated (J^). T h e r e a f t e r , t h i s i n f o r m a t i o n can be manipu-
l a t e d to y i e l d a d i s t r i b u t i o n of outputs e x p r e s s i n g p r o b a b i l i t y
of o c c u r r e n c e f o r any g i v e n v a l u e . A l s o , a r e c e n t s t u d y by
Whitmore G O d e v e l o p s the c o n c e p t s of Walentowicz and F a l c o and
o f f e r s c o n c l u s i o n s on the form of f i n a l l i m i t i n g d i s t r i b u t i o n s
( e . g . , s i m u l a t e d o u t p u t s f o r product f u n c t i o n s approach l o g
normal) i f s p e c i f i c m a t h e m a t i c a l c o n d i t i o n s a r e met. The p r e c i s e
degree t o which the c o n d i t i o n s must be f u l f i l l e d f o r the t e c h -
n i q u e t o y i e l d a u s e f u l r e s u l t i n the p r e s e n t a p p l i c a t i o n have
not y e t been f u l l y e x p l o r e d .
While the examples c o n s i d e r e d h e r e a r e e x p e r i m e n t a l
d e t e r m i n a t i o n of (1) water s o l u b i l i t y , (2) o c t a n o l - w a t e r p a r t i -
t i o n c o e f f i c i e n t , (3) v a p o r p r e s s u r e , and (4) v o l a t i l i z a t i o n
from water, the r e s u l t i n g d i s t r i b u t i o n s presumably then c o u l d
become i n p u t s t o l a r g e r problems such as d e t e r m i n i n g media-
s p e c i f i c e n v i r o n m e n t a l c o n c e n t r a t i o n , i n t u r n e x p r e s s e d as a
well-characterized distribution.
S i m u l a t i o n of Method Error
The p r o c e s s used f o r d e t e r m i n i n g a d i s t r i b u t i o n of aqueous

s o l u b i l i t y v a l u e s i n v o l v e s assuming a " t r u e " s o l u b i l i t y v a l u e
e q u a l t o 1 . 0 0 a r b i t r a r y u n i t s , a s s i g n i n g an e r r o r d i s t r i b u t i o n
f o r each r e c o g n i z e d e r r o r s o u r c e , and c a l c u l a t i n g the e f f e c t on
t r u e v a l u e of the s e v e r a l s o u r c e s of e r r o r . After assigning
3. COY E T A L . Determining Uncertainty in Physical Parameter Measurements 41
the " t r u e " v a l u e , random numbers g e n e r a t e d by computer program

were used t o p i c k i n p u t v a l u e s w i t h i n t h e s o l u b i l i t y range of
concern. The c o r r e s p o n d i n g e r r o r was then c a l c u l a t e d f o r t h e
s o u r c e f i r s t a f f e c t i n g t h e s o l u b i l i t y d e t e r m i n a t i o n . The
r e s u l t i n g d i s c r e t e e r r o r was added t o o r s u b t r a c t e d from t h e
t r u e v a l u e and t h e r e s u l t a n t used as i n p u t t o t h e d i s t r i b u t i o n
for the second-occurring e r r o r source. C o n t r i b u t i o n s from
s o u r c e s o p e r a t i n g s i m u l t a n e o u s l y , r a t h e r than s e q u e n t i a l l y ,
were c a l c u l a t e d and summed s i m u l t a n e o u s l y . This process i s
r e p e a t e d t o i n c l u d e a l l r e c o g n i z e d s o u r c e s and r e s u l t s i n a
s i n g l e s o l u b i l i t y v a l u e c o r r e s p o n d i n g t o t h e s i n g l e random
number o r i g i n a l l y chosen.
The p r o c e s s o f c h o o s i n g a random number and c a l c u l a t i o n o f
c a s c a d i n g e r r o r i s r e p e a t e d 10,000 t i m e s , g e n e r a t i n g a d i s t r i b u -
t i o n o f s o l u b i l i t y v a l u e s r e l a t i v e t o t h e " t r u e " v a l u e which c a n
be c h a r a c t e r i z e d m a t h e m a t i c a l l y , p l o t t e d , and used t o f u r n i s h
the l i k e l i h o o d o r p r o b a b i l i t y o f any p a r t i c u l a r s o l u b i l i t y v a l u e
i n the range b e i n g exceeded. E s s e n t i a l l y t h e same s t e p s were
f o l l o w e d i n s i m u l a t i o n s f o r o t h e r parameters i n v e s t i g a t e d , even
f o r t h o s e on v a p o r p r e s s u r e , where e f f e c t s of temperature v a r i a -
t i o n are compound-specific.
The c a l c u l a t i o n procedures used a r e a v a i l a b l e i n s o f t w a r e
of the S t a t i s t i c a l A n a l y s i s System (SAS), v e r s i o n 82-3. Central
p r o c e s s i n g u n i t time p e r output d i s t r i b u t i o n on a main frame
computer (IBM Model 3280) was around 20 seconds and c o s t per
o u t p u t d i s t r i b u t i o n was l e s s than $6.
D i s t r i b u t i o n s g e n e r a t e d by t h e p r o c e s s d e s c r i b e d above
may n o t be easy t o l a b e l as "normal" o r "skewed l o g - n o r m a l " ,
f o r example, b u t i n g e n e r a l ( f o r P e a r s o n d i s t r i b u t i o n s ) they
a r e c o m p l e t e l y c h a r a c t e r i z e d by s p e c i f y i n g t h e f i r s t f o u r
s t a t i s t i c a l moments, i . e . mean, v a r i a n c e , skew, and k u r t o s i s ( 3 ) .
C o n s e q u e n t l y , r a t h e r than s u p p l y i n g l e s s q u a n t i t a t i v e l a b e l s ,
t h e s e moments a r e p r o v i d e d f o r a l l output d i s t r i b u t i o n s which
follow. Comparisons w i t h e x p e r i m e n t a l r e s u l t s i n t h e t e x t a r e
l i m i t e d t o d i s c u s s i o n of t h e mean and t h e square r o o t o f v a r i a n c e
or s t a n d a r d d e v i a t i o n , because few e x p e r i m e n t s (and none l o c a t e d
i n t h i s s t u d y ) a r e r e p e a t e d o f t e n enough t o g e n e r a t e d a t a s e t s
a l l o w i n g m e a n i n g f u l c a l c u l a t i o n o f t h i r d and f o u r t h moments.
"Beta f u n c t i o n s " have been used t o r e p r e s e n t s e v e r a l s o u r c e s
of e r r o r . The b e t a f u n c t i o n i s e x t r e m e l y f l e x i b l e i n t h e sense
t h a t i t can assume a g r e a t v a r i e t y o f shapes depending on v a l u e s
chosen f o r exponents, as seen i n F i g u r e 1, and seems p a r t i c u l a r l y
useful i n representing negative bias.
E x p e r i m e n t a l Methods f o r S o l u b i l i t y Determination
S o l u b i l i t y d a t a f o r o r g a n i c compounds i n water a r e o b t a i n e d
r e a d i l y f o r h i g h l y soluble m a t e r i a l s , but f o r s p a r i n g l y soluble
compounds measurements can be d i f f i c u l t due t o p o t e n t i a l l o s s e s
to a i r o r t o t h e c o n t a i n e r w a l l s , l o n g e q u i l i b r a t i o n t i m e s ,
need f o r extreme p u r i t y i n s t a r t i n g m a t e r i a l s , and p o s s i b l y
u n a n t i c i p a t e d minor r e a c t i o n s i n s o l u t i o n . As a r e s u l t , e r r o r s
of an o r d e r o f magnitude f o r some compounds have been r e p o r t e d
by MacKay e t a l . ( 4_).
For s l i g h t l y s o l u b l e compounds, two methods dominate the

c u r r e n t l i t e r a t u r e , t h e s h a k e - f l a s k method, and t h e g e n e r a t o r
column method. I n t h e s h a k e - f l a s k ( o r s t i r - f l a s k ) method, a
known amount o f s o l u t e e x c e e d i n g t h e a n t i c i p a t e d s o l u b i l i t y l i m i t
i s added t o a measured w a t e r sample i n a s e a l e d c o n t a i n e r . This
m i x t u r e i s shaken o r s t i r r e d t h o r o u g h l y and t h e n a l l o w e d t o s i t
f o r e i g h t hours t o s e v e r a l days t o e n s u r e t h a t s o l u t e - s o l v e n t
e q u i l i b r i u m i s a t t a i n e d . The m i x t u r e i s then f i l t e r e d o r c e n t r i -
fuged t o remove suspended p a r t i c l e s , and t h e s o l u t i o n c o n c e n t r a -
t i o n i s determined u s i n g customary chromatographic o r s p e c t r a s c o -
p i c t e c h n i q u e s . Changing range w i t h i n a method may a f f e c t e r r o r .
The column g e n e r a t o r (and r e l a t e d HPLC) method o f d e t e r -
m i n i n g aqueous s o l u b i l i t y has become t h e predominant method i n
the l i t e r a t u r e o v e r t h e past 5 y e a r s . I n t h i s method, a column
i s packed w i t h an i n e r t s o l i d s u p p o r t w h i c h p r o v i d e s a h i g h
s u r f a c e a r e a f o r t h e s o l u t e t o i n s u r e q u i c k e q u i l i b r a t i o n between
i t and t h e aqueous phase. A f t e r t h e s u p p o r t i s impregnated w i t h

the s o l u t e of i n t e r e s t and excess s o l u t e has been d i s p l a c e d , t h e
column i s b r o u g h t t o t h e d e s i r e d t e m p e r a t u r e and t h e aqueous
c o n c e n t r a t i o n i s determined as a f u n c t i o n of f l o w r a t e . The
e q u i l i b r i u m c o n c e n t r a t i o n corresponds to the h i g h e s t e l u t i n g
f l o w r a t e where s o l u t e c o n c e n t r a t i o n remains flow-independent.
Sources o f E r r o r i n S o l u b i l i t y Determination
The s h a k e - f l a s k method f o r d e t e r m i n i n g s o l u b i l i t y has f o u r major

sources of determinate e r r o r a s s o c i a t e d w i t h i t . In the f i r s t
c a t e g o r y a r e l o s s e s from a d s o r p t i o n o f t h e s o l u t e on t h e f l a s k
walls or to evaporation. T h i s q u a n t i t y i s somewhat dependent on
the v a p o r p r e s s u r e of the s o l u t e i n q u e s t i o n , b u t i f t h e q u a n t i t y
of s o l u t i o n used i s f a i r l y l a r g e ( i . e . , 250 m l ) , t h e s e l o s s e s may
r e p r e s e n t a maximum o f 5 p e r c e n t o f t h e t o t a l s o l u t e . A b e t a
d i s t r i b u t i o n was chosen f o r t h i s e r r o r s o u r c e . The presence o f
u n d i s s o l v e d s o l u t e suspended i n t h e water phase may cause a
sample t o r e g i s t e r anomalously h i g h s o l u b i l i t y . Centrifuging or
f i l t e r i n g reduces t h i s c o n t r i b u t i o n , a l t h o u g h t h e problem may
p e r s i s t f o r more n e u t r a l l y bouyant s o l u t e s . T h i s e r r o r i s r e p r e -
s e n t e d by an e x p o n e n t i a l d i s t r i b u t i o n w i t h t h e v e r y low s t a n d a r d
d e v i a t i o n expected i f t h e t e c h n i q u e d e s c r i b e d by K a r i c k h o f f and
Brown (_5) i s p r o p e r l y f o l l o w e d (jf2 p e r c e n t w i t h 95-percent con-
fidence).
The t h i r d s o u r c e a r i s e s from t h e e x t r a c t i o n e f f i c i e n c y f o r
the removal of s o l u t e from water, a t e c h n i q u e common t o most
methods. P e t e r s ( 6 ) , has shown t h i s t o i n t r o d u c e a n o t h e r nega-
t i v e b i a s w i t h i n 8 percent; t h e r e f o r e a beta d i s t r i b u t i o n with a
95-percent c o n f i d e n c e l e v e l o f -8 p e r c e n t was s e l e c t e d . F i n a l l y ,
the a c c u r a c y o f t h e d e t e c t i o n method was modeled by a normal
d i s t r i b u t i o n w i t h a 95-percent c o n f i d e n c e l e v e l of +2 p e r c e n t as
recommended by M a l l o n and H a r r i s o n (7^)
Note t h a t t h e e r r o r i n t r o d u c e d by each s t e p i s based upon
the e x i t c o n c e n t r a t i o n of s o l u t e from t h e p r e v i o u s s t e p and,
therefore, i s m u l t i p l i c a t i v e i n nature. In l i n e with the
c o n c l u s i o n s o f Whitmore (2), t h e r e s u l t i n g output d i s t r i b u t i o n
3. COY ET AL. Determining Uncertainty in Physical Parameter Measurements
might then be expected t o approximate log-normality However,

the r e s u l t s o f t h e computer s i m u l a t i o n o f e r r o r f o r aqueous
s o l u b i l i t y by t h e s h a k e - f l a s k method shown i n F i g u r e 2 c l e a r l y
e x h i b i t a n e g a t i v e b i a s . T h i s b i a s was i n t r o d u c e d by p o t e n t i a l
l o s s e s and by e x t r a c t i o n e f f i c i e n c y , a l t h o u g h the s t a n d a r d d e v i a -
t i o n o f 3,9 p e r c e n t compares q u i t e f a v o r a b l y t o t h a t c i t e d by
s e v e r a l r e s e a r c h e r s . The mean s i m u l a t e d v a l u e u n d e r e s t i m a t e s
the t r u e v a l u e by s l i g h t l y over 2 p e r c e n t .
The column method a l s o has s e v e r a l s t e p s which may r e s u l t
i n a n e g a t i v e b i a s on measured aqueous s o l u b i l i t y . The l a c k o f
w a t e r - s o l u t e e q u i l i b r i u m i n t h e g e n e r a t o r column i t s e l f may
produce an o u t l e t c o n c e n t r a t i o n l o w e r than t h e " t r u e " s o l u b i l i t y
a c c o r d i n g t o S t o l z e n b u r g and Andren ( 8 ) . T h i s r e s u l t a l s o has
been modeled w i t h a b e t a d i s t r i b u t i o n ( 9 5 - p e r c e n t c o n f i d e n c e
l e v e l o f -3 p e r c e n t ) .
The e f f i c i e n c i e s f o r a d s o r p t i o n and e x t r a c t i o n s t e p s a g a i n
a r e e s t i m a t e d t o be s i m i l a r t o t h o s e suggested by P e t e r s ( 6 ) ,
t h e r e f o r e , t h e same b e t a d i s t r i b u t i o n s as b e f o r e a r e employed.
However, note t h a t f o r t h e column g e n e r a t o r , two-step o r g a n i c
removal t y p i c a l l y i s u s e d . F i n a l l y , one may a s c r i b e t h e same
d e t e c t i o n l i m i t s as those o b t a i n e d f o r t h e s h a k e - f l a s k method.
The column method r e s u l t s ( F i g u r e 3) e x h i b i t a mean
s i m u l a t e d v a l u e 7 percent under t h e t r u e v a l u e , o r 5 percent
l e s s than t h a t o b t a i n e d s i m u l a t i n g t h e s h a k e - f l a s k method. The
d i f f e r e n c e may be a t t r i b u t e d t o t h e a d d i t i o n a l e x t r a c t i o n s t e p
and s o l u t e - e q u i l i b r a t i o n s t e p i n t h e column method. The tendency
of t h i s method t o u n d e r p r e d i c t r e a f f i r m s the need f o r c a l i b r a t i o n
of t h e column system v i a s h a k e - f l a s k s t a n d a r d s p r i o r t o u s e ,
although the p r e d i c t e d standard d e v i a t i o n of 4 percent i s q u i t e
good.
Methods and E r r o r i n O c t a n o l - W a t e r P a r t i t i o n Coefficient

Determinations
The o c t a n o l - w a t e r - p a r t i t i o n c o e f f i c i e n t ( K ) i s the most f r e -

o w
q u e n t l y c i t e d measure of e n v i r o n m e n t a l p a r t i t i o n i n g b e h a v i o r .
P a r t i t L o n c o e f f i c i e n t s t r a d i t i o n a l l y have been determined by
some v a r i a t i o n on t h e s h a k e - f l a s k method, however, o v e r t h e past
s e v e r a l y e a r s h i g h - p r e s s u r e l i q u i d chromatography has been shown
to measure o c t a n o l - w a t e r p a r t i t i o n c o e f f i c i e n t s a c c u r a t e l y over a
wide range o f v a l u e s w i t h g r e a t e r e a s e .
S i n c e t h e column/HPLC and s h a k e - f l a s k methods a r e a l s o t h e
main s o u r c e o f s o l u b i l i t y v a l u e s , t h e e v a l u a t i o n o f e r r o r f o r
K Q W i s very s i m i l a r . Loss o f s o l u t e t o w a l l s o r t h e atmosphere
a r e s t i l l o f c o n c e r n , as a r e t h e e x t r a c t i o n e f f i c i e n c i e s f o r
s o l u t e removal from water. E q u i l i b r a t i o n o f each of the t h r e e
phases i n v o l v e d ( i n s t e a d o f two f o r s o l u b i l i t y ) i s o f c o n c e r n .
The s h a k e - f l a s k method f o r K Q W d i f f e r s from t h e s o l u b i l i t y
d e t e r m i n a t i o n o n l y i n the measurement of s o l u t e c o n c e n t r a t i o n i n
the o c t a n o l phase. Since t h i s t y p i c a l l y i n v o l v e s standard chro-
matographic o r s p e c t r o s c o p i c t e c h n i q u e s , e r r o r a g a i n was assumed
t o be n o r m a l l y d i s t r i b u t e d about t h e t r u e c o n c e n t r a t i o n
w i t h a 95-percent c o n f i d e n c e l e v e l o f +2 p e r c e n t .
3.0 3.0
2.0 2.0
h(y) h(y)
1.0 1.0
F i g u r e 1. B e t a d e n s i t y f u n c t i o n s . Reproduced w i t h p e r m i s s i o n
from R e f . 20. C o p y r i g h t 1970, Houghton M i f f l i n Co..
0 775
0. 800
d 0 825

0 850
3

>
0 875
0 900
u
0 925

0 950

0 975
1 000
>

+J 1 025
<0

CJ
1 050
te 1 075
1 100
400 800 1,200 1,600 2,000 2,400
Frequency o f Occurrence per 10,000 Simulations
F i g u r e 2. D i s t r i b u t i o n o f s i m u l a t e d aqueous s o l u b i l i t y from t h e
s h a k e - f l a s k method ( t r u e v a l u e = 1.00).
3. COY ET AL. Determining Uncertainty in Physical Parameter Measurements
E x a m i n a t i o n o f F i g u r e 4 i l l u s t r a t e s t h e tendency o f t h i s
technique t o s l i g h t l y o v e r p r e d i c t K . o w The mean v a l u e o b s e r v e d
exceeds t h e t r u e v a l u e by 2.3 p e r c e n t . The s t a n d a r d d e v i a t i o n
of 10 p e r c e n t i s somewhat i n excess o f t h e 6.1 p e r c e n t g i v e n by
Unger e t a l . ( 9 ) and the 8 p e r c e n t g i v e n b y Bowman and Sans ( 1 0 ) .
The column method f o r d e t e r m i n i n g K o winvolves the e q u i l i -
b r a t i o n o f a s o l u t e from a s t a t i o n a r y phase ( i n t h i s case a
s i m u l a t e d o c t a n o l phase) i n t o an aqueous phase ( o r methanol-water
phase). The s o l u t e i s then e x t r a c t e d from water and a n a l y z e d
u s i n g an a p p r o p r i a t e d e t e c t o r .
Comparison o f t h e column method K Q W r e s u l t s w i t h the r e s u l t s
g i v e n by t h e column method f o r s o l u b i l i t y i n F i g u r e 3 shows t h e
shape o f t h e d i s t r i b u t i o n s t o be v i r t u a l l y i d e n t i c a l w i t h s t a n d a r d
d e v i a t i o n s b e i n g 4.0 p e r c e n t f o r s o l u b i l i t y and 4.2 p e r c e n t f o r
K . o w T h i s c o r r e s p o n d s to t h e s i m i l a r i t i e s noted by DeVoe e t
a l . , ( 1 1 ) . The column method, however, d i f f e r s from t h e shake-
f l a s k by 9.2 percent i n t h e case o f K Q W (versus 5 percent f o r

solubility). Woodburn e t a l . (12) quote a d i f f e r e n c e o f 10
p e r c e n t between t e c h n i q u e s . As i n d i c a t e d by comparing s t a n d a r d
d e v i a t i o n s , t h e column method seems as r e p r o d u c i b l e as t h e shake-
f l a s k method, b u t a c c u r a t e c a l i b r a t i o n i s even more n e c e s s a r y to
prevent u n d e r p r e d l c t i o n t h a n was the case f o r column method f o r
solubility.
Methods f o r Vapor P r e s s u r e Determination
Methods used t o determine t h e vapor p r e s s u r e of pure compounds a r e

u s u a l l y d i v i d e d i n t o two groups based on p r e s s u r e ranges t o which
they a p p l y : ( 1 ) between 1.0 and 760 t o r r , and ( 2 ) below 1.0 t o r r .
Manometric Methods. D i r e c t manometry methods such as t h e i s o t e n -

i s c o p e method a r e most o f t e n used f o r t h e p r e s s u r e range o f 1.0
to 760 t o r r . The method f o r t h e i s o t e n i s c o p e i s d e s c r i b e d i n
d e t a i l i n ASTM Method D-2879-70 ( 1 3 ) . F i g u r e 5 shows a schematic
of t h e i s o t e n i s c o p e . The sample b u l b and s h o r t l e g o f t h e mano-
meter a r e f i l l e d w i t h the l i q u i d o f i n t e r e s t and i s o t e n i s c o p e i s
a t t a c h e d t o a vacuum s o u r c e . D i s s o l v e d gases a r e removed from
the l i q u i d by r e d u c i n g t h e system p r e s s u r e t o a p p r o x i m a t e l y 1
t o r r and c a r e f u l l y warming t h e l i q u i d t o i t s b o i l i n g p o i n t . The
r e s u l t i n g vapor i s used t o f o r c e a s m a l l amount o f t h e l i q u i d
i n t o t h e manometer s e c t i o n which t r a p s some vapor between t h e
manometer and b u l b . The e n t i r e d e v i c e i s p l a c e d i n a c o n s t a n t
temperature b a t h u n t i l e q u i l i b r i u m between l i q u i d and v a p o r i s
achieved. N i t r o g e n i s added t o t h e s i d e o f t h e manometer o p p o s i t e
to t h e sample b u l b , u n t i l b o t h l i q u i d l e g s i n t h e manometer
s e c t i o n a r e equal. At that p o i n t , the n i t r o g e n pressure i s
determined and r e c o r d e d . A McLeod gauge u s u a l l y i s used between
15 and 760 t o r r . T h i s procedure t y p i c a l l y i s r e p l i c a t e d f o r
temperature increments o f 25C u n t i l a system p r e s s u r e o f 760
torr i s obtained.
The d a t a o b t a i n e d i n t h i s manner a r e p l o t t e d i n terms o f
the A n t o i n e e q u a t i o n , which r e l a t e s t h e n a t u r a l l o g a r i t h m o f
p r e s s u r e t o the r e c i p r o c a l o f a b s o l u t e t e m p e r a t u r e :
0.74
0.76
mean = 0.930
0.78
variance = 0.0016054
0.80 (std. dev. = 0.0401)
0.82 skew = -0.910
kurtosis = 1.090
0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98
1.00
I
200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000
Frequency of Occurrence per 10,000 Simulations
F i g u r e 3. D i s t r i b u t i o n o f s i m u l a t e d aqueous s o l u b i l i t y from t h e
column method ( t r u e v a l u e = 1.00).
0 900
0 925
0 950

<C
0 975
> 1 000
Q
+-> 1 025
Ci
H

1 050
3

1 075
s
1 100
> mean = 1.023

1 125
variance = 0.0017936
C0 1 150
. (std. dev. = 0.0424)
<
& 1 175 skew = 0.733
kurtosis = 1.200
1 .200
1 225
-L -L
400 800 -1,200 1,600 2,000 2,400

Figure 4 . D i s t r i b u t i o n of simulated octanol-water p a r t i t i o n
c o e f f i c i e n t from t h e s h a k e - f l a s k method ( t r u e v a l u e = 1.00).
3. COY ET AL. Determining Uncertainty in Physical Parameter Measurements 47

l n P
vapor = A + (T + C) (1)
where A, B, and C a r e c o n s t a n t s f o r a g i v e n compound. (For t h i s

s t u d y , rounded " t r u e v a l u e s " were assumed f o r vapor p r e s s u r e , as
noted i n the t e x t and f i g u r e s which f o l l o w , r a t h e r than i n s e r t i n g
s p e c i f i c v a l u e s o f A, B, and C f o r each compound.)
The i s o t e n i s c o p e measurement c o n t a i n s t h r e e major s o u r c e s of
error. Two of these s o u r c e s a r e independent of p r e s s u r e . The
mercury manometer a c c u r a c y of j h l t o r r i s s e t as a s t a n d a r d normal
d i s t r i b u t i o n about the " t r u e " p r e s s u r e . The q u e s t i o n of sample
p u r i t y i s a d d r e s s e d i n the ASTM methodology, w i t h a maximum
upward b i a s of 1 t o r r on t h e v a p o r p r e s s u r e a s s u r e d by u s i n g t h i s
technique. A l o g - n o r m a l d i s t r i b u t i o n w i t h a mean to 0.1 t o r r i s
chosen as the r e p r e s e n t a t i v e model based upon s u g g e s t i o n s by
O s b o m and S c o t t ( 1 4 ) . S i n c e t h e s e e r r o r s a r e s i m u l t a n e o u s i n
n a t u r e and independent of sample p r e s s u r e , t h e y a r e t a k e n to be

additive.
To determine the o v e r a l l e f f e c t on p r e s s u r e e r r o r of n o r m a l l y
d i s t r i b u t e d v a r i a t i o n i n t e m p e r a t u r e , the A n t o i n e e q u a t i o n must
be employed. Thus, the p r e s s u r e e r r o r i s a f u n c t i o n o f the
compound of i n t e r e s t . To f o c u s on t y p i c a l s i t u a t i o n s , t h r e e
compounds r e p r e s e n t a t i v e of the range o f a p p l i c a t i o n of the
i s o t e n i s c o p e were used. These were: benzene w i t h a r e l a t i v e l y
h i g h v a p o r p r e s s u r e ("true v a l u e " = 95 t o r r a t 2 5 C ) ; t o l u e n e f o r
a medium vapor p r e s s u r e ("true v a l u e " = 28 t o r r a t 2 5 C ) ; and
c h l o r o b e n z e n e f o r a low v a p o r p r e s s u r e ("true v a l u e " = 12 t o r r a t
25C).
The r e s u l t s of i s o t e n i s c o p e s i m u l a t i o n s show a s l i g h t o v e r -
p r e d i c t i o n f o r a l l t h r e e compounds w i t h a skewed d i s t r i b u t i o n i n
each case ( F i g u r e s 6, 7, and 8 ) . P r e d i c t a b l y , the lower the vapor
p r e s s u r e , the l a r g e r the r e l a t i v e s t a n d a r d d e v i a t i o n . On the
o t h e r hand, the a b s o l u t e s t a n d a r d d e v i a t i o n i s r e l a t i v e l y un
changed over the range of vapor p r e s s u r e s examined, v a r y i n g
between about 0.72 and 0.77 t o r r f o r the extreme c a s e s . The
maximum skewedness of the d i s t r i b u t i o n i s found f o r t o l u e n e , the
medium-vapor p r e s s u r e c a s e . The s t a n d a r d d e v i a t i o n o f 2.7 p e r c e n t
found f o r t o l u e n e c o r r e s p o n d s q u i t e w e l l to the 3 p e r c e n t e r r o r
e s t i m a t e made by MacKay e t a l . (4_). The 6 percent s t a n d a r d
d e v i a t i o n f o r the c h l o r o b e n z e n e case shows i t t o be a t the
lower end o f the range recommended f o r r e l i a b l e measurement.
F i g u r e 9 summarizes the i s o t e n i s c o p e s i m u l a t i o n s , i n d i c a t i n g a
s m a l l tendency o f the method t o o v e r p r e d i c t i n the o v e r a l l
p r e s s u r e range f o r the t h r e e compounds c o n s i d e r e d .
Gas S a t u r a t i o n Method. F o r v a p o r p r e s s u r e s l e s s than 1 t o r r , a

gas s a t u r a t i o n method i s most o f t e n employed. The e f f u s i o n
method o r Knudsen method a l s o has been used i n t h i s p r e s s u r e
range, but i t has proved q u i t e i m p r e c i s e ( 1 5 ) .
The gas s a t u r a t i o n method r e l i e s upon measurement of v a p o r
l o s s r a t e s from s u r f a c e s f o r a known volume of gas passed over
the s u r f a c e . While t h e r e a r e s e v e r a l v a r i a t i o n s on the t e c h n i q u e ,
i n c l u d i n g ones u s i n g HPLC, the one d e s c r i b e d by Spencer e t a l .
(15) i s t y p i c a l . Dry n i t r o g e n i s passed through a q u a r t z sand

Library
1155 16th St., N.W.
Washington, D.C. 20036
E V A L U A T I O N O F PESTICIDES IN G R O U N D WATER
TO PRESSURE CONTROL AND

\ MEASUREMENT SYSTEM
F i g u r e 5. Schematic o f an i s o t e n i s c o p e . Reproduced w i t h
p e r m i s s i o n from R e f . 13. C o p y r i g h t 1974, American S o c i e t y f o r
T e s t i n g and M a t e r i a l s .
COY ET AL. Determining Uncertainty in Physical Parameter Measurements 49
111 5 1
105 5 1
104 5 1 mean = 94.7
103 5 1 variance = 0.57077
102 5 1 (std. dev.= 0.755)
101 5 1 skew = 3.60
kurtosis = 46.1
100 5 1
99 5 1
98 5 1
97 5 1
96 5
95
94
93 5
92 5 1
i i 1 1 1
a
0 1,200 2,400 3,600 4,800 6,0
F i g u r e 6. D i s t r i b u t i o n o f s i m u l a t e d v a p o r p r e s s u r e f o r benzene
u s i n g t h e i s o t e n i s c o p e ("true v a l u e " = 95.0 mm H g ) .
49.5 1
40.5 1
39.5 1 mean = 28.4
38.5 1 variance = 0.59036
37.5 1 (std. dev. = 0.768)
36.5 1 skew = 4.70
kurtosis = 78.3
35.5 1
34.5 1
33.5 1
32.5 1
31.5 1
30.5
29.5
28.5
27.5
26.5 1
... 1 1 1 1 1 1 1 1 1
0 1,200 2,400 3,600 4,800 6,000
F i g u r e 7. D i s t r i b u t i o n o f s i m u l a t e d v a p o r p r e s s u r e f o r t o l u e n e
u s i n g t h e i s o t e n i s c o p e ("true v a l u e " = 28.0 mm H g ) .
25 5
22 5
i mean = 12.0(475)
variance = 0.532534
19 5 (std. dev. = 0.780)
skew = 2.79
kurtosis = 27.2
16 5
ft
> 13 5

10 .5
1 1 1 1 1 1 1 J 1
1,200 2,400 3,600 4,800 6,000
F i g u r e 8. D i s t r i b u t i o n o f s i m u l a t e d v a p o r p r e s s u r e f o r
c h l o r o b e n z e n e u s i n g t h e i s o t e n i s c o p e ("true v a l u e " = 12.0 mm Hg).
-3.2
-1.6
0.0
1.6
3.2

3 4.8
CO
'$ 6.4 mean = 0,247
<u variance = 0,57077
Q 8.0 (std. dev. = 0.755)
a 9.6
<u
skew = 3,60
S .2 kurtosis = 46.1
<u
* 12.8
14.4
16.0
17.6 J I I I I I I 1 L J I I L
1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000
F i g u r e 9. D i s t r i b u t i o n o f r e l a t i v e e r r o r f o r t h e t h r e e v a p o r
p r e s s u r e s i m u l a t i o n s ( t r u e v a l u e = 0.00).
3. COY E T A L . Determining Uncertainty in Physical Parameter Measurements 51
( o r o t h e r s u p p o r t m a t e r i a l ) t h a t has been s a t u r a t e d p r e v i o u s l y
w i t h t h e compound o f i n t e r e s t . The vapor t h a t i s e v o l v e d from
t h i s column i s t r a p p e d on a a p p r o p r i a t e s o r b e n t m a t e r i a l , which
i s s u b s e q u e n t l y e x t r a c t e d and c o n c e n t r a t e d w i t h a hexane/acetone
solution. The c o n c e n t r a t i o n o f t h e sample compound i n t h e e x t r a c t
may then be determined u s i n g g a s chromatography o r o t h e r d e t e c t i o n
methods. The v a p o r phase c o n c e n t r a t i o n a t e q u i l i b r i u m c o n d i t i o n s
may be c a l c u l a t e d based upon t h e volume o f c a r r i e r gas t h a t i s
used t o c o l l e c t a measured amount o f s o l u t e i n t h e e x t r a c t .
T h i s procedure i s r e p e a t e d f o r 10C temperature i n c r e m e n t s , and
the d a t a a r e p l o t t e d as I n P p o v e r s u s r e c i p r o c a l a b s o l u t e
v a r
temperature ( A n t o i n e e q u a t i o n ) .
The g a s s a t u r a t i o n method o b v i o u s l y s u f f e r s from e r r o r s o f
a d i f f e r e n t n a t u r e than t h e i s o t e n i s c o p e method. Vapor l o s t t o
s u r f a c e s w i t h i n the measurement system and low v a p o r - t r a p p i n g
e f f i c i e n c y may l e a d t o s i g n i f i c a n t e r r o r s f o r l o w v a p o r p r e s s u r e
compounds. Spencer e t a l . (15) found v a p o r c a p t u r e e f f i c i e n c i e s

as l o w as 90 p e r c e n t , w h i l e Wasik, e t a l . (16) a r r i v e d a t a
95-percent c o n f i d e n c e l e v e l o f +9 p e r c e n t . Thomas and S i e b e r (17)
r e p o r t e d l y o b t a i n e d an e r r o r o f +1 t o 3 p e r c e n t u s i n g a column-gas
saturator. Spencer n o t e d , however, t h a t f o r some v e r y low vapor
p r e s s u r e compounds, up t o an o r d e r o f magnitude v a r i a t i o n has
been r e p o r t e d .
F o r t h e gas s a t u r a t i o n method, t h e e r r o r s o u r c e s and t h e i r
approximate v a l u e s a r e v e r y s i m i l a r t o p r e v i o u s column t e c h n i q u e s .
[At 95% c o n f i d e n c e , temperature c o n t r o l = +0.05K ( n o r m a l ) , l a c k
of v a p o r - l i q u i d e q u i l i b r i u m = - 5 % ( b e t a ) , t r a p p i n g e f f i c i e n c y =
-8% ( b e t a ) , e x t r a c t i o n e f f i c i e n c y - -8% ( b e t a ) , gas c h r o m a t o g r a p h i c
measurement = +2% ( n o r m a l ) . ] Consequently, the e r r o r d i s t r i b u t i o n
f o r a l l t h r e e column methods s h o u l d be a p p r o x i m a t e l y t h e same.
T h i s means a g e n e r a l u n d e r p r e d i c t i o n o f v a p o r p r e s s u r e as shown
i n F i g u r e 3.
E f f u s i o n Method. The e f f u s i o n o r Knudsen c e l l method i s

much l e s s r e l i a b l e than t h e gas s a t u r a t i o n method. The measure
ment i s based upon weighing a pure sample b e f o r e and a f t e r
d i f f u s i o n o f v a p o r from t h e sample through an a p p e r t u r e o f known
c r o s s s e c t i o n i n t o a h i g h vacuum system. Weight l o s s p e r u n i t
time t h e n i s used t o c a l c u l a t e v a p o r p r e s s u r e . U n f o r t u n a t e l y ,
the weight l o s s i s t h e s m a l l d i f f e r e n c e between two r e l a t i v e l y
l a r g e numbers and a l s o proves t o be h i g h l y dependent on e f f u s i o n
times u s e d , temperature c o n t r o l , and sample p u r i t y . Although
e f f u s i o n method d a t a have been r e p o r t e d f o r m a t e r i a l s w i t h vapor
p r e s s u r e s as low as 5 10~6 t o r r , DePablo (18) r e p o r t e d up t o
+0.3 t o r r e r r o r a t measurements o f 1 t o r r ( o r 30-percent e r r o r
w i t h 95-percent c o n f i d e n c e ) . C o n s e q u e n t l y , d e t a i l e d s t a t i s t i c a l
a n a l y s i s was not c o n s i d e r e d w o r t h w h i l e .
V o l a t i l i z a t i o n from Water
V o l a t i l i z a t i o n from water, t h e t r a n s p o r t o f a c h e m i c a l i n s o l u t i o n
i n a water body t o t h e atmosphere, i s b e l i e v e d t o be t h e p r i n c i p a l
a q u a t i c f a t e o f low m o l e c u l a r w e i g h t , n o n p o l a r compounds t h a t
a r e not o t h e r w i s e r a p i d l y degraded o r t r a n s f o r m e d ( 1 9 ) . The

e s t i m a t i o n o f compound v o l a t i l i z a t i o n from a n a t u r a l water body
can be made on t h e b a s i s o f l a b o r a t o r y - m e a s u r e d r a t e c o n s t a n t s ,
with e x t r a p o l a t i o n to estimate the a c t i v i t y i n the n a t u r a l en-
vironment t y p i c a l l y performed i n subsequent c a l c u l a t i o n s . F o r
compounds o f d i f f e r i n g l e v e l s o f v o l a t i l i t y , t h e r a t e c o n s t a n t s
that are required f o r e x t r a p o l a t i o n d i f f e r . S e l e c t i o n o f the
a p p r o p r i a t e r a t e c o n s t a n t may be made u s i n g r e s u l t s of s c r e e n i n g
tests.
T e s t p r o t o c o l s a r e a v a i l a b l e f o r h i g h , medium, and low
v o l a t i l i t y compounds. However, o n l y t h e h i g h v o l a t i l i t y compound
p r o t o c o l has undergone more than p r e l i m i n a r y v a l i d a t i o n s t u d i e s .
The c a t e g o r i z a t i o n o f compounds i n t o h i g h , medium, and low v o l a -
t i l i t y c l a s s e s i s a c c o m p l i s h e d by performance of a s c r e e n i n g
t e s t p r o t o c o l on t h e s e l e c t e d compound. The p r i n c i p a l r e f e r e n c e
f o r the t e s t p r o t o c o l d e s c r i p t i o n and background i n f o r m a t i o n i s
a r e p o r t p r e p a r e d by SRI I n t e r n a t i o n a l under c o n t r a c t t o t h e
U.S. E n v i r o n m e n t a l P r o t e c t i o n Agency by M i l l , e t a l . ( 1 9 ) .
The recommended e r r o r e s t i m a t i o n methods f o r h i g h v o l a t i l i t y
compounds from t h e r e f e r e n c e a r e reviewed i n t h i s s e c t i o n o f t h e
report a f t e r d e s c r i b i n g the t e s t p r o t o c o l procedures. A Monte
C a r l o s i m u l a t i o n o f e x p e r i m e n t a l r e s u l t s was then performed
f o l l o w e d by s t a t i s t i c a l a n a l y s e s t o determine t h e d i s t r i b u t i o n
and amount o f e r r o r a s s o c i a t e d w i t h e s t i m a t i o n o f v o l a t i l i z a t i o n
from water f o r a h i g h v o l a t i l i t y compound.
D e s c r i p t i o n of Procedures Screening T e s t . Because t h e e x p e r i -

mental p r o t o c o l s a r e o f r e c e n t o r i g i n and the r e f e r e n c e i s n o t
r e a d i l y a v a i l a b l e t o many r e a d e r s , they a r e d e s c r i b e d h e r e i n
some d e t a i l . The i n i t i a l s t e p i n the SRI procedure i s t o c l a s s i f y
the compound as low, medium, o r h i g h v o l a t i l i t y and t o i d e n t f y
t h o s e compounds w i t h a v o l a t i l i z a t i o n h a l f - l i f e o f l e s s than 3
months. The f o l l o w i n g p h y s i c a l p r o p e r t y d a t a a r e n e c e s s a r y t o
perform the s c r e e n i n g t e s t : ( 1 ) m e l t i n g p o i n t , (2) Henry's Law
c o n s t a n t , o r ( 3 ) water s o l u b i l i t y and v a p o r p r e s s u r e a t 20C,
and (4) heat o f f u s i o n , i f t h e c h e m i c a l i s s o l i d a t 20C
and t h e v a p o r p r e s s u r e d a t a used t o c a l c u l a t e the Henry's
Law c o n s t a n t a r e f o r a l i q u i d . The compounds a r e c l a s s i f i e d by
c a l c u l a t i n g t h e Henry's law c o n s t a n t , H . c The f o l l o w i n g c l a s s -
i f i c a t i o n scheme a p p l i e s :
High v o l a t i l i t y : H >1,000 t o r r / m o l e / l i t e r
c
Intermediate v o l a t i l i t y : 10 <H <1,000 t o r r / m o l e / l i t e r

C
Low v o l a t i l i t y : H <10 t o r r / m o l e / l i t e r
c
The d e t a i l e d t e s t p r o t o c o l s a r e recommended f o r t h o s e compounds

f a l l i n g i n t h e c l a s s of h i g h o r i n t e r m e d i a t e v o l a t i l i t y . For
low v o l a t i l i t y compounds, t h e d e t a i l e d t e s t p r o t o c o l i s recom-
mended i f t h e s c r e e n i n g s t u d y s u g g e s t s t h a t o t h e r processes,
such as p h o t o l y s i s and biodgradation, a r e slow.
High V o l a t i l i t y Compounds P r o t o c o l . The e s t i m a t e d r a t e c o n s t a n t

s
of v o l a t i l i z a t i o n i n t h e n a t u r a l environment, ( ^ ) > i v e n v
3. COY E T A L . Determining Uncertainty in Physical Parameter Measurements
based on t h e l a b o r a t o r y - m e a s u r e d r a t i o o f v o l a t i l i z a t i o n r a t e
0 0
c o n s t a n t t o t h e oxygen r e a e r a t i o n r a t e c o n s t a n t ( K y / ^ ) ] ^
by t h e e q u a t i o n :
c c o
K
( v)env = K K
( v / v ) l a b ( v)env K
(2)
The e n v i r o n m e n t a l oxygen r e a e r a t i o n r a t e c o n s t a n t s ( K ) v e n v
a r e a v a i l a b l e f o r r e p r e s e n t a t i v e b o d i e s o f water i n M i l l , e t a l .
(19). The d e t a i l e d t e s t p r o t o c o l p r o v i d e s t h e p r o c e d u r e s f o r
C
estimating ( \ / \ ) *
l a h
Measurements a r e performed i n a 2 - l i t e r beaker w i t h two

t u b i n g c o n n e c t i o n s a t the bottom, a c o n s t a n t - s p e e d s t i r r i n g
motor w i t h p r o p e l l e r t o s t i r t h e s o l u t i o n s , and a r e c i r c u l a t i n g
pump t h a t draws s o l u t i o n out o f t h e b e a k e r past a d i s s o l v e d
oxygen a n a l y z e r membrane and r e t u r n s i t t o t h e b e a k e r . The
i n i t i a l measurments determine t h e r e l a t i o n s h i p between K and v
s t i r r i n g r a t e i n t h e beaker w i t h o u t any o f t h e compound p r e s e n t

i n the d i s t i l l e d water. A f t e r e s t a b l i s h i n g the s t i r r i n g r a t e to
r e l a t i o n s h i p , s t o c k s o l u t i o n on t h e t e s t compound i s added

C K
t o t h e d i s t i l l e d water, and t h e d e t e r m i n a t i o n of ( ^ / ) i ] v v a 5
i s begun.
Each e x p e r i m e n t a l r u n i s performed a t a c o n s t a n t s t i r r i n g
speed. Oxygen c o n t e n t i n t h e s o l u t i o n i s m o n i t o r e d and t h e
content recorded p e r i o d i c a l l y . A l i q u o t s o f the s o l u t i o n a r e
withdrawn from t h e beaker p e r i o d i c a l l y , and t h e c o n c e n t r a t i o n o f
compound i n t h e a l i q u o t i s measured. F o r each e x p e r i m e n t a l r u n
a t a s t i r r i n g speed, a t l e a s t 10 measurements o f c o n c e n t r a t i o n o f
compound must be made, and a t l e a s t 15 o b s e r v a t i o n s o f oxygen
c o n c e n t r a t i o n must be made b e f o r e t h e r u n i s completed.
A d d i t i o n a l e x p e r i m e n t a l runs a r e r e q u i r e d so t h a t d a t a a r e ob
t a i n e d a t no l e s s than s i x s t i r r i n g r a t e s , p r o d u c i n g a wide
range o f values.
The v o l a t i l i z a t i o n r a t e o f t h e c h e m i c a l compound i s g i v e n
by t h e e q u a t i o n ,
Rv = d[C] = -4 [C] t (3)

dt
0
where K y i s t h e v o l a t i l i z a t i o n r a t e c o n s t a n t and [ C ] i s t h e t
c o n c e n t r a t i o n o f t h e c h e m i c a l compound i n s o l u t i o n a t time t .
The oxygen r e a e r a t i o n r a t e o f t h e s o l u t i o n i s g i v e n by t h e
equation,
Rv = d[0 ] 9 = -K ([0 ] 2 s - [0 ] )
2 t W
dt
s
where K i s t h e oxygen r e a e r a t i o n r a t e c o n s t a n t , l ^ l g I
v the
d i s s o l v e d oxygen c o n c e n t r a t i o n o f t h e s o l u t i o n a t s a t u r a t i o n ,
and [02]^ i s t h e d i s s o l v e d oxygen c o n c e n t r a t i o n i n s o l u t i o n a t
time t .
54 EVALUATION O F PESTICIDES IN GROUND WATER
Error Analysis H i g h V o l a t i l i t y Compounds. The t e s t p r o t o c o l

r e q u i r e s measurements o f b o t h d i s s o l v e d oxygen and chemical
compound as a f u n c t i o n of t i m e . E q u a t i o n s 2 and 3, when i n t e
g r a t e d , show the l i n e a r r e l a t i o n s h i p between l n [ C ] and time t
f o r the c h e m i c a l compound, and I n ([02] s ~ [O2D and time t f o r
d i s s o l v e d oxygen c o n t e n t . The r e s p e c t i v e s l o p e s f o r e a c h l i n e
c 0
are ^ and K y , t h e r a t e c o n s t a n t s . P o t e n t i a l s o u r c e s of
e r r o r i n t h i s p r o t o c o l a r e the i n d i v i d u a l d i s s o l v e d oxygen and
c h e m i c a l compound c o n c e n t r a t i o n measurements.
c
The e s t i m a t e d v o l a t i l i z a t i o n r a t e c o n s t a n t , i s r e l a t e d
t o t h e measured c o n c e n t r a t i o n and time by the f o l l o w i n g r e g r e s s i o n
equation:
nltlnC-Zt ZlnC (5)

2 2
nZt -(Et)
where i s the number of c o n c e n t r a t i o n measurements. At time

t = 0, the i n t e r c e p t C can be c a l c u l a t e d from the f o l l o w i n g
Q
equation:
In C n 1/n (ElnC - K v It) (6)
No i n f o r m a t i o n p r e s e n t e d i n the r e f e r e n c e document s u g g e s t s
t y p i c a l v a l u e s f o r e r r o r s a s s o c i a t e d w i t h the c o n c e n t r a t i o n
measurements, o r the type of s t a t i s t i c a l d i s t r i b u t i o n t h a t might
r e p r e s e n t t h e s e e r r o r s . The document does s u g g e s t t h a t the
p r e f e r r e d measurement of e r r o r i s a 9 5 - p e r c e n t c o n f i d e n c e l i m i t
based on the t - s t a t i s t i c , i m p l y i n g t h a t the e r r o r d i s t r i b u t i o n
i s normal i n a p p e a r a n c e . The e q u a t i o n p r e s e n t e d t o compute the
9 5 - p e r c e n t c o n f i d e n c e l i m i t was i n c o r r e c t i n the r e f e r e n c e . The
f o l l o w i n g e q u a t i o n i s the c o r r e c t form:
1/2
2
Z(lnC) - lnC ZlnC 0 - K^(lnC)(t)
CL (95%) = t _ ,0.05
n 2
(n-2) [Zt 2
- 2
(Zt) /n] (7)
where t _2 0.05 *
n
s t n e
t w o - t a i l e d t - s t a t i s t i c f o r n-2 degrees
o f freedom. The c o n f i d e n c e i n t e r v a l on i s as f o l l o w s :
CL < < + CL
The e s t i m a t e d oxygen r e a e r a t i o n r a t e c o n s t a n t i s r e l a t e d t o
the d i s s o l v e d oxygen c o n c e n t r a t i o n measurements and time by the
following regression equations:
nZ(t) [ I n ( C - C)] - Et ( C - C)
s s
(8)
2 2
nit - (Et)
where C and C a r e s u b s t i t u t e d f o r [ 0 ]
s and [ 0 ] i n E q u a t i o n 3. 2 s 2 t
S i m i l a r i t y between E q u a t i o n s 4 and 7 i s r e a d i l y a p p a r e n t . The

equation f o r the i n t e r c e p t C i s : Q
ln(C s
C )
0 = 1/n [ ( C - C) - K
s v It] (9)
a l s o s i m i l a r t o E q u a t i o n 5. As i n t h e case o f , t h e r e i s no
information i n the reference text regarding t y p i c a l e r r o r values
f o r measurements o f d i s s o l v e d oxygen c o n c e n t r a t i o n o r t h e type
of s t a t i s t i c a l d i s t r i b u t i o n r e p r e s e n t a t i v e o f t h o s e e r r o r s . An
e q u a t i o n i s p r e s e n t e d t o c a l c u l a t e a 95-percent c o n f i d e n c e l i m i t
u s i n g t h e t - s t a t i s t i c , thus making the assumption o f near n o r m a l l y
d i s t r i b u t e d e r r o r s apparent. The t e x t l i s t e d an i n c o r r e c t form
of t h e e q u a t i o n ; t h e c o r r e c t form i s as f o l l o w s :
CL(95%) = t _ n 2 > 0 .05
2 1/2
[1(0 -] -1(0 - )1(0 --()[1(0 -
3 8 8 3
(n-2) [It 2
- ( /] 2
(10)
As i n t h e case o f E q u a t i o n 6, t i s t h e t w o - t a i l e d t - s t a t i s t i c
w i t h n-2 degrees o f freedom.
G i v e n a t l e a s e s i x v a l u e s o f and o b t a i n e d o v e r a
range o f s t i r r i n g r a t e s , t h e r a t i o o f ( K / ) c a n be o b t a i n e d v
by p l o t t i n g t h e d a t a p o i n t s and f i t t i n g l i n e a r l e a s t squares
l i n e through t h e d a t a p o i n t s f o r c e d through t h e o r i g i n . The
equation f o r t h i s regression l i n e i s given a s :
^ ^
c
2 (ID
S(K )j v
t n
where t h e s u b s c r i p t j r e f e r s t o t h e j measurement ( s t i r r i n g
c C
rate) of K andy . The q u o t i e n t ( \ / \ ) i s a l s o
assumed t o be t - d i s t r i b u t e d i n t h e r e f e r e n c e . The e q u a t i o n f o r
the 95-percent c o n f i d e n c e l e v e l i s g i v e n a s :
56 EVALUATION O F PESTICIDES IN G R O U N D WATER
c 2 c 1/2
S(K )j v (K /K )E(K )
V V V j (Ky)j
(12)
CL (95%) = t . n l f o.05 2
(n-1) liKyXj
The r e f e r e n c e i n d i c a t e s t h a t the 95-percent c o n f i d e n c e l i m i t on

0
the average o f ( / ) f o r h i g h v o l a t i l i t y compounds i s

C
about 5 t o 10 p e r c e n t of the magnitude o f ( K y / K y ) .
S i m u l a t i o n o f E x p e r i m e n t a l R e s u l t s and E r r o r E s t i m a t i o n . An
a n a l y s i s o f i m p l i e d n o r m a l i t y o f e r r o r a s s o c i a t e d w i t h measure
c
ments of K and i s not p o s s i b l e because of the l a c k of
v
experimental data. However, even i f the n o r m a l i t y of e r r o r i n

C
measuring K y and i s assumed, i t i s not n c e s s a r i l y t r u e t h a t

c
t h e e s t i m a t e d r a t i o of the two r a t e c o n s t a n t s , ( K / K ) > w i l l v v
have n o r m a l l y d i s t r i b u t e d e r r o r s as i s assumed i n the r e f e r e n c e

text. F u r t h e r , the use o f the l i n e a r r e g r e s s i o n approach t o
0
determine ( K ^ / K y ) may t e n d t o u n d e r e s t i m a t e (
because the e r r o r s i n d e t e r m i n i n g Ky a r e t a k e n i n t o a c c o u n t .
c
L i k e w i s e , the v a r i a n c e of ( K / K ) may be u n d e r e s t i m a t e d
v v
f o r the same r e a s o n .
To examine t h e r e a s o n a b l e n e s s o f the assumed n e a r n o r m a l i t y
c
f o r ( K / K ) and the p o t e n t i a l f o r the u n d e r e s t i m a t i o n of
v v
the s l o p e and i t s v a r i a n c e , Monte C a r l o s i m u l a t i o n s were performed.

c
F o r the s i m u l a t i o n s , a t r u e mean v a l u e of ( K / K ) was s e l e c t e d v v
as 0.71. The s e l e c t i o n was based on an a c t u a l l y measured v a l u e

c
of ( K / K ) f o r 1 , 1 - d i c h l o r o e t h a n e o v e r a range o f
v v values of
0.3 t o 12.0 hr~"l ( 1 9 ) . U s i n g t h i s r a t i o and s i x assumed v a l u e s

of Ky c o r r e s p o n d i n g t o v a r i e d s t i r r i n g r a t e s ) w i t h i n the
recommended e x p e r i m e n t a l range of 1 t o 15 h r " " l , a s e t o f s i x
c
corresponding were c a l c u l a t e d . These mean v a l u e s a r e
shown i n T a b l e I .
F o r the f i r s t s i m u l a t i o n , i t was assumed t h a t the r e l a t i v e
a c c u r a c y of d e t e r m i n i n g K and was such t h a t 95 p e r c e n t
v
of the measured v a l u e s would f a l l w i t h i n the range o f +5 p e r c e n t

of t h e i r t r u e mean v a l u e s , l i s t e d i n T a b l e I . I t was a l s o assumed
t h a t the measured v a l u e e r r o r s were t - d i s t r i b u t e d , thus a l l o w i n g
computation of s t a n d a r d d e v i a t i o n s a l s o shown i n T a b l e I . For
the second s i m u l a t i o n , i t was assumed t h a t 95 p e r c e n t of the
measured K and would f a l l w i t h i n the range of +10 p e r c e n t
v
0 C
u s i n g t h e same mean and K y as assumed f o r the f i r s t
simulation. The r e s u l t a n t s t a n d a r d d e v i a t i o n s a r e a l s o shown i n
Table I.
C
A f t e r c o m p l e t i n g t h e computation o f t h e mean Ky and K y and
s t a n d a r d d e v i a t i o n s , a random number g e n e r a t o r was used t o d e v e l o p
c
1,000 n o r m a l l y d i s t r i b u t e d v a l u e s o f each K and K , having v y
the l i s t e d s t a n d a r d d e v i a t i o n s . V e r i f i c a t i o n of the n o r m a l i t y
of the randomly g e n e r a t e d number s e t s was done by a C h i - s q u a r e
t e s t on each number s e t .
The next s t e p s were t o compute the r a t i o of ( / )
3
Table I . S i m u l a t i o n Mean and Standard Deviations
Simulation 1 Simulation 2
Run No. Mean V a l u e Standard D e v i a t i o n Standard D e v i a t i o n

1 2.5 0.0486 0.0972
2 4.0 0.0778 0.1556
3 6.0 0.1167 0.2334
4 8.3 0.1615 0.3229
5 10.6 0.2062 0.4123
6 13.1 0.2548 0.5095
1 1.78 0.0345 0.0690

2 2.84 0.0552 0.1105
3 4.26 0.0828 0.1657

4 5.89 0.1146 0.2292
5 7.53 0.1464 0.2927
6 9.30 0.1809 0.3618
a
A t o t a l o f 1,000 v a l u e s were used i n each s i m u l a t i o n .
0
c o r r e s p o n d i n g t o each o f t h e s i x v a l u e s o f K^ ( s i x s t i r r i n g
0
speeds) and t o compute ( K ^ / K y ) from E q u a t i o n 11 f o r each
of t h e 1,000 t r i a l s . The s t a n d a r d d e v i a t i o n c o r r e s p o n d i n g t o
C
each o f t h e 1,000 e s t i m a t e d (K / K ) were computed u s i n g
the b r a c k e t e d p o r t i o n o f E q u a t i o n 12. The r e s u l t s o f t h e s e
computations a r e summarized i n T a b l e I I f o r b o t h s i m u l a t i o n s .
Table I I . Simulation Test R e s u l t s
Parameter Simulation 1 Simulation 2

c
K / K mean
v v 0.7098 0.7107
Low v a l u e 0.6779 0.6380

High value 0.7472 0.7766
Standard d e v i a t i o n 0.0104 0.0208

of mean v a l u e
Average s t a n d a r d 0.00693 0.01359

deviation of individual
slopes
Other p r o p e r t i e s o f
distribution
C o e f f i c i e n t o f skewness 0.9551 0.03318
Kurtosis -94.8748 4.6605
C h i - s q u a r e sum 11.44 2.02

0 0
The e s t i m a t e d average v a l u e s o f ( K y / ! ^ ) were i n good a g r e e
ment w i t h t h e t r u e v a l u e , 0.71 (0.7098 and 0.7107 f o r t h e +5
p e r c e n t and +_10 p e r c e n t s i m u l a t i o n s , r e s p e c t i v e l y ) . Chi-square
t e s t s performed on b o t h d i s t r i b u t i o n s o f ( K / K ) d i d not
v
r e j e c t t h e h y p o t h e s e s of n o r m a l i t y a t t h e 5 Yevel o f s i g n i f i
cance. T h e r e f o r e , f o r t h e two s i m u l a t i o n s performed, t h e assump
t i o n o f n o r m a l i t y f o r the e r r o r d i s t r i b u t i o n a s s o c i a t e d w i t h
c
( K / K ) seems r e a s o n a b l e .
v v
c
The q u e s t i o n o f whether t h e v a r i a n c e o f ( ^ / \ ) i s u n d e r
v
e s t i m a t e d by u s i n g t h e r e g r e s s i o n procedure o f E q u a t i o n 11 was
s t u d i e d i n t h e f o l l o w i n g way. F o r each o f t h e 1,000 e s t i m a t e d
0
s l o p e s , ( K ^ / K y ) t h e 9 5 - p e r c e n t c o n f i d e n c e i n t e r v a l was
c a l c u l a t e d u s i n g E q u a t i o n 12. I f E q u a t i o n 12 i s a s a t i s f a c t o r y
e s t i m a t o r f o r t h e 9 5 - p e r c e n t c o n f i d e n c e i n t e r v a l , t h e n about 95
p e r c e n t o f t h e computed c o n f i d e n c e i n t e r v a l s s h o u l d c o n t a i n t h e
t r u e s l o p e , 0.71. When t h e s e c a l c u l a t i o n s were performed on t h e
c
s i m u l a t i o n g e n e r a t e d d i s t r i b u t i o n s o f ( K / K ) , o n l y about
v v
86 p e r c e n t o f t h e supposed 95 p e r c e n t c o n f i d e n c e i n t e r v a l s i n
each s i m u l a t i o n c o n t a i n e d t h e t r u e s l o p e , 0.71. Because t h e
C
s i m u l a t i o n g e n e r a t e d e s t i m a t e s o f average ( \ / \ ) were so n e a r
the t r u e v a l u e o f 0.71, i t i s presumed t h a t t h e p r i n c i p a l r e a s o n
fewer c o n f i d e n c e i n t e r v a l s c o n t a i n e d 0.71 t h a n e x p e c t e d i s t h a t
the v a r i a n c e i s u n d e r e s t i m a t e d by E q u a t i o n 12.
As a p o t e n t i a l means f o r c o r r e c t i n g f o r t h e u n d e r e s t i m a t e d
v a r i a n c e , t h e f o l l o w i n g computations were made. I n computing
the 95-percent c o n f i d e n c e i n t e r v a l , t h e s t a n d a r d d e v i a t i o n o f
c
the i n d i v i d u a l ( K / K ) i n t h e s i m u l a t i o n s were m u l t i p l i e d
v v
by Sga/S>iavg where S g i s t h e o v e r a l l s t a n d a r d d e v i a t i o n o f
a
e
1,000 (K / K ) i n each s i m u l a t i o n and S.
v i s t h e average o f
the s t a n d a r d d e v i a t i o n s computed f o r each or t h e 1,000 i n d i v i d u a l
c
(K /K ).
v v When t h i s c o r r e c t i o n was a p p l i e d t o computed
c o n f i d e n c e i n t e r v a l s i n b o t h s i m u l a t i o n s , about 96 p e r c e n t o f
the 9 5 - p e r c e n t c o n f i d e n c e i n t e r v a l s c o n t a i n e d t h e t r u e s l o p e o f
0.71. When a p p l i e d t o t h e s t a n d a r d d e v i a t i o n o f i n d i v i d u a l
c
( K / K ) t h i s c o r r e c t i o n f a c t o r had a v a l u e of about 1.5
v v
f o r both s i m u l a t i o n s . T h i s suggests that the bracketed p o r t i o n

c
of E q u a t i o n 12 may u n d e r e s t i m a t e t h e v a r i a n c e o f ( K / K ) v v
by as much as a f a c t o r o f 2.3 ( i . e . , s t a n d a r d d e v i a t i o n by a
f a c t o r o f 1.5).
Conclusions
Column and h i g h performance l i q u i d chromatography (HPLC) methods

f o r measurement o f s o l u b i l i t y , o c t a n o l - w a t e r p a r t i t i o n c o e f f i c i e n t ,
and v a p o r p r e s s u r e which a r e r e p l a c i n g t h e o l d e r e q u i l i b r i u m
methods t e n d t o u n d e r e s t i m a t e aqueous s o l u b i l i t y and v a p o r p r e s
s u r e and tend t o o v e r e s t i m a t e t h e o c t a n o l - w a t e r p a r t i t i o n c o e f f i
cient. The s t a n d a r d d e v i a t i o n f o r b o t h t h e e q u i l i b r i u m and
dynamic systems a r e s i m i l a r , b u t c a l i b r a t i o n between systems i s
necessary to i n s u r e that they agree. The range o f e r r o r s f o r
b o t h t y p e s o f measurement as mentioned i n t h e l i t e r a t u r e a r e
w e l l w i t h i n t h e range p r e d i c t e d by t h e c o m p u t e r - s i m u l a t e d error
d i s t r i b u t i o n s g e n e r a t e d i n t h i s r e p o r t . The measurement e r r o r
3. COY ET AL. Determining Uncertainty in Physical Parameter Measurements 59
d i s t r i b u t i o n s t h a t were determined a r e not n o r m a l l y d i s t r i b u t e d

and show a d e f i n i t e b i a s f o r each measured parameter.
The p r e c i s e number o f s i m u l a t i o n s needed t o p r o v i d e adequate
" r e s o l u t i o n " f o r the o u t p u t d i s t r i b u t i o n s was n o t e x p l o r e d as
p a r t o f the c u r r e n t study b u t seems l i k e l y t o be a s i m p l e f u n c t i o n
of the number o f s u b d i v i d i o n s f o r t h e range o f output parameter
b e i n g examined and a l s o s h o u l d depend, n o t so s i m p l y , on t h e
number and r e s o l u t i o n of i n p u t d i s t r i b u t i o n s , as w e l l as on t h e
p r o b a b i l i t y requirements of the output ( i . e . , l e s s r e s o l u t i o n
needed t o a s s u r e a d i s c r e t e v a l u e , " a " , w i l l be exceeded i n o n l y
1 o u t o f 10 cases than i s needed f o r o n l y 1 out o f 100 c a s e s ) .
F o r v o l a t i l i z a t i o n from w a t e r , t h e measurement method e r r o r
a s s o c i a t e d with d e t e r m i n a t i o n of the r a t i o of r a t e constants,
C
K y / K , i s t y p i c a l l y r e p o r t e d i n terms o f 95-percent c o n f i d e n c e
v
l i m i t s on t h e average v a l u e . F o r h i g h v o l a t i l i t y compounds, t h e
95-percent c o n f i d e n c e l i m i t s a r e r e p o r t e d t o be 5 t o 10 percent
c
of t h e magnitude o f ( K / K ) . The r e g r e s s i o n a p p r o a c h t y p i c a l l y
v
0
used t o determine ( K ^ / K ^ ; and t h e s p e c i f i c a t i o n o f c o n f i d e n c e
l i m i t s based on the t - d i s t r i b u t i o n imply t h a t the e r r o r d i s t r i b u -
t i o n s a r e assumed t o be normal. However, even i f the e r r o r s o f
c
K v and K e s t i m a t e s a r e each n o r m a l l y d i s t r i b u t e d , t h e
v
e r r o r d i s t r i b u t i o n a s s o c i a t e d w i t h t h e q u o t i e n t o f t h e two i s
not n e c e s s a r i l y n o r m a l l y d i s t r i b u t e d . The r e g r e s s i o n approach
c
assumed may produce an e s t i m a t e d v a l u e o f ( K / K ) l o w e r than t h e
v v
t r u e v a l u e and u n d e r e s t i m a t e t h e v a r i a n c e . Monte C a r l o s i m u l a t i o n
o f t h e r e g r e s s i o n approach d i d not c o n f i r m u n d e r e s t i m a t i o n o f
c
( K / K ) ; however, t h e v a r i a n c e s appeared t o be u n d e r e s t i m a t e d
v v
by a f a c t o r o f 2.3.
Acknowledgments
The a u t h o r s w i s h t o e x p r e s s t h e i r g r a t i t u d e t o Dr. James W. F a l c o

f o r t h e i n i t i a l s u g g e s t i o n t h a t a s t o c h a s t i c approach might be
a p p l i c a b l e t o u n c e r t a i n t y c o n s i d e r a t i o n s and a l s o thank Mr.
R i c h a r d Walentowicz f o r h e l p f u l d i s c u s s i o n o f R e f e r e n c e 1.
Literature Cited
1. Walentowicz, R.; Falco, J.W. "Stochastic Processes Applied

to Risk Analysis of TCDD Contaminated Soil: A Case Study",
Unpublished Report, 1984; Exposure Assessment Group, ORD,
US EPA, Washington, DC 20460.
2. Whitmore, R.W. "Methodology for Characterization of
Uncertainty in Exposure Assessments", 1985; EPA 600/8-85/009,
NTIS No. PB85-240445, p. 26.
3. Kendall, M.G.; Stuart, A. "The Advanced Theory of
Statistics; Volume 1, Distribution Theory"; Charles Griffin
and Co. Ltd.: London, 1958; pp. 152-153.
4. MacKay, D.; Mascarenhas, R; Shiu, W.Y.; Chemosphere, 1980,
9, 257-264.
5. Karickhoff, S.W.; Brown, D.S. "Determination of Octanol-
Water-Distribution Coefficients, Water Solubilities, and
Sediment-Water-Partition Coefficients for Hydrophobic
Organic Pollutants", 1979; EPA-600/4-79-032, NTIS No. PB

80-103591, U.S. Environmental Protection Agency, Athens, GA.
6. Peters, R.L. Anal. Chem., 1982, 54, 1913-1914.
7. Mallon, B.J.; Harrison, F.L. Bull. Environ. Contam.
Toxicol., 1984, 32(3), 316-323.
8. Stolzenburg, T.R.; Andren, A.W. Analytica Chimica Acta
1983, 151, 271-274.
9. Unger, S.H.; Cook, J.R.; Hollenberg, J. J. Pharm. Sci.
1978, 67(10), 1364-1367.
10. Bowman, B.T.; Sans, W.T. Env. Sci. Health, 1983, 18(6), 667-683.
11. DeVoe, H.; M. Miller; Wasik, S. J. Rsch. Natl. Bur. Stds.,
1981, 86(4), 361-366.
12. Woodburn, K.B.; Doucette, W.; Andren, A. Environ. Sci.
Technol. 1984, 18(6), 457-459.
13. American Society for Testing and Materials (ASTM), ASTM
Method D-2879-70. ASTM Standards, Part 24, 1974,
Philadelphia, PA.
14. Osborn, A.G.; Scott, D.W. J. Chem. Thermodynamics, 1980,

12, 429-438.
15. Spencer, W.F.; Shoup, T.; Cliath, M. J. Agric. Food Chem.
1979, 27(2), 273-278.
16. Wasik, S.; Tewari, Y; Miller, M. J. Rsch. Natl. Bur.
Stds. 1982, 87(4), 311-315.
17. Thomas, T.C.; Sieber, A. Bui. Environ. Contam. Toxicol.
1974, 12, 17-21.
18. DePablo, R.S. J. Phys. D.: Appl. Phys., 13, 313-319.
19. Mill, T.; Mabey, W.R.; Bomberger, D.C. "Laboratory Protocols
for Evaluating the Fate of Organic Chemicals in Air and
Water." 1982, EPA-600/382-022, NTIS No. PB 3-150888, U.S.
Environmental Protection Agency, Athens, GA.
20. Johnson, N.L.; Kotz, S. "Distributions in Statistics:
Continuous Univariate Distributions-2"; Houghton Mifflin
Co.: Boston, 1970; p. 44.
4
Quantifying Pesticide Adsorption and Degradation
during Transport through Soil to Ground Water
1 1 2
W. Z. Zhong , A . T. Lemley , and R. J. Wagenet
1
College of Human Ecology, Cornell University, Ithaca, NY 14853
2
Department of Agronomy, Cornell University, Ithaca, NY 14853
We describe a rapid experimental method and a basis for

analyzing the results that will allow quantitative

determination of pesticide adsorption and degradation
during displacement through soil. A soil column meth-
odology employing commercially available equipment de-
veloped for high-pressure liquid chromatography studies
was used in the experiments. The movement and trans-
formation of aldicarb, aldicarb sulfoxide and aldicarb
sulfone were studied with this approach. Analytical
solutions to the convection-dispersion equation that
included description of linear adsorption and first-
order transformation were used to interpret the data.
Experiments were conducted in two soils, at two flow
velocities, in sterile and non-sterile conditions, and
at two initial influent concentrations to demonstrate
the usefulness of the method, and to better define the
adsorption and microbial and chemical conversion of al-
dicarb. Data from these experiments are presented and
discussed in the context of this method and other
studies on aldicarb. The method appears useful as a
generalizeable protocol for the study of any pesticide
in soil.
P e s t i c i d e l e a c h i n g from t h e r o o t zone and t h r o u g h t h e s o i l p r o f i l e

i n t o groundwater i s a s e r i o u s c o n c e r n . C o n t a m i n a t i o n o f groundwater
by such c h e m i c a l s may r e n d e r t h a t s u p p l y h a z a r d o u s f o r human consump-
tion. A d d i t i o n a l l y , passage o f t h e c h e m i c a l beyond t h e r o o t zone
p r e v e n t s f u r t h e r impact upon t h e t a r g e t p e s t . The r e s i d e n c e time o f
a p p l i e d p e s t i c i d e s w i t h i n the r o o t zone s h o u l d t h e r e f o r e be maximized
so t h a t t h e d u a l o b j e c t i v e s o f h i g h a g r i c u l t u r a l p r o d u c t i v i t y and low
e n v i r o n m e n t a l h a z a r d from l e a c h i n g can be met.
P e s t i c i d e and s o i l p r o p e r t i e s determine the m o b i l i t y and d e g r a -
dation o f applied chemicals. The i n t e r a c t i o n o f the o r g a n i c mole-
c u l e s with s o i l s o l i d s v a r i e s according t o chemical s t r u c t u r e , organ-
i c matter and c l a y c o n t e n t , s o i l pH, and i n some c a s e s c o n c e n t r a t i o n .
D e g r a d a t i o n r a t e s a r e i n f l u e n c e d by pH, s u b s t r a t e c o n c e n t r a t i o n ,
0097-6156/ 86/ 0315-0061 $06.00/0

t e m p e r a t u r e , s o i l m i c r o b i o l o g i c a l p o p u l a t i o n s , and s o i l water
content. A l t h o u g h i t i s p o s s i b l e to measure the r e l a t i v e e f f e c t o f
t h e s e v a r i a b l e s i n i n c u b a t i o n - t y p e l a b o r a t o r y s t u d i e s , i t i s not ob-
v i o u s how to e x t r a p o l a t e the r e s u l t s o f such e x p e r i m e n t s to f i e l d
conditions. A r e l a t i v e l y r a p i d method i s needed f o r s t u d y i n g both
m o b i l i t y and d e g r a d a t i o n under c o n d i t i o n s t h a t more a c c u r a t e l y repre-
s e n t the f i e l d regime. S o i l column t e c h n i q u e s p r o v i d e the experimen-
t a l framework f o r such a method. A l t h o u g h s o i l columns do not com-
p l e t e l y r e p r e s e n t the f i e l d c o n d i t i o n s , they do approximate t r a n s i e n t
f l o w i n g c o n d i t i o n s b e t t e r than i n c u b a t i o n - t y p e e x p e r i m e n t s . They may
t h e r e f o r e be more u s e f u l i n i n f e r r i n g the f i e l d c o n d i t i o n . Analytic
s o l u t i o n s o f t r a n s p o r t e q u a t i o n s t h a t c o n s i d e r a d s o r p t i o n and d e g r a -
d a t i o n p r o v i d e t h e o r e t i c a l models t h a t can be used to i n t e r p r e t the
results quantitatively. T h i s paper p r e s e n t s an e x p e r i m e n t a l and t h e -
o r e t i c a l methodology t h a t a l l o w s r e l a t i v e l y r a p i d assessment o f pes-
t i c i d e f a t e i n s o i l , and i l l u s t r a t e s the a p p l i c a t i o n o f the method t o
a l d i c a r b , a p e s t i c i d e o f both e n v i r o n m e n t a l and a g r i c u l t u r a l i n t e r -
est.
Theoretical Methods
A l d i c a r b (A) i s both c h e m i c a l l y and b i o l o g i c a l l y o x i d i z e d t o a l d i c a r b

s u l f o x i d e (A-SO), which i s then f u r t h e r o x i d i z e d by s i m i l a r p r o c e s s e s
to a l d i c a r b sulfone ( A - S 0 ) . These compounds are s i m u l t a n e o u s l y sub-
2
j e c t to o t h e r dgradtive c h e m i c a l p r o c e s s e s dominated by h y d r o l y -
sis. These r e a c t i o n s have been s u c c e s s f u l l y d e s c r i b e d by f i r s t - o r d e r
k i n e t i c s (J[), and can be g e n e r a l l y summarized as:
k* x k * 2
A A-SO A-S0 2
+ k l k 2 k 3 (1)
A-oxime A-SO oxime A-S0 2 oxime
where k l f k
2 and k r e p r e s e n t h y d r o l y s i s , and k * and k * i n d i c a t e
3 x 2
oxidation. E x p r e s s e d i n f i r s t - o r d e r k i n e t i c terms, assuming t h a t

o x i d a t i o n and h y d r o l y s i s o c c u r i n s o l u t i o n , and w i t h r e f e r e n c e to a
s o i l system i n which o n l y p a r t o f the t o t a l volume i s o c c u p i e d by
water, the f o l l o w i n g can be f o r m u l a t e d :
= - (k x + k^)(A) (2)
d (
^ S Q )
= 6k * x (A) - 9(k 2 + k *)(A-SO)
2 (3)
d ( S O
*~ a> = 9k *(A-S0) - 9 k ( A - S 0 )
2 3 2 (4)
4. Z H O N G ET A L . Quantifying Pesticide Adsorption and Degradation 63
3 3
where = v o l u m e t r i c water c o n t e n t ( c m c m " ) , t h e p a r e n t h e s e s i n d i
c a t e c o n c e n t r a t i o n , and t h e t r a n s f o r m a t i o n o f c h e m i c a l i s d e f i n e d
w i t h r e s p e c t t o t h e u n i t volume o f t h e system. The assumption t h a t
d e g r a d a t i o n o c c u r s i n s o l u t i o n i s a good one i n t h e case o f a l d i c a r b
and i t s m e t a b o l i t e s s i n c e t h e r e i s l i t t l e a d s o r p t i o n .
These e q u a t i o n s p r e d i c t t h a t t h e c o n c e n t r a t i o n o f a l d i c a r b i s
m o n o t o n i c a l l y d e c r e a s i n g , w h i l e t h e s u l f o n e and s u l f o x i d e forms
change i n c o n c e n t r a t i o n depending on t h e v a l u e o f t h e r a t e
coefficients.
The d e s c r i p t i o n o f t h e s e s e q u e n t i a l and s i m u l t a n e o u s r e a c t i o n s
d u r i n g t r a n s p o r t through a s o i l system i s a c c o m p l i s h e d u s i n g m i s c i b l e
d i s p l a c e m e n t t h e o r y , which can be f o r m u l a t e d f o r an i n t e r a c t i n g ,
d e g r a d i n g s o l u t e ( e . g . an o r g a n i c m o l e c u l e ) a s ( 2 ) :
' W- i 1
M <" t - - 1 *
1
where c = s o l u t e c o n c e n t r a t i o n i n t h e l i q u i d phase (]ig ml"" ), s =
1
s o l u t e c o n c e n t r a t i o n i n t h e sorbed phase (ug g " ) , = s o i l b u l k
3 3 3
d e n s i t y ( g c m " ) , = volume water c o n t e n t ( c m c m " ) , D(6, v) =
2 1
apparent d i f f u s i o n c o e f f i c i e n t (cm h r " ) , = pore water v e l o c i t y ,
1
d e f i n e d a s q/, where q = v o l u m e t r i c water f l u x (cm h r " ) , and and
t a r e d i s t a n c e (cm) and time ( h r ) , r e s p e c t i v e l y . The f o r m a t i o n o r
l o s s o f t h e s o l u t e d u r i n g d i s p l a c e m e n t i s c o n c e p t u a l l y r e p r e s e n t e d by
1 1
<j)(ug m l " h r " ) . S o l u t i o n o f E q u a t i o n 5 f o r a p p r o p r i a t e i n i t i a l and
boundary c o n d i t i o n s w i l l p r o v i d e a method o f p r e d i c t i n g c ( z , t ) t h a t
can be used t o f i t measured e f f l u e n t c o n c e n t r a t i o n s t o q u a n t i f y
d i s t r i b u t i o n o f t h e c h e m i c a l between s o r b e d and s o l u t i o n phases and
the d e g r a d a t i o n r a t e . E q u a t i o n 5 i s g e n e r a l i n form, and a l t h o u g h
d e v e l o p e d below i n more d e t a i l f o r a l d i c a r b can be used a s the
s t a r t i n g p o i n t f o r d e s c r i p t i o n o f t h e movement o f any p e s t i c i d e
through s o i l . I n t h i s way, t h e t h e o r e t i c a l methods used i n t h i s
paper r e p r e s e n t a b r o a d l y a p p l i c a b l e approach t o s t u d y o f p e s t i c i d e
fate i n s o i l .
In t h e case o f l a b o r a t o r y s o i l column s t u d i e s , u n i f o r m l y packed
columns w i t h c o n s t a n t water c o n t e n t s and f l o w v e l o c i t i e s a r e used
(steady-state conditions). E q u a t i o n 5 r e d u c e s f o r such c a s e s t o :
where i t has been assumed t h a t s o l u t i o n and s o r b e d c o n c e n t r a t i o n s a r e

l i n e a r l y r e l a t e d by s=K^c, w i t h r e p r e s e n t i n g an i n s t a n t a n e o u s and
reversible adsorption/desorption reaction. The v a l u e s o f D and i n
E q u a t i o n 6 a r e r e p r e s e n t e d a s c o n s t a n t s when d e s c r i b i n g s t e a d y s t a t e
water flow c o n d i t i o n s , as they depend upon q and , which a r e
themselves c o n s t a n t f o r a p a r t i c u l a r s t e a d y s t a t e e x p e r i m e n t .
E q u a t i o n 6 can be s i m p l i f i e d t o ( 2 ) :
1
where D = (D)/(1+pK / ) , v'(v)/(1+pK / ) , and = ( / ) / ( 1 ^ ^ / ) .
When a n o n - i n t e r a c t i n g , non-degrading s o l u t e such a s c h l o r i d e i s t o
be d e s c r i b e d , then K =0 and =0, and E q u a t i o n 7 r e d u c e s t o the c l a s s

d
i c a l d i s p e r s i o n - c o n v e c t i o n e q u a t i o n , which has o f t e n been used t o

d e s c r i b e the movement o f such s o l u t e s as c h l o r i d e or t r i t i u m i n
soil. The s o l u t i o n o f E q u a t i o n 7 s u b j e c t t o a p p r o p r i a t e i n i t i a l and
boundary c o n d i t i o n s can then be used t o e s t i m a t e the v a l u e o f D by
m e a s u r i n g q and ( t o g i v e v) and curve f i t t i n g p r e d i c t e d c ( z , t ) t o
measured e f f l u e n t c h l o r i d e c o n c e n t r a t i o n s . I f an i n t e r a c t i n g s o l u t e
s u b j e c t t o d e g r a d a t i o n i s to be d e s c r i b e d , then can be more e x p l i
c i t l y d e f i n e d , such as by f i r s t - o r d e r k i n e t i c s as i n E q u a t i o n 2-4,
and used as the b a s i s f o r d e t e r m i n i n g K^^ and k^. A number o f e x p e r
i m e n t a l s t u d i e s (2,3) have used such c u r v e - f i t t i n g t e c h n i q u e s to e s
timate K and k i n the p r e s e n c e o f c o n s t a n t v a l u e s o f D and v.
d These
t e c h n i q u e s u t i l i z e the d i s t i n c t and d i f f e r e n t i n f l u e n c e o f , D,
and k upon the shape o f the e f f l u e n t c o n c e n t r a t i o n c u r v e t o determine
the unique c o m b i n a t i o n o f the v a r i a b l e s t h a t d e s c r i b e s the p r o c e s s e s
a c t i n g upon the s o l u t e d u r i n g d i s p l a c e m e n t .
R e c o g n i z i n g the above f a c t s , the f o l l o w i n g e q u a t i o n s based on

E q u a t i o n 7 and u s i n g E q u a t i o n 2-4 t o r e p r e s e n t can be d e v e l o p e d t o
d e s c r i b e the s i m u l t a n e o u s t r a n s p o r t and t r a n s f o r m a t i o n o f A, A-SO and
A-S0 : 2
3c ! 2
3 c x 3c j
- D - (8)
3t 3z
2
3c 2 3 c 2 3c 2
(1+R ) 2
= D -
2
at 3z 3z
2
3c 3 3 c 3 3c 3
= D (10)
2

at 3z 3z
where R i s d e f i n e d by R. = ^ / .
i E q u a t i o n s 8-10 d e s c r i b e the
t r a n s p o r t and transformaion i n s o l u t i o n o f A, A-SO, and A - S 0 , 2
r e s p e c t i v e l y , w i t h the s u b s c r i p t s used t o d i s t i n g u i s h each s p e c i e s .

In t h i s s t u d y , E q u a t i o n s 8-10 were s o l v e d f o r the c o n d i t i o n s o f a
s o i l column i n i t i a l l y f r e e o f a l l a l d i c a r b s p e c i e s , t o which i s
a p p l i e d a p u l s e o f A c o n t a i n i n g no A-SO or A - S 0 . That i s : 2
Ci=c =c =0 2 3 z>0 t=0 (11a)
0
c^C! z=0 0<t<tj (11b)
Ci=c =c =0 2 3 z=0 t_>t! (11c)
c = c
i 2=c =03 z- t>0 (11d)
The s o l u t i o n t o a v e r y s i m i l a r s e t o f e q u a t i o n s w i t h R * 0 has 3
been p r e s e n t e d (4) and used i n a study o f the t r a n s f o r m a t i o n o f urea

+
to NH and N 0 " d u r i n g l e a c h i n g ( 5 ) . E q u a t i o n s 8-10 have been s o l -
3
ved by s i m i l a r t e c h n i q u e s and the s o l u t i o n s used t o p r o v i d e e s t i -

mates o f c ( z , t ) as a f u n c t i o n o f D, v, c ^ , , , . and k. . I t i s
t h e r e f o r e n e c e s s a r y t o measure or e s t i m a t e D, , ana" so hat
4. ZHONG ET AL. Quantifying Pesticide Adsorption and Degradation 65
and k. can be d e t e r m i n e d by c u r v e - f i t t i n g t h e measured e f f l u e n t con

c e n t r a t i o n s o f the a l d i c a r b s p e c i e s .
E x p e r i m e n t a l Methods
The e x p e r i m e n t a l a p p a r a t u s ( F i g u r e 1) c o n s i s t s o f a c o n t i n u o u s d e l i v
ery i n f i n i t e volume s y r i n g e pump d e l i v e r i n g i n f l u e n t s o l u t i o n t o a
s o i l column from which e f f l u e n t i s c o l l e c t e d i n d i s t i n c t i n c r e m e n t s
in a f r a c t i o n c o l l e c t o r . The column was adapted from equipment
r e a d i l y a v a i l a b l e f o r h i g h p r e s s u r e l i q u i d chromatography (HPLC)
work, and c o n s i s t s o f a Beckman g l a s s column 25 mm d i a m e t e r and 250
mm l o n g made o f p r e c i s i o n bore b o r o s i l i c a t e g l a s s . A bed s u p p o r t
used on b o t h ends c o n s i s t s o f a woven FEP t e f l o n d i f f u s i o n mesh i n
c o n t a c t w i t h a porous t e f l o n f i l t e r d i s k o f pore s i z e 30-60 . The
d i f f u s i o n mesh causes the i n j e c t e d l i q u i d t o s p r e a d r a d i a l l y and
e v e n l y b e f o r e e n t e r i n g the f i l t e r d i s k on t h e i n l e t s i d e , and works
i n r e v e r s e on the o u t l e t s i d e t o p r e v e n t zone s p r e a d i n g . T h i s column

i s s u r r o u n d e d by a g l a s s water j a c k e t w i t h i n l e t and o u t l e t connec
t i o n s t o a c o n t r o l l e d temperature water b a t h t h a t i s used t o m a i n t a i n
a c o n s t a n t s o i l column temperature o f 250.5C i n a l l e x p e r i m e n t s .
I n f l u e n t s o l u t i o n i s d e l i v e r e d by a Sage Model 220 s y r i n g e pump w i t h
two i n d e p e n d e n t l y c o n t r o l l e d s y r i n g e s d e s i g n e d t o c o n t i n u o u s l y d e l i v
er a u n i f o r m and p u l s e - f r e e f l o w . E f f l u e n t i s c o l l e c t e d i n a B u c h l e r
LC-100 f r a c t i o n c o l l e c t o r .
Two s o i l s , a Palmyra sandy loam from c e n t r a l New York s t a t e and
a R i v e r h e a d sandy loam from e a s t e r n Long I s l a n d , New York were used
( T a b l e I ) . S o i l was a i r - d r i e d at room temperature and passed t h r o u g h
a 2 mm s i e v e . A subsample o f each s o i l was s t e r i l i z e d w i t h d r y heat
(120C f o r 5 hours) f o r use i n s e l e c t e d e x p e r i m e n t s . Each column was
f i l l e d t o an average b u l k d e n s i t y ( w i t h e x p e r i m e n t a l e r r o r g i v e n i n
T a b l e I I ) and was wetted from below by a p p l y i n g a s l i g h t l y p o s i t i v e
pressure. T h i s r e s u l t e d i n 90% s a t u r a t i o n f o r t h e Palmyra s o i l and
85% s a t u r a t i o n f o r t h e R i v e r h e a d s o i l . Steady s t a t e f l o w at a p r e
d e t e r m i n e d water f l u x was e s t a b l i s h e d u s i n g 0.01 CaSO,,, a t which
time t h e column was p l a c e d i n a h o r i z o n t a l p o s i t i o n and t h e e x p e r i
ment i n i t i a t e d . The i n f l u e n t was a b r u p t l y changed t o a 0.01 CaSO,,
s o l u t i o n c o n t a i n i n g 100 ug/ml c h l o r i d e as KC1 and 10 yg/ml A, A-SO o r
A - S 0 , depending upon the e x p e r i m e n t .
2 After application of approxi
mately 100 ml o f t h i s s o l u t i o n , t h e unamended CaSO,, s o l u t i o n was
a g a i n c o n t i n u o u s l y a p p l i e d t o d i s p l a c e the c h l o r i d e s p e c i e s t h r o u g h
the column.
The c o l l e c t e d e f f l u e n t was a n a l y z e d f o r C1 , A, A-SO, and
A-S0 . 2 C h l o r i d e was d e t e r m i n e d u s i n g a B u c h l e r - C o t l o v e c h l o r i d o -
meter. A l d i c a r b , A-SO and A - S 0 were e x t r a c t e d w i t h methylene c h l o
2
r i d e and a n a l y z e d u s i n g a H e w l e t t - P a c k a r d model 5880A gas chromato-

g r a p h w i t h a n i t r o g e n - p h o s p h o r u s d e t e c t o r and a f u s e d s i l i c a c a p i l
l a r y column c o a t e d w i t h methyl s i l i c o n e . F u r t h e r d e t a i l s o f the a l
d i c a r b a n a l y t i c a l techniques are r e p o r t e d elsewhere ( 6 ) .
S i n c e t h e s e s t u d i e s were performed t o e l u c i d a t e r a t e s o f d e g r a
d a t i o n by o x i d a t i o n , ( e i t h e r c h e m i c a l l y o r b i o l o g i c a l l y mediated) i t
EVALUATION O F PESTICIDES IN G R O U N D WATER
2. S Y R I N G E PUMP
3. S O I L - F I L L E D G L A S S COLUMN
4. W A T E R JACKET
5. W A T E R BATH
6. FRACTION COLLECTOR
Figure 1. Experimental apparatus for laboratory pesticide

leaching studies.
Table I . P h y s i c a l and C h e m i c a l Soil Characteristics
Property Palmyra Riverhead
O r g a n i c M a t t e r (%) 2.0 4.0

pH (1:1) 4.9 4.5
C a t i o n Exch. C a p a c i t y (me/100g) 8.2 15.0
+
Exch. H (me/100g) 7 16
E x t r a c t a b l e Elements (ug/g)
12.5 39
115 105
Mg 85 40
Ca 400 300
P a r t i c l e S i z e (%)
Sand 53 75
Silt 37 21
Clay 10 4
was i m p o r t a n t t o e s t a b l i s h t h a t t h e column was b e i n g o p e r a t e d under

a e r o b i c and not a n a e r o b i c c o n d i t i o n s . The s o i l columns were n o t com
p l e t e l y s a t u r a t e d ; some oxygen was a v a i l a b l e i n t h e s o i l . In addi
t i o n , a s i m p l e c a l c u l a t i o n demonstrates t h a t t h e r e i s a p p r o x i m a t e l y
ten t i m e s more d i s s o l v e d oxygen (8-10 mg/L) i n t h e water than i s
needed t o c o n v e r t a l l o f t h e a p p l i e d a l d i c a r b t o a l d i c a r b s u l f o n e .
T h i r t e e n experiments ( T a b l e I I ) were c o n d u c t e d on both s o i l s i n
s t e r i l i z e d and u n s t e r i l i z e d c o n d i t i o n s , a t two pore water v e l o c i t i e s ,
and w i t h s e v e r a l c o m b i n a t i o n s o f i n f l u e n t p e s t i c i d e c o n c e n t r a t i o n .
C h l o r i d e was a p p l i e d i n a l l e x p e r i m e n t s , and e f f l u e n t d a t a were ana
l y z e d u s i n g t h e s o l u t i o n t o E q u a t i o n s 7, 8, 9 or 10 a s a p p r o p r i a t e .
R e s u l t s And D i s c u s s i o n
The a p p a r e n t d i f f u s i o n c o e f f i c i e n t , D, was determined f o r t h e p a r t i c

u l a r l e a c h i n g c o n d i t i o n s o f each o f the t h i r t e e n e x p e r i m e n t s . This
was a c c o m p l i s h e d u s i n g the measured c h l o r i d e b r e a k t h r o u g h ( e f f l u e n t
c o n c e n t r a t i o n ) c u r v e and t h e a n a l y t i c a l s o l u t i o n t o E q u a t i o n 7 w i t h
^==0. Examples o f t h e o b s e r v e d and c a l c u l a t e d c h l o r i d e c o n c e n t r a
t i o n s ( d e t e r m i n e d by adjustment o f D u n t i l a b e s t f i t was o b t a i n e d )
are p r e s e n t e d f o r t h r e e d i f f e r e n t e x p e r i m e n t s ( E x p e r i m e n t s 7, 8, 11)
i n F i g u r e s 2-4. V a l u e s o f D and t h e pore water v e l o c i t y (v) d e t e r
mined f o r each experiment a r e p r e s e n t e d i n T a b l e I I I . The v a l u e o f D
i n c r e a s e d f o r c a s e s w i t h l a r g e v, and was d i f f e r e n t between s o i l s f o r
any p a r t i c u l a r v . T h i s i s c o n s i s t e n t w i t h t h e b a s i c r e l a t i o n s h i p be-
Table I I . Experimental Designation
Water (0.01) C 1
3 3 3 1 1 1 1
Experiment S o i l Sterilized Flux gem" cm cm"* Ugml" ygml" Ugml" ygml"
1 Palmyra yes high 1.52 0.39 98.1 10.5 - -

2 Palmyra yes low 1.47 0.39 99.9 9.02 - -
3 Palmyra yes high 1 .49 0.41 102 - 9.97 -
4 Palmyra yes low 1 .49 0.40 94.0 - 9.88 -
5 Palmyra yes high 1.50 0.39 95.5 - - 10.1
6 Palmyra yes low 1.49 0.40 97.0 - - 10.0
7 Palmyra no high 1 .49 0.40 98.6 10.9 - -

8 Palmyra no low 1 .51 0.38 99.8 10.5 - -
9 Palmyra no low 1.47 0.41 99.5 98.6 - -
10 Riverhead no high 1.27 0.42 99.7 10.1 - -
11 Riverhead no low 1.29 0.44 103 10.8 -
12 Riverhead no low 1.25 0.42 105 - 11.6 -
13 Riverhead no low 1.27 0.44 102 - - 10.1
4. Z H O N G ET AL. Quantifying Pesticide Adsorption and Degradation 69
F i g u r e 2 . Measured and c a l c u l a t e d e f f l u e n t c o n c e n t r a t i o n s o f
c h l o r i d e (CI ) , a l d i c a r b ( A ) and a l d i c a r b s u l f o x i d e (A-SO) from
experiment 7.
co 0.

? 0
PALMYRA SANDY LOAM V-0.97 cm h r - 1
-3
C =10.5 ug cm
A
2
D = 1.0 cm hr~ 1
10 Kd 0.07 cm
1=s ki + ki*= 0.026 hr~
3 1
Kd =0.00 cm g~
2 k-,*=0.017 hr~ 1
r
Kd3=0.02 cm k + k *= 0.003 hr"
2 2
-1
k*=0.0021 hr
2
-1
k3=0.0018 hr

3
=1.51 g cm"
3 3
0.38 cm cm"
J 4
H 20
40 60
TIME ( h r )
c h l o r i d e (CI ), a l d i c a r b ( A ) , a l d i c a r b s u l f o x i d e (A-SO) and
a l d i c a r b s u l f o n e ( A - S 0 ) from e x p e r i m e n t 8.
2
100
40 60
TIME (hr)
c h l o r i d e (CI ), a l d i c a r b ( A ) , and a l d i c a r b s u l f o x i d e (A-SO) from
e x p e r i m e n t 11.
Table I I I . Data f o r Study o f the D e g r a d a t i o n o f A l d i c a r b
V D K K k-j * k-l* k +k ** k * k
2 2 2 k
d1 K 2 d d3 *1 2 3
Exper
2 1 , hi~1 .
iment cm hr~1 c m h r ~ ml g" >
1 9.80 10. 0.05 - - 0.015 - - - - - -

2 0.93 1.0 0.07 0 0.02 0.013 0.004 0.009 0.002 0.0014 0.0006 0.0018
3 9.20 10. - 0 - (98? r e c o v e r y )
4 1.06 1.0 - 0 - - - - 0.002 0.0014 0.0006 -

5 9.70 10. - - 0.02 (99% r e c o v e r y )
6 1.10 1.0 - - 0.02 - - - - - - 0.0018 m

$
9.80 10. 0 0.028 0.018 0.010 0.003 r
7 0.05 - - - - c

8 0.97 1.0 0.07 0 0.02 0.026 0.017 0.009 0.003 0.0021 0.0009 0.0018

9 0.97 1.0 0.06 0 0.02 0.024 0.015 0.009 0.003 0.0023 0.0007 0.0018
-D
m
GO
10 9.40 25. 0.15 0.04 - 0.060 0.007 0.053 0.008 - - - H

m
en
11 0.95 2.8 0.12 0.04 - 0.070 0.004 0.066 0.008 - - -
z

12 0.97 2.8 - 0.04 - - - - 0.008 0.0005 0.0075 0.006 73

C
13 0.95 2.8 - - 0.05 - - - - - - 0.006 z
D
%
m
73
4. Z H O N G ET A L . Quantifying Pesticide Adsorption and Degradation 73
tween water f l o w and d i s p e r s i o n and t h e dependence o f t h e l a t t e r upon

the geometry o f t h e porous media ( 7 ) . The v a l u e o f D determined i n
t h i s manner was used w i t h i n t h e s o l u t i o n t o E q u a t i o n s 8-10;
and ^ were then determined by c u r v e - f i t t i n g .
_
Experiments 1-2, 3 4 , and 5-6 r e p r e s e n t p a i r e d c a s e s o f i n v e s t i
g a t i o n o f A, A-SO and A-S0 i n Palmyra s o i l . 2 S t e r i l i z e d s o i l was
used i n these c a s e s t o i s o l a t e c h e m i c a l o x i d a t i o n and h y d r o l y s i s from
b i o l o g i c a l c o n v e r s i o n p r o c e s s e s , and t o determine whether the c u r v e -
f i t t e d values o f and k^ depend on water v e l o c i t y . The o n l y d i f
f e r e n c e w i t h i n a p a i r o f experiments was i n t h e flow v e l o c i t y ( v ) .
Between p a i r s , t h e d i f f e r e n c e was t h e a l d i c a r b m e t a b o l i t e a p p l i e d .
The r e s u l t s ( T a b l e I I I ) demonstrate t h a t e s s e n t i a l l y i d e n t i c a l v a l u e s
of were determined i n each c a s e , i n d i c a t i n g t h a t f o r t h i s chemi-
i c a l t h e a d s o r p t i o n i s independent o f f l o w v e l o c i t y . The v a l u e o f
K r e r e s e n t i n
dt' P 8 a l d i c a r b a d s o r p t i o n by Palmyra s o i l , was 0.05-0.07,
i n d i c a t i n g very s l i g h t c h e m i c a l - s o i l i n t e r a c t i o n . This i s consistent
w i t h o t h e r s t u d i e s (8, 9, J_0) conducted i n medium t o c o a r s e t e x t u r e d

K = o f
soils. No i n t e r a c t i o n ( ) a l d i c a r b s u l f o x i d e with the s o i l
d 2
was d e t e c t e d , and t h e i n t e r a c t i o n o f a l d i c a r b s u l f o n e , =0.02, was

even l e s s than measured f o r a l d i c a r b and a l s o independent o f f l o w
velocity.
In both Experiments 1 and 2, t h e measured t o t a l r a t e o f a l d i c a r b
d e g r a d a t i o n ( k j + k ^ ) was a p p r o x i m a t e l y e q u a l , r a n g i n g from 0.015 t o
1
0.013 hr"" . The r a t e c o e f f i c i e n t f o r a l d i c a r b d e g r a d a t i o n (ki+k^)
c o u l d not be s e p a r a t e d i n t o i n d i v i d u a l components o f h y d r o l y s i s and
o x i d a t i o n u s i n g t h e r e s u l t s from t h e h i g h v e l o c i t y experiment (Exper
iment 1 ) , as t h e r e s i d e n c e time w i t h i n t h e column was t o o s h o r t f o r
a n a l y t i c a l l y d e t e c t a b l e l e v e l s o f A-SO t o be produced and appear i n
the e f f l u e n t . However, i n t h e same experiment conducted a t slower
v e l o c i t y (Experiment 2 ) , t h e p r o d u c t i o n o f A-SO was h i g h enough t h a t
c u r v e - f i t t i n g o f e f f l u e n t c o n c e n t r a t i o n d a t a o f A-SO and A p r o v i d e d
1
the o p p o r t u n i t y t o s e p a r a t e t h e r a t e o f h y d r o l y s i s , kj=0.009 h r " ,
1
from t h e r a t e o f o x i d a t i o n , k *=0.00M h r " . 1S i m i l a r l y , experiments 4
and 6, c o n d u c t e d a t slow f l o w v e l o c i t i e s ( b u t w i t h A-SO and A - S 0 a s 2
the s t a r t i n g m a t e r i a l , r e s p e c t i v e l y ) p r o v i d e d t h e o p p o r t u n i t y t o sep
1
a r a t e s u l f o x i d e h y d r o l y s i s (k =.0006 h r " ) from s u l f o x i d e o x i d a t i o n
2
1
(k *=0.00l4 h r " ) , with a t o t a l s u l f o x i d e t r a n s f o r m a t i o n r a t e
2
1
( k + k * ) o f 0.002 h r " measured i n both e x p e r i m e n t s .
2 2 T h i s i s exem
p l i f i e d by F i g u r e s 2 and 3, which p r e s e n t r e s u l t s f o r an u n s t e r i l i z e d
case ( d i s c u s s e d . b e l o w ) o f f a s t and slow f l o w v e l o c i t y . The two h i g h
v e l o c i t y c a s e s i n w h i c h A-SO and A - S 0 were a p p l i e d ( E x p e r i m e n t s
2 3
and 5) r e s u l t e d i n such r a p i d l e a c h i n g t h a t no d e g r a d a t i o n c o u l d be
measured, i n d i c a t i n g t h a t use o f a h i g h v e l o c i t y may not be a s u i t
a b l e t e c h n i q u e f o r study o f weakly i n t e r a c t i n g c h e m i c a l s . Similarly,
c h e m i c a l s w i t h a l o n g h a l f - l i f e c o u l d not be e a s i l y s t u d i e d by t h i s
method even w i t h a low f l o w v e l o c i t y .
T r a n s f o r m a t i o n o f a l d i c a r b and i t s d e r i v a t i v e s was a l s o s t u d i e d
i n t h r e e e x p e r i m e n t s i n u n s t e r i l i z e d Palymra s o i l ( E x p e r i m e n t s 7-9)
to determine t h e b i o l o g i c a l component o f each t r a n s f o r m a t i o n p r o c e s s .
The v a l u e o f k i n u n s t e r i l i z e d s o i l ranged from 0.009-0.010 h r - ,
x
1
1
compared t o 0.009 h r " i n t h e s t e r i l i z e d s o i l o f experiment 2. T h i s
r e s u l t i m p l i e s that a l d i c a r b h y d r o l y s i s i s p r i m a r i l y a chemical
process. The v a l u e o f ^ * was a p p r o x i m a t e l y f o u r t i m e s the v a l u e i n
1
u n s t e r i l i z e d s o i l (0.015-0.018 h r " ) than i n s t e r i l i z e d s o i l (0.004
hr"'). T h i s i n d i c a t e s t h a t a l d i c a r b o x i d a t i o n (k<|*) i s e q u a l l y
mediated by b i o l o g i c a l and c h e m i c a l p r o c e s s e s . Similarly, hydrolysis
1
o f A-SO ( k ) was n e a r l y i d e n t i c a l i n s t e r i l i z e d (0.0006 h r " ) and
2
1
u n s t e r i l i z e d (0.0007 -0.0009 h r " ) c a s e s , but the r a t e o f A-SO
1
o x i d a t i o n ( k * ) was a p p r o x i m a t e l y 50% g r e a t e r ( a v e r a g e 0.0022 h r "
2
1
compared t o 0.0014 h r " ) i n u n s t e r i l i z e d s o i l . The d e g r a d a t i o n o f
A - S 0 ( k 3 ) was not i n f l u e n c e d by s t e r i l i z a t i o n , i n d i c a t i n g t h a t o n l y
2
c h e m i c a l p r o c e s s e s were r e s p o n s i b l e . Such p r o c e s s e s have been shown

by o t h e r work (JJ_) t o be m a i n l y h y d r o l y s i s . v a l u e s f o r each o f
the t h r e e s p e c i e s were u n a f f e c t e d by s t e r i l i z a t i o n .
The u s e f u l n e s s o f the t e c h n i q u e d e v e l o p e d here was f u r t h e r de
monstrated by employing a second s o i l f o r l i m i t e d comparison purposes
( E x p e r i m e n t s 10-13). The o b j e c t i v e was not a comprehensive s t u d y o f
a l d i c a r b , but the e x e c u t i o n o f s e v e r a l e x p e r i m e n t s i d e n t i c a l t o t h o s e
a c c o m p l i s h e d on Palmyra s o i l . The second s o i l , R i v e r h e a d sandy loam,
was c o a r s e r t e x t u r e d , s l i g h t l y lower i n pH and h i g h e r i n o r g a n i c mat
t e r ( T a b l e I ) . Agreement between t h e o r y and experiment was a c c e p t

a b l e i n a l l c a s e s , as i l l u s t r a t e d i n F i g u r e s 4-5. The v a l u e o f D a t
the h i g h f l o w v e l o c i t y i n the R i v e r h e a d s o i l was 2.5 t i m e s g r e a t e r
than i n Palmyra s o i l , but was w e l l - d e s c r i b e d by the s o l u t i o n t o Equa
2
t i o n 7 (Figure 4). At the lower v e l o c i t y , D was 2.8 cm /hr compared
2
t o 1.0 cm /hr i n the Palmyra, but was e q u a l l y w e l l f i t t e d by the
s o l u t i o n t o E q u a t i o n 7.
D e g r a d a t i o n and a d s o r p t i o n were measured o n l y i n u n s t e r i l i z e d
R i v e r h e a d s o i l , w i t h the l a t t e r a l r e a d y shown t o be independent o f
sterilization. The v a l u e o f f o r a l d i c a r b i n the R i v e r h e a d s o i l
was 0.12-0.15, a p p r o x i m a t e l y double the v a l u e o f 0.05-0.07 measured
i n the Palmyra s o i l . The v a l u e o f K^ , d e s c r i b i n g A-SO
2 interaction
w i t h s o i l , was determined t o be 0.04 i n the R i v e r h e a d s o i l , i n d i c a
t i n g some s l i g h t i n t e r a c t i o n o f the s u l f o x i d e w i t h t h e s o i l . The
v a l u e o f Kg^ was n e a r l y the same as ^ , but was double the v a l u e o f
2
K 3 (0.02) found i n the Palmyra s o i l .

d C l e a r l y , the s o r p t i o n o f a l d i
c a r b and i t s d e r i v a t i v e s i n c r e a s e d i n the R i v e r h e a d s o i l due t o the
p r e s e n c e o f h i g h e r o r g a n i c m a t t e r c o n t e n t and can be d i s t i n g u i s h e d
f o r the two s o i l s by the e x p e r i m e n t a l and t h e o r e t i c a l methods used
here.
The v a l u e o f the d i s t r i b u t i o n c o e f f i c i e n t , K i , v a r i e s w i t h s e v
d
e r a l s o i l p r o p e r t i e s , most n o t a b l y the o r g a n i c carbon c o n t e n t . This

has l e d t o the d e f i n i t i o n o f a n o r m a l i z e d s o r p t i o n c o e f f i c i e n t , K , o c
w h i c h i s c a l c u l a t e d as (12);
K = K / f
oc di oc
where f o ci s the f r a c t i o n o f o r g a n i c c a r b o n . Assuming t h a t o r g a n i c

matter i s 58% c a r b o n , K v a l u e s f o r a l d i c a r b and i t s m e t a b o l i t e s can
o c
be c a l c u l a t e d f o r b o t h s o i l s . The v a l u e s a r e q u i t e low compared w i t h

v a l u e s f o r o t h e r o r g a n i c c h e m i c a l s i n s o i l ( J 2 ) , and a r e ( T a b l e IV)
n e a r l y i d e n t i c a l f o r the two s o i l s . Such c a l c u l a t i o n s i n d i c a t e t h a t
even on a n o r m a l i z e d b a s i s , almost no a l d i c a r b a d s o r p t i o n o c c u r s i n
t h e s e two p r e d o m i n a n t l y m i n e r a l s o i l s .
4. Z H O N G ET AL. Quantifying Pesticide Adsorption and Degradation 75
T a b l e IV. Values of Kfl and K for A l d i c a r b Species in

o c
Palmyra
and R i v e r h e a d S o i l s
Species Parameter Palmyra Riverhead
0.05-0.07 0.12-0.15
Aldicarb K
oc 4.3 -6.0 5.2 -6.5
*d 0 0.04
Aldicarb Sulfoxide K
oc 0 1 .7
K 0.02 0.05
d
Aldicarb Sulfone K
oc 1.7 2.2
O x i d a t i o n o f a l d i c a r b , found i n Palmyra s o i l t o be about double

the r a t e o f h y d r o l y s i s under u n s t e r i l i z e d c o n d i t i o n s , was i n t h e
R i v e r h e a d s o i l much l e s s important than h y d r o l y s i s . In the l a t t e r
c a s e , t h e h y d r o l y s i s r a t e (k-j), was found t o be 8-16 times g r e a t e r
than t h e o x i d a t i o n r a t e (k-j*), w i t h t h e t o t a l d e g r a d a t i o n r a t e
1
(0.06-0.07 h r " ) 2-3 times g r e a t e r i n t h e h i g h e r o r g a n i c matter
soil. S i m i l a r b e h a v i o r o f A - S 0 was measured, w i t h t h e d e g r a d a t i o n
2
r a t e a p p r o x i m a t e l y t h r e e times g r e a t e r i n t h e R i v e r h e a d s o i l . It i s
e x p e c t e d t h a t a c i d c a t a l y z e d h y d r o l y s i s might be enhanced by s o r p t i o n
to s o i l , b u t from p r e v i o u s work (J_3), the a c i d c a t a l y z e d h y d r o l y s i s
r a t e f o r a l d i c a r b s u l f o n e i n s o l u t i o n i s 10^ slower than the base hy-
drolysis rate. A c i d c a t a l y z e d h y d r o l y s i s o f a l d i c a r b under f l o w con-
d i t i o n s on a r e a c t i v e i o n exchange r e s i n , a l t h o u g h enhanced, i s s t i l l
2
1 0 s l o w e r than n u c l e o p h i l i c c l e a v a g e (j_4). S i n c e base h y d r o l y s i s
predominates, t h i s type o f enhancement most p r o b a b l y does not account
for the f a s t e r h y d r o l y s i s r a t e i n the Riverhead s o i l . The r e a s o n f o r
these d i f f e r e n c e s i s not c l e a r , b u t c o u l d be s t u d i e d by f u r t h e r
a p p l i c a t i o n o f t h e methods developed here, perhaps combined w i t h
study o f the s o r p t i o n p r o p e r t i e s o f t h e s o i l or c o n d i t i o n s i n t h e
column.
The v a l u e s o f t h e r a t e c o e f f i c i e n t s determined by t h e methods o f
t h i s s t u d y compare w e l l w i t h those r e p o r t e d elsewhere ( T a b l e V ) . Ex-
a c t agreement would not be e x p e c t e d because o f d i f f e r e n t s o i l s . We
d i d l i m i t comparisons t o s t u d i e s done a t t h e same t e m p e r a t u r e . Con-
t r a r y t o o t h e r e x p e r i m e n t a l d e s i g n s , t h e methods used here r e q u i r e
o n l y 4-6 days p e r experiment. T h i s makes the column d e s i g n p o t e n -
t i a l l y u s e f u l a s a s c r e e n i n g method f o r s t u d y i n g the r e a c t i o n s o f
p e s t i c i d e s i n a wide range o f s o i l s . A d d i t i o n a l l y , t h e method can be
a p p l i e d i n a r i g o r o u s manner t o study a d s o r p t i o n and d e g r a d a t i o n un-
der dynamic c o n d i t i o n s o f water and s o l u t e movement, r a t h e r than i n
comparatively s t a t i c batch-type experiments. An a n a l y t i c a l method o f
c u r v e - f i t t i n g (J_5) c o u l d be developed t o p r e c i s e l y determine v a l u e s
of and k^, w i t h methods developed by van Genuchten and A l v e s (16)
d e m o n s t r a t i n g a u s e f u l approach. Such methods w i l l become more im-
p o r t a n t as more c o m p l i c a t e d r e l a t i o n s h i p s a r e used t o r e p r e s e n t p a r -
t i t i o n i n g between s o r b e d and s o l u t i o n c o n c e n t r a t i o n s , or as more sub-
t l e e n v i r o n m e n t a l e f f e c t s upon d e g r a d a t i o n a r e s t u d i e d .
T a b l e V. Degradation Rates f o r A l d i c a r b and i t s M e t a b o l i t e s Measured

i n Other S t u d i e s a t 25C
k^+ki* k +k *
2 2
3
k
Soil Sterile (hr- )1

(hr-1)
yes 0.012
1
Plow Layer
no 0.029
C l a y Loam 2
no 0.0021 0.0021
4.5% o.m., k * - 0.0008
2
pH = 7.2, 3% c l a y k 2 = 0.0013
Greenhouse S o i l 2
no 0.016 0.0014
16.5% o.m., k * = 0.0011
2
pH = 6.0, 17% c l a y k 2 = 0.0005
Clay3 0.0033 0.0015 0.0013

pH = 8.0
S i l t y Clay Loam3 0.0046 0.00083 0.0006

pH = 8.0
Fine Sand3 0.0021 0.0004 0.0013

pH = 6 . 3
Reference (17); R e f e r e n c e (18); 3R ference

e (10)
A n a l y t i c a l s o l u t i o n s to transport equations that simultaneously

c o n s i d e r a d s o r p t i o n and t r a n s f o r m a t i o n , when used i n c o n c e r t w i t h ap-
p r o p r i a t e s o i l column t e c h n i q u e s , o f f e r s u b s t a n t i a l promise f o r study
of the environmental f a t e o f o r g a n i c chemicals. Such methods can be
w i d e l y used s i n c e a number o f such s o l u t i o n s a l r e a d y e x i s t i n the
scientific literature. I t remains o n l y t o d e s i g n r e s e a r c h programs
i n which t h o s e who u n d e r s t a n d such e q u a t i o n s a r e working w i t h those
who can d e s i g n and execute complementary c h e m i c a l s t u d i e s .
Acknowledgments
The a u t h o r s g r a t e f u l l y acknowledge the f i n a n c i a l s u p p o r t o f USGS

under t h e C o o p e r a t i v e S t a t e Water Resources R e s e a r c h Program and o f
the U n i t e d S t a t e s Department o f A g r i c u l t u r e .
4. Z H O N G E T AL. Quantifying Pesticide Adsorption and Degradation 11
Literature Cited
1. Lemley, A.T.; Zhong, W.Z. J. Agric. Food Chem., 1984, 32,

714-719.
2. Wagenet, R.J. Principles of salt movement in soils. In;
Chemical Mobility and Reactivity in Soil Systems, Nelson, D.W.;
Elrick, D.E.; Tanji, K.K., Ed. SSSA Special Publ. No. 11,
Amer. Soc. of Agronomy, 1983, 123-140, (Ch. 9).
3. van Genuchten, M.Th.; Clearly, R.W. Movement of solutes in
soil: Computer simulated and laboratory results. In: Soil
Chemistry: B. Physico-chemical models, Bolt, G.H., Ed.
Elsevier Scientific Publ. Co. Amsterdam, 1979, 349-386.
4. Wagenet, R.J.; Biggar, J.W.; Nielsen, D.R. Soil Sci. Soc.
Amer. J., 1976, 41, 896-902.
5. Wagenet, R.J.; Nielsen, D.R.; Biggar, J.W. Analytical solutions
of miscible displacement equations describing the sequential
microbiological transformations of urea, ammonium and nitrate.
Water Sci. and Eng. Papers No. 6001, Dept. of LAWR, University
of California, Davis, CA.
6. Zhong, W.Z.; Lemley, A.T.; Spalik, J. Journal of Chromt.,
1984, 299, 269-274.
7. Kirda, C.; Nielsen, D.R.; Biggar, J.W. Soil Sci. Soc. Amer.
Proc, 1973, 37, 339-345.
8. Bromilow, R.H. Ann. Appl. Biol., 1973, 75, 473-479.
9. Bromilow, R.H.; Baker, R.J.; Freeman, M.A.H.; Gorog, K.
Pestic. Sci., 1980, 11, 371-378.
10. Hough, .; Thomason, I.J.; Farmer, W.J. J. Nematology, 1975, 7,
214-221.
11. Leistra, M. J. Environ. Sci. Health, 1978, B13(4), 343-360.
12. Rao, P.S.C.; Davidson, J.M. Estimation of pesticide retention
and transformation parameters required in nonpoint source
pollution models. In: Environmental impact of nonpoint source
pollution, Overcash, M.R.; Davidson, J.M., Ed. Ann Arbor
Science Publ., Inc., Ann Arbor, MI, 1980, 23-67.
13. Lemley, A.T.; Zhong, W.Z. J. Environ. Sci. Health, 1983,
B18(2), 189-206.
14. Lemley, A.T.; Zhong, W.Z.; Janauer, G.E.; Rossi, R. In
"Treatment and Disposal of Pesticide Wastes," Krueger, R.F.;
Seiber, J.N.; Eds.; ACS SYMPOSIUM SERIES No. 259, American
Chemical Society: Washington, DC, 1984; pp. 245-259.
15. Parker, J.C.; van Genuchten, M.Th. Virginia Agr. Exp. Station
Bull., 1984, 84-3, 96p.
16. van Genuchten, M.Th.; Alves, W.J. U.S. Dept. of Agriculture
Technical Bull., 1982, No. 1661, 151 p.
17. Romine, R.R.; Hansen, J.L.; Jones, R.L. Aldicarb oxidation
mechanism studies, Union Carbide Agricultural Products Company,
Inc., Preliminary Draft, 1984.
18. Smelt, J.H.; Leistra, M.; Houx, N.W.H.; Dekker, A. Pestic.
Sci., 1978, 9, 279-300.
5
Geohydrology of a Field Site
Study of Pesticide Migration in the Unsaturated and Saturated Zones
of Dougherty Plain, Southwest Georgia
Sandra C. Cooper
Water Resources Division, U.S. Geological Survey, Doraville, GA 30360
A 10-acre area of a peanut field in southeastern Lee

County, Georgia, was selected to investigate the

migration of the pesticide aldicarb in the unsaturated
and saturated zones, and to assess the potential for
degradation of the ground-water resource. The
hydrogeologic framework was determined from sample
cuttings, a continuous core, and geophysical logs
obtained from test wells drilled in the field, and
from bimonthly and continuously recorded water-level
measurements. The study site is underlain, in
descending order, by the undifferentiated residuum,
which forms the water-table aquifer, and by the Ocala
Limestone, the Clinchfield Sand, and the Lisbon
Formation of Eocene age, which form the Upper
Floridan aquifer. Geohydrologic data indicate that
in the area of the study site, the Upper Floridan
aquifer consists of an upper and a lower permeable
zone; the upper permeable zone is hydraulically
connected to the water-table aquifer. Precipitation
entering the residuum generally moves downward and
recharges the Upper Floridan aquifer. Water
recharging the Upper Floridan moves laterally
downgradient to points of natural discharge and to
pumping centers. Because of the hydraulic connection
between the residuum and the Upper Floridan aquifer,
the potential exists for pesticides to migrate into
the ground-water system.
A g r i c u l t u r e i s a major i n d u s t r y i n t h e S o u t h e a s t e r n U n i t e d S t a t e s
and p a r t i c u l a r l y i n G e o r g i a . Increased a g r i c u l t u r a l p r o d u c t i v i t y i n
G e o r g i a has been a c h i e v e d t h r o u g h the use of l a r g e - s c a l e i r r i g a t i o n
and m u l t i c r o p p i n g p r a c t i c e s , and t h e a p p l i c a t i o n of f e r t i l i z e r s and
T h i s chapter not subject to U.S. copyright.

Published 1986, A m e r i c a n C h e m i c a l Society
5. COOPER Geohydrology of a Field Site 79
pesticides. A l t h o u g h f a r m i n g t e c h n i q u e s have changed c o n s i d e r -

a b l y over t h e y e a r s , one of t h e most s i g n i f i c a n t changes has been
the i n c r e a s e d use of c h e m i c a l s i n c o n t r o l l i n g i n s e c t s , weeds, and
p l a n t d i s e a s e s . E a r l y e f f o r t s i n the development of c h e m i c a l p e s -
t i c i d e s were c o n c e n t r a t e d on p r o d u c i n g s t a b l e p e s t i c i d e s t h a t were
relatively persistent i n soils. A l t h o u g h the p e r s i s t e n c e of t h e s e
c h e m i c a l s was advantageous i n c o n t r o l l i n g p e s t s , i t became d i s a d v a n -
tageous when the p e s t i c i d e s m i g r a t e d i n t o o t h e r p a r t s of the
environment p o s i n g r i s k s t o n o n t a r g e t s p e c i e s . As a r e s u l t , many of
t h e s e c h e m i c a l s were r e p l a c e d by l e s s p e r s i s t e n t and l e s s s t r o n g l y
s o r b e d , but g e n e r a l l y more t o x i c , organophosphates and
carbamates (_0
In 1965, a new c l a s s of carbamate i n s e c t i c i d e known as oxime
carbamate was d e v e l o p e d by Union C a r b i d e . The t e c h n i c a l name
a s s i g n e d to the new s o i l - a p p l i e d , s y s t e m i c carbamate i n s e c t i c i d e was
a l d i c a r b (2, 3).
A l d i c a r b [2-methyl-2-(methylthio) propionaldehyde 0-
( m e t h y l c a r b a m o y l ) oxime] i s a n o n c o r r o s i v e , nonflammable i n s e c t i -
c i d e i n c o r p o r a t e d i n t o the seeded f u r r o w d u r i n g p l a n t i n g t o c o n t r o l
s e v e r a l s p e c i e s of i n s e c t s , m i t e s , and nematodes. Aldicarb i s
e x t r e m e l y t o x i c to mammals, and i t s o x i d a t i o n produces two t o x i c
m e t a b o l i t e s , a l d i c a r b s u l f o x i d e and a l d i c a r b s u l f o n e . Both
a l d i c a r b and i t s t o x i c d e r i v a t i v e s a r e v e r y s o l u b l e i n w a t e r .
Recent i n c i d e n t s of c h e m i c a l c o n t a m i n a t i o n of ground-water
r e s e r v o i r s have l e d t o i n c r e a s e d c o n c e r n about the p o t e n t i a l f o r
p e s t i c i d e s , such as a l d i c a r b , to l e a c h t h r o u g h the s o i l p r o f i l e i n t o
the ground water _5, 6_, 7_, 8^, 9_ 10, 11).
9 To d e v e l o p needed
i n f o r m a t i o n on the p o t e n t i a l problem, the U.S. G e o l o g i c a l Survey and
the U.S. E n v i r o n m e n t a l P r o t e c t i o n Agency i n i t i a t e d a 5-year f i e l d
s t u d y i n a h i g h l y p r o d u c t i v e a g r i c u l t u r a l a r e a of s o u t h w e s t e r n
G e o r g i a to i n v e s t i g a t e p e s t i c i d e m i g r a t i o n .
The o b j e c t i v e s of the s t u d y a r e t w o f o l d . The f i r s t i s t o
e v a l u a t e the l o n g - t e r m consequences of c o n t i n u e d use of the p e s t i -
c i d e a l d i c a r b on the q u a l i t y of the ground-water r e s o u r c e by f i e l d
measuring t h e m i g r a t i o n and d e g r a d a t i o n of a l d i c a r b t h r o u g h the
u n s a t u r a t e d and s a t u r a t e d zones. The second o b j e c t i v e i s to d e v e l o p
a d a t a base to t e s t m a t h e m a t i c a l models f o r use i n e v a l u a t i n g t h e
p o t e n t i a l f o r d e g r a d a t i o n of the ground-water r e s o u r c e owing t o i n -
c r e a s e d a p p l i c a t i o n s of p e s t i c i d e s . T h i s r e p o r t d e s c r i b e s work
completed d u r i n g the f i r s t y e a r of the s t u d y . Background d a t a
c o l l e c t e d on the g e o l o g y , s o i l s , and h y d r o l o g y of the s t u d y s i t e
d u r i n g the f i r s t y e a r were used to c h a r a c t e r i z e and d e f i n e the
h y d r o g e o l o g i c environment of the u n s a t u r a t e d and s a t u r a t e d zones.
D e s c r i p t i o n of Study Area
The f i e l d s i t e s e l e c t e d f o r the s t u d y of p e s t i c i d e m i g r a t i o n i s i n
a major a g r i c u l t u r a l a r e a w i t h i n the Dougherty P l a i n t o p o g r a p h i c
d i v i s i o n of the C o a s t a l P l a i n p h y s i o g r a p h i c p r o v i n c e ( 1 2 ) . The
10-acre s t u d y s i t e i s i n s o u t h e a s t e r n Lee County, Ga., approximately
10 mi n o r t h e a s t of the c i t y of A l b a n y , and 1.3 mi e a s t of G e o r g i a
Highway 91 ( F i g u r e 1 ) .
Figure 1. Location of the study site.

The s t u d y s i t e was s e l e c t e d so t h a t i t would ( 1 ) have m u l t i -

l a y e r e d s o i l s , ( 2 ) have r e l a t i v e l y f l a t topography ( t o m i n i m i z e
r u n o f f ) , ( 3 ) be o f manageable s i z e ( l e s s t h a n 20 a c r e s ) , ( 4 ) have a
s h a l l o w water t a b l e , ( 5 ) be i s o l a t e d from d o m e s t i c w e l l s , ( 6 ) be
w i t h i n c l o s e p r o x i m i t y o f a ground-water d i v i d e , ( 7 ) be a v a i l a b l e
f o r a 5-year s t u d y , w i t h owner c o o p e r a t i o n , and ( 8 ) be i n a major
a g r i c u l t u r a l area.
The s t u d y s i t e l i e s i n a w e l l - d r a i n e d p l a i n h a v i n g a g e n t l y
u n d u l a t i n g l a n d s u r f a c e ( 1 3 , 1 4 ) . The maximum r e l i e f of t h e a r e a
s u r r o u n d i n g t h e s t u d y s i t e does not exceed 80 f t . The s i t e has a
r e l i e f s l i g h t l y g r e a t e r than 3 f t ( F i g u r e 2 ) .
The s i t e i s u n d e r l a i n a t s h a l l o w depths by t h e O c a l a L i m e s t o n e .
D i s s o l u t i o n of t h e l i m e s t o n e and c o l l a p s e of s o l u t i o n c a v i t i e s has
produced numerous s h a l l o w , s a u c e r - s h a p e d s i n k s o r d e p r e s s i o n s i n t h e
a r e a s u r r o u n d i n g t h e s t u d y s i t e ( F i g u r e 1 ) . Most s i n k s a r e n e a r l y
c i r c u l a r and f l a t bottomed, and have g e n t l y s l o p i n g s i d e s . Sinks
v a r y i n s i z e from s m a l l , s h a l l o w d e p r e s s i o n s t o l a r g e s i n k s c o v e r i n g
s e v e r a l a c r e s ( 1 5 ) . Many o f t h e l a r g e r s i n k s a r e f i l l e d w i t h water
throughout t h e y e a r and form ponds o r l a k e s , whereas o t h e r s a r e wet
o n l y i n w i n t e r and s p r i n g ( 1 6 ) . S t o c k s Pond, about 500 f t e a s t -
n o r t h e a s t of t h e s i t e ( F i g u r e 1 ) , i s an example of a l a r g e s i n k t h a t
i s f i l l e d w i t h w a t e r throughout t h e y e a r . The n o r t h s i d e of t h e
s i t e i s b o r d e r e d by a d r a i n a g e d i t c h t h a t i s 6 f t wide and 8 f t
deep. The d r a i n a g e d i t c h i s f i l l e d w i t h water o n l y d u r i n g w i n t e r
and s p r i n g when p r e c i p i t a t i o n i n c r e a s e s .
The s t u d y s i t e l i e s e n t i r e l y w i t h i n t h e F l i n t R i v e r d r a i n a g e
basin. The F l i n t R i v e r f l o w s i n t o t h e C h a t t a h o o c h e e R i v e r , which
discharges to the Gulf of Mexico. The F l i n t R i v e r l i e s e a s t of t h e
s i t e and has downcut about 15 f t i n t o t h e O c a l a L i m e s t o n e . As a
r e s u l t , t h e F l i n t R i v e r f l o w s i n a w e l l - d e f i n e d c h a n n e l b o r d e r e d by
a r e l a t i v e l y narrow f l o o d p l a i n .
West of t h e s t u d y s i t e l i e s Muckalee Creek. I t flows i n t o
K i n c h a f o o n e e Creek, which d i s c h a r g e s t o t h e F l i n t R i v e r j u s t n o r t h
of t h e c i t y o f A l b a n y . Muckalee Creek has downcut about 10 t o 15 f t
i n t o t h e l i m e s t o n e t o produce a s t e e p - s i d e d , narrow c h a n n e l . There
i s a d i s t i n c t absence of s m a l l t r i b u t a r i e s i n t h i s a r e a because most
of t h e d r a i n a g e i s s u b t e r r a n e a n ( 1 5 , 1 7 ) . Ground water t h a t
m i g r a t e s i n t o f r a c t u r e s i n t h e l i m e s t o n e commonly d i s c h a r g e s as
s p r i n g s a l o n g t h e banks of s t r e a m s .
S o i l s i n t h e s t u d y s i t e and s u r r o u n d i n g a r e a a r e g e n e r a l l y l e v e l
to g e n t l y s l o p i n g . S o i l s i n l o w - l y i n g a r e a s and d e p r e s s i o n s a r e
moderately w e l l drained t o very p o o r l y d r a i n e d . These s o i l s a r e
a s s o c i a t e d w i t h a r e a s t h a t have a s e a s o n a l l y h i g h water t a b l e and,
t h e r e f o r e , g e n e r a l l y a r e f l o o d e d each y e a r . S o i l s on broad r i d g e s
a r e w e l l d r a i n e d , a n d , because t h e water t a b l e l i e s s e v e r a l f e e t
below l a n d s u r f a c e , f l o o d i n g i s not a problem ( 1 6 ) .
Field Methods
Background d a t a d e s c r i b i n g t h e h y d r o g e o l o g i c environment of t h e
s i t e were c o l l e c t e d d u r i n g 1983. The f i e l d work c o n c e n t r a t e d on
d e f i n i n g s o i l p r o p e r t i e s , g e o l o g i c c h a r a c t e r i s t i c s of t h e residuum
and of t h e O c a l a L i m e s t o n e , and e x i s t i n g ground-water c o n d i t i o n s a t
the s i t e .
- TOPOGRAPHIC CONTOUR--Shows a l t i t u d e of
land surface, December 1 9 8 2 . Contour i n t e r v a l
I f o o t . Datum is sea level
TEST HOLE AND IDENTIFICATION NUMBER
Augered to depth greater^than 5 0 feet c
' ' Augered to top of limestone
5
' D r i l l e d to depth greater than 150 feet
OBSERVATION WELL AND IDENTIFICATION NUMBER
1
P a r t i a l l y penetrates Upper Floridan aquifer and eq;

1
"
Abandonedfinished
GEOPHYSICAL WELL L O G S L o g
i parentheses
G Natural gamma DDensity
Electric CCaliper
Neutron AAcoustic m
m
RAIN GAGE AND IDENTIFICATION NUMBER-
0 100

ll I
. Nash, I 9 8 2 , U . S . D e p a r t
s t e d by D . J . Tomaszewsk
C
Figure 2. L o c a t i o n of t e s t h o l e s and o b s e r v a t i o n w e l l s , and

topography of t h e study s i t e .
A s o i l s u r v e y o f t h e s t u d y s i t e was conducted by t h e U.S. S o i l

C o n s e r v a t i o n S e r v i c e t o determine t h e number of s o i l s e r i e s p r e s e n t .
The s o i l s u r v e y p r o v i d e d a b a s i s f o r d e t e r m i n i n g t h e l o c a t i o n and
s e l e c t i n g t h e optimum number o f m o n i t o r i n g s i t e s .
G e o l o g i c i n f o r m a t i o n was g a t h e r e d from 13 t e s t h o l e s and 21
o b s e r v a t i o n w e l l s d r i l l e d i n the study s i t e ( F i g u r e 2 ) . F i v e of t h e
13 t e s t h o l e s were augered t o t h e t o p o f l i m e s t o n e ; f i v e were
augered i n t o t h e l i m e s t o n e ; and t h r e e were d r i l l e d deeper than
200 f t . G e o l o g i c e v a l u a t i o n o f t h e residuum and t h e O c a l a L i m e s t o n e
was based on a n a l y s e s o f sample c u t t i n g s , a c o n t i n u o u s c o r e ,
f i e l d n o t e s , and b o r e h o l e g e o p h y s i c a l l o g s .
H y d r o l o g i e i n f o r m a t i o n was g a t h e r e d from 16 temporary w e l l s
cased i n t h e r e s i d u u m w i t h s l o t t e d PVC p i p e and f o u r permanent
w e l l s c a s e d t h r o u g h t h e r e s i d u u m and open t o t h e O c a l a L i m e s t o n e .
B i m o n t h l y w a t e r - l e v e l measurements were made and h y d r o g r a p h s p l o t t e d
f o r 14 o b s e r v a t i o n w e l l s . Two o b s e r v a t i o n w e l l s (0W1 and 0W3) open
t o t h e O c a l a L i m e s t o n e were equipped w i t h c o n t i n u o u s w a t e r - l e v e l
r e c o r d e r s , and d a i l y mean hydrographs were p l o t t e d f o r b o t h w e l l s .
P r e c i p i t a t i o n d a t a were c o l l e c t e d c o n t i n u o u s l y from two r a i n gages
equipped w i t h F i s h e r - P o r t e r d i g i t a l r e c o r d e r s ( F i g u r e 2 ) .
Geology
Sedimentary r o c k s u n d e r l y i n g t h e s t u d y s i t e range i n age from Upper

C r e t a c e o u s t o l a t e Eocene. A t h i n s u r f i c i a l d e p o s i t of
u n c o n s o l i d a t e d , p o s t - E o c e n e residuum o v e r l i e s t h e bedrock. The
g e o l o g i c u n i t s pertinent to the study are, i n ascending order, the
L i s b o n F o r m a t i o n , t h e C l i n c h f i e l d Sand, t h e O c a l a L i m e s t o n e , and t h e
u n d i f f e r e n t i a t e d residuum ( F i g u r e 3 ) .
L i s b o n Formation. The L i s b o n F o r m a t i o n o f m i d d l e Eocene age i s

about 72 f t t h i c k i n t h e s t u d y a r e a . The b a s a l p a r t of t h e L i s b o n
F o r m a t i o n c o n s i s t s of about 37 f t of g r e e n i s h - g r a y , g l a u c o n i t i c ,
a r g i l l a c e o u s sand i n t e r b e d d e d w i t h f o s s i l i f e r o u s , sandy l i m e s t o n e .
The b a s a l sequence i s succeeded by about 35 f t of sandy, g l a u c o n i t i c
l i m e s t o n e t h a t i n t e r f i n g e r s w i t h t h i n sand s t r i n g e r s . This
d e s c r i p t i o n of t h e b a s a l sequence agrees w i t h t h e s t r a t i g r a p h i e
d e s c r i p t i o n of t h e L i s b o n F o r m a t i o n as g i v e n by H e r r i c k (18) f o r t h e
w e l l d r i l l e d a t D i x i e P i n e s P l a n t a t i o n i n n o r t h w e s t e r n L e e County,
Ga., about 19 mi n o r t h w e s t of t h e s i t e . The s e c t i o n c o n t a i n s abun-
dant s h e l l f r a g m e n t s , and t h e degree o f c e m e n t a t i o n o f t h e q u a r t z
sand i s v a r i a b l e . The p r e s e n c e of t h e t h i n sand s t r i n g e r s w i t h t h e
l i m e s t o n e s u g g e s t s t h a t t h e q u a r t z sand was o r i g i n a l l y d e p o s i t e d i n
a s h a l l o w marine environment. Minor t r a n s g r e s s i v e p u l s e s of t h e s e a
t e m p o r a r i l y suspended c l a s t i c s e d i m e n t a t i o n i n t h e s h a l l o w marine
environment, thus a l l o w i n g t h e a c c u m u l a t i o n o f c a r b o n a t e . The
v a r y i n g extent of c a l c a r e o u s cementation of the quartz g r a i n s i s a
s e c o n d a r y d e p o s i t i o n a l f e a t u r e a t t r i b u t e d t o t h e c i r c u l a t i o n of
ground w a t e r a f t e r d e p o s i t i o n .
F i g u r e 3. S t r a t i g r a p h i e s e c t i o n and borehole geophysical logs

f o r test hole DH3.
C l i n c h f t e l d Sand. The L i s b o n F o r m a t i o n i s unconformably o v e r l a i n by

about 27 f t of i n t e r f i n g e r i n g u n c o n s o l i d a t e d q u a r t z sand and q u a r t z
sand c o n t a i n i n g c a l c a r e o u s cement. The medium-grained, w e l l - s o r t e d
q u a r t z sand i s s t r a t i g r a p h i c a l l y e q u i v a l e n t t o t h e b a s a l upper
Eocene sand d e p o s i t t h a t H e r r i c k (19) d e s c r i b e d as t h e C l i n c h f i e l d
Sand.
The u n c o n s o l i d a t e d sand c o n t a i n s abundant s h e l l m a t e r i a l and
e c h i n o i d f r a g m e n t s , and forms i n d i v i d u a l beds t h a t have a maximum
t h i c k n e s s of about 5 f t . The cemented sand c o n t a i n s abundant s h e l l
molds and forms beds up t o 10 f t t h i c k . The abundance of q u a r t z ,
s h e l l m a t e r i a l , and e c h i n o i d fragments i n t h e s e c t i o n i n d i c a t e s t h a t
i t was d e p o s i t e d i n a beach e n v i r o n m e n t .
The sand grades upward i n t o an 1 1 - f o o t - t h i c k zone o f
f o s s i l i f e r o u s , sandy l i m e s t o n e i n t e r b e d d e d w i t h t h i n l e n s e s o f
u n c o n s o l i d a t e d q u a r t z sand. T h i s p a r t of t h e sequence was d e p o s i t e d
i n a s h a l l o w marine environment ( 1 9 ) .
Ocala Limestone. The C l i n c h f i e l d Sand i s o v e r l a i n by t h e O c a l a

L i m e s t o n e o f l a t e Eocene age, which c o n s i s t s of about 124 f t of
w h i t e , p o r o u s , c a l c i t i z e d , f o s s i l i f e r o u s l i m e s t o n e . The O c a l a
L i m e s t o n e was d e p o s i t e d i n a m a r g i n a l marine, c o a s t a l environment as
a r e s u l t of a major t r a n s g r e s s i o n o f t h e s e a t h a t was p u n c t u a t e d by
s e v e r a l minor r e g r e s s i o n s . The l i t h o l o g i e c h a r a c t e r of t h e O c a l a
L i m e s t o n e beneath t h e s t u d y f i e l d i s d e s c r i b e d i n t h e s t r a t i g r a p h i e
s e c t i o n f o r t e s t w e l l DH3 ( F i g u r e 3 ) , which p e n e t r a t e s t h e O c a l a
L i m e s t o n e , t h e C l i n c h f i e l d Sand, and t h e L i s b o n F o r m a t i o n , and t h e
l o c a t i o n o f DH3 i s shown on F i g u r e 2.
The b a s a l p a r t o f t h e O c a l a L i m e s t o n e c o n s i s t s o f about 29 f t o f
w h i t e , c o a r s e l y c r y s t a l l i n e , f o s s i l i f e r o u s l i m e s t o n e . T h i s sequence
i s o v e r l a i n by about 43 f t of dense a r g i l l a c e o u s , f o s s i l i f e r o u s
l i m e s t o n e i n t e r b e d d e d w i t h t h i n c l a y laminae and about 5 t o 8 f t o f
s o f t , c h a l k y l i m e s t o n e . The v o i d s p a c e s w i t h i n t h e a r g i l l a c e o u s
l i m e s t o n e have been p a r t i a l l y f i l l e d w i t h c l a y , and t h e u n i t h a s low
permeability.
The upper p a r t o f t h e O c a l a Limestone c o n s i s t s o f about 52 f t o f
porous, c o a r s e l y c r y s t a l l i n e limestone c o n t a i n i n g f i n e d e t r i t a l
q u a r t z and abundant s h e l l f r a g m e n t s . The f o s s i l i f e r o u s l i m e s t o n e
i n c l u d e s t h i n beds of u n c o n s o l i d a t e d q u a r t z sand; t h i n laminae
of s i l i c e o u s , l i g h t - g r a y c l a y ; and s m a l l q u a n t i t i e s of p y r i t e ,
p h o s p h a t e , and g l a u c o n i t e . L i m o n i t e o c c u r s as s t a i n i n g a l o n g
f r a c t u r e s i n the limestone.
The upper s u r f a c e o f t h e O c a l a L i m e s t o n e i s h i g h l y i r r e g u l a r ,
and b e n e a t h most of t h e s t u d y f i e l d i t ranges from about 35 t o 52 f t
below l a n d s u r f a c e .
Residuum. A t t h e s t u d y s i t e t h e O c a l a L i m e s t o n e i s o v e r l a i n by sand
and c l a y d e r i v e d from w e a t h e r i n g of t h e l i m e s t o n e . The s t r a t i -
g r a p h i c s e c t i o n i n F i g u r e 3 shows t h e l i t h o l o g i e v a r i a t i o n
of t h e upper 20 f t of t h e r e s i d u u m . The r e s i d u u m c o n s i s t s o f l a y e r s
and l e n s e s of p o o r l y s o r t e d , v e r y f i n e t o v e r y c o a r s e , a n g u l a r
to subrounded q u a r t z sand and g r a v e l t h a t i n t e r f i n g e r w i t h l e n s e s
of c l a y e y sand, sandy c l a y , and c l a y . The c l a y c o n t e n t of the

r e s i d u u m ranges from about 10 t o 70 p e r c e n t . The h i g h e s t p e r c e n t a g e
of c l a y o c c u r s i n the form of l e n s e s t h a t v a r y i n t h i c k n e s s and
l a t e r a l extent. Fragments of s i l i c i f i e d l i m e s t o n e and c h e r t o c c u r
t h r o u g h o u t the s e c t i o n and a r e abundant near the base of the
residuum. The average t h i c k n e s s of the r e s i d u u m a t the s t u d y s i t e
i s about 44 f t .
A few t h i n l e n s e s of t i g h t , g r a y , p l a s t i c c l a y a l s o o c c u r i n the
residuum beneath the s t u d y f i e l d . The c l a y i s dense and c o n t a i n s
s m a l l fragments of c h e r t and s i l i c i f i e d l i m e s t o n e . The maximum
o b s e r v e d t h i c k n e s s of the c l a y l e n s e s i s 5 f t i n the s o u t h e a s t e r n
c o r n e r of the f i e l d . A l t h o u g h they a r e a r e a l l y r e s t r i c t e d , t h e c l a y
l e n s e s a c t as s e m i c o n f i n i n g zones.
Soils
S o i l s i n s o u t h e a s t e r n Lee County a r e c l a s s i f i e d as U l t i s o l s . They

a r e moist s o i l s t h a t have a r g i l l i c h o r i z o n s and base s a t u r a t i o n s of
l e s s than 35 p e r c e n t . U l t i s o l s d e v e l o p i n a r e a s t h a t have l o n g
f r o s t - f r e e s e a s o n s , abundant r a i n f a l l , and adequate ground-water
supplies.
The s u b s u r f a c e h o r i z o n s are commonly r e d o r y e l l o w owing t o the
a c c u m u l a t i o n of f r e e o x i d e s of i r o n , a l t h o u g h some w e a t h e r a b l e
m i n e r a l s a r e r e t a i n e d i n the s o i l p r o f i l e . U l t i s o l s a r e a c i d i c and
have low f e r t i l i t y and low base s t a t u s . U l t i s o l s a r e not n a t u r a l l y
f e r t i l e , but have enormous p o t e n t i a l f o r a g r i c u l t u r a l p r o d u c t i v i t y
when p r o p e r l y managed t h r o u g h a p p l i c a t i o n s of l i m e and f e r t i l i z e r
(20, 21).
U l t i s o l s form on r e l a t i v e l y o l d g e o l o g i c t e r r a n e s , where abundant
p r e c i p i t a t i o n produces d e e p l y weathered s o i l s . Extensive leaching
and warm s o i l temperatures o v e r p r o l o n g e d p e r i o d s r e s u l t i n r a p i d and
n e a r l y complete a l t e r a t i o n of w e a t h e r a b l e m i n e r a l s i n t o secondary
c l a y s and o x i d e s . S o i l s i n the s t u d y s i t e a r e c l a s s i f i e d as
P a l e u d u l t s , i n w h i c h " u d u l t " r e f e r s t o the s u b o r d e r of U l t i s o l s and
" p a l e " means " o l d development". U d u l t s o i l s have low o r g a n i c - m a t t e r
content. They form i n humid c l i m a t e s where d r y p e r i o d s a r e of s h o r t
d u r a t i o n and t h e w a t e r t a b l e remains below the solum t h r o u g h o u t most
of t h e y e a r ( 2 1 ) .
Two common f e a t u r e s of s o i l s i n the s t u d y s i t e a r e p l i n t h i t e and
fragipan. Both a r e cemented m a t e r i a l s t h a t tend to r e s t r i c t water
movement and r o o t p e n e t r a t i o n . P l i n t h i t e forms i n s u b s o i l s t h a t have
d e v e l o p e d i n the o l d e s t a r e a s of the l a n d s c a p e .
F r a g i p a n s a r e common i n d i c a t o r s of poor d r a i n a g e . A fragipan i s
a loamy, b r i t t l e , s u b s u r f a c e h o r i z o n t h a t i s low i n p o r o s i t y ,
o r g a n i c - m a t t e r c o n t e n t , and c l a y c o n t e n t , but h i g h i n s i l t o r f i n e
sand. F r a g i p a n s can, but do not n e c e s s a r i l y , o c c u r i n the p r e s e n c e
of p l i n t h i t e . Where t h e y o c c u r , f r a g i p a n s can c r e a t e a perched water
t a b l e (16, 21_).
The t h r e e major s o i l s e r i e s found a t the s i t e a r e the C l a r e n d o n ,
t h e A r d i l l a , and t h e T i f t o n ( F i g u r e 4 ) . A f o u r t h s o i l s e r i e s , the
L u c y , i s p r e s e n t i n the f i e l d ; however, due t o i t s l i m i t e d a r e a l
e x t e n t ( l e s s t h a n 0.5 a c r e ) and the p h y s i c a l s i m i l a r i t y between the
Lucy s e r i e s and t h e T i f t o n s e r i e s , i t i s not r e c o g n i z e d as a s e p a r a t e
and d i s t i n c t s o i l s e r i e s i n the s i t e .
0 100 200 3 0 0 FEET

ll. M I I
F i g u r e 4. Major s o i l series i n the study site.

The C l a r e n d o n s e r i e s c o v e r s s l i g h t l y more t h a n 45 p e r c e n t of t h e
area i n the f i e l d . C l a r e n d o n s o i l s a r e c l a s s i f i e d as members of t h e
fine-loamy, s i l i c e o u s , thermic family of P l i n t h a q u i c P a l e u d u l t s .
The t y p i c a l C l a r e n d o n p r o f i l e c o n s i s t s of a dark g r a y i s h - b r o w n ,
sandy h o r i z o n u n d e r l a i n by a y e l l o w i s h - b r o w n , sandy c l a y loam
h o r i z o n , which i s u n d e r l a i n by a m o t t l e d y e l l o w i s h - b r o w n ,
r e d , and g r a y , sandy c l a y loam h o r i z o n t h a t c o n t a i n s 5 t o 30
percent p l i n t h i t e . C l a r e n d o n s o i l s o r i g i n a t e from u n c o n s o l i d a t e d
sediments of medium t e x t u r e . They a r e t y p i c a l l y found on u p l a n d s
and have a s l o p e g r a d i e n t o f l e s s t h a n 2 p e r c e n t . The s o i l s a r e
m o d e r a t e l y w e l l d r a i n e d and have slow r u n o f f . The upper p a r t of t h e
s o i l p r o f i l e i s more permeable than t h e lower p a r t .
A p p r o x i m a t e l y 29 p e r c e n t of t h e s t u d y s i t e i s c o v e r e d by t h e
Ardilla series. These s o i l s a r e c l a s s i f i e d as members of t h e f i n e -
loamy, s i l i c e o u s , t h e r m i c f a m i l y o f F r a g i a q u i c P a l e u d u l t s . The
t y p i c a l p r o f i l e of t h e A r d i l l a s e r i e s c o n s i s t s of a f i n e , sandy
loam h o r i z o n u n d e r l a i n by a y e l l o w i s h - b r o w n , sandy c l a y loam h o r i z o n

which i s u n d e r l a i n by a m o t t l e d y e l l o w i s h - b r o w n , r e d , and gray
h o r i z o n t h a t c o n t a i n s 5 t o 30 p e r c e n t p l i n t h i t e . Ardilla soils
o r i g i n a t e from t h i c k beds of weathered sediments of marine o r i g i n ,
and c o n s i s t of sandy c l a y loam and sandy c l a y . They commonly o c c u r
on l e v e l to g e n t l y s l o p i n g u p l a n d s , and have a s l o p e r a n g i n g from 0
t o 5 p e r c e n t . A r d i l l a s o i l s a r e p o o r l y d r a i n e d and have slow
runoff. P e r m e a b i l i t y i s moderate i n t h e upper p a r t of t h e s o i l
p r o f i l e and m o d e r a t e l y low i n t h e lower p a r t . Ardilla soils
r e c e i v e runoff from s u r r o u n d i n g s o i l s . The a r e a l e x t e n t of t h e
A r d i l l a s e r i e s i n t h e s t u d y s i t e i s r e s t r i c t e d t o t o p o g r a p h i c lows
or d e p r e s s i o n s . A f t e r p e r i o d s of i n c r e a s e d r a i n f a l l , water t e n d s t o
pond i n low a r e a s u n d e r l a i n by A r d i l l a s o i l s , and t h e s e a r e a s tend t o
remain f l o o d e d s e v e r a l days a f t e r t h e r e s t of t h e f i e l d has d r i e d .
The remainder f t h e s t u d y s i t e (26 p e r c e n t ) i s c o v e r e d by t h e
Tifton soil series. The T i f t o n s o i l i s c l a s s i f i e d as a member of
the fine-loamy, s i l i c e o u s , thermic f a m i l y of P l i n t h i c P a l e u d u l t s .
The g e n e r a l s o i l p r o f i l e c o n s i s t s of a dark g r a y i s h - b r o w n , loamy
sand h o r i z o n u n d e r l a i n by a y e l l o w i s h - b r o w n , sandy c l a y loam h o r i z o n
which i s u n d e r l a i n by a c o a r s e l y m o t t l e d brown, r e d , g r a y , and
y e l l o w h o r i z o n c o n t a i n i n g 5 t o 15 p e r c e n t p l i n t h i t e . Tifton soils
o r i g i n a t e from weathered sediments of marine o r i g i n t h a t were
p r e d o m i n a n t l y loamy. The s o i l s o c c u r on l e v e l t o g e n t l y u n d u l a t i n g
u p l a n d s and have a s l o p e r a n g i n g from 0 t o 8 p e r c e n t . T i f t o n s o i l s
a r e m o d e r a t e l y permeable, w e l l d r a i n e d , and have medium r u n o f f .
The o c c u r r e n c e of T i f t o n s o i l s i n t h e s t u d y s i t e i s r e s t r i c t e d t o
t o p o g r a p h i c h i g h s ; t h e s e a r e a s d r a i n f a s t e r t h a n o t h e r a r e a s of t h e
field. S m a l l i r o n s t o n e n o d u l e s a r e common s u r f a c e f e a t u r e s i n a r e a s
u n d e r l a i n by T i f t o n s o i l s .
Hydrology
The p r i m a r y h y d r o l o g i e u n i t s of i n t e r e s t i n t h i s s t u d y a r e , i n
descending v e r t i c a l order: ( 1 ) t h e r e s i d u u m which forms t h e w a t e r -
t a b l e a q u i f e r and a c t s as an upper c o n f i n i n g u n i t , ( 2 ) t h e Upper
F l o r i d a n a q u i f e r ( f o r m e r l y t h e p r i n c i p a l a r t e s i a n a q u i f e r ) , which
c o n s i s t s of t h e O c a l a L i m e s t o n e , t h e C l i n c h f i e l d Sand, and t h e upper
p a r t of t h e L i s b o n F o r m a t i o n , and ( 3 ) t h e b a s a l p a r t of t h e L i s b o n
F o r m a t i o n w h i c h h y d r a u l i c a l l y s e p a r a t e s t h e Upper F l o r i d a n a q u i f e r
from u n d e r l y i n g sediments and s e r v e s as t h e lower c o n f i n i n g u n i t
(Figure 3 ) .
Residuum W a t e r - T a b l e A q u i f e r . Because o f i t s v a r i e d l i t h o l o g y t h e
r e s i d u u m i s a h e t e r o g e n e o u s , a n i s o t r o p i c g e o l o g i c u n i t . The
p r o p e r t i e s of a n i s o t r o p y and h e t e r o g e n e i t y r e f e r s p e c i f i c a l l y t o
v a r i a t i o n s i n t h e p e r m e a b i l i t y o r h y d r a u l i c c o n d u c t i v i t y of a
geologic unit. An a n i s o t r o p i c , h e t e r o g e n e o u s u n i t i s one i n which
the v a l u e s of h y d r a u l i c c o n d u c t i v i t y v a r y d i r e c t i o n a l l y a t a p o i n t
and from p o i n t t o p o i n t w i t h i n t h e u n i t . Because l e n s e s of sandy
c l a y and c l a y i n t e r f i n g e r w i t h sand and c l a y e y sand t h r o u g h o u t t h e
t h i c k n e s s o f t h e residuum, v a l u e s o f h y d r a u l i c c o n d u c t i v i t y v a r y
d i r e c t i o n a l l y and from p o i n t t o p o i n t w i t h i n t h e residuum.
C o n s e q u e n t l y , water i n f i l t r a t i n g t h e r e s i d u u m m i g r a t e s i n v a r y i n g
d i r e c t i o n s and a t d i f f e r i n g r a t e s , depending on t h e h y d r a u l i c
c o n d u c t i v i t y o f the m a t e r i a l through which t h e water i s m i g r a t i n g .

In t h e a r e a s u r r o u n d i n g t h e s t u d y s i t e , Hayes (22) r e p o r t e d a
wide range of e s t i m a t e d v a l u e s f o r h y d r a u l i c c o n d u c t i v i t y and f o r
t r a n s m i s e i v i t y of t h e residuum. The h y d r a u l i c c o n d u c t i v i t y was
c a l c u l a t e d from a q u i f e r t e s t s , b o r e h o l e g e o p h y s i c a l l o g s , and s i e v e
analyses of d r i l l cuttings. The t r a n s m i s s i v i t y was c a l c u l a t e d u s i n g
an average v a l u e of s a t u r a t e d t h i c k n e s s , which was based on measured,
s e a s o n a l w a t e r - l e v e l changes a t each i n d i v i d u a l w e l l . The e s t i m a t e s
of t r a n s m i s s i v i t y r e p r e s e n t o n l y average c o n d i t i o n s ( 2 2 ) .
E s t i m a t e d v a l u e s of t r a n s m i s s i v i t y and average h y d r a u l i c
c o n d u c t i v i t y were d e t e r m i n e d f o r w e l l TW1 a t Piedmont P l a n t Farm
which i s 4 mi n o r t h w e s t of t h e s t u d y s i t e , and f o r w e l l TW1 a t
S t o c k s Farm which i s 3 mi southwest of t h e s t u d y s i t e ( F i g u r e 1 ) .
The e s t i m a t e d average v e r t i c a l and h o r i z o n t a l h y d r a u l i c
c o n d u c t i v i t i e s a t Piedmont P l a n t Farm were 0.003 and 0.02 f t / d ,
respectively. The r a t i o of t h e average h o r i z o n t a l t o v e r t i c a l
h y d r a u l i c c o n d u c t i v i t y was 7.
The r e s i d u u m i s 47 f t t h i c k a t Piedmont P l a n t Farm. The w a t e r
l e v e l was measured from J a n u a r y 1980 t o September 1981, and t h e
average r e s i d u u m w a t e r l e v e l a t Piedmont P l a n t Farm was 32.9 f t
below l a n d s u r f a c e . C o n s e q u e n t l y , t h e average s a t u r a t e d thickness
was 14.1 f t . Based on a s a t u r a t e d t h i c k n e s s o f 14.1 f t , t h e
e s t i m a t e d t r a n s m i s s i v i t v o f t h e r e s i d u u m a t Piedmont P l a n t Farm was
c a l c u l a t e d t o be 0.3 f t * / d .
South of t h e s t u d y s i t e , a t S t o c k s Farm, e s t i m a t e d v a l u e s o f
h y d r a u l i c c o n d u c t i v i t y and t r a n s m i s s i v i t y were much g r e a t e r t h a n a t
Piedmont P l a n t Farm. The e s t i m a t e d average v e r t i c a l and h o r i z o n t a l
h y d r a u l i c c o n d u c t i v i t i e s a t S t o c k s Farm were 9 and 30 f t / d ,
respectively. The r a t i o o f t h e average h o r i z o n t a l t o v e r t i c a l
h y d r a u l i c c o n d u c t i v i t y was 3.
The r e s i d u u m i s 50 f t t h i c k a t S t o c k s Farm. Residuum w a t e r -
l e v e l measurements made from J a n u a r y 1980 t o September 1981 showed
t h a t t h e average r e s i d u u m w a t e r l e v e l a t S t o c k s Farm was 13.0 f t
below l a n d s u r f a c e . I n c o n t r a s t t o Piedmont P l a n t Farm, t h e average
s a t u r a t e d t h i c k n e s s a t S t o c k s Farm was 37.0 f t , which r e s u l t e d
i n a higher estimated t r a n s m i s s i v i t y . The t r a n s m i s s i v i t y of t h e
r e s i d u u m a t S t o c k s Farm was e s t i m a t e d t o be 1,000 f t ^ / d , based
on t h e s a t u r a t e d t h i c k n e s s of t h e residuum.
D u r i n g 1983, p r e c i p i t a t i o n t h a t i n f i l t r a t e d t h r o u g h the r e s i d u u m
at t h e s t u d y s i t e e i t h e r p e r c o l a t e d v e r t i c a l l y downward to r e c h a r g e
the Upper F l o r i d a n a q u i f e r o r moved l a t e r a l l y t o p o i n t s of
discharge. The d r a i n a g e d i t c h b o r d e r i n g the n o r t h s i d e of t h e f i e l d
and a low, swampy a r e a a l o n g t h e w e s t - c e n t r a l s i d e of the f i e l d
a c t e d as i n t e r m i t t e n t d i s c h a r g e p o i n t s f o r t h e w a t e r - t a b l e a q u i f e r
d u r i n g w i n t e r and s p r i n g when the water t a b l e was h i g h ( F i g u r e 2 ) .
The r e s i d u u m w a t e r - t a b l e a q u i f e r responded r a p i d l y ( w i t h i n
hours) to seasonal v a r i a t i o n s i n p r e c i p i t a t i o n . F i g u r e 5 shows t h e
1983 h y d r o g r a p h f o r w e l l 0W3, which f u l l y p e n e t r a t e s the residuum,
and a g r a p h showing a c c u m u l a t e d r a i n f a l l f o r t h e same p e r i o d .
F l u c t u a t i o n s of t h e water t a b l e were d i r e c t l y r e l a t e d to v a r i a t i o n s
i n t h e amounts and i n t e n s i t y o f r a i n f a l l , so r a p i d f l u c t u a t i o n s i n
the water t a b l e were common. The water t a b l e g e n e r a l l y began r i s i n g
w i t h i n 8 h o u r s a f t e r t h e s t a r t of heavy r a i n f a l l . During w i n t e r
and e a r l y s p r i n g 1983, when vapotranspiration was low, i n c r e a s e d
p r e c i p i t a t i o n caused t h e w a t e r t a b l e t o r i s e . Although p r e c i p i t a -
t i o n was g e n e r a l l y heavy from A p r i l t h r o u g h September 1983, water
l o s t t o vapotranspiration was g r e a t and t h e reduced amount of water
a v a i l a b l e f o r r e c h a r g e c a u s e d t h e water l e v e l to d e c l i n e . Because
the w a t e r t a b l e responded r a p i d l y t o changes i n p r e c i p i t a t i o n and
because t h e water l e v e l i n the r e s i d u u m f l u c t u a t e d s e a s o n a l l y , the
t h i c k n e s s of t h e u n s a t u r a t e d zone a l s o v a r i e d s e a s o n a l l y .
B e g i n n i n g i n A p r i l 1983, t h e water l e v e l was measured s e m i -
monthly i n 16 temporary o b s e r v a t i o n w e l l s f i n i s h e d i n t h e r e s i d u u m
( F i g u r e 2 ) . The water t a b l e underwent an average d e c l i n e o f 12.1 f t
from A p r i l t o November 1983 ( F i g u r e 6 ) . T o t a l r a i n f a l l a t t h e s t u d y
s i t e d u r i n g 1983 was 50.4 i n .
D u r i n g t h e two subsequent y e a r s f o l l o w i n g 1983, e v a p o r a t i o n d a t a
were c o l l e c t e d d a i l y from an e v a p o r a t i o n pan t h a t was i n s t a l l e d as
p a r t of a weather s t a t i o n a t t h e s t u d y s i t e . From m i d - f a l l t o e a r l y
s p r i n g , the a v e r a g e 2-year v a l u e f o r e v a p o r a t i o n ranged from about
0.07 t o 0.17 i n / d , and v a l u e s of l e s s t h a n 0.05 i n / d were common.
From l a t e s p r i n g to e a r l y f a l l , the average 2-year pan e v a p o r a t i o n
v a l u e ranged f r o m about 0.2 t o 0.26 i n / d , but v a l u e s as h i g h as 0.34
in/d were common d u r i n g b o t h J u l y and August o f 1984 and 1985.
D u r i n g w i n t e r and s p r i n g 1983, p r e c i p i t a t i o n i n c r e a s e d ,
r e s u l t i n g i n a t o t a l a c c u m u l a t i o n o f 21.7 i n . from F e b r u a r y
to mid-May 1983. The average 2-year pan e v a p o r a t i o n f o r t h e same
p e r i o d was about 0.11 i n / d o r a t o t a l of about 13.2 i n . The s u r p l u s
w a t e r i n f i l t r a t e d downward c a u s i n g t h e w a t e r l e v e l i n t h e r e s i d u u m
to r i s e . V e r t i c a l l e a k a g e t h r o u g h the base of the r e s i d u u m a l s o
i n c r e a s e d , w h i c h r e s u l t e d i n r e c h a r g e t o t h e Upper F l o r i d a n a q u i f e r .
D u r i n g summer and f a l l 1983, t o t a l p r e c i p i t a t i o n d e c r e a s e d t o
about 17.5 i n . f r o m mid-May t o mid-November 1983. The 2-year
average v a l u e f o r e v a p o r a t i o n was about 0.23 i n / d o r a t o t a l of
about 33.2 i n . D u r i n g t h i s p e r i o d , e v a p o r a t i o n exceeded p r e c i p i t a -
t i o n , and i n r e s p o n s e , t h e water l e v e l i n the r e s i d u u m d e c l i n e d .
The d e c r e a s e d i n f i l t r a t i o n of water i n t o t h e r e s i d u u m caused a
d e c r e a s e i n t h e v e r t i c a l l e a k a g e t h r o u g h the base of the residuum,
and so r e c h a r g e t o t h e Upper F l o r i d a n a q u i f e r d e c r e a s e d . Water
l e v e l s c o n t i n u e d to d e c l i n e i n b o t h t h e w a t e r - t a b l e a q u i f e r and the
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F i g u r e 6. A l t i t u d e of water table i n the residuum at the s t u d y

s i t e , J a n u a r y 1984.
Upper F l o r i d a n a q u i f e r u n t i l s i g n i f i c a n t p r e c i p i t a t i o n o c c u r r e d
i n l a t e November 1983 and water l o s t t o t h e atmosphere t h r o u g h
e v a p o r a t i o n and t r a n s p i r a t i o n d i m i n i s h e d .
The c o n f i g u r a t i o n s and t h e g r a d i e n t s of t h e water t a b l e a r e
i n f l u e n c e d n o t o n l y by g e o h y d r o l o g i c p r o p e r t i e s of t h e residuum, but
a l s o by changes i n t h e amount of p r e c i p i t a t i o n and t h e r a t e of
vapotranspiration. I n c r e a s e d p r e c i p i t a t i o n and d e c r e a s e d
vapotranspiration d u r i n g w i n t e r and s p r i n g 1983 caused t h e water
t a b l e t o r i s e and ground water t o t e m p o r a r i l y mound i n t h e c e n t r a l
p a r t of t h e f i e l d ( F i g u r e 6 ) . D u r i n g J a n u a r y 1984, t h e d i r e c t i o n o f
ground-water f l o w was away from t h e mound. D u r i n g summer and f a l l
1983 when p r e c i p i t a t i o n d e c r e a s e d and vapotranspiration i n c r e a s e d ,
the w a t e r t a b l e d e c l i n e d and t h e d i r e c t i o n o f ground-water f l o w
s h i f t e d to the east-southeast ( F i g u r e 7 ) . The h y d r a u l i c g r a d i e n t
was n e a r l y f l a t i n t h e n o r t h - n o r t h w e s t c o r n e r of t h e f i e l d , w h i l e
the g r a d i e n t s t e e p e n e d i n t h e s o u t h e a s t e r n p a r t of t h e f i e l d .
S m a l l q u a n t i t i e s o f water were o b t a i n e d from t h e s h a l l o w w e l l s

f i n i s h e d i n t h e residuum. The w e l l y i e l d s ranged from l e s s than
3 gal/min to 5 gal/min.
Upper F l o r i d a n A q u i f e r . The Upper F l o r i d a n a q u i f e r i s formed by t h e

O c a l a L i m e s t o n e , t h e C l i n c h f i e l d Sand, and t h e upper p a r t of t h e
L i s b o n F o r m a t i o n w h i c h a r e , f o r t h e most p a r t , h i g h l y permeable.
The a q u i f e r i s c o n f i n e d above by t h e b a s a l p a r t of t h e r e s i d u u m and
below by t h e lower p a r t o f t h e L i s b o n F o r m a t i o n ( F i g u r e 3 ) .
In t h e a r e a s u r r o u n d i n g t h e s t u d y s i t e and away from s t r e a m s ,
Hayes (22) e s t i m a t e d t h a t t h e t r a n s m i s s i v i t y o f t h e Upper F l o r i d a n
a q u i f e r ranged from about 4,000 t o 6,000 f t ^ / d . The e f f e c t i v e
h y d r a u l i c c o n d u c t i v i t y of t h e a q u i f e r i n t h i s a r e a was e s t i m a t e d t o
be about 100 f t / d , and t h e e f f e c t i v e p o r o s i t y was e s t i m a t e d t o be
about 20 p e r c e n t ( 2 2 ) . Hayes (22) r e p o r t e d t h a t t h e h y d r a u l i c
g r a d i e n t i n t h e n o r t h e r n p a r t of t h e Dougherty P l a i n was about 2
f t / m i , and so t h e average v e l o c i t y o f ground-water f l o w i n t h e
v i c i n i t y o f t h e s t u d y s i t e i s about 0.2 f t / d .
L a r g e q u a n t i t i e s of water have been o b t a i n e d from nearby w e l l s
t h a t p a r t i a l l y p e n e t r a t e t h e Upper F l o r i d a n a q u i f e r . Hayes ( 2 2 )
r e p o r t e d t h a t t h e y i e l d f r o m s e v e r a l w e l l s i n Lee County, Ga.,
ranged from 150 t o 225 g a l / m i n . Well y i e l d s at the study s i t e
exceeded 100 g a l / m i n .
G e o l o g i c and h y d r o l o g i e d a t a from t h e s t u d y s i t e i n d i c a t e t h a t
the Upper F l o r i d a n a q u i f e r i n c l u d e s upper and lower permeable zones
t h a t a r e h y d r a u l i c a l l y s e p a r a t e d by a m i d d l e , s e m i c o n f i n i n g u n i t .
B o r e h o l e g e o p h y s i c a l l o g s r u n i n t e s t h o l e DH3, which f u l l y
p e n e t r a t e s t h e Upper F l o r i d a n a q u i f e r , show t h e two permeable zones
and t h e s e m i c o n f i n i n g u n i t ( F i g u r e 3 ) .
The upper permeable zone c o n s i s t s o f 52 f t of c o a r s e l y
c r y s t a l l i n e , f o s s i l f e r o u s limestone. P e r m e a b i l i t y i s mainly of
s e c o n d a r y o r i g i n and i n c l u d e s openings d e v e l o p e d by f r a c t u r i n g and
d i s s o l u t i o n of the limestone. The lower permeable zone i s 102 f t
t h i c k , and c o n s i s t s of sand t h a t i n t e r t o n g u e s w i t h sandy l i m e s t o n e .
The sand i n t h e l o w e r p a r t of t h e a q u i f e r i s more permeable t h a n t h e
l i m e s t o n e i n t h e upper p a r t and i t has a h i g h e r w a t e r - b e a r i n g
potential. The h i g h p e r m e a b i l i t y of t h e sand i s m a i n l y from p r i m a r y

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porosity. The s e m i c o n f i n i n g u n i t n e a r t h e m i d d l e o f t h e a q u i f e r i s
47 f t t h i c k and h a s low p e r m e a b i l i t y owing t o h i g h c l a y c o n t e n t ;
t h e r e f o r e , i t p e r m i t s o n l y minor v e r t i c a l l e a k a g e between t h e two
permeable zones.
The upper permeable zone i s c o n n e c t e d h y d r a u l i c a l l y t o t h e
r e s i d u u m which a l l o w s v e r t i c a l l e a k a g e t h r o u g h t h e base of t h e
r e s i d u u m , and t h u s r e s p o n s e by t h e upper permeable zone t o changes
in precipitation i s rapid. P r e c i p i t a t i o n i n f i l t r a t i n g the residuum
r e c h a r g e s t h e upper permeable zone, and t h e r a t e o f r e c h a r g e i s
dependent upon such f a c t o r s as t h e head d i f f e r e n t i a l between
t h e w a t e r t a b l e i n t h e r e s i d u u m and t h e w a t e r l e v e l i n t h e upper
permeable zone, v a r i a t i o n s i n h y d r a u l i c c o n d u c t i v i t i e s between t h e
r e s i d u u m and t h e upper permeable zone, and t h e t h i c k n e s s o f t h e
c o n f i n i n g u n i t , which i s t h e r e s i d u u m .
The h y d r o g r a p h s i n F i g u r e 8 r e v e a l t h a t a head d i f f e r e n t i a l
e x i s t s between t h e upper and lower permeable z o n e s , i n d i c a t i n g t h a t
t h e two a r e h y d r a u l i c a l l y s e p a r a t e d . D u r i n g 1983, t h e w a t e r l e v e l
i n w e l l 0W3, which p a r t i a l l y p e n e t r a t e s t h e upper permeable zone,
ranged from about 4 t o 16 f t below l a n d s u r f a c e , whereas t h e water
l e v e l i n w e l l 0W1, which t a p s t h e lower permeable zone, ranged
from about 18 t o 34 f t below l a n d s u r f a c e .
T a b l e 1 shows w a t e r - l e v e l measurements made a t t h e same t i m e i n
t h e w a t e r - t a b l e a q u i f e r , t h e upper permeable zone, and t h e lower
permeable zone.
Table 1 . W a t e r l e v e l s and head d i f f e r e n c e s between t h e w a t e r t a b l e

and t h e two permeable zones i n t h e Upper F l o r i d a n a q u i f e r
[WT = w a t e r t a b l e ; UPZ = upper permeable zone;
LPZ = lower permeable zone]
Date W a t e r - l e v e l measurements ( f t ) Head d i f f e r e n c e s ( f t )

WT UPZ LPZ WT and UPZ UPZ and LPZ
Apr 1983 3.19 2.34 18.27 0.85 15.93
May 1983 4.24 3.65 20.38 .59 16.73
Nov 1983 12.50 12.43 29.38 .07 16.95
Based on a c o m p a r i s o n o f t h e head d i f f e r e n c e s shown i n T a b l e 1,

t h e degree o f h y d r a u l i c s e p a r a t i o n i s much g r e a t e r between t h e upper
and lower permeable zones i n t h e Upper F l o r i d a n a q u i f e r t h a n between
t h e upper permeable zone and t h e w a t e r - t a b l e a q u i f e r .
The s m a l l head d i f f e r e n t i a l , e x h i b i t e d t h r o u g h o u t t h e y e a r ,
between t h e w a t e r - t a b l e a q u i f e r and t h e upper permeable zone
i n d i c a t e s t h a t a l t h o u g h t h e r e s i d u u m a c t s as a c o n f i n i n g u n i t
f o r t h e Upper F l o r i d a n a q u i f e r , v e r t i c a l l e a k a g e does o c c u r t h r o u g h
the base of t h e r e s i d u u m , and t h e r e i s some degree of h y d r a u l i c
c o n n e c t i o n between t h e two h y d r o l o g i e z o n e s .
ON
A l a r g e head d i f f e r e n t i a l e x i s t s between t h e upper and l o w e r

permeable zones i n d i c a t i n g t h a t t h e 47 f t of s e m i c o n f i n i n g m a t e r i a l
( F i g u r e 3) s e p a r a t i n g t h e two permeable zones a l l o w s o n l y minor
v e r t i c a l l e a k a g e downward t o r e c h a r g e t h e lower permeable zone.
The h y d r o g r a p h s i n F i g u r e 8 show t h a t t h e upper and lower
permeable zones r e s p o n d d i f f e r e n t l y t o p r e c i p i t a t i o n and pumping.
C l i m a t o l o g i c a l v a r i a t i o n s and w a t e r - l e v e l changes i n t h e r e s i d u u m
and t h e upper permeable zone have l i t t l e e f f e c t on t h e lower
permeable zone. Moreover, when nearby i r r i g a t i o n w e l l s t h a t
tap o n l y t h e lower permeable zone a r e pumped, t h e water l e v e l i n
the lower permeable zone responds r a p i d l y , b u t t h e r e i s almost no
change i n t h e water l e v e l i n t h e upper permeable zone.
The 1983 h y d r o g r a p h of w e l l 0W1 shows t h a t between mid-May and
l a t e O c t o b e r , t h e water l e v e l i n t h e lower permeable zone f l u c t u a t e d
i n r e s p o n s e t o n e a r b y a g r i c u l t u r a l pumping. By c o n t r a s t , d u r i n g t h e
same p e r i o d , t h e water l e v e l i n t h e upper permeable zone d e c l i n e d
s t e a d i l y and showed minor f l u c t u a t i o n s , owing t o p e r i o d s of reduced

p r e c i p i t a t i o n and i n c r e a s e d vapotranspiration. W e l l 0W3 e x h i b i t e d
l i t t l e , i f any, r e s p o n s e t o nearby i r r i g a t i o n pumping, t h u s , once
a g a i n i n d i c a t i n g t h a t l e a k a g e t h r o u g h t h e s e m i c o n f i n i n g u n i t was
p r o b a b l y minor.
Summary and C o n c l u s i o n
T h i s s t u d y was d e s i g n e d t o i n v e s t i g a t e t h e m i g r a t i o n and d e g r a d a t i o n
of t h e p e s t i c i d e a l d i c a r b i n a f i e l d e n v i r o n m e n t . To e v a l u a t e t h e
p o t e n t i a l f o r the p e s t i c i d e to l e a c h through the s o i l p r o f i l e i n t o
the ground-water system, d e t a i l e d i n f o r m a t i o n was g a t h e r e d
c o n c e r n i n g t h e p h y s i c a l n a t u r e of t h e u n s a t u r a t e d and s a t u r a t e d
zones and t h e r e l a t i o n between them.
The 10-acre s t u d y s i t e i s u n d e r l a i n , i n d e s c e n d i n g o r d e r , by t h e
u n d i f f e r e n t i a t e d r e s i d u u m , which forms t h e w a t e r - t a b l e a q u i f e r , and
the O c a l a L i m e s t o n e , t h e C l i n c h f i e l d Sand, and t h e L i s b o n F o r m a t i o n ,
which f o r m t h e Upper F l o r i d a n a q u i f e r . Geohydrologic data i n d i c a t e
t h a t i n t h e a r e a o f t h e s t u d y s i t e , t h e Upper F l o r i d a n a q u i f e r
i n c l u d e s upper and lower permeable z o n e s . The upper permeable zone
i s h y d r a u l i c a l l y c o n n e c t e d t o the r e s i d u u m w a t e r - t a b l e a q u i f e r and
i s r e c h a r g e d d i r e c t l y by water i n f i l t r a t i n g t h r o u g h t h e residuum. A
s e m i c o n f i n i n g u n i t s e p a r a t e s t h e lower permeable zone from t h e upper
permeable zone. There i s , however, minor v e r t i c a l l e a k a g e t h r o u g h
the s e m i c o n f i n i n g u n i t i n t o t h e lower permeable zone.
Because t h e r e s i d u u m w a t e r - t a b l e a q u i f e r and t h e upper permeable
zone a r e h y d r a u l i c a l l y c o n n e c t e d , t h e y respond r a p i d l y ( w i t h i n
hours) to seasonal f l u c t u a t i o n s i n p r e c i p i t a t i o n . During winter
and s p r i n g of 1983, t h e water l e v e l s i n t h e r e s i d u u m and t h e
upper permeable zone r o s e i n r e s p o n s e t o i n c r e a s e d p r e c i p i t a t i o n
and d e c r e a s e d vapotranspiration. Water l e v e l s i n t h e r e s i d u u m and
the upper permeable zone d e c l i n e d d u r i n g t h e summer and f a l l as
p r e c i p i t a t i o n d e c r e a s e d and vapotranspiration i n c r e a s e d . D u r i n g
l a t e f a l l , d e c r e a s e d vapotranspiration and i n c r e a s e d p r e c i p i t a t i o n
caused t h e water l e v e l s t o r i s e .
S e a s o n a l w a t e r - l e v e l changes i n the r e s i d u u m and t h e upper

permeable zone have l i t t l e e f f e c t on the lower permeable zone.
The w a t e r l e v e l i n t h e l o w e r permeable zone does, however, r e s p o n d
r a p i d l y ( w i t h i n h o u r s ) t o t h e pumping of i r r i g a t i o n w e l l s t h a t
tap the lower permeable zone, whereas the water l e v e l i n t h e upper
permeable zone shows almost no change.
From t h e i n i t i a l background f i e l d d a t a , t h e f o l l o w i n g
c o n c l u s i o n s were drawn c o n c e r n i n g the h y d r o g e o l o g i c environment of
the field site:
1. The t h i c k n e s s of t h e u n s a t u r a t e d zone v a r i e s , depending on the

water l e v e l i n the r e s i d u u m which i s d i r e c t l y a f f e c t e d by
f l u c t u a t i o n s i n p r e c i p i t a t i o n and vapotranspiration.
2. The r e s i d u u m i s a t h i n , s u r f i c i a l l a y e r of v a r i a b l e l i t h o l o g y .
Sand, g r a v e l , and c l a y e y sand i n t e r f i n g e r w i t h l e n s e s of sandy
c l a y and c l a y t h r o u g h o u t the r e s i d u u m , but the l e n s e s o f c l a y
and sandy c l a y a r e r e s t r i c t e d i n b o t h t h e i r l a t e r a l and v e r t i -

cal extent. As a r e s u l t , p e r m e a b i l i t y o r h y d r a u l i c c o n d u c t i v i t y
i n the r e s i d u u m i s v a r i a b l e , which c a u s e s w a t e r i n f i l t r a t i n g
t h r o u g h the r e s i d u u m t o m i g r a t e i n v a r y i n g d i r e c t i o n s and a t
differing rates.
3. The w a t e r - t a b l e a q u i f e r i s h y d r a u l i c a l l y c o n n e c t e d t o t h e upper
permeable zone of the Upper F l o r i d a n a q u i f e r , and water
i n f i l t r a t e s t h r o u g h t h e r e s i d u u m t o r e c h a r g e t h e upper permeable
zone.
4. The lower permeable zone i s h y d r a u l i c a l l y s e p a r a t e d f r o m t h e
upper permeable zone by a s e m i c o n f i n i n g u n i t t h a t a l l o w s o n l y
minor v e r t i c a l l e a k a g e i n t o the l o w e r permeable zone.
In g e n e r a l , water i n f i l t r a t i n g the s o i l p r o f i l e m i g r a t e s
v e r t i c a l l y downward f r o m t h e u n s a t u r a t e d zone t o t h e s a t u r a t e d zone
and e v e n t u a l l y i n t o t h e ground-water system. C o n s e q u e n t l y , the
p o t e n t i a l e x i s t s f o r a p e s t i c i d e t o m i g r a t e from t h e c r o p - r o o t zone
i n t o t h e w a t e r - t a b l e a q u i f e r and the Upper F l o r i d a n a q u i f e r .
As the s t u d y moves i n t o the second phase when f i e l d d a t a w i l l be
c o l l e c t e d f o r a n a l y s i s a f t e r a p p l i c a t i o n of the p e s t i c i d e a l d i c a r b ,
background d a t a w i l l c o n t i n u e t o be c o l l e c t e d t o b e t t e r d e f i n e and
c h a r a c t e r i z e the l o c a l ground-water s y s t e m and i t s r e l a t i o n t o the
u n s a t u r a t e d zone.
Literature Cited
1. Supak, J. R. Ph.D. Thesis, Texas A & M University, College

Station, Texas, 1972.
2. Martin, ., Ed. "Pesticide Manual" 2nd ed.; British Crop
Protection Council, Worchester, England, 1971.
3. "Initial Scientific and Minieconomic Review of Aldicarb," U.S.
Environmental Protection Agency, 1975.
4. Zaki, M. H.; Moran, D.; Harris, D. Amer. J. Pub. Health 1982,
72, 1391-1395.
5. Hebb, . .; Wheeler, W. B. J. Environ. Quality 1978, 7, 598-
601.
6. Peoples, S. .; Maddy, K, T.; Cusick, W.; Jackson, T.; Cooper,

C.; Frederickson, A. S. Bull. Environ. Contam. Toxic* 1980,
24, 611-618.
7. Rothschild, E. R.; Manser, R. J.; Anderson, M. J. Ground Water
1982, 20, 437-445.
8. Spalding, R. F.; Exner, M. E.; Sullivan, J. J.; Sullivan, P. A.
J. Environ. Quality 1979, 8, 374-383.
9. Spalding, R. F.; Junk, G. .; Richard, J. J. Pest. Mon. J.
1980, 14, 70-73.
10. Todd, D. K.; McNulty, D. E. "Polluted Ground Water: A Review
of Significant Literature", U.S. Environmental Protection
Agency, 1974.
11. Wehtje, G. R.; Spalding, R. F.; Burnside,O.C.;Lowry, S. R.;
Leavitt, J. R. C. Weed Science 1983, 31, 610-618.
12. Fenneman, . M. "Physiography of Eastern United States"; McGraw-
Hill: New York, 1938; p. 714.
13. Owen, V. Jr. "Geology and Ground Water Resources of Lee and
Sumter Counties, Southwest Georgia," U.S. Geological Survey

Water-Supply Paper 1666, U.S. Government Printing Office,
Washington, D.C. 1963.
14. Moon, J. W. "Soil Survey of Lee County, Georgia," U.S.
Department of Agriculture, Bureau of Chemistry and Soils,
Series 1927, No. 4, 1927.
15. LaForge, L.; Cooke, C. W.; Keith, .; Campbell, M. R. "Physical
Geography of Georgia," Georgia Geol. Surv. Bull. 42, 1925.
16. Pilkinton, J. A. "Soil Survey of Lee and Terrell Counties,
Georgia," U.S. Department of Agriculture, 1978.
17. Veatch, J. O.; Stephenson, L. W. "Geology of the Coastal Plain
of Georgia," Georgia Geol. Surv. Bull. 26, 1911.
18. Herrick, S. M. "Wel Logs of the Coastal Plain of Georgia,"
Georgia Geol. Surv. Bull. 70, 1961.
19. Herrick, S. M. "Age and Correlation of the Clinchfield Sand in
Georgia," U.S. Geological Survey Bulletin 1354-E, U.S.
Government Printing Office, Washington, D.C, 1972.
20. Brady, N. C. "The Nature and Properties of Soils" 8th ed.;
MacMillan: New York, 1974; p. 639.
21. Buol, S. W.; Hole, F. D.; McCracken, R. J. "Soil Genesis and
Classification"; The Iowa State University Press: Iowa, 1973;
p. 360.
22. Hayes, L. R.; Maslia, M. L.; Meeks, W. C. "Hydrology and Model
Evaluation of the Principal Artesian Aquifer, Dougherty Plain,
Southwest Georgia," Georgia Geol. Surv. Bull. 97, 1983.
6
Spatial Variability of Pesticide Sorption and Degradation
Parameters
1
P. S. C. Rao , K. S. V. Edvardsson, L . T. Ou, R. E . Jessup, P. Nkedi-Kizza, and
A. G. Hornsby
Soil Science Department, University of Florida, Gainesville, F L 32611
Data were collected at two field sites, one in Florida

and the other in Georgia, to evaluate the variability

in pesticide concentrations and in pesticide sorption
and degradation parameters. The observed variability
can be attributed to intrinsic factors leading to
inherent variability, and to extrinsic factors resul-
ting in imposed variability. Data are presented to
demonstrate the predominant effects of the method of
pesticide application and tillage operations in intro-
ducing significant extrinsic variability in pesticide
concentrations. Variability introduced at the soil
surface may persist as the pesticide leaches to deeper
depths. At both field sites, a close relationship
was found between the spatial variations in soil
organic carbon content and pesticide sorption coef-
ficients. At the Georgia field site, small varia-
tions (coefficient of variation < 30%) were noted
in measured pesticide degradation half-lives in soil
samples collected from several locations and four
morphologic horizons. Spatial patterns in pesticide
sorption and degradation parameters did not correspond
to spatial boundaries of the soil series.
Recent r e p o r t s o f i n c r e a s i n g i n c i d e n c e o f p e s t i c i d e s and t o x i c
o r g a n i c p o l l u t a n t s i n groundwater ( i , 2 ) have prompted a number
o f l a b o r a t o r y and f i e l d i n v e s t i g a t i o n s o f t h e p r o c e s s e s and f a c t o r s
i n f l u e n c i n g p e s t i c i d e b e h a v i o r i n s o i l s and groundwater. Several
s i m u l a t i o n models have been d e v e l o p e d f o r f o r e c a s t i n g p e s t i c i d e
7
C u r r e n t address: A g r o n o m y a n d S o i l Science Department, University o f H a w a i i ,
H o n o l u l u , H I 96822
0097-6156/ 86/ 0315-0100S06.00/ 0

6. RAO ET A L . Spatial Variability of Pesticide Parameters 101
f a t e i n s o i l s ( 3, A ) . To v a l i d a t e t h e s e models and t o u s e them

f o r e i t h e r management o r r e g u l a t o r y p u r p o s e s , s e v e r a l s i t e - s p e c i f i c
v a l u e s f o r s o i l and p e s t i c i d e parameters a r e needed.
A t y p i c a l f i e l d s i t e , v a r y i n g i n a r e a from about 1 t o 10 h a ,
may i n c l u d e s e v e r a l s o i l s e r i e s . The model parameter v a l u e s may be
d i f f e r e n t n o t o n l y f o r each o f t h e s e s o i l s e r i e s , b u t may a l s o v a r y
considerably within a single series. Such v a r i a b i l i t y i n a number
of s o i l h y d r a u l i c p r o p e r t i e s ( e . g . , s o i l h y d r a u l i c c o n d u c t i v i t y ,
s o i l water f l u x , e t c . ) has been w i d e l y r e p o r t e d i n t h e l i t e r a t u r e
( 5 - 1_ ). The model parameter v a l u e s f o r a g i v e n l o c a t i o n i n t h e
f i e l d may a l s o v a r y w i t h p r o f i l e depth depending upon s o i l
h o r i z o n a t i o n as w e l l as a f u n c t i o n o f t h e s o i l and e n v i r o n m e n t a l
f a c t o r s ( e . g . , s o i l a e r a t i o n , temperature, e t c . ) . S i n c e s o i l and
e n v i r o n m e n t a l f a c t o r s undergo dynamic changes w i t h t i m e , model
parameters a r e a l s o e x p e c t e d t o e x h i b i t t e m p o r a l v a r i a b i l i t y . A t
p r e s e n t , o n l y l i m i t e d d a t a a r e a v a i l a b l e t o c h a r a c t e r i z e such
s p a t i a l and t e m p o r a l v a r i a b i l i t y i n p e s t i c i d e s o r p t i o n and degrada-

t i o n parameters r e q u i r e d i n s e v e r a l s i m u l a t i o n models.
In t h i s paper, we w i l l d i s c u s s d a t a c o l l e c t e d as a p a r t o f two
r e c e n t f i e l d s t u d i e s , one i n G e o r g i a and t h e o t h e r i n F l o r i d a . The
o b j e c t i v e o f b o t h s t u d i e s was t o m o n i t o r t h e e n v i r o n m e n t a l dynamics
of p e s t i c i d e s i n t h e c r o p r o o t zone and t o u s e t h e s e d a t a t o
e v a l u a t e t h e p r e d i c t i v e c a p a b i l i t y o f s e v e r a l s i m u l a t i o n models.
S p e c i f i c a t t e n t i o n w i l l be f o c u s e d on t h e d a t a c h a r a c t e r i z i n g t h e
s p a t i a l v a r i a b i l i t y o f p e s t i c i d e s o r p t i o n and d e g r a d a t i o n parame-
t e r s measured a t t h e s e two f i e l d s i t e s .
Description of the F i e l d Sites
The G e o r g i a f i e l d s t u d y was a c o o p e r a t i v e e f f o r t between t h e U.S.

E n v i r o n m e n t a l P r o t e c t i o n Agency, t h e U.S. G e o l o g i c a l Survey, and
the U n i v e r s i t y o f F l o r i d a . The 4.5-ha f i e l d s i t e , p l a n t e d t o
peanuts, was l o c a t e d near A l b a n y , GA. A t t h i s s i t e d a t a a r e b e i n g
c o l l e c t e d to characterize p e s t i c i d e migration within the unsaturat-
ed and t h e s a t u r a t e d zones. The c r i t e r i a used i n s e l e c t i n g t h i s
f i e l d s i t e and i n d e s i g n i n g t h e s t u d y a r e d i s c u s s e d by C a r s e l e t
a l . ( 8 ). Cooper ( 9 ) p r e s e n t e d a d e t a i l e d g e o h y d r o l o g i c de-
scription of this s i t e . B u l k samples o f s u r f a c e s o i l (0-20 cm)
were c o l l e c t e d u s i n g a bucket auger from 20 l o c a t i o n s , d e s i g n a t e d
as t h e p r i m a r y s i t e s ( 8 ), and an a d d i t i o n a l 16 random l o c a t i o n s
at t h i s f i e l d s i t e . Each sample was i d e n t i f i e d by i t s l o c a t i o n
w i t h r e f e r e n c e t o an a r b i t r a r y g r i d ( 8 ). S o i l o r g a n i c carbon
c o n t e n t (OC) o f t h e s e samples was determined by d r y combustion
method u s i n g a LECO Carbon A n a l y z e r . Pesticide sorption coeffi-
c i e n t s (K,) were determined u s i n g t h e b a t c h e q u i l i b r i u m t e c h n i q u e s
( 10, 11_ The p e s t i c i d e s used were: a l d i c a r b [ ( m e t h y l t h i o )
p r o p i o n a l d e h y d e 0 - ( m e t h y l c a r b a m o y l ) oxime]; m e t o l a c h l o r
[ 2 - c h l o r o - N - ( 2 - e t h y l - 6 - m e t h y l p h e n y l ) - N - (2-methoxy-1-methyl e t h y l )
acetamide; and d i u r o n [ 3 - ( 3 , 4 - d i c h l o r o p h e n y l ) - 1,1-dimethyl u r e a ] .
A t t h e 20 p r i m a r y l o c a t i o n s , s o i l c o r e s were a l s o c o l l e c t e d from
each o f t h e f o u r m o r p h o l o g i c h o r i z o n s (0-20, 25-45, 48-63, and
94-107 cm) u s i n g a s e p t i c sampling t e c h n i q u e s ( 12 ) . A l d i c a r b and
m e t o l a c h l o r d e g r a d a t i o n i n t h e s e s o i l samples under a e r o b i c c o n d i -
t i o n s was measured u s i n g b a t c h i n c u b a t i o n t e c h n i q u e s ( 13^ ). These
o r
d a t a were used t o c a l c u l a t e t h e h a l f - l i v e s ( t j ^ ) ^ disappearance
of t h e p a r e n t compound.
The second f i e l d s t u d y was c o n d u c t e d on a 0.8-ha c i t r u s g r o v e ,
l o c a t e d n e a r Davenport, F l o r i d a . T h i s s t u d y was a c o o p e r a t i v e
e f f o r t between t h e U n i v e r s i t y o f F l o r i d a and t h e Union C a r b i d e
A g r i c u l t u r a l P r o d u c t s Company, I n c . The s o i l a t t h i s s i t e i s
c l a s s i f i e d as C a n d l e r sand ( h y p e r t h e r m i c , T y p i c Q u r t z i p s a m m e n t s ) ,
w h i c h i s t y p i c a l o f t h e deep, sandy, and w e l l - d r a i n e d s o i l s p l a n t e d
t o c i t r u s on t h e c e n t r a l r i d g e o f F l o r i d a . B u l k samples o f s u r f a c e
s o i l (0-15 and 15-30 cm) were c o l l e c t e d u s i n g bucket auger a t 29
l o c a t i o n s , 12.5 m a p a r t , on a n o r t h - s o u t h (N-S) t r a n s e c t . On a
w e s t - e a s t (W-E) t r a n s e c t , s o i l samples were c o l l e c t e d i n a s i m i l a r
manner a t a n o t h e r 17 l o c a t i o n s . The N-S and W-E t r a n s e c t s s h a r e d
one s o i l sample a t t h e p o i n t o f t h e i r i n t e r s e c t i o n . Additional
s o i l samples were t a k e n from 26 s i t e s s e l e c t e d randomly w i t h i n t h e
field. The e x a c t l o c a t i o n o f each s a m p l i n g s i t e was n o t e d and was
used t o i d e n t i f y t h e samples. OC v a l u e s f o r t h e s e s o i l s were

d e t e r m i n e d by t h e d r y combustion method. A l d i c a r b v a l u e s were
measured u s i n g t h e b a t c h e q u i l i b r i u m t e c h n i q u e .
Types o f S p a t i a l Variability
Rao and Wagenet ( 14 ) have proposed t h a t t h e t o t a l v a r i a b i l i t y

observed i n a given s o i l property i s t h e sum o f i n t r i n s i c and
extrinsic variability. The former a r i s e s from i n h e r e n t v a r i a b i l i t y
i n s o i l p r o p e r t i e s due t o p e d o g e n i c p r o c e s s e s , w h i l e t h e l a t t e r i s
t h e r e s u l t o f v a r i o u s s o i l and c r o p management p r a c t i c e s a t a
specific field site. They s u g g e s t e d t h a t t h e s p a t i a l v a r i a b i l i t y
i n s o i l p r o p e r t i e s such as s o i l h y d r a u l i c c o n d u c t i v i t y o r p e s t i c i d e
s o r p t i o n c o e f f i c i e n t s might be i n f l u e n c e d p r i m a r i l y by i n t r i n s i c
f a c t o r s , whereas v a r i a b i l i t y i n p e s t i c i d e c o n c e n t r a t i o n s and f l u x e s
might e x h i b i t t h e combined i n f l u e n c e o f b o t h i n t r i n s i c and e x t r i n -
sic factors. G i v e n d a t a on t o t a l v a r i a b i l i t y , i t i s n o t always
p o s s i b l e t o q u a n t i f y t h e c o n t r i b u t i o n s o f each t y p e o f v a r i a b i l i t y .
In t h i s paper, we w i l l p r e s e n t d a t a r e p r e s e n t i n g b o t h t y p e s o f
variability.
Extrinsic Variability
P e s t i c i d e s and f e r t i l i z e r s a r e u s u a l l y a p p l i e d a t t h e s o i l s u r f a c e
e i t h e r i n g r a n u l a r o r l i q u i d f o r m u l a t i o n s and a r e s u b s e q u e n t l y
i n c o r p o r a t e d by some s o r t o f t i l l a g e o p e r a t i o n ( e . g . , d i s c i n g ) .
T h i s o p e r a t i o n can i n d u c e e x t r i n s i c v a r i a b i l i t y i n a g r o c h e m i c a l
c o n c e n t r a t i o n s and f l u x e s i n s o i l s due t o v a r i a b i l i t y i n a p p l i c a -
t i o n i t s e l f (random i f b r o a d c a s t ; nonrandom i f banded) and t h e
t i l l a g e o p e r a t i o n . Weed s c i e n t i s t s have examined such v a r i a b i l i t y ,
i n p a r t i c u l a r as r e l a t e d t o h e r b i c i d e e f f i c a c y ( 15 - 21_ ). Such
e x t r i n s i c v a r i a b i l i t y i n p e s t i c i d e c o n c e n t r a t i o n s can a l s o pose
s e r i o u s problems i n o b t a i n i n g r e p r e s e n t a t i v e s o i l samples f o r
p e s t i c i d e concentration determinations.
A t t h e F l o r i d a f i e l d s i t e , we e v a l u a t e d t h e s i g n i f i c a n c e o f
t i l l a g e - i n d u c e d e x t r i n s i c v a r i a b i l i t y i n bromide ( B r ) and
a l d i c a r b * s t o t a l t o x i c r e s i d u e s (TTR) v a r i a b i l i t y .
Bromide was a p p l i e d i n a 3-m s t r i p c e n t e r e d between t h e c i t r u s
t r e e s t h a t were p l a n t e d about 8 m a p a r t . A c o n c e n t r a t e d KBr
s o l u t i o n was s p r a y e d on t h e s o i l s u r f a c e u s i n g a t r a c t o r - m o u n t e d
boom s p r a y r i g . The s p r a y n o z z l e s were s e t such t h a t s o l u t i o n
s p r a y from a d j a c e n t n o z z l e s o v e r l a p p e d and p r o v i d e d e s s e n t i a l l y a
uniform Br a p p l i c a t i o n . On t h e same 3-m s t r i p t o w h i c h Br was
a p p l i e d , a l d i c a r b (Temik 15-G; g r a n u l a r f o r m u l a t i o n ) was a p p l i e d i n
16 p a r a l l e l bands t h a t were spaced 20-cm a p a r t . Br and a l d i c a r b
were t h e n i n c o r p o r a t e d i n t o t h e s o i l t o a depth o f about 10 cm
u s i n g a t r a c t o r - m o u n t e d m u l t i p l e d i s k implement w i t h 24 d i s k s t h a t
were s e t about 12.5 cm a p a r t . Immediately f o l l o w i n g d i s c i n g , s o i l
samples were c o l l e c t e d t o a depth o f 30 cm as shown s c h e m a t i c a l l y
i n F i g u r e 1. Note t h a t a t o t a l o f 16 samples were t a k e n , 8 each on
two p a r a l l e l t r a n s e c t s s e t 0.67 m a p a r t and p e r p e n d i c u l a r t o t h e
a p p l i c a t i o n band. S o i l samples were c o l l e c t e d i n t h i s manner i n
each o f t h e f o u r q u a d r a n t s o f t h e f i e l d .
The v a r i a t i o n s i n Br and a l d i c a r b TTR c o n c e n t r a t i o n s a c r o s s
t h e a p p l i c a t i o n band a r e shown i n F i g u r e s 2 and 3. Note t h a t b o t h
Br and a l d i c a r b TTR c o n c e n t r a t i o n s a r e h i g h l y v a r i a b l e w i t h i n t h e
a p p l i c a t i o n band, w i t h s e v e r a l o r d e r s o f magnitude d i f f e r e n c e i n
c o n c e n t r a t i o n s even i n a d j a c e n t s o i l samples. Note t h a t even
though Br was a p p l i e d e s s e n t i a l l y u n i f o r m l y t o t h e s o i l s u r f a c e ,
t h e v a r i a t i o n s i n Br c o n c e n t r a t i o n s a r e q u i t e s i m i l a r t o t h a t o f
a l d i c a r b TTR c o n c e n t r a t i o n s . T h i s s u g g e s t s t h a t p o s t - a p p l i c a t i o n
d i s c i n g was t h e p r i m a r y s o u r c e o f t h e o b s e r v e d e x t r i n s i c v a r i a b i l i -
ty. These r e s u l t s a r e c o n s i s t e n t w i t h t h e f i n d i n g s o f o t h e r
workers ( 8, 18, 21^ ). We have a l s o o b s e r v e d s i m i l a r v a r i a b i l i t y
p a t t e r n s i n a l d i c a r b TTR c o n c e n t r a t i o n s i n f i e l d s t u d i e s conducted
d u r i n g 1983 a t two o t h e r l o c a t i o n s i n F l o r i d a ( 22 ). S o i l samples
c o l l e c t e d up t o 4-m depth d u r i n g 1983, and up t o a d e p t h o f 10 m i n
1984 showed t h a t such v a r i a b i l i t y w i l l p e r s i s t t h r o u g h o u t t h e y e a r
and a t a l l d e p t h s . We a r e p r e s e n t l y a n a l y z i n g o u r 1983 and 1984
a l d i c a r b and B r f i e l d d a t a i n o r d e r t o c a l c u l a t e a s t a t i s t i c a l l y
v a l i d "average" c o n c e n t r a t i o n s which can be, i n t u r n , compared w i t h
t h e v a l u e s p r e d i c t e d by s i m u l a t i o n models. A d i s c u s s i o n o f t h e s e
model v a l i d a t i o n e f f o r t s i s beyond t h e scope o f t h i s paper.
Intrinsic Variability i n PC and
V a r i a t i o n s i n OC v a l u e s i n s o i l samples c o l l e c t e d a l o n g t h e N-S and

W-E t r a n s e c t s a t t h e F l o r i d a s i t e a r e shown i n F i g u r e 4. Note t h a t
f o r both t h e t r a n s e c t s , OC i n s o i l s from t h e 0-15 cm depth were
more v a r i a b l e t h a n i n samples c o l l e c t e d from t h e 15-30 cm d e p t h .
V a r i o g r a m s ( 14 ) c a l c u l a t e d u s i n g t h e s e d a t a i n d i c a t e d t h a t f o r
t h e 0-15 cm depth, OC v a l u e s i n s o i l samples c o l l e c t e d w i t h i n a
s e p a r a t i o n d i s t a n c e ( i . e . , l a g ) o f 15 m would be s p a t i a l l y c o r r e -
lated. On t h e o t h e r hand, OC v a l u e s f o r t h e 15-30 cm d e p t h a r e
s p a t i a l l y independent. OC d a t a f o r b o t h depth i n c r e m e n t s c o u l d be
f i t t e d t o a normal f r e q u e n c y d i s t r i b u t i o n ; t h e n o r m a l i t y was
c o n f i r m e d by t h e Kolmogorov- Smirnov D - s t a t i s t i c ( 23 ). The
c o e f f i c i e n t o f v a r i a t i o n (CV) i n OC d a t a f o r both depths was l e s s
t h a n 20%.
The measured d a t a f o r OC and a l d i c a r b were used t o g e n e r a t e
3-dimensional p l o t s d e p i c t i n g t h e i r s p a t i a l v a r i a t i o n s a t t h e
Florida field site. These p l o t s , shown i n F i g u r e 5, i n d i c a t e a
c l o s e , b u t n o t e x a c t , c o r r e s p o n d e n c e i n t h e s p a t i a l p a t t e r n s o f OC
and K,. The OC d a t a and K, v a l u e s f o r t h r e e p e s t i c i d e s measured
FIGURE 1. Schematic diagram showing t h e s a m p l i n g

d e s i g n used t o e v a l u a t e t h e e x t r i n s i c v a r i a b i l i t y
i n bromide and a l d i c a r b TTR c o n c e n t r a t i o n s a t t h e
Florida site.
6. RAO ET AL. Spatial Variability of Pesticide Parameters 105
Sampling Date : Feb 1 4 , 8 4

Across T r e a t m e n t Band
NW Quadrant
40
30
20
10
0
1.5 3.0 4.5 1.5 3.0 4.5
\ DISTANCE, meters
m SE Quadrant SW Quadrant
1.5 3.0 4.5 1.5 3.0 4.5
DISTANCE, meters
FIGURE 2. V a r i a t i o n s i n bromide ( B r ) c o n c e n t r a -
t i o n s i n s o i l samples t a k e n a c r o s s t h e a p p l i c a t i o n
band. V e r t i c a l arrows i n d i c a t e t h e w i d t h o f t h e
a p p l i c a t i o n band.
Sampling D a t e : Feb 1 4 , 8 4
A c r o s s T r e a t m e n t Band
NE Q u a d r a n t 15,720 SE Quadrant
1000
bO
1.5 3.0 4.5 1.5 3.0 4.5
CO
CO

ce
NW Q u a d r a n t 2946 SW Quadrant
2000
1000
1.5 3.0 4.5 0 1.5 3.0 4.5
DISTANCE, meters
FIGURE 3. V a r i a t i o n s i n a l d i c a r b TTR c o n c e n t r a t i o n s
i n s o i l samples t a k e n a c r o s s t h e a p p l i c a t i o n band.
V e r t i c a l arrows i n d i c a t e t h e w i d t h o f t h e
a p p l i c a t i o n band.
0 - 1 5 cm W-E TRANSECT
0.5-]
I 5 - 3 0 cm
0.4
0.3
0.2
2 . -!
\ 1
20 40 60 80 100

- 5 cm N-S TRANSECT
0.5-J
1 5 -3 o0 w cm
t >J tm A
0.2-
. I
~~I 1 1 1 1 1 1 1 1 -
0 20 40 60 80 100
D I S T A N C E ALONG T R A N S E C T , meters
FIGURE 4. V a r i a t i o n s i n s o i l o r g a n i c c a r b o n c o n t e n t
(OC) a t two depths (0-15 and 15-30 cm) i n samples
t a k e n a l o n g two t r a n s e c t s a t t h e F l o r i d a s i t e .
u s i n g t h e s u r f a c e s o i l (0-20 cm) samples c o l l e c t e d a t t h e G e o r g i a

s i t e a r e p r e s e n t e d i n F i g u r e 6; t h e s e p l o t s were g e n e r a t e d i n
manner s i m i l a r t o t h o s e shown i n F i g u r e 5. As w i t h t h e d a t a f o r
t h e F l o r i d a s i t e , s p a t i a l p a t t e r n s i n p e s t i c i d e K, v a l u e s and OC
values are very s i m i l a r . These r e s u l t s may be a n t i c i p a t e d because
OC i s t h e s i n g l e most i m p o r t a n t d e t e r m i n a n t o f for nonionic
p e s t i c i d e s ( 1, 24 - 2 6 ) . Thus, i t would appear t h a t g i v e n a
v a l u e r e f e r e n c e d t o OC, denoted as , the s p a t i a l v a r i a t i o n s i n
j f o r a p e s t i c i d e a t a f i e l d s i t e may be e s t i m a t e d by m e a s u r i n g
t h e v a r i a t i o n s i n OC. Green e t a l . ( 27 ) p r e s e n t d a t a f o r
nematicide s o r p t i o n to support t h i s c o n c l u s i o n .
I n t r i n s i c V a r i a b i l i t y of Degradation H a l f - L i v e s
On t h e b a s i s o f an a n a l y s i s o f p u b l i s h e d d a t a , Rao and D a v i d s o n
( 1_1 ) n o t e d t h a t f o r s e v e r a l p e s t i c i d e s t h e v a r i a t i o n i n p e s t i c i d e
degradation h a l f - l i v e s (two) among s e v e r a l s o i l s was s u r p r i s i n g l y

s m a l l (CV < 100%), e s p e c i a l l y g i v e n t h e range i n s o i l t y p e s and t h e
e n v i r o n m e n t a l c o n d i t i o n s a t w h i c h d e g r a d a t i o n was measured. Data
c o l l e c t e d by Ou e t a l . ( 28 ) f o r d e g r a d a t i o n o f s e v e r a l p e s t i c i d e s
i n s e l e c t e d U.S. s o i l s c o n f i r m e d t h i s o b s e r v a t i o n . More r e c e n t l y ,
Walker and Brown ( 29 ) measured t h e d e g r a d a t i o n o f two t r i a z i n e
h e r b i c i d e s i n s o i l samples c o l l e c t e d from s e v e r a l l o c a t i o n s w i t h i n
a 0.64-ha f i e l d . They r e p o r t e d a s m a l l v a r i a t i o n i n t . ,^ v a l u e s
(CV < 25 %) f o r b o t h h e r b i c i d e s . D a t a p r e s e n t e d by Walker and
Z i m d h a l ( 30 ) i n d i c a t e t h a t t h e h a l f - l i v e s f o r p e s t i c i d e degrada
t i o n i n s o i l s c o l l e c t e d from t h r e e s t a t e s i n t h e U.S. d i d n o t v a r y
by more t h a n a f a c t o r o f 2. I t s h o u l d be n o t e d t h a t i n a l l o f t h e
above c i t e d s t u d i e s p e s t i c i d e d e g r a d a t i o n was measured i n s o i l s
t h a t had been a i r - d r i e d and r e - w e t t e d t o some d e s i r e d s o i l - w a t e r
c o n t e n t . I n h e r e n t d i f f e r e n c e s i n t h e d i v e r s i t y and t h e s i z e o f
m i c r o b i a l p o p u l a t i o n s may have been r e d u c e d by a i r - d r y i n g t h e
s o i l s , w h i c h c o u l d e x p l a i n t h e absence o f s i g n i f i c a n t v a r i a b i l i t y
i n laboratory-measured p e s t i c i d e degradation r a t e s .
I n c o n t r a s t t o measuring OC o r v a l u e s , t h e measurement o f
n
p e s t i c i d e degradation h a l f - l i v e s ( ) ^ s o i l s i s a much more
d i f f i c u l t and time-consuming t a s k . Hence, t h e s p a t i a l v a r i a t i o n s
i n t - i 2 c o u l d n o t be a s s e s s e d i n as much d e t a i l as we d i d w i t h OC
and ,. M e t o l a c h l o r and a l d i c a r b TTR h a l f - l i v e s were measured i n a
s e l e c t e d number o f s o i l samples c o l l e c t e d from t h e G e o r g i a f i e l d
site. S o i l samples were s e l e c t e d t o r e p r e s e n t t h e t h r e e major s o i l
s e r i e s p r e s e n t a t t h e s i t e ( C l a r e n d o n , A r d i l l a , and T i f t o n ) and t h e
f o u r major m o r p h o l o g i c s o i l h o r i z o n s (0-20, 25-46, 48-63, and
94-107 cm) w i t h i n t h e c r o p r o o t zone. S o i l samples c o l l e c t e d from
4 depths a t 10 s i t e s were u s e d t o c h a r a c t e r i z e a l d i c a r b TTR d e g r a
dation rates. M e t o l a c h l o r h a l f - l i v e s were measured i n s o i l s t a k e n
from f o u r d e p t h s a t one s i t e f o r each s o i l s e r i e s and a l s o i n
samples c o l l e c t e d a t two depths (0-20 cm and 94-107 cm) a t 6 s i t e s .
The d a t a f o r o b s e r v e d v a r i a t i o n s i n m e t o l a c h l o r t . ,^ a r e
p r e s e n t e d i n T a b l e I . Of t h e t h r e e sampling s i t e s w i t n m t h e
C l a r e n d o n s e r i e s , t h e s h o r t e s t d i s t a n c e between two s i t e s (G-13 t o
K-15) was about 60 m, w h i l e t h e s i t e s K-15 and H-9 were t h e f a r
t h e s t , l o c a t e d about 100 m from each o t h e r . Of t h e f i v e s a m p l i n g
l o c a t i o n s , t h e g r e a t e s t s e p a r a t i o n d i s t a n c e was about 200 m between
J-4 ( T i f t o n ) and J-18 ( A r d i l l a ) . M e t o l a c h l o r t , v a l u e s measured
1 n
RAO ET A L . Spatial Variability of Pesticide Parameters 109
A : ORGANIC CARBON CONTENT
B : ALDICARB K D
FIGURE 5. S p a t i a l v a r i a t i o n s i n s o i l o r g a n i c c a r b o n
c o n t e n t (OC) and a l d i c a r b s o r p t i o n c o e f f i c i e n t
(K. ) a t t h e F l o r i d a s i t e .
A : ORGANIC CARBON CONTENT : ALDICARB K d
C : METOLACHLOR K d D: DIURON K d
FIGURE 6. S p a t i a l v a r i a t i o n s i n OC and K, v a l u e s f o r
t h r e e p e s t i c i d e s ( a l d i c a r b , m e t o l a c h l o r , and d i u r o n )
at the Georgia s i t e .
i n a l l s u r f a c e s o i l s (0-20 cm) were e s s e n t i a l l y i d e n t i c a l . The

t / 1 ?v a l u e s a r e l a r g e r by about a f a c t o r o f 2 f o r t h e s u b s o i l s
(25-46, 48-63, 94-107 cm) and t e n d t o be more v a r i a b l e (CV < 3 8 % ) .
The m e t o l a c h l o r h a l f - l i v e s shown i n T a b l e I a r e s m a l l e r t h a n t h o s e
r e p o r t e d by e a r l i e r workers ( 30, 31^ ).
Table I. V a r i a t i o n s i n Metolachlor Degradation H a l f - L i v e s

( d a y s ) Measured i n S o i l s from t h e G e o r g i a S i t e
S o i l Depth Increment (cm)

Soil Series
0-20 25-46 48-63 94-107
C l a r e n d o n (G-13) 19 17 ^ 44 41
C l a r e n d o n (H- 9) 19 N.D. N.D. 35
C l a r e n d o n (K-15) 17 N.D. N.D. 20
Ardilla (J-18) 18 34 44 53
Ardilla (B-13) 14 N.D. N.D. 68
Tifton (J-4) 19 31 39 41
Average 18 27 42 43
CV (%) 11 33 7 38
* Code f o r s a m p l i n g l o c a t i o n on an a r b i t r a r y grid
** Not d e t e r m i n e d
Table I I . V a r i a t i o n s i n A l d i c a r b TTR H a l f - L i v e s ( d a y s )
Measured i n S o i l s from t h e G e o r g i a S i t e
S o i l Depth S o i l Series Average

(cm)
Clarendon Ardilla Tifton
0-20 42 (26) 45 (24) 37 (11) 42 (21)

25-46 51 (26) 44 (46) 28 (25) 42 (38)
48-63 51 (26) 47 (36) 39 (13) 47 (26)
94-107 67 (21) 54 (30) 63 ( 5) 62 (21)
Average 53 (28) 48 (30) 42 (34) 48 (31)
* numbers i n p a r e n t h e s i s a r e % CV
The measured v a r i a b i l i t y i n a l d i c a r b TTR d e g r a d a t i o n

h a l f - l i v e s a r e summarized i n T a b l e I I . Data shown f o r C l a r e n d o n
s o i l were a v e r a g e d o v e r 4 s i t e s , and t h e v a l u e s f o r A r d i l l a and
T i f t o n s o i l s a r e averages f o r 3 s i t e s . Among t h e s a m p l i n g s i t e s ,
J-4 and J-18 were t h e f a r t h e s t a p a r t (about 233 m), whereas t h e
s i t e s 1-15 and K-15 were t h e c l o s e s t (about 30 m). The g r e a t e s t
d i s t a n c e between two sampling s i t e s w i t h i n a s o i l s e r i e s was: 126 m

f o r C l a r e n d o n ; 157 m f o r A r d i l l a ; and 195 m f o r T i f t o n . The
v a r i a t i o n s i n a l d i c a r b TTR t - , ^ v a l u e s w i t h d e p t h and l o c a t i o n a r e
somewhat l a r g e r (CV < 50%) t h a n t h o s e f o r m e t o l a c h l o r t - / ^ .
However, t h e v a r i a t i o n i n TTR t - , ~ v a l u e s w i t h i n a s o i l s e r i e s a r e
e q u a l t o o r l a r g e r t h a n t h e v a r i a t i o n s among t h e s e r i e s . An o v e r a l l
average t- ,~ f o r a l d i c a r b TTR d e g r a d a t i o n i n t h e s e s o i l s ( T a b l e I I )
was 48 days (CV = 31 % ) .
I t s h o u l d be n o t e d t h a t i n o u r s t u d y , s o i l samples c o l l e c t e d
from t h e f i e l d were s t o r e d a t t h e same water c o n t e n t a t w h i c h t h e y
were sampled. P e s t i c i d e d e g r a d a t i o n was measured i n t h e s e s o i l s
under i d e n t i c a l e n v i r o n m e n t a l c o n d i t i o n s ( i . e . , s u b s t r a t e concen
t r a t i o n , a e r a t i o n s t a t u s , t e m p e r a t u r e , and s o i l - w a t e r content).
Thus, t h e l a c k o f s p a t i a l v a r i a b i l i t y i n p e s t i c i d e d e g r a d a t i o n
rates suggests that the inherent c a p a c i t y o f the s o i l microorgan
isms t o degrade t h e s e p e s t i c i d e s might be s i m i l a r a t t h e G e o r g i a
site. T h i s does n o t n e c e s s a r i l y imply t h a t t h e a c t u a l i n s i t u

d e g r a d a t i o n r a t e s would n o t v a r y s p a t i a l l y o r t e m p o r a l l y w i t h i n a
field. L o c a l s o i l e n v i r o n m e n t a l f a c t o r s may be e x p e c t e d t o v a r y as
a r e s u l t o f s p a t i a l and t e m p o r a l v a r i a t i o n s i n o t h e r s o i l p r o p e r
t i e s as w e l l as v a r i a t i o n s i n c r o p / s o i l management p r a c t i c e s
( i r r i g a t i o n , r a i n f a l l , f e r t i l i z a t i o n , e t c . ) . Thus, a knowledge o f
t h e r e l a t i o n s h i p between p e s t i c i d e d e g r a d a t i o n r a t e s and s o i l
e n v i r o n m e n t a l f a c t o r s and t h e v a r i a b i l i t y o f t h e s e f a c t o r s i n a
f i e l d i s necessary f o r p r e d i c t i n g the s p a t i a l v a r i a b i l i t y of
p e s t i c i d e residue concentrations. We a r e n o t aware o f any pub
l i s h e d data f o r assessing i n s i t u s p a t i a l v a r i a t i o n s i n p e s t i c i d e
degradation rates. Such d a t a have been c o l l e c t e d f o r s p a t i a l
v a r i a t i o n s i n d e n i t r i f i c a t i o n r a t e s ( 32, 33> ) .
S o i l - w a t e r c o n t e n t () and t e m p e r a t u r e ( T ) a r e t h e two major
s o i l environmental f a c t o r s that c o n t r o l p e s t i c i d e degradation
rates. Walker ( 34 ) and Walker and Barnes ( 35 ) have p r o p o s e d a
model f o r p e s t i c i d e p e r s i s t e n c e i n s o i l s . I n t h e i r model t h e
=
-depgndence o f t ^ ,^ i s d e s c r i b e d by a power f u n c t i o n ^^,^
, where A and a r e c o n s t a n t s ] , w h i l e t h e r e l a t i o n s h i p
between t ^ y ^ and i s d e s c r i b e d by t h e A r r h e n i u s e q u a t i o n . Walker
and co-workers ( 36 - 40 ) d e t e r m i n e d t h e v a l u e s o f t h e n e c e s s a r y
model p a r a m e t e r s from l a b o r a t o r y measurements o f p e s t i c i d e degrada
t i o n under c o n t r o l l e d c o n d i t i o n s . These parameter v a l u e s and
weather d a t a were used as model i n p u t s t o p r e d i c t t h e p e r s i s t e n c e
of s e v e r a l p e s t i c i d e s i n f i e l d p l o t s a t s e v e r a l l o c a t i o n s . Walker
e t a l . ( 41 ) summarized t h e r e s u l t s o f an i n t e r n a t i o n a l c o o p e r a
t i v e s t u d y , i n which s i m a z i n e h e r b i c i d e d e g r a d a t i o n was measured i n
s o i l s c o l l e c t e d from 21 l o c a t i o n s i n 11 c o u n t r i e s . As i n e a r l i e r
s t u d i e s ( 36 - 40 ) , model parameters were e s t i m a t e d on t h e b a s i s
l a b o r a t o r y s t u d i e s , and were used t o p r e d i c t s i m a z i n e p e r s i s t e n c e
i n f i e l d p l o t s a t 16 l o c a t i o n s . They a l s o s i m u l a t e d s i m a z i n e
d e g r a d a t i o n i n f i e l d p l o t s a t 5 o t h e r l o c a t i o n s f o r w h i c h companion
l a b o r a t o r y d a t a were n o t a v a i l a b l e . I n a l l t h e s e s t u d i e s ( 36 -
41 ), t h e model g e n e r a l l y u n d e r e s t i m a t e d t h e amount o f p e s t i c i d e
residues remaining i n t h e s o i l . Walker and co-workers c o n s i d e r e d
t h e model t o be s u f f i c i e n t l y a c c u r a t e f o r p r a c t i c a l a p p l i c a t i o n s
g i v e n t h e u n c e r t a i n t i e s i n measured p e s t i c i d e c o n c e n t r a t i o n s and
the p o s s i b i l i t y t h a t processes other than m i c r o b i a l degradation
( e . g . , l e a c h i n g p a s t t h e s a m p l i n g depth; v o l a t i l i z a t i o n ; and
c h e m i c a l o r p h o t o l y t i c d e g r a d a t i o n ) may have been r e s p o n s i b l e f o r

pesticide dissipation.
Summary
We have attempted t o show t h a t b o t h i n t r i n s i c and e x t r i n s i c f a c t o r s

c o n t r i b u t e t o t h e o b s e r v e d s p a t i a l v a r i a b i l i t y i n p e s t i c i d e concen-
trations. The method o f p e s t i c i d e a p p l i c a t i o n and subsequent
t i l l a g e o p e r a t i o n s can have a major impact on t h e e x t r i n s i c v a r i -
a b i l i t y i n t h e measured p e s t i c i d e c o n c e n t r a t i o n s and f l u x e s . Such
v a r i a b i l i t y needs t o be t a k e n i n t o a c c o u n t i n d e s i g n i n g s o i l
s a m p l i n g s t r a t e g i e s and i n i n t e r p r e t i n g t h e f i e l d d a t a . Intrinsic
v a r i a b i l i t y i n p e s t i c i d e s o r p t i o n and d e g r a d a t i o n p a r a m e t e r s
appears t o be s m a l l (CV < 3 0 % ) . Because p e s t i c i d e s o r p t i o n c o e f f i -
c i e n t s a r e s t r o n g l y c o r r e l a t e d t o s o i l o r g a n i c carbon c o n t e n t s ,
t h e r e i s a c l o s e c o r r e s p o n d e n c e between t h e measured s p a t i a l
d i s t r i b u t i o n s o f OC and K^. Thus, a f i e l d - a v e r a g e v a l u e may be

e s t i m a t e d g i v e n t h e average OC v a l u e . P e s t i c i d e degradation rates
i n s o i l samples c o l l e c t e d from d i f f e r e n t l o c a t i o n s and s u b j e c t e d t o
i d e n t i c a l e n v i r o n m e n t a l c o n d i t i o n s were n o t v a r i a b l e . However, i n
s i t u d e g r a d a t i o n r a t e s may v a r y as f u n c t i o n o f v a r i a t i o n s i n s o i l
environmental c o n d i t i o n s .
Acknowledgments
F i n a n c i a l s u p p o r t f o r t h i s s t u d y was p r o v i d e d , i n p a r t , by t h e
C o o p e r a t i v e Agreement No. CR-810464 between t h e U.S. E n v i r o n m e n t a l
P r o t e c t i o n Agency and t h e U n i v e r s i t y o f F l o r i d a ; and a g r a n t from
t h e Union C a r b i d e A g r i c u l t u r a l P r o d u c t s Co., I n c . A s s i s t a n c e o f
R.F. C a r s e l and C.N. Smith, AERL, USEPA, Athens, GA; Ms. S.C.
Cooper, USGS, A l b a n y , GA; and J . F . McNabb, RSKERL, USEPA, Ada, OK
i n c o l l e c t i n g t h e s o i l samples a t t h e G e o r g i a s i t e i s acknowledged.
R.L. Jones and R.R. Romine, U n i o n C a r b i d e , a s s i s t e d i n c o l l e c t i n g
t h e s o i l samples a t t h e F l o r i d a s i t e and a n a l y z e d t h e samples f o r
bromide ancjlâldicarb TTR. We a r e g r a t e f u l t o Union C a r b i d e f o r
Ojroviding C - a l d i c a r b and t o C i b a - G e i g y f o r s u p p l y i n g
C - m e t o l a c h l o r used i n t h e s o r p t i o n and d e g r a d a t i o n s t u d i e s .
F i n a l l y , we a p p r e c i a t e Ms. L i n d a Lee's a s s i s t a n c e i n d a t a a n a l y s i s
and i n d r a f t i n g t h e f i g u r e s .
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7
Applications of Surface Geophysical Methods
to Ground Water Pollution Investigations
Nicholas De Rose
Roy F. Weston, Inc., Raritan Center, Edison, NJ 08837
Several surface geophysical survey methods are pre-

sented and the principles of operation for each tech-
nique discussed. These methods include seismic

refraction, resistivity, electromagnetic conductivity,
ground penetrating radar and magnetometry. Applica-
tions of these geophysical methods to groundwater
contamination investigations include; determining
lateral and vertical variations in soil, rock and
groundwater characteristics; mapping the extent of
groundwater contaminants present within aquifers; and
locating buried objects. The suitability and potential
application of surface geophysical surveys to monitor
the migration of field-applied pesticides, and pesti-
cides from waste disposal sites within the unsaturated
and saturated zones is also discussed. An example to
illustrate the use of geophysical techniques at a
hypothetical pesticide field-application site is out-
lined. The example details the application of seismic
refraction and electromagnetic conductivity techniques
to define erratic subsurface conditions at a site where
groundwater contamination is suspected. The site is
underlain by an unconsolidated deposit of varying
thickness and composition which is underlain by caver-
nous limestone. A groundwater monitoring system is
designed based upon interpretation of the geophysical
data obtained. By utilizing surface geophysical
methods, extensive site coverage can be completed cost
effectively and groundwater monitoring systems designed
efficiently, thereby increasing the quality and success
of site groundwater investigations.
The s c i e n c e o f g e o p h y s i c s was o r i g i n a l l y d e v e l o p e d as t h e s t u d y o f
1
the p h y s i c s o f t h e e a r t h s s t r u c t u r e and shape. G e o p h y s i c s i n c l u d e s
measuring g r a v i t a t i o n a l , e l e c t r i c a l , e l e c t r o m a g n e t i c and magnetic
f i e l d s , and r e c o r d i n g s e i s m i c v i b r a t i o n s t o i d e n t i f y c o m p o s i t i o n a l
f
and s t r u c t u r a l f e a t u r e s o f t h e e a r t h . Developments from t h e 1 9 2 0 s
0097-6156/ 86/0315-0118S06.75 / 0
7. D E R O S E Applications of Surface Geophysical Methods 119
through lSO's r e s u l t e d i n the a p p l i c a t i o n o f g e o p h y s i c a l methods t o

l o c a t e p o t e n t i a l m i n e r a l resource deposits i n c l u d i n g petroleum-
b e a r i n g g e o l o g i c s t r u c t u r e s and m e t a l l i c o r e b o d i e s . More r e c e n t
advancements i n a p p l i e d g e o p h y s i c s have produced equipment and t e c h -
nology which a r e e a s i l y a c c e s s i b l e to p r o f e s s i o n a l c o n s u l t a n t s ,
i n d u s t r y and government through s e v e r a l r e l i a b l e m a n u f a c t u r e r s and
s c i e n t i f i c equipment s u p p l i e r s .
The f i e l d p o r t a b i l i t y , c o s t - e f f e c t i v e n e s s , and a b i l i t y t o c o l l e c t
d a t a w h i c h does n o t r e q u i r e o b t a i n i n g a c t u a l samples o f s u b s u r f a c e
material provides several considerations f o r incorporating surface
g e o p h y s i c a l s u r v e y s i n t o groundwater contaminant i n v e s t i g a t i o n
programs ( 1 ) . As p a r t o f a p r e l i m i n a r y s i t e i n v e s t i g a t i o n , s u r f a c e
g e o p h y s i c a l s u r v e y s may be conducted t o i d e n t i f y p o t e n t i a l t r e n d s o r
anomalous a r e a s p r i o r t o s e l e c t i n g t h e l o c a t i o n s o f s a m p l i n g p o i n t s
f o r t h e m o n i t o r i n g system. U t i l i z i n g g e o p h y s i c a l s u r v e y s t o s c r e e n
a r e a s o f i n v e s t i g a t i o n w i l l i n c r e a s e t h e e f f e c t i v e n e s s o f t h e moni-
t o r i n g systems and s i t e e v a l u a t i o n by p r o v i d i n g a g e o p h y s i c a l - d a t a
base f o r c o r r e l a t i o n w i t h samples o b t a i n e d i n t h e f i e l d and a n a l y t i -
c a l d a t a from t h e l a b o r a t o r y ( 2 ) .
Surface Geophysical Survey T e c h n i q u e s
T h i s paper d i s c u s s e s f i v e o f t h e most w i d e l y used t e c h n i q u e s f o r con-

d u c t i n g groundwater contaminant i n v e s t i g a t i o n s . They a r e c h a r a c t e r -
i z e d by r e l a t i v e l y s i m p l e o p e r a t i o n a l p r i n c i p l e s , f i e l d p r o c e d u r e s ,
and d a t a a n a l y s e s and i n t e r p r e t a t i o n . The f i v e s u r f a c e t e c h n i q u e s
include: s e i s m i c r e f r a c t i o n , ground p e n e t r a t i n g r a d a r , e l e c t r i c a l
r e s i s t i v i t y , e l e c t r o m a g n e t i c c o n d u c t i v i t y and magnetometry. Seismic
r e f r a c t i o n and ground p e n e t r a t i n g r a d a r b o t h i d e n t i f y s u b s u r f a c e
i n t e r f a c e s w h i c h a r e used t o d e t e r m i n e t h e t h i c k n e s s and d e p t h o f
m a t e r i a l s and t o l o c a t e i s o l a t e d b u r i e d o b j e c t s . E l e c t r i c a l r e s i s -
t i v i t y , e l e c t r o m a g n e t i c c o n d u c t i v i t y , and magnetometry i d e n t i f y
l a t e r a l and v e r t i c a l v a r i a t i o n s i n s u b s u r f a c e g e o l o g i c f o r m a t i o n s
by l o c a t i n g l a t e r a l and v e r t i c a l v a r i a t i o n s i n b u l k e l e c t r i c a l , and
magnetic p r o p e r t i e s o f the subsurface m a t e r i a l s .
V a l i d i n t e r p r e t a t i o n s of geophysical data c o l l e c t e d i n the f i e l d
r e q u i r e c o r r e l a t i o n w i t h i n f o r m a t i o n o b t a i n e d from b o t h c o n v e n t i o n a l
sampling and a n a l y t i c a l programs. The t y p e s o f g e o p h y s i c a l and
c o n v e n t i o n a l d a t a r e q u i r e d t o d e s c r i b e t h e s u b s u r f a c e environment
w i l l v a r y , depending upon t h e p h y s i c a l , c h e m i c a l , and s t r u c t u r a l
c o m p l e x i t y o f t h e s u b s u r f a c e , and t h e i n t e n d e d a p p l i c a t i o n o f t h e
f i e l d study.
S e i s m i c R e f r a c t i o n . S e i s m i c methods a r e u s e f u l t o o l s i n d e t e r m i n i n g
the t h i c k n e s s and d e p t h o f g e o l o g i c u n i t s . I n a d d i t i o n , the v e l o c i t y
w i t h w h i c h s e i s m i c waves a r e e i t h e r r e f l e c t e d o r r e f r a c t e d i s an
i n d i c a t i o n of the p h y s i c a l p r o p e r t i e s of the subsurface m a t e r i a l s .
S e i s m i c r e f r a c t i o n s u r v e y s c o n s i s t o f t r a n s m i t t i n g a wave i n t o t h e
s u b s u r f a c e by means o f an a c o u s t i c s o u r c e . The wave t r a v e l s t h r o u g h
the s u b s u r f a c e i n a l l d i r e c t i o n s and a t d i f f e r i n g v e l o c i t i e s u n t i l
c o n t a c t i s made w i t h a g e o l o g i c i n t e r f a c e . The wave i s r e f r a c t e d
to t h e s u r f a c e and r e c e i v e d by an a r r a y o f geophones. The t r a v e l
time o f t h e r e f r a c t e d wave i s r e c o r d e d on a s e i s m o g r a p h . F i g u r e 1
p r e s e n t s a s c h e m a t i c c r o s s s e c t i o n o f a l l t h e components used t o
conduct a s e i s m i c r e f r a c t i o n survey t o determine the t h i c k n e s s of

l a y e r V-j^ w h i c h o v e r l i e s l a y e r V .
2
The seismograph p r o d u c e s a s e i s m i c r e c o r d w h i c h g r a p h i c a l l y
d e p i c t s a l l t h e v i b r a t i o n s r e c e i v e d a t each geophone d u r i n g t h e s u r -
vey. The s e i s m i c r e c o r d i s i n t e r p r e t e d t o i d e n t i f y t h e " t r a v e l t i m e "
of t h e s e i s m i c wave from t h e a c o u s t i c s o u r c e t o e a c h geophone.
T r a v e l times o f r e f r a c t e d waves a r e i d e n t i f i e d on t h e s e i s m i c r e c o r d
as " f i r s t a r r i v a l s " a t each geophone, and they a r e dependent upon t h e
d e p t h t o w h i c h t h e r e f r a c t e d wave t r a v e l e d , and t h e s e i s m i c v e l o c i t y
of t h e wave ( 3 ) .
F i r s t a r r i v a l times a t each geophone a r e p l o t t e d on a r i t h m e t i c
graph paper as time v s d i s t a n c e p l o t s f o r d a t a i n t e r p r e t a t i o n ( F i g u r e
2). The t r a v e l times and c o r r e s p o n d i n g d i s t a n c e s a t each geophone
w i l l g e n e r a l l y p l o t a l o n g one o f s e v e r a l l i n e a r segments on t h e
graph. The s l o p e o f each l i n e a r segment c o r r e s p o n d s t o t h e s e i s m i c
v e l o c i t y o f each s e i s m i c l a y e r . The v e l o c i t y and e i t h e r t h e i n t e r -
c e p t time o r t h e c r i t i c a l d i s t a n c e a r e used t o c a l c u l a t e t h e d e p t h t o
the i n t e r f a c e between t h e l a y e r s ( F i g u r e 2 ) .
Seismic v e l o c i t i e s a r e d i r e c t l y r e l a t e d to m a t e r i a l d e n s i t y .
B u l k d e n s i t i e s may v a r y a s a r e s u l t o f c o m p o s i t i o n , w a t e r c o n t e n t ,
age and d e p t h , w e a t h e r i n g , f r a c t u r i n g , and degree and type o f c o n -
solidation. D i f f e r e n t s o i l and r o c k types a r e c h a r a c t e r i z e d by
c e r t a i n overlapping ranges i n s e i s m i c v e l o c i t y . By c o r r e l a t i n g
o b s e r v e d d a t a w i t h i n f o r m a t i o n o b t a i n e d from c o n v e n t i o n a l s t u d i e s ,
the t y p e s and d i s t r i b u t i o n o f g e o l o g i c u n i t s p r e s e n t may be i n t e r -
p r e t e d ( 2 ) . The most common a p p l i c a t i o n o f s e i s m i c r e f r a c t i o n
s u r v e y s i n groundwater c o n t a m i n a n t i n v e s t i g a t i o n s i s t o d e f i n e t h e
t h i c k n e s s o f t h e o v e r b u r d e n ( s o i l ) and t o map the s t r a t i g r a p h y .
L i m i t a t i o n s t o c o n s i d e r when e v a l u a t i n g t h e s u i t a b i l i t y o f t h e
s e i s m i c r e f r a c t i o n method f o r a g i v e n s i t e i n c l u d e t h e f o l l o w i n g :
(1) s u b s u r f a c e l a y e r s o f l i m i t e d t h i c k n e s s ( g e n e r a l l y l e s s t h a n f i v e
f e e t ) a r e n o t d e t e c t e d ; (2) s u f f i c i e n t c o n t r a s t i n s e i s m i c v e l o c i -
t i e s ( b u l k d e n s i t y ) between s u b s u r f a c e l a y e r s must be p r e s e n t f o r t h e
a c c u r a t e l o c a t i o n o f i n t e r f a c e s ; (3) b u l k d e n s i t i e s o f s u b s u r f a c e
m a t e r i a l s must i n c r e a s e w i t h d e p t h .
Electrical Resistivity. Bulk e l e c t r i c a l r e s i s t i v i t i e s of subsurface

m a t e r i a l s a r e d e t e r m i n e d by i n j e c t i n g an e l e c t r i c c u r r e n t i n t o t h e
ground by a p a i r o f e l e c t r o d e s and m e a s u r i n g t h e r e s u l t i n g drop i n
v o l t a g e t h r o u g h t h e ground by a second p a i r o f e l e c t r o d e s ( F i g u r e 3 ) .
The magnitude o f t h e v o l t a g e drop depends upon t h e l i t h o l o g y ,
m o i s t u r e c o n t e n t and c o n c e n t r a t i o n s o f d i s s o l v e d s o l i d s i n p o r e
water o f t h e s u b s u r f a c e m a t e r i a l s . By v a r y i n g t h e s p a c i n g and
p o s i t i o n o f t h e e l e c t r o d e a r r a y , l a t e r a l and v e r t i c a l r e s i s t i v i t y
t r e n d s c a n be d e t e r m i n e d . R e s u l t s from a r e s i s t i v i t y s u r v e y c a n be
used t o (1) map l a t e r a l and v e r t i c a l v a r i a t i o n s i n t h e t h i c k n e s s e s
o f s u b s u r f a c e m a t e r i a l s w i t h s i m i l a r r e s i s t i v i t i e s ; (2) d e l i n e a t e
r e s i s t i v i t y b o u n d a r i e s a s s o c i a t e d w i t h v a r i a t i o n s i n groundwater
q u a l i t y ; and (3) i d e n t i f y waste b u r i a l a r e a s o r l o c a t e b u r i e d t a n k s
a s s o c i a t e d w i t h l o c a l r e s i s t i v i t y anomalies ( 2 ) .
F i e l d s u r v e y s a r e c o n d u c t e d t o complete e i t h e r l a t e r a l p r o f i l e s
or v e r t i c a l e l e c t r i c a l s o u n d i n g s (VES). R e s i s t i v i t y p r o f i l e s are
completed by u t i l i z i n g a f i x e d e l e c t r o d e s p a c i n g and o b t a i n i n g an
e l e c t r i c a l r e s i s t i v i t y v a l u e a t each s e l e c t e d s t a t i o n a l o n g t h e
7. D E ROSE Applications of Surface Geophysical Methods 121
F i g u r e 2. Time v s . d i s t a n c e p l o t o f " f i r s t a r r i v a l s " f o r

s e i s m i c r e f r a c t e d waves a t c o r r e s p o n d i n g geophones.
p r o f i l e traverse (Figure 4). A number o f p r o f i l e s may be completed

t o c o n s t r u c t a r e s i s t i v i t y map of an e n t i r e s i t e or of s e l e c t e d
features at a s i t e . L a t e r a l v a r i a t i o n s i n subsurface e l e c t r i c a l
r e s i s t i v i t y may be used t o a s s e s s : (1) changes i n groundwater q u a l i -
t y ; (2) groundwater contaminant plumes and s a l t w a t e r i n t r u s i o n ; and
(3) v a r i a t i o n s i n the c o m p o s i t i o n o f s u b s u r f a c e m a t e r i a l s ( 2 ) .
V e r t i c a l e l e c t r i c a l s o u n d i n g s a r e completed by m e a s u r i n g a
s e r i e s o f e l e c t r i c a l r e s i s t i v i t y v a l u e s a t one l o c a t i o n . Each
measured v a l u e c o r r e s p o n d s t o one o f a s e r i e s of s e l e c t e d e l e c t r o d e
spacings. The r e s u l t i n g s e t of e l e c t r i c a l r e s i s t i v i t y v a l u e s ob-
t a i n e d a t each VES s t a t i o n a r e g e n e r a l l y p l o t t e d a g a i n s t e l e c t r o d e
s p a c i n g to p r o d u c e sounding c u r v e s t h a t may be e m p i r i c a l l y e v a l u a t e d
to i d e n t i f y trends (Figure 4 ) . The d a t a may a l s o be s o l v e d g r a p h i -
c a l l y by u s i n g master c u r v e s to d e t e r m i n e r e s i s t i v i t y l a y e r t h i c k -
n e s s e s , d e p t h s , and t r u e r e s i s t i v i t i e s .
E l e c t r i c a l r e s i s t i v i t y s u r v e y s have been s u c c e s s f u l l y used to
l o c a t e groundwater a q u i f e r s , d e l i n e a t e groundwater contaminant plumes,

map s a l t water i n t r u s i o n , d e t e r m i n e s u b s u r f a c e s t r a t i g r a p h y , map
t h i c k n e s s e s o f s u r f i c i a l d e p o s i t s , map f r a c t u r e zones i n b e d r o c k
a r e a s , map k a r s t f e a t u r e s , l o c a t e b u r i e d man-made o b j e c t s and to
implement i n - p l a c e e l e c t r i c a l l e a k d e t e c t i o n systems f o r s u r f a c e im-
poundments and underground s t o r a g e t a n k s (2,4,5,6,7). In a d d i t i o n
r e s e a r c h i s o n - g o i n g t o e v a l u a t e the a b i l i t y o f r e s i s t i v i t y f o r
d e t e c t i n g and mapping o r g a n i c plumes ( 8 ) .
The f i e l d a p p l i c a t i o n o f e l e c t r i c a l r e s i s t i v i t y t e c h n i q u e s can
be a f f e c t e d by the p r e s e n c e of nearby power l i n e s , f e n c e s , r a i l r o a d
t r a c k s , and b u r i e d p i p e s and c a b l e s . These c u l t u r a l f e a t u r e s may
c r e a t e e l e c t r i c a l i n t e r f e r e n c e o r a l t e r the s u b s u r f a c e p a t t e r n o f
c u r r e n t f l o w d i s t r i b u t i o n . I n a d d i t i o n , i n o r d e r to complete
e l e c t r i c a l r e s i s t i v i t y s u r v e y s you must be a b l e t o " s e a t " the e l e c -
t r o d e s i n the ground to e s t a b l i s h e l e c t r i c a l c o n t i n u i t y w i t h the
s u b s u r f a c e m a t e r i a l s to be s t u d i e d .
D a t a a n a l y s i s and i n t e r p r e t a t i o n of e l e c t r i c a l r e s i s t i v i t y d a t a
may be l i m i t e d b e c a u s e : (1) r e s i s t i v i t y v a l u e s may be a s s o c i a t e d
w i t h any one of s e v e r a l g e o l o g i c u n i t s ( i . e . a s i l t y sand u n i t may
have s i m i l a r r e s i s t i v i t y v a l u e s as a sand u n i t s a t u r a t e d w i t h s a l t
w a t e r ) ; (2) t h i n beds of lower r e s i s t i v i t y w i l l be masked when they
a r e sandwiched between two l a y e r s o f h i g h e r r e s i s t i v i t y ; and (3) the
i n t e r p r e t e d l a y e r t h i c k n e s s w i l l be g r e a t e r t h a n the a c t u a l t h i c k n e s s
due to the a n i s o t r o p i c n a t u r e o f the i n d i v i d u a l l a y e r s , w h i c h a r e
g e n e r a l l y c h a r a c t e r i z e d as h a v i n g g r e a t e r v e r t i c a l r e s i s t i v i t y v a l u e s
than h o r i z o n t a l ( 9 ) .
Electromagnetic Conductivity. The e l e c t r o m a g n e t i c conductivity sur-

vey i s s i m i l a r to the e l e c t r i c a l r e s i s t i v i t y s u r v e y i n the sense t h a t
b o t h methods q u a n t i f y e l e c t r i c a l c h a r a c t e r i s t i c s o f s u b s u r f a c e
materials. However, t h e r e a r e v a s t d i f f e r e n c e s between the f i e l d
t e c h n i q u e s and the data and a n a l y s e s w h i c h c h a r a c t e r i z e the i n d i v i d u a l
methods. The e l e c t r o m a g n e t i c c o n d u c t i v i t y s u r v e y c o n s i s t s of d i r e c t -
i n g an e l e c t r o m a g n e t i c f i e l d i n t o the ground from an above ground
s o u r c e to c r e a t e a s e c o n d a r y e l e c t r o m a g n e t i c f i e l d t h a t i s measured
by a r e c e i v e r . As a r e s u l t , d i r e c t measurements o f b u l k s u b s u r f a c e
c o n d u c t i v i t i e s a r e o b t a i n e d (10) ( F i g u r e 5 ) .
DE ROSE Applications of Surface Geophysical Methods
F i g u r e 4. R e s i s t i v i t y p l o t s f o r (A) l a t e r a l p r o f i l e and f o r
(B) v e r t i c a l s o u n d i n g .
F i e l d equipment r e q u i r e d f o r a s u r v e y c o n s i s t s o f a low f r e q u e n -
cy t r a n s m i t t e r c o i l and a r e c e i v e r c o i l . The r e c e i v e r c o i l i n t e r -
c e p t s a p o r t i o n o f t h e s e c o n d a r y e l e c t r o m a g n e t i c f i e l d and p r o d u c e s
an o u t p u t v o l t a g e w h i c h i s l i n e a r l y r e l a t e d t o s u b s u r f a c e conduc-
tivity (11).
I n d u c i n g an e l e c t r o m a g n e t i c f i e l d e l i m i n a t e s t h e need f o r an
e l e c t r o d e a r r a y and, t h e r e f o r e , t h e e l e c t r o m a g n e t i c f i e l d method i s
a more r a p i d t o o l f o r s u r v e y i n g . The e l i m i n a t i o n o f e l e c t r o d e s t o
measure e l e c t r i c a l p r o p e r t i e s o f s u b s u r f a c e m a t e r i a l s a l s o e n a b l e s
e l e c t r o m a g n e t i c s u r v e y s t o be conducted i n many a r e a s where r e s i s -
t i v i t y s u r v e y s cannot be c o n s i d e r e d ( i . e . pavement a r e a s , v e r y d r y
sandy s o i l s , f r o z e n ground, r a i l r o a d t r a c k s , e t c . ) . Electromagnetic
c o n d u c t i v i t y s u r v e y s may a l s o be u s e d t o p r o d u c e r a p i d c o n t i n u o u s
p r o f i l e s up t o depths o f 15 m e t e r s .
E l e c t r o m a g n e t i c (EM) s u r v e y s a r e most w i d e l y used t o c r e a t e
p r o f i l e s o r maps o f s u b s u r f a c e c o n d u c t i v i t y . L a t e r a l v a r i a t i o n s i n
c o n d u c t i v i t y , a t a g i v e n d e p t h , may be i n t e r p r e t e d a s contaminant
plumes, sand and g r a v e l d e p o s i t s , c l a y d e p o s i t s , k a r s t f e a t u r e s ,
s a l t water i n t r u s i o n o r b u r i e d o b j e c t s ( F i g u r e 6 ) . Because f i e l d
s u r v e y s may be completed r a p i d l y , EM t e c h n i q u e s a r e o f t e n i m p l e -
mented t o map l a r g e s i t e s and t o p r o v i d e d e t a i l e d maps o f v a r i a b l e
s i t e s u b s u r f a c e f e a t u r e s such a s i s o l a t e d k a r s t f e a t u r e s , and b u r i e d
tanks o r 55 g a l l o n drums.
Computer-data p r o c e s s i n g t e c h n i q u e s c a n be u t i l i z e d t o i n t e r p r e t
and p r e s e n t r e s u l t s o b t a i n e d from s i t e s u r v e y s i n o r d e r t o f i l t e r o u t
unwanted c u l t u r a l i n t e r f e r e n c e s , and t o e v a l u a t e plume c h a r a c t e r i s -
tics. C o r r e l a t i o n o f EM maps w i t h f i e l d - c o l l e c t e d g e o l o g i c i n f o r -
mation i s e s s e n t i a l f o r the f i n a l i n t e r p r e t a t i o n o f the survey d a t a .
Two and t h r e e l a y e r c o n d u c t i v i t y models c a n be c o n s t r u c t e d u s i n g
q u a n t i t a t i v e techniques. The r e s u l t i n g models a r e g e n e r a l l y l e s s
d e t a i l e d i n the v e r t i c a l r e s o l u t i o n of the subsurface l a y e r s than
t h o s e produced from v e r t i c a l e l e c t r i c a l s o u n d i n g s .
E l e c t r o m a g n e t i c s u r v e y s may n o t be conducted i n a r e a s c h a r a c -
t e r i z e d by u n u s u a l l y h i g h o r low v a l u e s o f s u b s u r f a c e c o n d u c t i v i t y .
I n a d d i t i o n , e l e c t r o m a g n e t i c methods a r e s u b j e c t t o i n t e r f e r e n c e
from many c u l t u r a l f e a t u r e s and t h e p r e s e n c e o f n e a r b y e l e c t r i c a l
fields. F i n a l l y , the a b i l i t y of electromagnetic c o n d u c t i v i t y sur-
v e y s t o i d e n t i f y groundwater c o n t a m i n a n t plumes r e q u i r e s t h a t a
s i g n i f i c a n t e l e c t r i c a l c o n d u c t i v i t y c o n t r a s t e x i s t s between contam-
i n a t e d and n a t u r a l groundwater ( 2 ) .
Ground P e n e t r a t i n g Radar. Ground p e n e t r a t i n g r a d a r (GPR) i s a n im-

p u l s e r a d a r system t h a t p r o v i d e s a c o n t i n u o u s p r o f i l e o f s u b s u r f a c e
c o n d i t i o n s by r a d i a t i n g e l e c t r o m a g n e t i c p u l s e s i n t o t h e s u b s u r f a c e
and d i s p l a y i n g t h e r e f l e c t i o n s from s u r f a c e and s u b s u r f a c e " i n t e r -
f a c e s " on a s t r i p c h a r t r e c o r d e r ( F i g u r e 7 ) . The term " i n t e r f a c e "
i n t h i s g e o p h y s i c a l method r e f e r s t o any d i s c o n t i n u i t y i n e l e c t r i c a l
p r o p e r t i e s such as s o i l o r g e o l o g i c b o u n d a r i e s o r imbedded o b j e c t s
such a s drums, o r b o u l d e r s .
The GPR system c o n s i s t s o f f i v e major components, these i n c l u d e :
1) power d i s t r i b u t i o n u n i t ; 2) r a d a r c o n t r o l u n i t ; 3) antenna t r a n s -
c e i v e r ; 4) g r a p h i c r e c o r d e r ; and 5) tape r e c o r d e r . The power d i s -
t r i b u t i o n u n i t p r o v i d e s p r o p e r AC/DC v o l t a g e s t o a l l t h e GPR e q u i p -
ment. The r a d a r c o n t r o l u n i t t r i g g e r s t h e antennae t r a n s c e i v e r t o
F i g u r e 5. C r o s s - s e c t i o n a l v i e w o f t r a n s m i t t e d e l e c t r o m a g n e t i c
f i e l d and g e n e r a t e d s e c o n d a r y e l e c t r o m a g n e t i c f i e l d measured
by a r e c e i v e r f o r c o m p l e t i n g e l e c t r o m a g n e t i c c o n d u c t i v i t y
surveys.
produce t h e e l e c t r o m a g n e t i c p u l s e . The r e f l e c t e d p o r t i o n s o f the

t r a n s m i t t e d p u l s e a r e r e c e i v e d by t h e antennae t r a n s c e i v e r , c o n v e r t e d
to the a u d i o f r e q u e n c y r a n g e and p r o c e s s e d by the r a d a r c o n t r o l u n i t .
P r o c e s s i n g i s an o p e r a t o r - i n i t i a t e d p r o c e d u r e and a l l o w s f o r t h e
s e l e c t i o n and enhancement o f t h a t p o r t i o n o f t h e d a t a w h i c h i s o f
g r e a t e s t importance t o the o b j e c t i v e of the survey. The p r o c e s s e d
d a t a i s sent t o t h e g r a p h i c r e c o r d e r w h i c h p r o d u c e s a permanent c h a r t
p r o f i l e o f t h e s u b s u r f a c e i n t e r f a c e s . P r o c e s s e d d a t a may a l s o be
s e n t t o t h e tape r e c o r d e r f o r s t o r a g e , r e p r o c e s s i n g , o r p r i n t i n g a t a
l a t e r date. D a t a may be c o l l e c t e d a t a r a t e as much as 16 t i m e s
f a s t e r than t h e g r a p h i c r e c o r d e r by tape r e c o r d i n g t h e d a t a ( 1 2 ) .
F i e l d s u r v e y s may be completed on f o o t o r by u t i l i z i n g v e h i c l e s
f o r mounting equipment and towing t h e antennae t r a n s c e i v e r . The
r e s u l t i n g GPR p r o f i l e w h i c h i s produced by t h e g r a p h i c r e c o r d e r
p r i n t s s t r o n g s i g n a l s as b l a c k and weak s i g n a l s as w h i t e ( F i g u r e 8 ) .
The r e s u l t i s a d i s p l a y o f d a r k bands e x t e n d i n g a c r o s s t h e p r o f i l e a t
v a r y i n g depths. These bands r e p r e s e n t t h e r e f l e c t i o n from an i n t e r -

face. The h o r i z o n t a l s c a l e o f t h e p r o f i l e i s dependent upon t h e
t r a v e l time o f t h e antennae t r a n s c e i v e r . The v e r t i c a l s c a l e i s
dependent upon t h e t r a v e l time o f t h e GPR p u l s e . The t r a v e l time o f
the GPR p u l s e may be c o n v e r t e d t o d e p t h i f e i t h e r t h e d i e l e c t r i c
c o n s t a n t o f t h e medium b e i n g p r o f i l e d o r t h e d e p t h t o a s p e c i f i c
i n t e r f a c e i s known.
T y p i c a l a p p l i c a t i o n s o f GPR s u r v e y s i n c l u d e , mapping d e p t h t o
b e d r o c k , and mapping i n t e r f a c e s i n c l u d i n g changes i n s o i l t y p e ,
g e o l o g i c f o r m a t i o n s , and d e p t h t o water t a b l e . B u r i e d o b j e c t s and
e x c a v a t i o n s may a l s o be l o c a t e d and i n some c a s e s i d e n t i f i e d , as w e l l
as b u r i e d c u l t u r a l f e a t u r e s i n c l u d i n g p i p e s , c a b l e s , and c o n d u i t s
(13).
The e f f e c t i v e p e n e t r a t i o n d e p t h s o f the GPR system i s dependent
upon t h e b u l k c o n d u c t i v i t y o f t h e s u b s u r f a c e m a t e r i a l s b e i n g p r o -
filed. The GPR s i g n a l i s r a p i d l y a t t e n u a t e d w i t h i n h i g h l y c o n d u c t i v e
m a t e r i a l s ( i . e . c l a y s , h i g h l y i o n i c groundwater) w h i c h s e v e r e l y
l i m i t s the p e n e t r a t i o n depths.
O t h e r l i m i t a t i o n s o f GPR p r o f i l e s i n c l u d e : 1) masking o f a
r e f l e c t i o n as a r e s u l t o f o v e r l a p p i n g i n t e r f a c e s , s u c h a s , where t h e
s u r f a c e o f t h e water t a b l e i s l e v e l w i t h t h e t o p o f a b u r i e d drum;
2) v a r i a t i o n i n i d e n t i f y i n g r e f l e c t o r s depending upon t h e o r i e n t a t i o n
of t h e t r a v e r s e t o t h e b u r i e d o b j e c t ; and 3) t h e p r e s e n c e o f v e g e t a -
t i v e c o v e r , s u r f i c i a l d e b r i s and i r r e g u l a r s u r f a c e topography w h i c h
may l i m i t t h e p e n e t r a t i o n d e p t h o f t h e r e t u r n s i g n a l o r t h e a b i l i t y
to t r a v e r s e t h e s i t e w i t h t h e GPR system.
Magnetometry. Magnetometers measure w i t h a c c u r a c y and p r e c i s i o n , t h e

i n t e n s i t y of t h e e a r t h ' s m a g n e t i c f i e l d . By mapping l a t e r a l and/or
v e r t i c a l m a g n e t i c g r a d i e n t s , s u b s u r f a c e f e a t u r e s s u c h as g e o l o g i c o r e
d e p o s i t s , b e d r o c k f e a t u r e s , b u r i e d drums and b u r i e d p i p e s may be
l o c a t e d ( F i g u r e 9 ) . N o n f e r r o u s m e t a l s such as aluminum, c o p p e r , t i n
and b r a s s cannot be d e t e c t e d by magnetometers ( 1 4 ) .
S e v e r a l t y p e s o f magnetometers a r e p r e s e n t l y a v a i l a b l e , however,
the two most w i d e l y r e f e r e n c e d i n e n g i n e e r i n g and groundwater pub-
l i c a t i o n s a r e the p r o t o n and t h e f l u x g a t e magnetometers. Proton
magnetometers measure t h e e a r t h ' s t o t a l m a g n e t i c f i e l d i n t e n s i t y by
u t i l i z i n g t h e p r e c e s s i o n o f s p i n n i n g p r o t o n s i n a sample o f h y d r o -
D E ROSE Applications of Surface Geophysical Methods
F i g u r e 8. Ground p e n e t r a t i n g r a d a r p r o f i l e r e c o r d . Hyper-
b o l i c r e f l e c t o r s (dark bands) r e p r e s e n t o u t l i n e o f b u r i e d
drums.
c a r b o n f l u i d t o g e n e r a t e a s m a l l s i g n a l whose f r e q u e n c y i s p r e c i s e l y
p r o p o r t i o n a l t o the t o t a l m a g n e t i c f i e l d i n t e n s i t y . F l u x g a t e magnet-
ometers measure v a r i a t i o n s i n the i n t e n s i t y o f the t o t a l e a r t h ' s
m a g n e t i c f i e l d by m e a s u r i n g changes i n t h e m a g n e t i c s a t u r a t i o n l e v e l
of an i r o n c o r e s e n s o r . U n l i k e the p r o t o n magnetometer, the s i g n a l
o u t p u t o f a s i n g l e f l u x g a t e magnetometer i s e x t r e m e l y s e n s i t i v e t o
orientation. To overcome t h i s s e n s i t i v i t y , the g r a d i e n t o f the
e a r t h ' s m a g n e t i c f i e l d may be measured by mounting two f l u x g a t e
s e n s o r s t o g e t h e r t o form a g r a d i o m e t e r . The g r a d i o m e t e r i s t h e most
common method o f o b t a i n i n g measurements w i t h the f l u x g a t e magnet-
ometer ( 1 4 ) .
P r o t o n magnetometers a r e g e n e r a l l y more s e n s i t i v e than f l u x g a t e
magnetometers, however, they a r e a l s o more s e n s i t i v e t o i n t e r f e r e n c e
from unwanted m a g n e t i c o b j e c t s ( i . e . f e n c e s , d e b r i s and a u t o m o b i l e s ) .
F l u x g a t e magnetometers a l s o p r o v i d e the advantage o f o b t a i n i n g con-
t i n u o u s measurements and d a t a r e a d o u t f o r c o n d u c t i n g t o t a l s i t e
surveys.
The magnitude o f an anomaly p r o d u c e d by a b u r i e d o b j e c t i s
d i r e c t l y r e l a t e d t o the m a g n e t i c mass and m a g n e t i c i n t e n s i t y of the
body, and i n v e r s e l y r e l a t e d t o the d e p t h o f the body. Magnetic
a n o m a l i e s , s u c h as the c o n t a c t between a non-magnetic s e d i m e n t a r y
d e p o s i t and a m a g n e t i c i g n e o u s r o c k body, t h a t a r e i d e n t i f i e d on
magnetic p r o f i l e s o r c o n t o u r maps can be l o c a t e d u s i n g q u a l i t a t i v e
t e c h n i q u e s ( F i g u r e 10). Computer d a t a p r o c e s s i n g and a n a l y t i c a l
t e c h n i q u e s can d e t e r m i n e the d e p t h o f b u r i a l , the mass of the b u r i e d
o b j e c t s , the g e o l o g i c s t r u c t u r e , and the d e p t h t o b e d r o c k .
Magnetometer s u r v e y s a r e l i m i t e d t o i d e n t i f y i n g o r l o c a t i n g
s u b s u r f a c e m a g n e t i c f e a t u r e s o r o b j e c t s . Magnetometer s u r v e y s may be
h i n d e r e d by the p r e s e n c e o f unwanted l o c a l m a g n e t i c f i e l d s a s s o c i a t e d
w i t h power l i n e s , r a i l r o a d t r a c k s , e t c . D i u r n a l v a r i a t i o n s , w h i c h
a r e n a t u r a l changes i n the e a r t h ' s m a g n e t i c f i e l d over time, must be
compensated f o r d u r i n g a magnetometer s u r v e y . During magnetic
storms, w h i c h may o c c u r as o f t e n as s e v e r a l times a month, s i g n i f i -
c a n t v a r i a t i o n s i n the e a r t h ' s m a g n e t i c f i e l d w i l l r e s u l t , making
completion of a magnetic survey i m p r a c t i c a l . Finally, identifica-
t i o n of l o c a l a n o m a l i e s a r e a f f e c t e d by the p r e s e n c e o f many
c u l t u r a l f e a t u r e s i n c l u d i n g s t e e l f e n c e s , v e h i c l e s , b u i l d i n g s and
i r o n d e b r i s . The s e a r c h f o r b u r i e d o b j e c t s may a l s o be l i m i t e d by
the p r e s e n c e of n a t u r a l i r o n o r e d e p o s i t s and bog i r o n s , o r by o t h e r
v a r i a t i o n s i n subsurface geology.
Groundwater A p p l i c a t i o n s
C u r r e n t l y , t h e r e a r e s e v e r a l p u b l i c a t i o n s w h i c h document a p p l y i n g
s u r f a c e g e o p h y s i c a l t e c h n i q u e s t o groundwater contaminant i n v e s t i g a -
t i o n s (2,8,15,16,17). Two c o n c l u s i o n s drawn i n a l l of the above
referenced p u b l i c a t i o n s are: (1) g e o p h y s i c a l s u r v e y s p r o v i d e
s e v e r a l u s e f u l n o n d e s t r u c t i v e t e s t methods f o r e v a l u a t i n g s u b s u r f a c e
g e o h y d r o l o g i c c o n d i t i o n s ; and (2) t h e s e methods may o f t e n improve the
q u a n t i t y and q u a l i t y of the d a t a base o b t a i n e d from c o n v e n t i o n a l
d e s t r u c t i v e t e s t methods, w h i l e r e d u c i n g o v e r a l l i n v e s t i g a t i o n and
monitoring costs.
Advantages of g e o p h y s i c a l s u r v e y s i n c l u d e the c o s t e f f e c t i v e
b e n e f i t s p r o v i d e d f o r by t h e r a p i d a c q u i s i t i o n of d a t a . Geophysical
F i g u r e 9. C r o s s s e c t i o n a l v i e w o f ground s u r f a c e t r a v e r s e ,
1
X-X , and the d i s t o r t i o n i n t h e m a g n e t i c f i e l d i n t e n s i t y
c r e a t e d by s e v e r a l b u r i e d drums.
F i g u r e 10. M a g n e t i c p r o f i l e a l o n g ground s u r f a c e t r a v e r s e ,
1
X-X , and t h e l o c a l anomaly c r e a t e d by b u r i e d drums.
s u r v e y t e c h n i q u e s can be implemented d u r i n g p r e l i m i n a r y p r o j e c t
s t a g e s i n o r d e r t o e s t a b l i s h a s i t e d a t a base, and t h e r e b y i d e n t i f y
a n o m a l i e s which r e q u i r e more d e t a i l e d e v a l u a t i o n s . I n a d d i t i o n ,
c o n t i n u o u s d a t a c o l l e c t i o n t e c h n i q u e s may be u t i l i z e d f o r mapping
f e a t u r e s t o a g r e a t e r degree o f r e s o l u t i o n n o t g e n e r a l l y a t t a i n a b l e
by u s i n g c o n v e n t i o n a l sampling t e c h n i q u e s .
A t h a z a r d o u s waste s i t e s the use o f g e o p h y s i c a l s u r v e y t e c h -
n i q u e s would be advantageous p r i o r t o c o m p l e t i n g o n - s i t e t e s t d r i l l -
ing or e x c a v a t i o n a c t i v i t i e s (1,13). The a p p l i c a t i o n of g e o p h y s i c a l
t e c h n i q u e s i n l o c a t i n g s u s p e c t e d c o n t a i n e r b u r i a l a r e a s would r e d u c e
the l i k e l i h o o d of unexpected c o n t a c t by p e r s o n n e l or equipment w i t h
b u r i e d hazardous, t o x i c or r a d i o a c t i v e m a t e r i a l s . S i t e c h a r a c t e r i -
z a t i o n with surface geophysical techniques a l s o helps i n i d e n t i f y i n g
the p r o p e r p r o c e d u r e s and p r e c a u t i o n s t h a t s h o u l d be implemented
d u r i n g t h e c o n v e n t i o n a l phases o f an i n v e s t i g a t i o n , i n o r d e r t o
e l i m i n a t e the p o s s i b l e spread or r e l e a s e of t o x i c or r a d i o a c t i v e
materials.
S e l e c t e d I l l u s t r a t i v e Models. Three i l l u s t r a t i v e models o f geo-

p h y s i c a l s u r v e y s a r e b r i e f l y p r e s e n t e d t o p r o v i d e examples o f the
r e s u l t s t h a t can be o b t a i n e d by c o m p l e t i n g s u r f a c e g e o p h y s i c a l
surveys. The models i n c l u d e : 1) a v e r t i c a l e l e c t r i c a l r e s i s t i v i t y
sounding program (VES) t h a t e v a l u a t e s s a l t water i n t r u s i o n ; 2) an
e l e c t r o m a g n e t i c c o n d u c t i v i t y s u r v e y t o i d e n t i f y groundwater c o n t a m i -
nant plumes and contaminant s o u r c e s ; and 3) an e v a l u a t i o n of l i m e -
s t o n e t e r r a i n w i t h s e i s m i c r e f r a c t i o n and e l e c t r o m a g n e t i c conduc-
t i v i t y surveys.
V e r t i c a l E l e c t r i c a l R e s i s t i v i t y Sounding. The f i r s t example i l l u s -

t r a t e s the a b i l i t y o f VES t e c h n i q u e s t o c h a r a c t e r i z e r e g i o n a l sub-
s u r f a c e g e o l o g y i n t o r e s i s t i v i t y l a y e r s t h a t have s i m i l a r r e s i s t i v i t y
v a l u e s a t s i m i l a r depths. Sediment l i t h o l o g i e s and groundwater
q u a l i t y c h a r a c t e r i s t i c s were d e t e r m i n e d f o r each u n i t based on
observed r e s i s t i v i t y v a l u e s . The s u r v e y was conducted i n Northampton
County, V i r g i n i a w h i c h i s l o c a t e d a t the s o u t h end of t h e Del-Mar-Va
P e n i n s u l a (9) ( F i g u r e 1 1 ) .
Data was c o l l e c t e d a t s i x VES s i t e s s e l e c t e d a t t h e s t u d y a r e a .
The VES d a t a were a n a l y z e d u s i n g computer p r o c e s s i n g t e c h n i q u e s t o
c r e a t e 5 and 10 l a y e r s u b s u r f a c e models (18,19). F i g u r e 12 p r e s e n t s
a t h r e e - d i m e n s i o n a l i s o m e t r i c p r o j e c t i o n p r e p a r e d from the computer-
g e n e r a t e d , 5 - l a y e r VES c u r v e s .
Three g e n e r a l l i t h o l o g i e s d e s c r i b e the s u b s u r f a c e c o n d i t i o n s .
The upper l a y e r , w h i c h p r o d u c e s h i g h r e s i s t i v i t y v a l u e s , c o n s i s t s
m o s t l y of u n s a t u r a t e d sand t h a t ranges i n d e p t h from about 0 t o 150
feet.
The second r e s i s t i v i t y l a y e r , w h i c h i s c h a r a c t e r i z e d by moder-
a t e l y low r e s i s t i v i t y v a l u e s , o c c u r s a t depths g e n e r a l l y r a n g i n g
between 150 t o 160 f e e t and c o n s i s t s of f r e s h w a t e r - b e a r i n g sands.
The Manokin and Pocomoke a c q u i f e r s a r e p r e s e n t w i t h i n t h i s l a y e r .
In a d d i t i o n , l e n s e s o f c l a y and/or b r a c k i s h water o c c u r w i t h i n t h i s
layer. V a l u e s of r e s i s t i v i t y w i t h i n the second l a y e r d e c r e a s e e a s t -
ward, i n d i c a t i n g an i n c r e a s e i n the t h i c k n e s s and/or f r e q u e n c y of the
c l a y l e n s e s and/or b r a c k i s h water zones.
D E ROSE Applications of Surface Geophysical Methods
VES
Profile -
Location
F i g u r e 11. VES s i t e a r e a l o c a t i o n i n Northampton County,

Virginia. Reproduced w i t h p e r m i s s i o n from Rf. 9.
F i g u r e 12. VES f i v e l a y e r , t h r e e - d i m e n s i o n a l i s o m e t r i c
projection. Reproduced w i t h p e r m i s s i o n from Ref. 9.
V e r y low r e s i s t i v i t y v a l u e s c h a r a c t e r i z e t h e d e e p e s t l a y e r ,
i n d i c a t i n g the presence of e i t h e r b r a c k i s h , or s a l i n e water-bearing
sediments. The v e r t i c a l e x t e n t o f t h i s l a y e r i s w e l l d e f i n e d by
sudden l a r g e s c a l e d e c r e a s e s i n r e s i s t i v i t y , however, t h e l a t e r a l
extent of the l a y e r i s not w e l l d e f i n e d .
E l e c t r o m a g n e t i c C o n d u c t i v i t y Survey. The r e s u l t s o f an e l e c t r o m a g -
n e t i c c o n d u c t i v i t y s u r v e y conducted a t a uranium m i l l t a i l i n g s s i t e
a r e shown i n F i g u r e s 13 and 14. The p u r p o s e o f t h i s s u r v e y was t o
i d e n t i f y s u b s u r f a c e c o n d u c t i v i t y a n o m a l i e s t h a t c o u l d be a s s o c i a t e d
w i t h v a r i a t i o n s i n groundwater q u a l i t y . Once t h e a n o m a l i e s were
i d e n t i f i e d , t e s t b o r i n g s and m o n i t o r i n g w e l l s were completed t o
determine t h e i r s i g n i f i c a n c e .
A s u r v e y g r i d was e s t a b l i s h e d a t t h e s i t e by m e a s u r i n g 150 and
300 f o o t i n t e r v a l s a c r o s s a 6,000 f o o t by 3,900 f o o t a r e a . The
s u r v e y a r e a i s p r e d o m i n a n t l y f l a t , w i t h t h e major t o p o g r a p h i c
f e a t u r e s b e i n g t a i l i n g s p i l e s and l e v e e s around t h e e v a p o r a t i o n
ponds. The s u b s u r f a c e s o i l s a r e composed o f s i l t y c l a y and g r a v e l
deposits. The d e p t h t o groundwater i s g e n e r a l l y l e s s t h a n 5 f e e t
below l a n d s u r f a c e .
E l e c t r o m a g n e t i c c o n d u c t i v i t y measurements were made a t 316
survey s t a t i o n s . Two s e t s o f s u b s u r f a c e c o n d u c t i v i t y v a l u e s were
o b t a i n e d a t each s u r v e y s t a t i o n . These c o n s i s t e d o f one s e t o f
r e a d i n g s t o an e f f e c t i v e measurement d e p t h o f 25 f e e t w i t h a l a r g e
p o r t i o n o f t h e t o t a l r e a d i n g c o n t r i b u t e d by near s u r f a c e m a t e r i a l s
( F i g u r e 13), and one s e t o f r e a d i n g s t o an e f f e c t i v e measurement
depth o f 50 f e e t w i t h a s m a l l p o r t i o n o f t h e t o t a l r e a d i n g c o n t r i b u -
t e d by near s u r f a c e m a t e r i a l s ( F i g u r e 1 4 ) . C o n d u c t i v i t y c o n t o u r maps
were computer g e n e r a t e d u s i n g each d a t a s e t . The c o n t o u r maps were
t h e n used t o i d e n t i f y anomalous a r e a s o f s u b s u r f a c e c o n d u c t i v i t y
( F i g u r e s 13 and 1 4 ) .
A comparison o f t h e r e s u l t i n g two c o n d u c t i v i t y c o n t o u r maps
shows a n o m a l o u s l y h i g h c o n d u c t i v i t y v a l u e s i n an a r e a e x t e n d i n g from
t h e s i t e c o o r d i n a t e s N8800, E4700 t o N6700, E3800. In addition,
h i g h e r v a l u e s were c o n s i s t e n t l y r e c o r d e d a t t h e g r e a t e r e f f e c t i v e
measurement depth i n comparison t o t h o s e v a l u e s o b t a i n e d a t t h e
s h a l l o w e r e f f e c t i v e measurement d e p t h . T h i s i n d i c a t e s that subsur-
f a c e m a t e r i a l s w i t h i n t h e anomalous a r e a have h i g h e r c o n d u c t i v i t y
v a l u e s a t depth r a t h e r t h a n near t h e s u r f a c e .
Those a n o m a l i e s t h a t a r e shown i n F i g u r e 13, b u t a r e n o t e v i d e n t
i n F i g u r e 14, a r e r e l a t e d t o near s u r f a c e v a r i a t i o n s i n s o i l t y p e
and/or t h e a c c u m u l a t i o n o f e v a p o r i t e d e p o s i t s . The i s o l a t e d anomaly
h i g h l i g h t e d on F i g u r e 14, i s p r o b a b l y r e l a t e d t o one o f s e v e r a l
geothermal s p r i n g s .
E l e c t r i c a l r e s i s t i v i t y measurements were a l s o t a k e n a t 28 l o c a -
t i o n s s e l e c t e d a c r o s s t h e s i t e t o v e r i f y t h e d a t a c o l l e c t e d by
e l e c t r o m a g n e t i c methods. The d a t a o b t a i n e d was i n agreement w i t h
the r e s u l t s o f t h e e l e c t r o m a g n e t i c c o n d u c t i v i t y s u r v e y .
The e n t i r e g e o p h y s i c a l s u r v e y o f t h e f i e l d s i t e was completed i n
f o u r days. L a t e r i n v e s t i g a t i o n s , i n c l u d i n g t h e i n s t a l l a t i o n and
sampling o f m o n i t o r i n g w e l l s and a n a l y s i s o f groundwater samples from
t h o s e w e l l s , c o n f i r m e d t h a t t h e anomaly o f h i g h c o n d u c t i v i t y was t h e
r e s u l t o f groundwater c o n t a m i n a t i o n o c c u r r i n g downgradient from t h e
tailings piles.
134
DE ROSE Applications of Surface Geophysical Methods 135
2500 3000 4doo 5000 5500 6000 6500 i 70.00
F i g u r e 14. C o n d u c t i v i t y c o n t o u r map r e s u l t i n g from e l e c t r o

m a g n e t i c c o n d u c t i v i t y s u r v e y completed a t an e f f e c t i v e
measurement d e p t h o f 50 f e e t .
Geophysical I n v e s t i g a t i o n at a P o t e n t i a l F i e l d - A p p l i c a t i o n S i t e .
Based upon s e v e r a l s u c c e s s f u l s i t e e v a l u a t i o n s t h a t employed geo-
p h y s i c a l methods combined w i t h c o n v e n t i o n a l e x p l o r a t o r y t e c h n i q u e s
i n i n v e s t i g a t i n g s i t e s u n d e r l a i n by l i m e s t o n e , t h e f o l l o w i n g p o t e n -
t i a l s i t e e v a l u a t i o n was d e v e l o p e d . The i n t e n t o f t h i s h y p o t h e t i c a l
s i t u a t i o n was t o i l l u s t r a t e the c o n c e p t of an i n t e g r a t e d s i t e
e v a l u a t i o n i n which g e o p h y s i c a l techniques are u t i l i z e d to i n c r e a s e
the e f f e c t i v e n e s s o f the groundwater m o n i t o r i n g system.
The a r e a of the proposed s i t e f o r the a p p l i c a t i o n o f p e s t i c i d e s
i s about t w e n t y - f i v e a c r e s and i s u n d e r l a i n by r e s i d u a l s o i l of
v a r i a b l e l i t h o l o g y which i s u n d e r l a i n by t h e L e i t h s v i l l e F o r m a t i o n
and the T r i a s s i c B o r d e r c o n g l o m e r a t e . The L e i t h s v i l l e F o r m a t i o n i s
a l i m e s t o n e o f Cambrian age. The s i t e i s a l s o c h a r a c t e r i z e d by a
r e l a t i v e l y s h a l l o w water t a b l e ( F i g u r e 1 5 ) .
The i n i t i a l s i t e i n v e s t i g a t i o n t o d e f i n e s u b s u r f a c e c o n d i t i o n s
i n c l u d e d s e i s m i c r e f r a c t i o n p r o f i l e s and a l i m i t e d number o f t e s t
borings. I n t e r p r e t a t i o n and c o r r e l a t i o n of s e i s m i c d a t a w i t h r e s u l t s
o b t a i n e d from the t e s t b o r i n g s i d e n t i f i e d a r e a s u n d e r l a i n by l i m e -
s t o n e a t s h a l l o w depths ( l e s s t h a n 10 f e e t ) , by l i m e s t o n e and a t
moderate depths (15 t o 25 f e e t ) , and a r e a s where d e p t h t o l i m e s t o n e
i s i r r e g u l a r ( F i g u r e 16). W i t h i n the a r e a c h a r a c t e r i z e d by moderate
d e p t h t o l i m e s t o n e , based upon comparison w i t h the r e s u l t s of the
s e i s m i c r e f r a c t i o n p r o f i l e s , f o u r t e s t b o r i n g s encountered limestone
at g r e a t depths a s s o c i a t e d w i t h l o c a l i z e d k a r s t f e a t u r e s . These d a t a
p o i n t s were t h e r e f o r e i d e n t i f i e d as anomalous v a l u e s . In a d d i t i o n ,
conglomerate was e n c o u n t e r e d u n d e r l y i n g a p o r t i o n o f the s i t e a r e a
at d e p t h s o f 15 t o 25 f e e t .
Based upon t e s t b o r i n g s , the s i t e was u n d e r l a i n a t s h a l l o w
depths by c o a r s e , l i g h t g r a y l i m e s t o n e and sand, w i t h minor amounts
of s i l t and c l a y . The s i t e a r e a c h a r a c t e r i z e d by moderate d e p t h to
l i m e s t o n e was u n d e r l a i n by f i n e , r e d d o l o m i t i c l i m e s t o n e and s i l t y
c l a y , w i t h minor amounts o f sand. The r e m a i n i n g s i t e a r e a was
u n d e r l a i n by c o a r s e sandstone and conglomerate and s i l t and c l a y w i t h
moderate amounts o f sand.
An e l e c t r o m a g n e t i c s u r v e y was r u n a t the s i t e a t s t a t i o n s p l a c e d
a l o n g a 50 f o o t g r i d . The r e s u l t s o f the s u r v e y c o r r e l a t e d f a v o r a b l y
w i t h the r e s u l t s o b t a i n e d from the i n i t i a l i n v e s t i g a t i o n . A Phase I
G e o l o g i c Map was p r e p a r e d f o r t h e s i t e based upon t h e r e s u l t s o f the
s e i s m i c r e f r a c t i o n p r o f i l e s , t e s t b o r i n g s and e l e c t r o m a g n e t i c c o n -
d u c t i v i t y survey ( F i g u r e 17). H i g h a r e a s of c o n d u c t i v i t y were
g e n e r a l l y a s s o c i a t e d w i t h t h e c e n t r a l p a r t o f the s i t e w h i c h i s
u n d e r l a i n by m o d e r a t e l y deep l i m e s t o n e and s i l t and c l a y . Low con-
d u c t i v i t y v a l u e s were g e n e r a l l y a s s o c i a t e d w i t h t h o s e a r e a s o f t h e
s i t e u n d e r l a i n by l i m e s t o n e a t s h a l l o w d e p t h s . I n a d d i t i o n , two
l i n e a r t r e n d i n g a r e a s of v a r i a b l e c o n d u c t i v i t y were mapped i n the
a r e a between the s h a l l o w and m o d e r a t e l y deep l i m e s t o n e a r e a s .
F o l l o w - u p t e s t b o r i n g s were completed f o r t h e f i n a l s i t e c h a r a c -
t e r i z a t i o n and i m p l e m e n t a t i o n of a groundwater m o n i t o r i n g system.
Based upon e v a l u a t i o n of the t e s t b o r i n g d a t a and the g e o p h y s i c a l
d a t a , t h e s i t e was found t o be u n d e r l a i n by t h r e e d i f f e r e n t l i m e s t o n e
members ( 2 0 ) . The two c o n t a c t zones w h i c h o c c u r between the t h r e e
members were a s s o c i a t e d w i t h the two l i n e a r t r e n d i n g a r e a s o f v a r i a -
ble conductivity. These zones were c h a r a c t e r i z e d by the development
of deep k a r s t zone t h a t r e s u l t e d from the d i s s o l u t i o n of the l i m e -
1
F i g u r e 15. G e o l o g i c map o f p r o p o s e d f i e l d - a p p l i c a t i o n site.
Legend
28 Depth (ft) to Bedrock Based on Test Borings
KN3 Seismic Refraction - Irregular Bedrock Depth
I I Seismic Refraction - Shallow Bedrock Depth
I I Seismic Refraction - Moderate Bedrock Depth
Anomdous Depth to Bedrock (Based on Comparison of Seismic

Refraction and Test Boring)
F i g u r e 16. G e o l o g i c map o f p r o p o s e d f i e l d - a p p l i c a t i o n s i t e
summarizing b e d r o c k depths d e t e r m i n e d from s e i s m i c r e f r a c t i o n
s u r v e y s and t e s t b o r i n g d a t a .
s t o n e by groundwater f l o w i n g a l o n g t h e c o n t a c t zone ( F i g u r e 1 7 ) .
K a r s t f e a t u r e s i n c l u d i n g p i n n a c l e s , c a v i t i e s , and v o i d s were found
e x t e n d i n g t o d e p t h s g r e a t e r t h a n 100 f e e t a l o n g t h e c o n t a c t z o n e s .
I n o r d e r t o map the e x t e n t of the minor s o l u t i o n c a v i t i e s found i n
o t h e r a r e a s of t h e s i t e , d e t a i l e d e l e c t r o m a g n e t i c c o n d u c t i v i t y s u r -
v e y s were completed on a g r i d s p a c i n g of twenty f e e t .
M o n i t o r i n g w e l l l o c a t i o n s were chosen based on r e s u l t s from t h e
g e o p h y s i c a l s u r v e y s and the t e s t d r i l l i n g w h i c h c h a r a c t e r i z e d the
s u b s u r f a c e c o n d i t i o n s u n d e r l y i n g the s i t e ( F i g u r e 1 8 ) . Without
u t i l i z a t i o n o f g e o p h y s i c a l techniques, c h a r a c t e r i z a t i o n o f t h e s i t e
would have been i m p r a c t i c a l w i t h o u t i n c u r r i n g e x c e s s i v e d r i l l i n g
costs.
Summary and P o t e n t i a l A p p l i c a t i o n s to the P e s t i c i d e I n d u s t r y
F i v e c o s t - e f f e c t i v e s u r f a c e g e o p h y s i c a l s u r v e y t e c h n i q u e s have been
d e s c r i b e d w h i c h a r e w i d e l y u s e d i n groundwater s i t e i n v e s t i g a t i o n s .
By employing g e o p h y s i c a l t e c h n i q u e s t o complement c o n v e n t i o n a l
methods of s u b s u r f a c e e x p o r a t i o n , a m o n i t o r i n g network can be de-
s i g n e d t h a t has an o v e r a l l i n c r e a s e i n e f f i c i e n c y and i s c o s t -
e f f e c t i v e (2,6).
The a p p l i c a t i o n of t h e s e s u r f a c e g e o p h y s i c a l t e c h n i q u e s t o
groundwater c o n t a m i n a n t i n v e s t i g a t i o n s i n c l u d e the f o l l o w i n g : 1)
r e g i o n a l and l o c a l e v a l u a t i o n s o f s u b s u r f a c e g e o h y d r o l o g i c c o n d i -
t i o n s ; 2) f e a s i b i l i t y s t u d i e s o f p r o p o s e d f i e l d a p p l i c a t i o n s i t e s
and m a n u f a c t u r i n g , s t o r a g e and d i s p o s a l f a c i l i t i e s ; 3) d e s i g n o f
m o n i t o r i n g systems; 4) c h a r a c t e r i z a t i o n o f e x i s t i n g f i e l d a p p l i c a t i o n
s i t e s and m a n u f a c t u r i n g , s t o r a g e and d i s p o s a l f a c i l i t i e s ; and 5)
d e s i g n o f l e a k d e t e c t i o n systems u t i l i z i n g e l e c t r i c a l r e s i s t i v i t y
techniques.
The d e t e c t i o n of p e s t i c i d e c o n t a m i n a n t plumes, o r i g i n a t i n g
from g e n e r a l l y n o n - i o n i c o r g a n i c c h e m i c a l s , p r e s e n t s a d i f f i c u l t
s i t u a t i o n t o e f f e c t i v e l y m o n i t o r by u t i l i z i n g a p p l i c a b l e g e o p h y s i c a l
t e c h n i q u e s s u c h as e l e c t r i c a l r e s i s t i v i t y and e l e c t r o m a g n e t i c c o n -
ductivity. However, t h i s r e p o r t e d l y has been s u c c e s s f u l l y accom-
p l i s h e d where contaminant c o n c e n t r a t i o n s i n groundwater a r e g r e a t e r
t h a n 10 mg/1. A t h i g h contaminant c o n c e n t r a t i o n s the d e t e c t i o n o f
o r g a n i c plumes may be p o s s i b l e as a r e s u l t o f the f o r m a t i o n of a
c o n d u c t i v i t y low w h i c h i s a s s o c i a t e d w i t h the n o n - i o n i c c o n t a m i n a n t s
i n c o n t r a s t to the s u r r o u n d i n g h i g h l y i o n i c groundwater. Hydraulic
p r o c e s s e s o c c u r r i n g i n the u n s a t u r a t e d zone of f i n e g r a i n e d s o i l s may
a l s o r e s u l t i n the a c c u m u l a t i o n o f o r g a n i c compounds above the water
t a b l e f o r m i n g a low c o n d u c t i v i t y anomaly o v e r l y i n g the o r g a n i c
contaminant plume. I t i s a l s o p o s s i b l e that degradation by-products
o f p e s t i c i d e s may c r e a t e a mappable i o n i c contaminant plume.
S e v e r a l r e p o r t s have been p u b l i s h e d w h i c h d e s c r i b e the d e s i g n
and i m p l e m e n t a t i o n o f e l e c t r i c a l and e l e c t r o m a g n e t i c e a r l y w a r n i n g
and/or l e a k d e t e c t i o n systems ( 7 ) . The g e n e r a l p r e m i s e by w h i c h t h e
systems o p e r a t e i s t h a t by e s t a b l i s h i n g an e l e c t r i c a l r e s i s t i v i t y or
c o n d u c t i v i t y map o f a s i t e o r f a c i l i t y i n i t s n a t u r a l s t a t e t h e
e f f e c t s of p o t e n t i a l s i t e d i s c h a r g e s t o groundwater can be m o n i t o r e d
by c o n t i n u e d s i t e s u r v e y i n g . I t i s also p o s s i b l e that f o r c e r t a i n
p e s t i c i d e f i e l d a p p l i c a t i o n s i t e s the e s t a b l i s h m e n t of a b a s e l i n e
c o n d u c t i v i t y map a t s e l e c t e d d e p t h s , f o r example 1.0 m e t e r s , 3.0
Legend
Triassic
M Border Conglomerate
Cambrian
I : ; y. /M Walkill Member
Leithsville
Formation I I Hamburg Member
|~.>3 Califon Member
Karst Contact Zone (Pinnacles)
F i g u r e 17. D e t a i l e d g e o l o g i c map o f proposed f i e l d - a p p l i c a t i o n

s i t e based upon r e s u l t s o f s e i s m i c r e f r a c t i o n and e l e c t r o
magnetic c o n d u c t i v i t y s u r v e y s and t e s t b o r i n g d a t a .
F i g u r e 18. G e o l o g i c map o f f i e l d a p p l i c a t i o n s i t e showing

k a r s t f e a t u r e s and proposed m o n i t o r i n g w e l l l o c a t i o n s .
m e t e r s , and 7.5 m e t e r s , may p r o v e t o be u s e f u l i n d e t e r m i n i n g a r e a s

where s u b s u r f a c e m i g r a t i o n o f p e s t i c i d e s o r t h e i r d e g r a d a t i o n
p r o d u c t s i s o c c u r r i n g . Such t e c h n i q u e s may be a p p l i c a b l e t o u n
s a t u r a t e d and s a t u r a t e d zone m o n i t o r i n g programs.
Literature Cited
1. Lord, A. E., Jr.; Koerner, R. M.; Freestone, F. J. J. of

Hazardous Materials 1982, 5, 221-233.
2. Benson, R.C.;Glaccum, R. .; Noel, M. R. "Geophysical
Techniques for Sensing Buried Wastes and Waste Mibratum"; U. S.
Environmental Protection Agency: Las Vegas, Nev., 1984; p. 236.
3. Griffiths, P. H.; King, R. F. "Applied Geophysics for Engineers
and Geologists"; Pergammon Press: Elmsford, . Y., 1975; p. 223.
4. Kelly, W. E.; Frohlich, R. K. Groundwater 1985, 23, 182-189.
5. Alao, D. A. Bull, of the Assoc. of Eng. Geologists 1985, 22,
95-100.
6. Schwartz, F. W.; McClymont, G. L. Groundwater 1977, 15, 197-202.

7. Schultz, D. W.; Duff, . M.; Peters, W. R. Proc. Intl. Conf. on
Geomembranes, 1984, p. 445-449.
8. Evans, R. B.; Schweitzer, G. E. Environ. Sci. Technol. 1984, 18,
330A-339A.
9. Cross, J. W.; Baine, E. H.; Baine, P. M.; Carroll, R. I.; DeRose,
N.; Foster, M. A. "Industrialization of Virginia's Eastern
Shore: An Environmental Impact Study in Northampton County"
Old Dominion Univ.: Norfolk, Va.; 1977, p. 271.
10. McNeill, J. D. Technical Note TN-5 Geonics Ltd.: Ontario,
Canada, 1980, p. 22.
11. Technical Note TN-6 Geonics Ltd.: Ontario,
Canada, 1980,p.15.
12. "Ground Penetrating Radar - Summary of Capabilities", Roy F.
Weston, Inc., West Chester, PA.; 1984.
13. Koerner, R. M.; Lord, . ., Jr. Proc. 5th Natl. Conf. on
Magmt. of Uncont. Haz. Waste Sites, 1984.
14. Breiner, S. "Applications Manual for Portable Magnetometers";
Geometries: Sonnyvale, Calif., 1973; p. 58.
15. Sendlein, L. V. .; Yazicigil, H. Groundwater Monitor Rev. Fall,
1981.
16. Yazicigil, H.; Sendlein, L. V. A. Groundwater Monitor Rev.
Winter, 1982.
17. Kaufmann, R. F.; Gleason, .; Ellwood, R. B.; Lindsey, G. P.
Groundwater Monitor Rev. Fall, 1981.
18. Zohdy, A. A. R. Computer Program, Ntl. Tech. Inf. Ser., No.
PB-232703, 1973.
19. Zohdy, A. A. R. Computer Program, Ntl. Tech. Inf. Ser., No.
PB-232056, 1974.
20. Markewicz, S. J., et al. Pennsylvania Geologists Field Confer
ence Annual Meeting, Guide Book 42, 1977, p. 117.

8
DRASTIC: A System to Evaluate the Pollution
Potential of Hydrogeologic Settings by Pesticides
Linda Aller, Truman Bennett, Jay H . Lehr, and Rebecca Petty
National Water Well Association, Worthington, O H 43085
A methodology is described which allows the

pollution potential of any area to be systematic-
ally evaluated anywhere in the United States. The

system, which optimizes the use of existing data,
has two major portions: the designation of
mappable units, termed hydrogeologic settings, and
the superposition of a relative ranking system
called DRASTIC. Hydrogeologic settings incorporate
the major hydrogeologic factors which are used to
infer the potential for pesticides to enter ground
water. These factors, which form the acronym
DRASTIC, include depth to water, net recharge,
aquifer media, soil media, topography, impact of
the vadose zone and hydraulic conductivity of the
aquifer. The relative ranking scheme uses a
combination of weights and ratings to produce a
numerical value, called the DRASTIC Index, which
helps prioritize areas with respect to pollution
potential.
O n l y i n t h e past few y e a r s has t h e n a t i o n become aware o f t h e
dangers o f ground-water c o n t a m i n a t i o n and o f the many ways i n
which ground water can become contaminated. The a p p l i c a t i o n o f
p e s t i c i d e s i s one such p r a c t i c e which may r e s u l t i n ground-water
c o n t a m i n a t i o n . The p o t e n t i a l f o r c o n t a m i n a t i o n t o occur i s
a f f e c t e d by the p h y s i c a l c h a r a c t e r i s t i c s o f t h e a r e a , t h e c h e m i c a l
n a t u r e o f t h e p e s t i c i d e and t h e r a t e , frequency and method o f
a p p l i c a t i o n . Ground-water c o n t a m i n a t i o n can be minimized by
c o n t r o l l i n g t h e p e s t i c i d e a p p l i c a t i o n r a t e and f r e q u e n c y , by t h e
c h o i c e o f a p p r o p r i a t e p e s t i c i d e s and by e v a l u a t i n g and managing
p e s t i c i d e a p p l i c a t i o n i n v u l n e r a b l e areas.
T h i s paper p r e s e n t s a s t a n d a r d i z e d system which can be used
t o e v a l u a t e the ground-water p o l l u t i o n p o t e n t i a l o f any
h y d r o g e o l o g i c s e t t i n g i n t h e U n i t e d S t a t e s . The system has been
designed t o use i n f o r m a t i o n which i s a v a i l a b l e through a v a r i e t y
0097-6156/ 86/ 0315-0141 $06.00/ 0

of s o u r c e s . I n f o r m a t i o n on t h e parameters i n c l u d i n g the depth t o

water i n an a r e a , net r e c h a r g e , a q u i f e r media, s o i l media, g e n e r a l
topography o r s l o p e , vadose zone media and h y d r a u l i c
c o n d u c t i v i t y of the a q u i f e r i s n e c e s s a r y t o e v a l u a t e the ground-
water p o l l u t i o n p o t e n t i a l o f any a r e a u s i n g h y d r o g e o l o g i c s e t t i n g s .
T h i s system has been p r e p a r e d t o a s s i s t p l a n n e r s , managers
and a d m i n i s t r a t o r s i n the t a s k of e v a l u a t i n g the r e l a t i v e
v u l n e r a b i l i t y of a r e a s t o ground-water c o n t a m i n a t i o n by p e s t i c i d e s .
I t has been assumed t h a t the r e a d e r has o n l y a b a s i c knowledge of
h y d r o g e o l o g y and the p r o c e s s e s which g o v e r n ground-water
c o n t a m i n a t i o n . T h i s methodology i s n e i t h e r d e s i g n e d nor i n t e n d e d
to r e p l a c e o n - s i t e i n s p e c t i o n s . R a t h e r , i t i s i n t e n d e d t o p r o v i d e
a b a s i s f o r c o m p a r a t i v e e v a l u a t i o n of a r e a s w i t h r e s p e c t t o
p o t e n t i a l f o r p o l l u t i o n of ground water.
C l a s s i f i c a t i o n Systems
One of the fundamental needs o f any n a t u r a l s c i e n c e i s the

development of an e f f e c t i v e system t o group s i m i l a r e n t i t i e s i n t o
c a t e g o r i e s . W e l l - e s t a b l i s h e d systems e x i s t i n the f i e l d s of botany,
g e o l o g y , and many o t h e r s c i e n c e s (1). These systems p e r m i t an
a p p r o p r i a t e l y t r a i n e d person t o g a i n c e r t a i n i n s i g h t about an
e n t i t y s i m p l y by knowing the a p p r o p r i a t e c a t e g o r y i n which i t i s
grouped.
T h i s s y s t e m a t i c and l o g i c a l way of i m p o s i n g an a r t i f i c i a l
system on n a t u r a l e n t i t i e s has l o n g been used i n the f i e l d o f
g e o l o g y a l s o . For example, r o c k s have been c l a s s i f i e d a c c o r d i n g
to o r i g i n and minerals grouped a c c o r d i n g t o c r y s t a l systems.
However, as a s c i e n c e expands and changes, so must the t y p e s of
systems used t o d e s c r i b e t h o s e c h a r a c t e r i s t i c s which need t o be
s t u d i e d . The f i e l d of h y d r o g e o l o g y i s one a r e a of g e o l o g y which
has o n l y been o v e r t l y r e c o g n i z e d s i n c e t h e term was c o i n e d by
Lucas i n 1879 (2). S i n c e t h a t time h y d r o g e o l o g y has expanded,
from a d i s c i p l i n e d e v o t e d t o water o c c u r r e n c e and a v a i l a b i l i t y ,
to i n c l u d e t h e broad a s p e c t of water q u a l i t y and s o l u t e c h e m i s t r y .
D e f i n i t i o n o f water q u a l i t y i s fundamental t o the p r o t e c t i o n o f
the ground-water r e s o u r c e from p o l l u t i o n .
The i d e a of an o r g a n i z e d way to d e s c r i b e ground water systems
i s not new. H e i n z e r (3) prepared a s m a l l - s c a l e map of the U n i t e d
S t a t e s showing g e n e r a l ground-water p r o v i n c e s . Thomas (4) and
Heath (5) prepared s i m i l a r but more d e t a i l e d maps and
d e s c r i p t i o n s which grouped a q u i f e r s m a i n l y on t h e i r w a t e r - b e a r i n g
c h a r a c t e r i s t i c s w i t h i n c e r t a i n g e o g r a p h i c a r e a s . B l a n k and
Schroeder (6) attempted t o c l a s s i f y a q u i f e r s based on the
p r o p e r t i e s of r o c k s which a f f e c t ground water. Of a l l t h e s e
systems, g e o g r a p h i c ones have been more w i d e l y accepted as ways t o
d e s c r i b e the q u a n t i t y o f water which i s a v a i l a b l e i n v a r i o u s r e g i o n s .
Some E x i s t i n g Systems Which E v a l u a t e Ground-Water P o l l u t i o n

Potential
W i t h i n the l a s t 20 y e a r s the need t o expand t h e s e systems o r t o

c r e a t e a new system t o a d d r e s s ground-water q u a l i t y has become
e v i d e n t . Many d i f f e r e n t systems have been d e v e l o p e d t o a d d r e s s
s i t e s e l e c t i o n f o r waste d i s p o s a l f a c i l i t i e s such as s a n i t a r y
8. A L L E R ET AL. DRASTIC: A System to Evaluate the Pollution Potential 143
l a n d f i l l s or l i q u i d waste ponds. Among t h e s e , the LeGrand System

(7) and the m o d i f i e d v e r s i o n used by the U.S. EPA i n the S u r f a c e
Impoundment Assessment (SIA) a r e p r o b a b l y the most w e l l known.
The LeGrand system uses n u m e r i c a l w e i g h t i n g t o e v a l u a t e ground-
water p o l l u t i o n p o t e n t i a l from a g i v e n waste d i s p o s a l s i t e . By
e v a l u a t i n g the s i t e t h r o u g h a s e r i e s of f o u r s t a g e s , a d e s c r i p t i o n
of the h y d r o g e o l o g y of the s i t e , the r e l a t i v e a q u i f e r s e n s i t i v i t y
combined w i t h the contaminant s e v e r i t y , the n a t u r a l p o l l u t i o n
p o t e n t i a l p r e s e n t e d a t t h a t s i t e , and the e n g i n e e r i n g m o d i f i c a t i o n s
which might change t h a t p o t e n t i a l a r e a l l e v a l u a t e d .
The LeGrand system presupposes o n l y a l i m i t e d t e c h n i c a l
knowledge but encourages t h e user t o become f a m i l i a r w i t h the
c o n c e p t s p r e s e n t e d i n the manual so t h a t s k i l l e d judgements can be
made i n the s u b j e c t i v e p o r t i o n of the system. The s i m i l a r i t i e s
between s i t e s a r e emphasized and the uniqueness of each s i t e i s
downplayed.
The U.S. EPA methodology (8) uses the b a s i c LeGrand System

to d e f i n e the h y d r o g e o l o g i c framework, but m o d i f i e s the system t o
p l a c e emphasis on e s t a b l i s h i n g a m o n i t o r i n g p r i o r i t y f o r the
f a c i l i t y . Once the h y d r o g e o l o g i c c h a r a c t e r i s t i c s have been r a t e d ,
a t a b l e i s used t o d e f i n e the m o n i t o r i n g p r i o r i t y . T h i s p r i o r i t y
may be a d j u s t e d by the r a t e r u s i n g p r e s c r i b e d t e c h n i q u e s . Once
a g a i n , o n l y a l i m i t e d t e c h n i c a l knowledge i s presupposed.
Other systems have been designed t o t a i l o r t h e r e s u l t s t o
more s p e c i f i c purposes. T h o r n t h w a i t e and Mather (9) and Fenn e t
a l . (10) d e v e l o p e d w a t e r - b a l a n c e methods t o p r e d i c t the l e a c h a t e
g e n e r a t i o n a t s o l i d waste d i s p o s a l s i t e s . T h i s approach i s based
on the premise t h a t by knowing the amount of i n f i l t r a t i o n i n t o the
l a n d f i l l and the d e s i g n of the c e l l , t h e l e a c h a t e q u a n t i t y f o r the
l a n d f i l l can be determined. The system i s i n t e n d e d t o be used a s
a t o o l by e n g i n e e r s i n the e a r l y d e s i g n phase of a f a c i l i t y .
Gibb e t a l . (11) d e v i s e d a r a t i n g scheme t o e s t a b l i s h
p r i o r i t i e s f o r e x i s t i n g waste d i s p o s a l s i t e s w i t h r e s p e c t t o t h e i r
t h r e a t t o human h e a l t h by ground water. V i a r a n k i n g the s i t e
through f o u r f a c t o r s , (1) h e a l t h r i s k o f the waste and h a n d l i n g
mode, (2) p o p u l a t i o n a t r i s k , (3) p r o x i m i t y t o w e l l s o r a q u i f e r s ,
and (4) s u s c e p t i b i l i t y of a q u i f e r s , a number t h a t ranges from 0-
100 was used t o d i s p l a y the r e l a t i v e r i s k . The system was used i n
a s p e c i f i c 2-county assessment by t e c h n i c a l l y q u a l i f i e d i n d i v i d u a l s .
Another r a t i n g scheme, d e v e l o p e d by the M i c h i g a n Department o f
N a t u r a l Resources (12), i s d e s i g n e d t o rank l a r g e r numbers o f
s i t e s i n terms of r i s k of e n v i r o n m e n t a l c o n t a m i n a t i o n . By
e v a l u a t i n g the f i v e c a t e g o r i e s : (1) r e l e a s e p o t e n t i a l , (2)
e n v i r o n m e n t a l exposure, (3) t a r g e t s , (4) c h e m i c a l h a z a r d , and
(5) e x i s t i n g exposure, the u s e r o b t a i n s a number r a n g i n g from 0 t o
2000 p o i n t s which e v a l u a t e s the r e l a t i v e hazard o f t h a t s i t e w i t h
respect t o other s i t e s i n Michigan.
S e l l e r and Canter (13) e v a l u t e d s e v e n e m p i r i c a l methods t o
determine t h e i r u s e f u l n e s s i n p r e d i c t i n g t h e ground-water p o l l u t i o n
e f f e c t s of a waste d i s p o s a l f a c i l i t y a t a p a r t i c u l a r s i t e . The
methods they r e v i e w e d i n c l u d e d r a t i n g schemes, a d e c i s i o n t r e e
approach, a m a t r i x and a c r i t e r i a - l i s t i n g method. They determined
t h a t each method took i n t o account the n a t u r a l c o n d i t i o n s and
f a c i l i t y d e s i g n and c o n s t r u c t i o n , but t h a t each method was b e s t
a p p l i e d t o the s p e c i f i c s i t u a t i o n f o r which i t was designed.
144 EVALUATION OF PESTICIDES IN G R O U N D WATER
T h i s b r i e f r e v i e w of s e l e c t e d e x i s t i n g systems r e v e a l s t h a t
t h e r e a r e a number o f methods t h a t can be a p p l i e d t o s i t e - s p e c i f i c
s i t u a t i o n s or t o e v a l u a t i o n of the p o l l u t i o n p o t e n t i a l of e x i s t i n g
s i t e s . However, a p l a n n i n g t o o l i s needed f o r use b e f o r e t h e
s i t e - s p e c i f i c methods a r e employed. The system must (1) f u n c t i o n
as a management t o o l , (2) be s i m p l e and easy-to-use, (3) u t i l i z e
a v a i l a b l e i n f o r m a t i o n , and (4) be a b l e t o be used by i n d i v i d u a l s
w i t h d i v e r s e backgrounds and l e v e l s of e x p e r t i s e . T h i s document
c o n t a i n s a system which attempts t o meet these needs and t o p r o v i d e
the p l a n n i n g t o o l n e c e s s a r y b e f o r e s i t e - s p e c i f i c e v a l u a t i o n s .
The DRASTIC System
The system presented h e r e i n i s p a r t of a more c o m p l e t e system

d e v e l o p e d f o r the U n i t e d S t a t e s E n v o r i n m e n t a l P r o t e c t i o n Agency.
A c o m p l e t e d e s c r i p t i o n i s c o n t a i n e d i n the d r a f t document if -
570/9-84-002 (14). The methodology has two major p o r t i o n s :

the d e s i g n a t i o n of mappable u n i t s , termed h y d r o g e o l o g i c s e t t i n g s ;
and the a p p l i c a t i o n of a scheme f o r r e l a t i v e r a n k i n g of
h y d r o g e o l o g i c parameters, c a l l e d DRASTIC, which h e l p s the u s e r
e v a l u a t e the r e l a t i v e ground-water p o l l u t i o n p o t e n t i a l of any
h y d r o g e o l o g i c s e t t i n g s . A l t h o u g h the two p a r t s of the system a r e
i n t e r r e l a t e d , they a r e d i s c u s s e d s e p a r a t e l y i n a l o g i c a l
progression.
Hydrogeologic Settings
T h i s document has been prepared u s i n g the concept of h y d r o g e o l o g i c

s e t t i n g s . A h y d r o g e o l o g i c s e t t i n g i s a composite d e s c r i p t i o n of
a l l the major g e o l o g i c and h y d r o l o g i e f a c t o r s which a f f e c t and
c o n t r o l ground-water movement i n t o , through and out of an a r e a .
I t i s d e f i n e d as a mappable u n i t w i t h common h y d r o g e o l o g i c
c h a r a c t e r i s t i c s , and as a consequence, common v u l n e r a b i l i t y t o
c o n t a m i n a t i o n by i n t r o d u c e d p o l l u t a n t s . From these f a c t o r s i t i s
p o s s i b l e t o make g e n e r a l i z a t i o n s about both ground-water
a v a i l a b i l i t y and ground-water p o l l u t i o n p o t e n t i a l .
I n o r d e r t o a s s i s t u s e r s who may have a l i m i t e d knowledge of
h y d r o g e o l o g y , the e n t i r e s t a n d a r d i z e d system f o r e v a l u a t i n g ground
water p o l l u t i o n p o t e n t i a l has been d e v e l o p e d w i t h i n the framework
of an e x i s t i n g c l a s s i f i c a t i o n system of ground-water r e g i o n s of
the U n i t e d S t a t e s . Heath (5}_ d i v i d e d t h e U n i t e d S t a t e s i n t o 15
ground-water r e g i o n s based on the f e a t u r e s i n a ground-water
system which a f f e c t the o c c u r r e n c e and a v a i l a b i l i t y of ground
water ( F i g u r e 1). These r e g i o n s i n c l u d e :
1. Western Mountain Ranges

2. A l l u v i a l Basins
3. Columbia Lava P l a t e a u
4. C o l o r a d o P l a t e a u and Wyoming B a s i n
5. High P l a i n s
6. N o n g l a c i a t e d C e n t r a l Region
7. G l a c i a t e d C e n t r a l Region
8. Piedmont and B l u e Ridge
9. N o r t h e a s t and S u p e r i o r U p l a n d s
10. A t l a n t i c and G u l f C o a s t a l P l a i n
8. ALLER ET AL. DRASTIC: A System to Evaluate the Pollution Potential 145
11. Southeast C o a s t a l P l a i n
12. A l l u v i a l V a l l e y s
13. Hawaiian I s l a n d s
14. Alaska
15. P u e r t o R i c o and V i r g i n I s l a n d s
For t h e purposes o f t h e p r e s e n t system, Region 12 ( A l l u v i a l

V a l l e y s ) has been r e i n c o r p o r a t e d i n t o each o f t h e o t h e r r e g i o n s
and Region 15 ( P u e r t o R i c o and V i r g i n I s l a n d s ) has been o m i t t e d .
S i n c e t h e f a c t o r s t h a t i n f l u e n c e ground-water o c c u r r e n c e and
a v a i l a b i l i t y a l s o i n f l u e n c e t h e p o l l u t i o n p o t e n t i a l o f an a r e a ,
t h i s r e g i o n a l framework i s used t o h e l p f a m i l i a r i z e t h e user w i t h
the b a s i c h y d r o g e o l o g i c f e a t u r e s o f t h e r e g i o n .
Because p o l l u t i o n p o t e n t i a l cannot be determined on a r e g i o n a l
s c a l e , s m a l l e r " h y d r o g e o l o g i c s e t t i n g s " were d e v e l o p e d w i t h i n each
of t h e r e g i o n s d e s c r i b e d by Heath (5). These h y d r o g e o l o g i c
s e t t i n g s c r e a t e u n i t s which a r e mappable and, a t t h e same time,

permit f u r t h e r d e l i n e a t i o n o f t h e f a c t o r s which a f f e c t p o l l u t i o n
potential.
Each h y d r o g e o l o g i c s e t t i n g i s d e s c r i b e d i n a w r i t t e n n a r r a t i v e
s e c t i o n and i l l u s t r a t e d i n a b l o c k diagram. F i g u r e 2 shows t h e
format which i s used. The d e s c r i p t i o n s a r e used t o h e l p o r i e n t
the user t o t y p i c a l g e o l o g i c and h y d r o l o g i e c o n f i g u r a t i o n s which
a r e found i n each r e g i o n and t o h e l p f o c u s a t t e n t i o n on s i g n i f i c a n t
parameters which a r e i m p o r t a n t i n p o l l u t i o n p o t e n t i a l assessment.
The b l o c k diagram e n a b l e s t h e user t o v i s u a l i z e t h e d e s c r i b e d
s e t t i n g by i n d i c a t i n g i t s g e o l o g y , geomorphology and hydrogeology.
A s e t o f h y d r o g e o l o g i c s e t t i n g s has been d e v e l o p e d f o r each
ground-water r e g i o n . To d a t e , h y d r o g e o l o g i c s e t t i n g s have been
i d e n t i f i e d and d e s c r i b e d i n the U n i t e d S t a t e s . A l t h o u g h s i m i l a r
h y d r o g e o l o g i c s e t t i n g s may appear i n more than one ground-water
r e g i o n , t h e document i s designed s o t h a t once t h e broad geographic
a r e a i s l o c a t e d the user does not have t o r e f e r t o o t h e r
h y d r o g e o l o g i c s e t t i n g s i n o t h e r r e g i o n s . T h i s means t h a t a l t h o u g h
s i m i l a r h y d r o g e o l o g i c s e t t i n g s may appear more than once i n t h e
document, they have been t a i l o r e d t o r e f l e c t t h e t y p i c a l
h y d r o g e o l o g i c c o n d i t i o n s w i t h i n each i n d i v i d u a l r e g i o n .
Factors Affecting P o l l u t i o n P o t e n t i a l
I n h e r e n t i n each h y d r o g e o l o g i c s e t t i n g a r e t h e p h y s i c a l
c h a r a c t e r i s t i c s which a f f e c t t h e ground-water p o l l u t i o n
p o t e n t i a l . Many d i f f e r e n t b i o l o g i c a l , p h y s i c a l and c h e m i c a l
mechanisms may a c t i v e l y a f f e c t t h e a t t e n u a t i o n o f a contaminant
and, t h u s , t h e p o l l u t i o n p o t e n t i a l o f t h a t system. Because i t i s
n e i t h e r p r a c t i c a l nor f e a s i b l e t o o b t a i n q u a n t i t a t i v e e v a l u a t i o n s
of i n t r i n s i c mechanisms from a r e g i o n a l p e r s p e c t i v e , i t i s
necessary t o l o o k a t the broader parameters which i n c o r p o r a t e t h e
many processes. A f t e r a c o m p l e t e e v a l u a t i o n o f many c h a r a c t e r -
i s t i c s and t h e m a p p a b i l i t y o f the d a t a , t h e most i m p o r t a n t
mappable f a c t o r s t h a t c o n t r o l t h e ground-water p o l l u t i o n p o t e n t i a l
were determined t o be:
D - Depth t o Water
R - (Net) Recharge
F i g u r e 2. Format o f h y d r o g e o l o g i c s e t t i n g . This setting i s

i d e n t i c a l t o 10Ba R i v e r A l l u v i u m w i t h Overbank e x c e p t t h a t no
s i g n i f i c a n t f i n e - g r a i n e d f l o o d p l a i n d e p o s i t s occupy the stream
valley. T h i s r e s u l t s i n s i g n i f i c a n t l y h i g h e r r e c h a r g e and sandy
s o i l s a t the s u r f a c e . Water l e v e l s a r e t y p i c a l l y c l o s e r t o the
s u r f a c e because banks o f f i n e - g r a i n e d d e p o s i t s a r e not p r e s e n t .
Throughout much o f t h i s r e g i o n , t h e r e i s an abundance o f c o u r s e -
g r a i n e d m a t e r i a l , which l i m i t s t h i s s e t t i n g f o r water s u p p l y .
These m a t e r i a l s however, p r o v i d e a good s o u r c e o f r e c h a r g e to the
u n d e r l y i n g c o n s o l i d a t e d and s e m i c o n s o l i d a t e d b e d r o c k . Reproduced
w i t h p e r m i s s i o n from r e f e r e n c e 14.
A - A q u i f e r Media
S - S o i l Media
T - Topography ( S l o p e )
I - Impact o f the Vadose Zone
C - ( H y d r a u l i c ) C o n d u c t i v i t y o f the A q u i f e r
These f a c t o r s have been a r r a n g e d t o form t h e acronym, DRASTIC

f o r ease o f r e f e r e n c e . W h i l e t h i s l i s t i s not a l l i n c l u s i v e ,
t h e s e f a c t o r s , i n c o m b i n a t i o n , were determined t o i n c l u d e t h e
b a s i c r e q u i r e m e n t s needed t o a s s e s s the g e n e r a l p o l l u t i o n p o t e n t i a l
of each h y d r o g e o l o g i c s e t t i n g . The DRASTIC f a c t o r s r e p r e s e n t
measurable parameters f o r which d a t a a r e g e n e r a l l y a v a i l a b l e from
a v a r i e t y of sources without d e t a i l e d reconnaissance. I t i s
r e c o g n i z e d t h a t many o f the f a c t o r s may be c o n s i d e r e d t o be o v e r -
l a p p i n g . However, g r e a t c a r e has been t a k e n t o t r y t o s e p a r a t e
the f a c t o r s f o r purposes o f the d e v e l o p e d system. A c o m p l e t e
d e s c r i p t i o n o f the i m p o r t a n t mechanisms c o n s i d e r e d w i t h i n each

f a c t o r and a d e s c r i p t i o n o f the s i g n i f i c a n c e o f the f a c t o r s f o l l o w s .
A D e s c r i p t i o n o f the DRASTIC F a c t o r s
Depth t o Water. The water t a b l e i s the e x p r e s s i o n o f the s u r f a c e

below the ground l e v e l where a l l the pore spaces a r e f i l l e d w i t h
water. Above the water t a b l e , the pore spaces a r e f i l l e d w i t h
water and a i r . The water t a b l e may be p r e s e n t i n any t y p e o f
media and may be e i t h e r permanent o r s e a s o n a l . Depth t o water
r e f e r s t o the depth t o the water s u r f a c e i n an u n c o n f i n e d a q u i f e r .
Depth t o water does not i n c l u d e s a t u r a t e d zones which have
i n s u f f i c i e n t p e r m e a b i l i t y t o y i e l d s i g n i f i c a n t enough q u a n t i t i e s
of water t o be c o n s i d e r e d an a q u i f e r .
T h i s document a l s o c a n be used t o e v a l u a t e u n c o n f i n e d a q u i f e r s .
For purposes o f t h i s document, depth t o water r e f e r s t o the top o f
the a q u i f e r where the a q u i f e r i s c o n f i n e d . I n t h i s case, depth t o
water may i n c l u d e s a t u r a t e d zones above t h e top o f the a q u i f e r .
The depth t o water i s i m p o r t a n t p r i m a r i l y because i t
d e t e r m i n e s t h e depth o f m a t e r i a l through which a contaminant must
t r a v e l b e f o r e r e a c h i n g the a q u i f e r , and i t may h e l p t o determine
the amount o f time d u r i n g which c o n t a c t w i t h the s u r r o u n d i n g media
i s m a i n t a i n e d . The depth t o water i s a l s o i m p o r t a n t because i t
p r o v i d e s t h e maximum o p p o r t u n i t y f o r o x i d a t i o n by a t m o s p h e r i c
oxygen. I n g e n e r a l , t h e r e i s a g r e a t e r chance f o r a t t e n u a t i o n t o
o c c u r a s t h e depth t o water i n c r e a s e s because deeper water l e v e l s
i n f e r longer t r a v e l times.
Net Recharge. The p r i m a r y s o u r c e o f ground water i s p r e c i p i t a t i o n

which i n f i l t r a t e s t h r o u g h the s u r f a c e o f t h e ground and p e r c o l a t e s
to the water t a b l e . Net r e c h a r g e i n d i c a t e s the amount o f v/ater
per u n i t a r e a o f l a n d which p e n e t r a t e s t h e ground s u r f a c e and
r e a c h e s the water t a b l e . A l t h o u g h t h i s amount o f water may v a r y
s e a s o n a l l y or a n n u a l l y , a water b a l a n c e i s u s u a l l y a c h i e v e d o r
l o n g - t e r m t r e n d s can be e s t a b l i s h e d . T h i s r e c h a r g e water i s thus
a v a i l a b l e t o t r a n s p o r t a contaminant v e r t i c a l l y t o t h e v/ater t a b l e
and h o r i z o n t a l l y w i t h i n t h e a q u i f e r . I n a d d i t i o n , the q u a n t i t y t o
water a v a i l a b l e f o r d i s p e r s i o n and d i l u t i o n i n the vadose zone and
i n t h e s a t u r a t e d zone is c o n t r o l l e d by. this,*parameter. I n a r e a s
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where the a q u i f e r i s u n c o n f i n e d , recharge t o the a q u i f e r u s u a l l y

o c c u r s more r e a d i l y and the p o l l u t i o n p o t e n t i a l i s g e n e r a l l y
g r e a t e r than i n a r e a s w i t h c o n f i n e d a q u i f e r s . C o n f i n e d a q u i f e r s
a r e p a r t i a l l y p r o t e c t e d from c o n t a m i n a n t s i n t r o d u c e d a t the
s u r f a c e by l a y e r s of low p e r m e a b i l i t y media ( a q u i t a r d s ) which
r e t a r d water movement t o the c o n f i n e d a q u i f e r . In p a r t s of some
c o n f i n e d a q u i f e r s , head d i s t r i b u t i o n i s such t h a t movement of
v/ater i s through the c o n f i n i n g bed from the c o n f i n e d a q u i f e r i n t o
the u n c o n f i n e d a q u i f e r . In t h i s s i t u a t i o n , t h e r e i s l i t t l e
o p p o r t u n i t y f o r l o c a l c o n t a m i n a t i o n of the c o n f i n e d a q u i f e r . The
p r i n c i p a l recharge a r e a f o r the c o n f i n e d a q u i f e r i s o f t e n many
m i l e s away. Many c o n f i n e d a q u i f e r s a r e not t r u l y c o n f i n e d and a r e
p a r t i a l l y recharged by m i g r a t i o n of water through the c o n f i n i n g
l a y e r s . The more water t h a t l e a k s through, the g r e a t e r the
p o t e n t i a l f o r recharge t o c a r r y p o l l u t i o n i n t o the a q u i f e r .
Recharge v/ater, then, i s a p r i n c i p a l v e h i c l e f o r l e a c h i n g and
t r a n s p o r t i n g s o l i d or l i q u i d contaminants t o the water t a b l e .

T h e r e f o r e , the g r e a t e r the recharge, the g r e a t e r the p o t e n t i a l
p o l l u t i o n . T h i s i s t r u e u n t i l the amount of recharge i s g r e a t
enough t o cause d i l u t i o n of any contaminant which would be
i n t r o d u c e d i n t o the system. At t h i s p o i n t , the p o l l u t i o n p o t e n t i a l
v/ould cease t o i n c r e a s e and might a c t u a l l y decrease. For purposes
of t h i s document, t h i s phenomenon has been acknowledged but the
system does not r e f l e c t the d i l u t i o n f a c t o r .
One a d d i t i o n a l f a c t o r w h i c h must be c o n s i d e r e d i s augmenta-
t i o n of n a t u r a l recharge through a r t i f i c i a l recharge or by
irrigation. When a range f o r net recharge i s a s s i g n e d , these
a d d i t i o n a l sources of water must be c o n s i d e r e d .
A q u i f e r Media. A q u i f e r media r e f e r s t o the c o n s o l i d a t e d or

u n c o n s o l i d a t e d medium which s e r v e s as an a q u f i e r (such as sand and
g r a v e l or l i m e s t o n e . An a q u i f e r i s d e f i n e d as a w a t e r - b e a r i n g
rock f o r m a t i o n which w i l l y i e l d s u f f i c i e n t q u a n t i t i e s of
v/ater f o r use. Water i s h e l d by a q u i f e r s i n the pore spaces of
g r a n u l a r and c l a s t i c rock and i n the f r a c t u r e s and s o l u t i o n
openings of n o n - c l a s t i c and n o n - g r a n u l a r rock. Rocks which y i e l d
v/ater from pore spaces have primary p o r o s i t y ; r o c k s where the
water i s h e l d i n openings such as f r a c t u r e s and s o l u l t i o n
openings which were c r e a t e d a f t e r the r o c k was formed have
secondary p o r o s i t y . The a q u i f e r medium e x e r t s the major c o n t r o l
o v e r the r o u t e and path l e n g t h which a contaminant must f o l l o w .
The path l e n g t h i s an i m p o r t a n t c o n t r o l ( a l o n g w i t h h y d r a u l i c
c o n d u c t i v i t y and g r a d i e n t ) i n d e t e r m i n i n g the time a v a i l a b l e f o r
a t t e n u a t i o n p r o c e s s e s such as s o r p t i o n , r e a c t i v i t y and d i s p e r s i o n
and a l s o the amount of e f f e c t i v e s u r f a c e a r e a of m a t e r i a l s
c o n t a c t e d i n the a q u i f e r . The r o u t e which a contaminant w i l l take
can be s t r o n g l y i n f l u e n c e d by f r a c t u r i n g or by any o t h e r f e a t u r e
such as i n t e r c o n n e c t e d s e r i e s of s o l u t i o n openings which may
p r o v i d e pathways f o r e a s i e r f l o w . In g e n e r a l , the l a r g e r the
g r a i n s i z e and the more f r a c t u r e s or openings w i t h i n the a q u i f e r ,
the h i g h e r the p e r m e a b i l i t y and the l o w e r the a t t e n u a t i o n c a p a c i t y ;
c o n s e q u e n t l y the g r e a t e r the p o l l u t i o n p o t e n t i a l .
S o i l Media. S o i l media r e f e r s t o t h a t uppermost p o r t i o n of the

vadose zone c h a r a c t e r i z e d by s i g n i f i c a n t b i o l o g i c a l a c t i v i t y . For
8. ALLER ET AL. DRASTIC: A System to Evaluate the Pollution Potential 149
purposes o f t h i s document, s o i l i s commonly c o n s i d e r e d t h e upper

weathered zone o f t h e e a r t h which a v e r a g e s s i x f e e t o r l e s s . Soil
has a s i g n i f i c a n t impact o f t h e amount o f r e c h a r g e which can
i n f i l t r a t e i n t o t h e ground and, hence, on t h e a b i l i t y o f a
contaminant t o move v e r t i c a l l y i n t o t h e vadose zone. M o r e o v e r ,
the a t t e n u a t i o n p r o c e s s e s o f f i l t r a t i o n , biodgradation, s o r p t i o n
and v o l a t i l i z a t i o n may be q u i t e s i g n i f i c a n t i n t h i s zone. Thus,
f o r c e r t a i n o n - l a n d s u r f a c e p r a c t i c e s such a s a p p l i c a t i o n s o f
p e s t i c i d e s , s o i l can be a p r i m a r y i n f l u e n c e on p o l l u t i o n p o t e n t i a l .
In g e n e r a l , t h e p o l l u t i o n p o t e n t i a l o f a s o i l i s l a r g e l y a f f e c t e d
by t h e type o f c l a y p r e s e n t , t h e s h r i n k / s w e l l p o t e n t i a l of t h a t
c l a y and t h e s o i l t e x t u r e . The q u a n t i t y o f o r g a n i c m a t e r i a l p r e s e n t
i n t h e s o i l may a l s o be a major f a c t o r . I n g e n e r a l , t h e l e s s t h e
c l a y s h r i n k s and s w e l l s and t h e f i n e r t h e t e x t u r e , and t h e g r e a t e r
the o r g a n i c c o n t e n t , t h e l e s s t h e p o l l u t i o n p o t e n t i a l . S o i l media
a r e b e s t d e s c r i b e d by r e f e r r i n g t o t h e b a s i c s o i l types a s
c l a s s i f i e d by t h e S o i l C o n s e r v a t i o n S e r v i c e .
Topography. As used here, topography r e f e r s t o t h e s l o p e and

s l o p e v a r i a b i l i t y o f t h e l a n d s u r f a c e . B a s i c a l l y , topography
helps c o n t r o l the l i k e l i h o o d that a p o l l u t a n t w i l l run o f f or
remain on t h e s u r f a c e i n one a r e a l o n g enough t o i n f i l t r a t e .
T h e r e f o r e , t h e g r e a t e r t h e chance of i n f i l t r a t i o n , t h e h i g h e r t h e
p o l l u t i o n p o t e n t i a l a s s o c i a t e d w i t h t h e s l o p e . Topography
i n f l u e n c e s s o i l development and t h e r e f o r e has an e f f e c t on
a t t e n u a t i o n . Topography i s a l s o s i g n i f i c a n t from t h e s t a n d p o i n t
t h a t t h e g r a d i e n t and d i r e c t i o n o f f l o w o f t e n can be i n f e r r e d by
water t a b l e c o n d i t i o n s from t h e g e n e r a l s l o p e o f t h e l a n d .
T y p i c a l l y , s t e e p e r s l o p e s s i g n i f y h i g h e r ground-water v e l o c i t y .
Impact o f Vadose Zone. The vadose zone i s d e f i n e d a s t h a t zone

above t h e water t a b l e and below t h e s o i l media which i s u n s a t u r a t e d .
For purposes o f t h i s document, t h i s s t r i c t d e f i n i t i o n can be
a p p l i e d t o a l l water t a b l e a q u i f e r s . However, when e v a l u a t i n g a
c o n f i n e d a q u i f e r , t h e "impact" o f t h e vadose zone i s expanded t o
i n c l u d e both t h e vadose zone and a n y s a t u r a t e d zones which o v e r l i e
the a q u i f e r . The s i g n i f i c a n t l y r e s t r i c t i v e zone above t h e a q u i f e r
which forms t h e c o n f i n i n g l a y e r i s used a s t h e type o f medium which
has t h e most s i g n i f i c a n t impact.
The type o f vadose zone media d e t e r m i n e s t h e a t t e n u a t i o n
c h a r a c t e r i s t i c s o f t h e m a t e r i a l below t h e t y p i c a l s o i l h o r i z o n and
above t h e water t a b l e . Biodgradation, n e u t r a l i z a t i o n , m e c h a n i c a l
f i l t r a t i o n , c h e m i c a l r e a c t i o n and d i s p e r s i o n a r e a l l p r o c e s s e s
which may o c c u r w i t h i n t h e vadose zone w i t h a g e n e r a l l e s s e n i n g o f
biodgradation w i t h depth. The media a l s o c o n t r o l t h e path l e n g t h
and r o u t i n g , thus a f f e c t i n g time a v a i l a b l e f o r a t t e n u a t i o n and t h e
q u a n t i t y o f m a t e r i a l encountered. The r o u t i n g i s s t r o n g l y i n f l u e n c e d
by any f r a c t u r i n g present. The m a t e r i a l s a t t h e t o p o f t h e vadose
zone a l s o e x e r t an i n f l u e n c e on s o i l development.
Hydraulic Conductivity of the Aquifer. Hydraulic c o n d u c t i v i t y

r e f e r s t o t h a a b i l i t y o f t h e a q u i f e r m a t e r i a l s t o t r a n s m i t water,
which i n t u r n , c o n t r o l s t h e r a t e a t which ground water w i l l f l o w
under a g i v e n h y d r a u l i c g r a d i e n t . The r a t e a t which t h e ground
w a t e r f l o w s a l s o c o n t r o l s t h e r a t e a t w h i c h a contaminant w i l l be
moved away from t h e p o i n t a t which i t e n t e r s t h e a q u i f e r . H y d r a u l i c

c o n d u c t i v i t y i s c o n t r o l l e d by t h e amount o f i n t e r c o n n e c t i o n o f
v o i d spaces w i t h i n t h e a q u i f e r which may occur a s a consequence o f
i n t e r g r a n u l a r p o r o s i t y , f r a c t u r i n g , bedding p l a n e s , e t c . F o r
purposes o f t h i s document, h i g h h y d r a u l i c c o n d u c t i v i t i e s a r e
a s s o c i a t e d w i t h h i g h e r p o l l u t i o n p o t e n t i a l . T h i s i s because t h e
p o l l u t a n t has t h e p o t e n t i a l f o r moving q u i c k l y away from t h e p o i n t
i n t h e a q u i f e r where i t i s i n t r o d u c e d . O b v i o u s l y , a wide range o f
h y d r a u l i c c o n d u c t i v i t i e s may be p r e s e n t i n a l l a r e a s .
DRASTIC
A n u m e r i c a l r a n k i n g system t o a s s e s s ground-water p o l l u t i o n
p o t e n t i a l i n h y d r o g e o l o g i c s e t t i n g s has been d e v i s e d u s i n g t h e
DRASTIC f a c t o r s . The system c o n t a i n s t h r e e s i g n i f i c a n t p a r t s :
w e i g h t s , ranges and r a t i n g s . A d e s c r i p t i o n of t h e t e c h n i q u e used
f o r w e i g h t s and r a t i n g s can be found i n Dee e t a l . (15).
Weights. Each DRASTIC f a c t o r has been e v a l u a t e d w i t h r e s p e c t t o

the o t h e r t o determine t h e r e l a t i v e importance o f each f a c t o r .
Each DRASTIC f a c t o r has been a s s i g n e d a r e l a t i v e weight r a n g i n g
from 1 t o 5 ( T a b l e I ) . The most s i g n i f i c a n t f a c t o r s have w e i g h t s
of 5; t h e l e a s t s i g n i f i c a n t , a weight o f 1. T h i s e x e r c i s e was
a c c o m p l i s h e d by an a d v i s o r y committee u s i n g a D e l p h i (consensus)
approach. These w e i g h t s a r e a c o n s t a n t and may n o t be changed
when u s i n g t h e system.
T a b l e I . A s s i g n e d Weights f o r DRASTIC F e a t u r e s
"Reproduced from Ref. 14"
Feature A g r i c u l t u r a l Weight
Depth t o Water T a b l e 5
Net Recharge 4
A q u i f e r Media 3
S o i l Media 5
Topography 3
Impact o f t h e Vadose Zone 4
Hydraulic C o n d u c t i v i t y of the Aquifer 2
Source: Reproduced w i t h p e r m i s s i o n from r e f e r e n c e 14.
Ranges. Each DRASTIC f a c t o r i s d i v i d e d i n t o e i t h e r ranges o r

s i g n i f i c a n t media t y p e s which have an impact on p o l l u t i o n p o t e n t i a l
( T a b l e s I I - V I I I ) . The media t y p e s have been a s s i g n e d d e s c r i p t i v e
names t o a s s i s t t h e user.
8. ALLER ET AL. DRASTIC: A System to Evaluate the Pollution Potential
Table II. Ranges and R a t i n g s f o r Depth t o Water
Depth t o Water (feet)
Range Rating
0-5 10
5-15 9
15-30 7
30-50 5
50-75 3
75-100 2
100+ 1
Source: Reproduced w i t h p e r m i s s i o n from r e f e r e n c e 1 4 .
Table I I I . Ranges and R a t i n g s f o r Met Recharge
Net Recharge (inches)
Range Rating
0-2 1
2-4 3
4-7 6
7-10 8
10+ 9
Table I V . Ranges and R a t i n g s f o r A q u i f e r M e d i a
A q u i f e r Media
Range Rating Typical Ratin
Massive Shale 1- 3 2
Metamorphic/Igneous 2- 5 3
Weathered Metamorphic/Igneous 3- 5 4
T h i n Bedded Sandstone,
Limestone, S h a l e Sequences 5-9 6
M a s s i v e Sandstone 4- 9 6
M a s s i v e Limestone 4-9 6
Sand and G r a v e l 4-9 8
Basalt 2-10 9
K a r s t Limestone 9-10 10

T a b l e V. Ranges and R a t i n g s f o r S o i l Media
S o i l Media
Range Rating
T h i n o r Absent 10
Gravel 10
Sand 9
Peat 8
S h r i n k i n g and/or Aggregated C l a y 7
Sandy Loam 6
Loam 5
S i l t y Loam 4
C l a y Loam 3
Muck 2
N o n s h r i n k i n g and Nonaggregated C l a y 1
Table V I . Ranges and R a t i n g s f o r Topography
Topography ( p e r c e n t slope)
Range Rating
0-2 10
2-6 9
6-12 5
12-18 3
18+ 1
T a b l e VI. Ranges and R a t i n g s f o r Impace o f Vadose Zone Media
Impact o f Vadose Zone Media
Range Rating Typical Rating
Silt/Clay 1-2 1
Shale 2-5 3
Limestone 2-7 6
Sandstone 4-8 6
Bedded Limestone, Sandstone, S h a l e 4-8 6
Sand and G r a v e l w i t h
s i g n i f i c a n t S i l t and C l a y 4-8 6
Metamorphic/Igneous 2-8 4
Sand and G r a v e l 6-9 S
Basalt 2-10 9
K a r s t Limestone 8-10 !P_
8. ALLER ET AL. DR/iSTIC: A System to Evaluate the Pollution Potential 153
Table VIII. Ranges and R a t i n g s f o r H y d r a u l i c C o n d u c t i v i t y
H y d r a u l i c C o n d u c t i v i t y (gpd/ft )
Range Rating
1-100 1
100-300 2
300-700 4
700-1000 6
1000-2000 8
2000+ 10

R a t i n g s . Each range f o r each DRASTIC f a c t o r has been e v a l u a t e d

w i t h r e s p e c t t o t h e o t h e r s t o determine t h e r e l a t i v e s i g n i f i c a n c e
of each range w i t h r e s p e c t t o p o l l u t i o n p o t e n t i a l . Based on
graphs, t h e range f o r each DRASTIC f a c t o r has been a s s i g n e d a
r a t i n g which v a r i e s between 1 and 10 ( T a b l e s I I - V I I I ) . The f a c t o r s
o f D, R, S, T, and C h a v e been a s s i g n e d one v a l u e p e r r a n g e . A
and I have been a s s i g n e d a " t y p i c a l " r a t i n g and a v a r i a b l e r a t i n g .
The v a r i a b l e r a t i n g a l l o w s t h e user t o choose e i t h e r a t y p i c a l
v a l u e o r t o a d j u s t t h e v a l u e based on more s p e c i f i c knowledge.
T h i s system a l l o w s t h e user t o determine a n u m e r i c a l v a l u e
f o r any h y d r o g e o l o g i c s e t t i n g by u s i n g an a d d i t i v e model. The
e q u a t i o n f o r d e t e r m i n i n g t h e DRASTIC Index i s :
DD +RR + A A + S S + T T + 1 1 + C C = Pol lution Potentia1

R V R W RW R W R W R V RW
Where :
R = rating
W = weight
Once a DRASTIC Index has been computed, i t i s p o s s i b l e t o

i d e n t i f y a r e a s which a r e l i k e l y t o be s u s c e p t i b l e t o ground v/ater
c o n t a m i n a t i o n r e l a t i v e t o one another. The h i g h e r t h e DRASTIC
Index, t h e g r e a t e r t h e ground-water p o l l u t i o n p o t e n t i a l . The
DRASTIC Index p r o v i d e s o n l y a r e l a t i v e e v a l u a t i o n t o o l and i s n o t
designed t o p r o v i d e a b s o l u t e answers.
T a b l e IX shows a t y p i c a l index computed f o r t h e h y d r o g e o l o g i c
s e t t i n g , lOBa R i v e r A l l u v i u m w i t h o u t Overbank, which i s d e s c r i b e d
i n F i g u r e 2. I n c o n t r a s t , T a b l e X and F i g u r e 3 i l l u s t r a t e a v e r y
s i m i l a r hydrogeologic s e t t i n g with a p o l l u t i o n p o t e n t i a l that i s
s i g n i f i c a n t l y lower. These numbers, a l t h o u g h not unique v a l u e s ,
can be e v a l u a t e d w i t h r e s p e c t t o one another by knowing t h a t f o r
a] 1 h y d r o g e o l o g i c s e t t i n g s e v a l u a t e d i n t h e U n i t e d S t a t e s , DRASTIC
I n d i c e s ranged from 53 t o 224. T h i s r e l a t i v e comparison h e l p s t h e
user e v a l u a t e p o l l u t i o n p o t e n t i a l w i t h r e s p e c t t c any o t h e r a r e a .
In a r e a s o f w i d e l y v a r i a b l e h y d r o g e o l o g y , t h e p o l l u t i o n p o t e n t i a l
T a b l e I X C o m p u t a t i o n o f the DRASTIC Index f o r S e t t i n g

10 B b - R i v e r A l l u v i u m W i t h o u t Overbank D e p o s i t
SETTING 10 Bb R i v e r A l l u v i u m Without AGRICULTURAL

Overbank D e p o s i t
FEATURE RANGE WEIGHT RATING NUMBER
Depth t o water table 5-15 5 9 45
Net Recharge 10+ 4 9 36
A q u i f e r Media Sand and G r a v e l 3 8 24
Soil Media Sand 5 9 45

Topography 0-2$ 3 10 30
Impact Vadose zone S & G w/sig. Silt 4 6 24
Hydraulic Conductivity 1000-2000 2 8 16
Agricultural
D r a s t i c Index 220
T a b l e X C o m p u t a t i o n o f t h e DRASTIC Index f o r S e t t i n g 10Ba-River

A l l u v i u m w i t h Overbank D e p o s i t
SETTING 10 Ba R i v e r A l l u v i u m With AGRICULTURAL

Overbank D e p o s i t
FEATURE RANGE WEIGHT RATING NUMBER
Depth t o Water T a b l e 15-30 5 7 35
Net Recharge 7-10 4 8 32
A q u i f e r Media Sand and G r a v e l 3 8 24
Soil Media Silty Loam 5 4 20
Topography 0-2? 3 10 30
Impact Vadose Silt/Clay 4 1 4
Hydraulic Conductivity 700-1000 2 6 12
Agricultural
D r a s t i c Index 157
SOURCE: Reproduced w i t h p e r m i s s i o n from r e f e r e n c e 14.

F i g u r e 3. Sample h y d r o g e o l o g i c s e t t i n g i n A t l a n t i c and G u l f
Coastal Plain. T h i s h y d r o g e o l o g i c s e t t i n g i s c h a r a c t e r i z e d by
low topography and t h i n t o m o d e r a t e l y t h i c k d e p o s i t s o f a l l u v i u m
along parts o f r i v e r v a l l e y s . The a l l u v i u m i s u n d e r l a i n by
c o n s o l i d a t e d and s e m i c o n s o l i d a t e d s e d i m e n t a r y r o c k s . Water i s
o b t a i n e d from sand and g r a v e l l a y e r s which a r e i n t e r b e d d e d w i t h
finer-grained a l l u v i a l deposits. The f l o o d p l a i n i s c o v e r e d by
varying thicknesses o f fine-grained, s i l t y deposits called
overbank d e p o s i t s . The overbank t h i c k n e s s i s u s u a l l y g r e a t e r
a l o n g major streams (as much as 40 f e e t ) and t h i n n e r a l o n g minor
streams. P r e c i p i t a t i o n i n t h e r e g i o n i s abundant, b u t r e c h a r g e
i s reduced because o f t h e s i l t y s o i l s which t y p i c a l l y c o v e r t h e
surface. Water l e v e l s a r e t y p i c a l l y m o d e r a t e l y s h a l l o w . The
a l l u v i u m may s e r v e as a s i g n i f i c a n t s o u r c e o f water and may be i n
d i r e c t h y d r a u l i c connection with the u n d e r l y i n g sedimentary r o c k s .
The a l l u v i u m may a l s o s e r v e as a s o u r c e o f r e c h a r g e t o t h e u n d e r l y i n g
bedrock. Many streams i n t h i s s e t t i n g p r o v i d e o n l y f i n e - g r a i n e d
d e p o s i t s ( s i l t s and c l a y s ) and as such do n o t form good a q u i f e r s .
They s t i l l , however, p r o v i d e a good s o u r c e o f r e c h a r g e . Reproduced
w i t h p e r m i s s i o n from r e f e r e n c e 14.
may a l s o v a r y w i d e l y w i t h an a s s o c i a t e d spread o f DRASTIC I n d i c e s .

I n a r e a s v/ith more s u b t l e changes i n h y d r o g e o l o g y , t h e DRASTIC
I n d i c e s would r e f l e c t more s u b t l e changes. The system does n o t
attempt t o d e f i n e "good" o r "bad" a r e a s , but s i m p l y o f f e r s t h e
user a t o o l t o e v a l u a t e t h e r e l a t i v e p o l l u t i o n p o t e n t i a l o f whatever
a r e a s a r e d e s i r e d . The user may wish t o then c o n s i d e r a d d i t i o n a l
f a c t o r s such as importance o f the a q u i f e r p o p u l a t i o n o r o t h e r
f a c t o r s i n f u l l y a s s e s s i n g t h e importance o f p o l l u t i o n p o t e n t i a l i n
any a r e a .
S t a t u s o f the P r o j e c t
T h i s paper summarizes t h e e f f o r t s t o produce a s t a n d a r d i z e d system

to e v a l u a t e ground water p o l l u t i o n p o t e n t i a l . The p r o j e c t was
designed t o span two years. During t h e f i r s t year, t h e
methodology was d e v e l o p e d w i t h t h e h e l p o f an a d v i s o r y committee.
The second phase o f t h e p r o j e c t comprises a year o f t e s t i n g o f

the system through a s e r i e s o f demonstration mapping p r o j e c t s
conducted i n t e n c o u n t i e s throughout t h e u n i t e d S t a t e s . These
c o u n t i e s a r e being chosen f o r t h e i r wide v a r i a b i l i t y i n
h y d r o g e o l o g y and t h e i r p o s i t i o n i n d i f f e r e n t ground-water r e g i o n s .
During t h i s v e r i f i c a t i o n s t a g e , t h e system w i l l be expanded and
changed t o more f u l l y i n c o r p o r a t e t h e e l e m e n t s which w i l l make t h e
DRASTIC methodology most u s e f u l t o u s e r s .
Conculsions
I t i s e v i d e n t t h a t a l l o f t h e DRASTIC parameters a r e i n t e r a c t i n g ,
dependent v a r i a b l e s . T h e i r s e l e c t i o n i s based on a v a i l a b l e data
q u a n t i t a t i v e l y d e v e l o p e d and r i g o r o u s l y a p p l i e d , but on a
s u b j e c t i v e understanding of " r e a l world" c o n d i t i o n s a t a g i v e n
a r e a . The v a l u e o f t h e DRASTIC parameters i s i n t h e f a c t t h a t
they a r e based on i n f o r m a t i o n t h a t i s r e a d i l y a v a i l a b l e f o r most
p o r t i o n s of t h e U n i t e d S t a t e s , and which can be o b t a i n e d and
m e a n i n g f u l l y mapped i n a minimum o f time and a t minimum c o s t . The
DRASTIC r a n k i n g scheme can then be a p p l i e d by e n l i g h t e n e d laymen
for v a l i d comparative e v a l u a t i o n s with acceptable r e s u l t s .
Acknowledgments
The work was funded by t h e U n i t e d S t a t e s E n v i r o n m e n t a l P r o t e c t i o n

Agency through t h e Robert S. K e r r Research L a b o r a t o r y , Ada,
Oklahoma. The a u t h o r s hereby extend t h e i r thanks t o Jack K e e l e y
and J e r r y T h o r n h i l l o f t h e U.S. EPA f o r t h e i r a s s i s t a n c e d u r i n g
the p r o j e c t . G r a t e f u l acknowledgment o f t h e c o n t r i b u t i o n s o f a
v e r y a b l e a d v i s o r y committee i s a l s o made:
M i c h a e l Apgar, De lav/are Department o f N a t u r a l Resources

J i m Bachmaier, U.S. EPA, O f f i c e o f S o l i d Waste
W i l l i a m Back, USGS
Harvey Banks, C o n s u l t i n g E n g i n e e r , I n c .
Truman Bennett, Bennett & W i l l i a m s , I n c .
Robert . Bergstrom, I l l i n o i s S t a t e G e o l o g i c a l Survey
Stephen Born, U n i v e r s i t y o f W i s c o n s i n
Keros C a r t w r i g h t , I l l i n o i s S t a t e G e o l o g i c a l S u r v e y
8. ALLER ET AL. DRASTIC: A System to Evaluate the Pollution Potential
S t u a r t Cohen, U.S. EPA, O f f i c e o f P e s t i c i d e Programs

S t e v e CorcHe, U.S. EPA, O f f i c e o f Research & Development
George H. D a v i s , USGS, r e t i r e d
Stan D a v i s , U n i v e r s i t y o f A r i z o n a
A r t Day, U.S. EPA, Land D i s p o s a l Branch, O f f i c e o f S o l i d
Waste
N o r b e r t Dee, U.S. EPA, O f f i c e o f Ground Water P r o t e c t i o n
Donald A. Duncan, South C a r o l i n a Department o f H e a l t h and
Environmental Control
C a t h e r i n e E i d e n , U.S. EPA, O f f i c e o f P e s t i c i d e Programs
G r o v e r Emrich, SMC M a r t i n , I n c .
G l e n G a l e n , U.S. EPA, Land D i s p o s a l Branch, O f f i c e o f S o l i d
Waste
P h y l l i s Carman, C o n s u l t a n t , Tennessee
J i m Gibb, I l l i n o i s S t a t e Water S u r v e y
Todd G i d d i n g s , Todd G i d d i n g s & A s s o c i a t e s , I n c .
R a l p h Heath, USGS, r e t i r e d
Ron H o f f e r , U.S. EPA, O f f i c e o f Ground Water P r o t e c t i o n
George Hughes, O n t a r i o M i n i s t r y o f t h e Environment
Jack K e e l e y , U.S. EPA, K e r r E n v i r o n m e n t a l Research
Laboratory
J e r r y Kotas, U.S. EPA, O f f i c e o f Waste Programs Enforcement
Harry LeGrand, C o n s u l t a n t , North C a r o l i n a
Fred L i n d s e y , U.S. EPA, Waste Managment and Economics
Division
M a r t i n M i f f l i n , U n i v e r s i t y o f Nevada
P a u l a Mugnuson, Geraghty & M i l l e r , I n c .
W a l t e r M u l i c a , IEP, I n c
John Osgood, P e n n s y l v a n i a Bureau o f Water Q u a l i t y
Wayne P e t t y j o h n , Oklahoma S t a t e U n i v e r s i t y
Paul Roberts, Stanford U n i v e r s i t y
J a c k Robertson, Weston D e s i g n e r s & C o n s u l t a n t s
Dave S e v e r n , U.S. EPA, Hazard E v a l u a t i o n D i v i s i o n
J e r r y T h o r n h i l l , U.S. EPA, K e r r Research Center
Frank T r a i n e r , USGS, r e t i r e d
Warren Wood, USGS
Literature Cited
1. Joel, A. H. In "Soil Classification"; C. W. Finkl, Jr.,

Ed.; Hutchinson Ross Publishing Co.: Stroudsburg,
Pennsylvania, 19S2, pp. 52-59.
2. Davis, S. N.; DeWiest, R. J. "Kydrogeology"; John Wiley &
Sons: New York, 1966, pp. 1-463.
3. Meinzer, O. E. "Outline of Ground-Water Hydrology";
USGS WATER SUPPLY PAPER No. 494, United States Geological
Survey: Washington, D.C., 1923; pp. 1-71.
4. Thomas, H. E. "Ground Water Regions of the United
States - Their Storage Facilities"; Interior and Insular
Affairs Committee, U.S. House of Representatives: Washington,
D.C., 1952; pp. 1-76.
5. Heath, R. C. "Ground Water Regions of the United
States"; USGS WATER SUPPLY PAPER No. 2242, United States
Geological Survey: Washington, D.C., 1984; pp. 1-78.
6. Blank, H. R.; Schroeder, M.C. Ground Water 1973, 11, 2,
3-5.
7. LeGrand, H. E., 1983. "A Standardized System for Evaluating

Waste-Disposal Sites"; National Water Well Association:
Worthington, Ohio, 1983; pp. 1-49.
8. "Surface Impoundment Assessment National Report," United
States Environmental Protection Agency, 1983, No. 570/9-
84/002.
9. Thornthwaite, S. W.; Mather, J. R. "Instructions and Tables
for Computing Potential Evapotranspiration and the Water
Balance"; Drexel Institute of Technology: Centerton, New
Jersey, 1957; Vol. 10, No. 3, pp. 1-311.
10. Fenn, D. G.; Hanley, K. J.; DeGeare, T. V. "Use of the
Water Balance Method for Predicting Leachate Generation from
Solid Waste Disposal Sites"; U.S. EPA Report No. 168, United
States Protection Agency: Cincinnati, Ohio, 1975, pp. 1-40.
11. Gibb, J. P.; Barcelona, M. J.; Schock, S.C.;Hampton, M.
W. "Hazardous Waste in Ogle and Winnebago Counties:
Potential Risk Via Ground Water Due to Past and Present

Activities"; Illinois Department of Energy and Natural
Resources Document No. 83/26, State of Illinois: Champaign,
Illinois, 1983, pp. 1-66.
12. "Site Assessment System (SAS) for the Michigan Priority
Ranking
System Under the Michigan Environmental Response Act," Michigan
Department of Natural Resources, 1983.
13. Seller, L. E.; Canter, L. W. "Summary of Selected Ground
Water Quality Impact Assessment Methods"; NCGWR Report No. 80-3,
National Center for Ground Water Research: Norman, Oklahoma,
1980, pp. 1-142.
14. Aller, L.; Bennett, T.; Lehr, J. H.; Petty, R. J. "DRASTIC:
A Standardized System for Evaluating Ground V/ater Pollution
Potential Using Hydrogeologic Settings"; USEPA No. 600/2-85/
018, United States Environmental Protection Agency: Ada,
Oklahoma, 1985; pp. 1-163.
15. Dee, N.; Baker, J.; Drobny, N.; Duke, K.; Whitman, I.;
Fahringer, D. Water Resources Research 1973, 9, 3, 523-
535.
9
Hydrogeologic Investigations of Pesticide Spills
Ralph E. Moon and Carol D. Henry
Geraghty & Miller, Inc., Ground Water Consultants, 14310 North Dale Malory Highway,
Tampa, FL 33618
A major reason for installing monitor wells is to

provide early warning of ground-water contamination.
If properly designed, monitor-well networks can also
aid in determining the effectiveness of ground-water

protection measures. The ultimate effectiveness of
monitor wells is dependent upon a clear definition of
the desired results. For example, a monitoring program
designed to supply information for litigation is quite
different from one implemented to determine whether
local agricultural practices adversely affect
ground-water quality. Monitoring based upon a
regulatory philosophy of zero discharge to ground water
will require a monitoring system substantially
different in design from one reflecting a regulatory
philosophy of containment within the boundaries of a
disposal site. Whatever the reason for installing a
ground-water monitoring system, its design should be
based on demonstrated hydrogeologic principles and
site-specific data.
C o n t a m i n a t i o n o f g r o u n d w a t e r w i t h p e s t i c i d e s c a n o c c u r i n two
d i s t i n c t l y d i f f e r e n t s i t u a t i o n s , those o r i g i n a t i n g from widespread
a g r i c u l t u r a l use and those a t t r i b u t e d t o a s p e c i f i c p o i n t s o u r c e
loss. Each o f these s i t u a t i o n s r e q u i r e s a d i f f e r e n t approach t o
ground-water m o n i t o r i n g .
Cases o f widespread p e s t i c i d e c o n t a m i n a t i o n can r e s u l t from
unusually high application rates under shallow water-table
c o n d i t i o n s , on e x t r e m e l y porous s o i l s , o r near g e l o g i c c o n d u i t s t h a t
c o n n e c t t h e s u r f a c e t o deeper a q u i f e r s . In these c a s e s , sampling o f
e x i s t i n g p u b l i c and p r i v a t e w a t e r - s u p p l y w e l l s g e n e r a l l y forms t h e
b a s i s o f the ground-water m o n i t o r i n g . In other cases of p e s t i c i d e
c o n t a m i n a t i o n on g r e a t expanses o f l a n d , t h e ground-water m o n i t o r i n g
network has been d e s i g n e d t o i d e n t i f y t h e " c l e a n " p o t a b l e s o u r c e s o f
ground water r a t h e r than t h e e x t e n t o f t h e c o n t a m i n a t i o n .
The f o c u s o f t h i s paper i s on s p i l l s and p o i n t s o u r c e l o s s e s o f
p e s t i c i d e s , which a r e g e n e r a l l y a s s o c i a t e d w i t h t h e manufacture and
0097-6156/ 86/ 0315-0159$06.00/ 0

160 EVALUATION O F PESTICIDES IN GROUND WATER
d i s p o s a l of p e s t i c i d e s . Commonly, the ground-water c o n t a m i n a t i o n

s t e m s from l e a k y p i p e s , used drums, l a g o o n s , l a n d f i l l s , and waste
s t r e a m s on p l a n t p r o p e r t y . The h y d r o g e o l o g i c i n v e s t i g a t i o n of
p e s t i c i d e c o n t a m i n a t i o n i s e s s e n t i a l l y no d i f f e r e n t from the h y d r o -
g e o l o g i c i n v e s t i g a t i o n o f most o t h e r hazardous c h e m i c a l c o n s t i t u e n t s .
The purpose o f the i n v e s t i g a t i o n i s to i d e n t i f y the v e r t i c a l and
h o r i z o n t a l e x t e n t of c o n t a m i n a t i o n so t h a t u l t i m a t e l y the c o n t a m i n a -
t i o n c a n be i s o l a t e d and the a q u i f e r r e m e d i a t e d . The r e g u l a t o r y and
h y d r o l o g i e r e q u i r e m e n t s o f the m o n i t o r i n g p l a n c o n s i s t o f f o u r b a s i c
e l e m e n t s : p r o b l e m i d e n t i f i c a t i o n , h e a l t h and s a f e t y requirements,
monitor-well network design, and drilling and well-installation
techniques.
Problem Identification
A l l i n v e s t i g a t i o n s of ground-water c o n t a m i n a t i o n problems i n v o l v e the

same b a s i c c o n s i d e r a t i o n s , namely the l o c a t i o n and n a t u r e of the

s o u r c e s o f the c o n t a m i n a t i o n , the mechanisms f o r i n t r o d u c i n g the
c o n t a m i n a n t s i n t o the ground, the paths of f l o w t h r o u g h the g r o u n d -
water system, and the l o c a t i o n s of w e l l s , s p r i n g s , and s u r f a c e - w a t e r
b o d i e s where the contaminants u l t i m a t e l y leave the ground-water
system. A d e t a i l e d r e v i e w o f the h i s t o r y of the s i t e can p r o v e
e x t r e m e l y u s e f u l i n d e f i n i n g the l o c a t i o n and n a t u r e o f s o u r c e s o f
contamination. Installation of m o n i t o r w e l l s and water-quality
sampling are the methods for defining subsurface transport of
contaminants.
Site History. A e r i a l photographs p r o v i d e v a l u a b l e i n f o r m a t i o n to

h e l p d i r e c t the c o u r s e of a ground-water i n v e s t i g a t i o n . I t has been
s a i d by t h o s e i n the l e g a l p r o f e s s i o n t h a t "The p a l e s t i n k s u r p a s s e s
the v a l u e o f the f i n e s t memory." A c c e s s t o h i s t o r i c a l photographs
s u p p o r t s t h i s statement, o f t e n r e v e a l i n g o l d a c t i v i t i e s long s i n c e
f o r g o t t e n by the most f a i t h f u l employees. P e r s o n n e l i n t e r v i e w s can
be h e l p f u l , but the b e s t way t o e s t a b l i s h a c h r o n o l o g i c a l sequence o f
d i s p o s a l and s t o r a g e p r a c t i c e s i s t h r o u g h s c r u t i n y o f photographs,
c o n s u l t i n g reports, corporate documents, and governmental records
( F e d e r a l and s t a t e r e g u l a t o r y a g e n c i e s ) .
Waste D i s p o s a l P r a c t i c e s . Maps showing p r e v i o u s waste d i s p o s a l s i t e s

may h e l p e x p l a i n the r e s u l t s o b t a i n e d from the a n a l y s i s o f g r o u n d -
w a t e r samples. I n f o r m a t i o n t h a t l o c a t e s s t o r a g e a r e a s and e f f l u e n t
d i s c h a r g e p o i n t s , c h a r a c t e r i z e s waste streams, and p r o v i d e s c h e m i c a l
a n a l y s e s o f s o i l , s u r f a c e w a t e r , and ground water can a l s o h e l p t o
d e f i n e the waste d i s p o s a l p r a c t i c e s o f a f a c i l i t y . In a d d i t i o n ,
i d e n t i f y i n g a d j a c e n t l a n d owners and l a n d use p r a c t i c e s a r e b e n e f i -
c i a l when i t i s n e c e s s a r y t o e x p l a i n the p r e s e n c e o f ground-water
c o n s t i t u e n t s t h a t c o u l d be a t t r i b u t e d t o u p g r a d i e n t p r a c t i c e s .
Geology. D r i l l i n g l o g s o f o n - s i t e water w e l l s , o n - s i t e m o n i t o r
w e l l s , f o u n d a t i o n b o r i n g s , and water w e l l s owned by a d j a c e n t property
owners, t o g e t h e r w i t h d a t a o b t a i n e d from the U.S. G e o l o g i c a l Survey
and state agencies, c a n be u s e f u l i n d e s i g n i n g a g r o u n d - w a t e r
monitoring p l a n and/or r e c o v e r y program. Lithologie descriptions
o b t a i n e d f r o m t h e s e s o u r c e s can d e f i n e the d e p t h to the water t a b l e ,
c h a r a c t e r i z e t h e s o i l t y p e s , and e s t a b l i s h t h e d e g r e e t o w h i c h
9. MOON A N D HENRY Hydrogeologic Investigations of Pesticide Spills 161
a q u i f e r s a r e i s o l a t e d from o r c o n n e c t e d t o one a n o t h e r . Geologic

information helps t o e s t a b l i s h t h e p o t e n t i a l r i s k t o underground
d r i n k i n g water s u p p l i e s and t o p r e d i c t t h e d i r e c t i o n and r a t e o f
movement o f t h e p e s t i c i d e plume.
F i e l d Reconnaissance. F i e l d reconnaissance techniques f o r e v a l u a t i n g

ground-water contamination i n c o r p o r a t e s e v e r a l methods o t h e r than
v i s u a l and o l f a c t o r y d e t e c t i o n . B i o l o g i c i n d i c a t o r s , f o r example,
can demonstrate t h e p r e s e n c e o f p e s t i c i d e s i f t h e p l a n t community i s
s p a r s e ( h e r b i c i d e s ) o r u n u s u a l l y dense ( i n s e c t i c i d e s ) . On a v i s i t t o
the h i s t o r i c l o c a t i o n o f a South F l o r i d a DDT f o r m u l a t i o n s i t e (15
y e a r s o l d ) , o l f a c t o r y d e t e c t i o n o f p e s t i c i d e l o s s was n o t a p p a r e n t .
I n s p e c t i o n o f t h e p l a n t community, however, showed s e v e r a l l a r g e
c i r c u l a r p a t c h e s (20 f e e t i n d i a m e t e r ) o f dense, l o w - l y i n g v e g e t a t i o n
at t h e s i t e . Removal o f t h e p l a n t s and s o i l w i t h a p i c k a x a l o n g t h e
periphery o f the community r e s u l t e d i n t h e immediate r e l e a s e o f
p e s t i c i d e , which was c o n f i r m e d w i t h an o r g a n i c v a p o r a n a l y z e r and by

smell.
Hydrogeologic Considerations. The d i r e c t i o n and r a t e o f movement o f

a contaminant plume c a n change i n r e s p o n s e t o h y d r o l o g i e c o n d i t i o n s .
Recharge from p r e c i p i t a t i o n , t h e m o l e c u l a r d e n s i t y o f t h e p e s t i c i d e ,
and t h e h y d r a u l i c g r a d i e n t ( s l o p e o f t h e water t a b l e ) a r e p r e d i c t a b l e
conditions that control t h e h o r i z o n t a l and v e r t i c a l extent of
contamination.
S p r i n g s , s t r e a m s , l a k e s , and r i v e r s a r e p r i n c i p a l a r e a s where
c o n t a m i n a n t s a r e d i s c h a r g e d from ground-water s y s t e m s . Stormwater
d i t c h e s , i r r i g a t i o n w e l l s , community w e l l f i e l d s , d o m e s t i c wastewater
s p r a y f i e l d s , i n f i l t r a t i o n ponds, i n d u s t r i a l impoundments, and l e a k i n g
municipal sewer l i n e s may a l t e r t h e ground-water f l o w p a t t e r n by
c r e a t i n g a r t i f i c i a l p o i n t s o f r e c h a r g e and d i s c h a r g e . These p o s s i b l e
h y d r o l o g i e i n f l u e n c e s s h o u l d be taken i n t o a c c o u n t when a n a l y s e s o f
g r o u n d - w a t e r samples show o r g a n i c compounds t h a t seem u n r e l a t e d t o
the l o c a t i o n o f t h e i n f e r r e d s o u r c e s .
Health and S a f e t y Requirements
Worker h e a l t h and s a f e t y a r e among t h e b a s i c c o n s i d e r a t i o n s i n a

ground-water i n v e s t i g a t i o n o f c h e m i c a l s w i t h harmful p r o p e r t i e s .
However, most i n s t a n c e s o f p e s t i c i d e c o n t a m i n a t i o n o t h e r than l o s s e s
o f f r e e p r o d u c t , i n v o l v e ground-water and s o i l c o n c e n t r a t i o n s much
lower than those p o s i n g an immediate o c c u p a t i o n a l h e a l t h t h r e a t .
In i n s t a n c e s where f r e e p r o d u c t i s l o s t , vacuum r e c o v e r y systems
a n d / o r a b s o r b e n t s may be used t o remove t h e s u r f a c e concentrations
before t h e ground-water i n v e s t i g a t i o n begins. These actions,
normally t a k e n as t h e f i r s t s t e p i n t h e r e m e d i a l a c t i o n p l a n , o f t e n
r e n d e r t h e l a n d s u r f a c e a t t h e s i t e n e a r l y c l e a n b e f o r e the g r o u n d -
water problem i s s t u d i e d .
P r o t e c t i v e wear and a s s o c i a t e d equipment a r e r e q u i r e d t o s a f e -
guard the worker. I n t h e f i e l d w h e r e no d e t e c t a b l e airborne
p e s t i c i d e emissions a r e p r e s e n t , b u t where t h e p o t e n t i a l f o r s k i n
contact i s h i g h , a hard h a t w i t h s p l a s h p r o t e c t o r , s a f e t y g l a s s e s ,
chemically r e s i s t a n t outer c l o t h i n g , gloves and b o o t s w i t h taped
w r i s t s and a n k l e s , and i n n e r s u r g i c a l g l o v e s would p r o v i d e a c o n -
s e r v a t i v e dress f o r f i e l d p r o t e c t i o n . The p r e s e n c e o f d e t e c t a b l e
concentrations of p e s t i c i d e d u s t or vapor r e q u i r e s supplemental

respiratory protection ranging from a combination particulate-
r e m o v i n g f i l t e r and o r g a n i c v a p o r / p e s t i c i d e f i l t e r t o a heavy d u t y
c a n i s t e r s i m i l a r l y equipped. Work c o n d i t i o n s t h a t r e q u i r e personal
p r o t e c t i o n above t h i s l e v e l may n e c e s s i t a t e a rvaluation o f the
d r i l l i n g o r s a m p l i n g l o c a t i o n s f o r ground-water m o n i t o r i n g . The
s p e c i f i c r e g u l a t o r y r e q u i r e m e n t s o f a H e a l t h and Safety Plan are
d e s c r i b e d i n " S t a n d a r d O p e r a t i n g S a f e t y G u i d e s . " (1)
Monitor-Well Design
The o b j e c t i v e s of i n s t a l l i n g a m o n i t o r - w e l l network must be c l e a r l y

d e f i n e d b e f o r e c h o o s i n g the s p e c i f i c l o c a t i o n s , numbers, and dimen-
s i o n s o f the w e l l s . The p r e f e r r e d d e s i g n depends on the p r o p o s e d
uses of the monitor-well network, the dimensions and chemical
c h a r a c t e r i s t i c s of the contaminant plume, and the s i t e hydrogeology.
L o c a t i o n and Number. The l o c a t i o n o f a m o n i t o r w e l l r e f e r s t o b o t h

i t s a r e a l l o c a t i o n i n r e l a t i o n to the waste s o u r c e and i t s v e r t i c a l
l o c a t i o n o r d e p t h i n the uppermost or o t h e r a q u i f e r . The number and
l o c a t i o n s o f the w e l l s depend on s e v e r a l f a c t o r s , i n c l u d i n g r e g u l a -
t o r y c o n s t r a i n t s and the c u r r e n t l e v e l of knowledge o f the site
h y d r o g e o l o g y and water q u a l i t y . S t a t e and F e d e r a l r e g u l a t i o n s , f o r
i n s t a n c e , g e n e r a l l y r e q u i r e t h a t a m i n i m a l number o f m o n i t o r w e l l s be
i n s t a l l e d a t o r near the s o u r c e o f ground-water c o n t a m i n a t i o n , i n
b o t h the u p g r a d i e n t and downgradient d i r e c t i o n s . However, i f o n l y
s c a n t h y d r o g e o l o g i c d a t a a r e a v a i l a b l e , i t may not be p o s s i b l e t o
determine in advance the horizontal and vertical direction of
ground-water f l o w . In t h e s e c a s e s , a presumed f l o w d i r e c t i o n , based
on the l o c a t i o n s of s u r f a c e water b o d i e s , the topography, and o t h e r
s u r f a c e i n d i c a t i o n s , i s used t o d e s i g n a t e the p r o p o s e d m o n i t o r - w e l l
l o c a t i o n s , b o t h u p g r a d i e n t and downgradient o f the waste s o u r c e s .
A d d i t i o n a l w e l l s a r e g e n e r a l l y r e q u i r e d f o r c h a r a c t e r i z a t i o n of the
s i t e hydrogeology.
W e l l s m o n i t o r i n g d i f f e r e n t a q u i f e r s o r d i f f e r e n t zones w i t h i n
a s i n g l e a q u i f e r a r e g e n e r a l l y i n s t a l l e d f o r two r e a s o n s : (1) t o
i d e n t i f y h y d r a u l i c c h a r a c t e r i s t i c s of and the r e l a t i o n s h i p between
the d i f f e r e n t zones or a q u i f e r s , and (2) to c h a r a c t e r i z e the g r o u n d -
water quality at d i f f e r e n t depths. Characterization of site
h y d r o g e o l o g y a l s o i n v o l v e s i n v e s t i g a t i n g the p r e s e n c e o f c o n f i n i n g
layers. To demonstrate the e f f e c t i v e n e s s of a c o n f i n i n g l a y e r i n
preventing the downward m i g r a t i o n of a plume, f o r i n s t a n c e , i t i s
o f t e n n e c e s s a r y to i n s t a l l w e l l s to a d e p t h b e n e a t h the c o n f i n i n g
l a y e r i n o r d e r t o c o l l e c t water samples and measure water l e v e l s
d u r i n g a pumping t e s t . I f the c o n f i n i n g l a y e r i s r e l a t i v e l y imper-
meable o r i f the h y d r a u l i c g r a d i e n t i s upward, m o n i t o r i n g of deeper
a q u i f e r s may not be r e q u i r e d . Where s h a l l o w and deep w e l l s are
needed, t h e y commonly a r e i n s t a l l e d a t the same l o c a t i o n and are
r e f e r r e d to as p a i r e d w e l l s or c l u s t e r w e l l s .
The c h o i c e of w e l l l o c a t i o n s can be i n f l u e n c e d by the t y p e s o f
wastes o r c o n t a m i n a n t s and t h e i r p r o p e n s i t y t o m i g r a t e from the waste
sources. Heavy o r g a n i c s , f o r i n s t a n c e , are l i k e l y to migrate to
d e e p e r a q u i f e r s zones, where t h e i r movement i s not t o t a l l y dependent
on ground-water f l o w d i r e c t i o n s but may be p a r t l y c o n t r o l l e d by the
slope o f the top o f the uppermost c o n f i n i n g d e p o s i t s . Thus, i n
9. M O O N A N D HENRY Hydrogeologic Investigations of Pesticide Spills 163
d e s i g n i n g a m o n i t o r - w e l l network t o d e t e c t h e a v i e r - t h a n - w a t e r s o l v e n t
plumes, c o n s i d e r a t i o n must be g i v e n t o i n s t a l l i n g w e l l s a t t h e base
o f t h e uppermost a q u i f e r t o d e t e c t g r a v i t y f l o w o f p u r e p r o d u c t away
from the s i t e . S h a l l o w m o n i t o r w e l l s a l s o must be i n s t a l l e d t o
d e t e c t d i s s o l v e d components moving i n t h e d i r e c t i o n o f ground-water
flow.
O f t e n , t h e p r e l i m i n a r y c h a r a c t e r i z a t i o n w e l l s c a n be i n c o r p o r -
a t e d i n t h e permanent m o n i t o r - w e l l network. However, i n c a s e s where
the i n i t i a l presumed ground-water f l o w d i r e c t i o n t u r n s o u t t o be
i n c o r r e c t , due t o t h e i n f l u e n c e s o f n e a r b y pumping w e l l s , tidal
fluctuations, ground-water mounds, o r o t h e r h y d r a u l i c phenomena,
a d d i t i o n a l r e g u l a t o r y w e l l s may be r e q u i r e d .
Dimensions. The d i m e n s i o n s o f a w e l l r e f e r t o i t s d e p t h , c a s e d
i n t e r v a l , l e n g t h o f the screened o r open-hole s a m p l i n g interval,
s c r e e n s l o t s i z e , and b o r e h o l e , s c r e e n , and c a s i n g d i a m e t e r s . The
l e n g t h o f t h e sampling i n t e r v a l depends on t h e purpose o f t h e w e l l ,

the site hydrogeology, and t h e ground-water quality. A very
p r e l i m i n a r y i n v e s t i g a t i o n t o d e t e r m i n e w h i c h , i f any, contaminants
h a v e m i g r a t e d from a s i t e may i n v o l v e t h e i n s t a l l a t i o n o f o n l y a few
s h a l l o w w e l l s w i t h a 3 t o 10 f t s c r e e n e d i n t e r v a l a t t h e water t a b l e .
Once c o n t a m i n a n t s a r e i d e n t i f i e d , deeper w e l l s may be i n s t a l l e d t o
d e t e r m i n e how t h o s e c o n t a m i n a n t s may have m i g r a t e d v e r t i c a l l y . In
d e t e r m i n i n g t h e l e n g t h o f t h e s a m p l i n g i n t e r v a l f o r t h e deeper h o l e s ,
a balance should be sought between s a m p l i n g a s m a l l i n t e r v a l t o
b e t t e r d e f i n e t h e contaminant plume and s a m p l i n g a l a r g e r i n t e r v a l t o
a v o i d m i s s i n g t h e plume. I f pumping t e s t s a r e t o be p e r f o r m e d , w e l l s
i n t h e same a q u i f e r s h o u l d be s c r e e n e d o r o p e n e d t o t h e same
i n t e r v a l s ; f u l l y penetrating wells are generally preferred.
S l o t s i z e s o f t h e s c r e e n s a r e chosen t o maximize w e l l y i e l d so
that r e l i a b l e water samples and w a t e r - l e v e l drawdown d a t a c a n be
c o l l e c t e d d u r i n g s p e c i f i c - c a p a c i t y and o t h e r f i e l d t e s t s . To accomp-
l i s h t h i s , s i e v e a n a l y s e s c a n be performed on s p l i t - s p o o n samples
from t h e i n t e r v a l t o be m o n i t o r e d . A g r a i n - s i z e d i s t r i b u t i o n curve
c a n be f i e l d p l o t t e d and a n a l y z e d t o e s t a b l i s h t h e s c r e e n s l o t s i z e
and t h e s i z e o f t h e g r a v e l pack. F o r w e l l s i n s t a l l e d i n competent
b e d r o c k , i t may be w i s e s t n o t t o i n s t a l l a s c r e e n b u t t o l e a v e t h e
h o l e open f o r maximum y i e l d . In t h e s e c a s e s , a s u r f a c e c a s i n g i s
i n s t a l l e d t o p r e v e n t t h e c o l l a p s e o f t h e u n c o n s o l i d a t e d sediments and
p o s s i b l e downward m i g r a t i o n o f c o n t a m i n a n t s .
The d i a m e t e r o f a w e l l i s d i c t a t e d by i t s proposed u s e s , i t s
d e p t h , and t h e d e p t h t o w a t e r . Wells i n s t a l l e d f o r water-level
measurements o n l y a r e commonly o n l y 1-1/4 t o 2 i n c h e s i n d i a m e t e r .
W e l l s t o be sampled c a n a l s o be t h i s s m a l l , b u t c o n s i d e r a t i o n s h o u l d
be g i v e n t o t h e d e p t h o f t h e w e l l and t h e d e p t h t o water. Centri-
f u g a l pumps a n d p e r i s t a l t i c pumps c a n be u s e d f o r s a m p l i n g i n
small-diameter w e l l s , i f t h e d e p t h t o water i s l e s s t h a n 25 f e e t
( i n c l u d i n g drawdown caused by t h e pumping); o t h e r w i s e , bailing i s
required. Because b a i l i n g i s l e s s e f f i c i e n t t h a n pumping, i t i s
often preferable to i n s t a l l a larger-diameter w e l l ; a submersible
pump t h e n c a n be u s e d f o r s a m p l i n g . I f automatic water-level
r e c o r d i n g i n s t r u m e n t s a r e t o be i n s t a l l e d o r i f g e o p h y s i c a l l o g g i n g
i s t o be performed on t h e w e l l s , i t i s g e n e r a l l y a d v i s a b l e t o i n s t a l l
4-inch-diameter or l a r g e r diameter w e l l s . The d i a m e t e r o f t h e b o r e -
h o l e s h o u l d be s u f f i c i e n t t o i n s t a l l t h e c a s i n g and/or s c r e e n and a
minimum 3 - i n c h - t h i c k g r a v e l pack. The g r o u t e n v e l o p e a l s o s h o u l d be

a t l e a s t 3 i n c h e s t h i c k t o i n s u r e t h a t i t c o m p l e t e l y surrounds the
well.
Materials. Polyvinyl chloride (PVC), black carbon steel, and

s t a i n l e s s s t e e l a r e commonly used m a t e r i a l s f o r c a s i n g s and s c r e e n s .
PVC and b l a c k c a r b o n s t e e l a r e l e s s e x p e n s i v e , but a r e sometimes not
c o m p a t i b l e w i t h contaminants found i n the ground water. Although
g e n e r a l l y immune t o c h e m i c a l a t t a c k by most n a t u r a l l y o c c u r r i n g
compounds, PVC may adsorb o r l e a c h o r g a n i c compounds (2^ _3, 4_) ; t h u s ,
PVC must be used w i t h c a r e i n s i t u a t i o n s where t h e r e i s a p o s s i b i l i t y
of o r g a n i c c o n t a m i n a t i o n . Where PVC i s deemed a p p r o p r i a t e , g e n e r a l l y
S c h e d u l e 40 s h o u l d be used f o r w e l l s l e s s t h a n 200 f e e t deep and
S c h e d u l e 80 f o r deeper w e l l s . Cement and o t h e r a d h e s i v e s s h o u l d be
a v o i d e d ; j o i n t s s h o u l d be t h r e a d e d and c o u p l e d o r f l u s h j o i n t e d .
B e c a u s e g a l v a n i z e d s t e e l i s not c o r r o s i o n - r e s i s t a n t , i t s h o u l d
n o t be u s e d i n plumes of an a c i d i c n a t u r e , o r i n water w i t h h i g h
e l e c t r i c a l c o n d u c t i v i t y due t o c h l o r i d e s or s u l f a t e s . Stainless
s t e e l i s much more r e s i s t a n t t o c o r r o s i o n and can o f t e n be used i n
p l a c e o f g a l v a n i z e d s t e e l , but i s s e v e r a l times more e x p e n s i v e . For
t h i s r e a s o n , w e l l s can be c a s e d w i t h a cheaper g a l v a n i z e d s t e e l above
the water t a b l e and w i t h more e x p e n s i v e s t a i n l e s s s t e e l c a s i n g o r
s c r e e n below the water t a b l e .
The g r a d i n g o f a g r a v e l pack i n a w e l l s h o u l d be based on a
s i e v e a n a l y s i s o f the f i n e s t a q u i f e r m a t e r i a l s o f the s c r e e n e d zone.
The s c r e e n s l o t opening s h o u l d r e t a i n 90 p e r c e n t o r more o f the
g r a v e l pack m a t e r i a l . The g r a v e l pack m a t e r i a l s h o u l d be c l e a n , w i t h
well-rounded grains that are smooth and uniform. These
c h a r a c t e r i s t i c s i n c r e a s e the p e r m e a b i l i t y and p o r o s i t y o f the pack
material.
Drilling and W e l l Installation Techniques
S e v e r a l methods a r e a v a i l a b l e f o r the d r i l l i n g and i n s t a l l a t i o n of

monitor w e l l s . The advantages and d i s a d v a n t a g e s r e l a t i n g t o ease of
c o n s t r u c t i o n , c h a r a c t e r o f f o r m a t i o n s p e n e t r a t e d , w e l l d i a m e t e r and
d e p t h , r i s k s o f c o n t a m i n a t i o n , and i n t e n d e d use o f the w e l l have been
r e p o r t e d by s e v e r a l i n v e s t i g a t o r s 5 , _6_> _ 7 ) . A l l f i e l d personnel
should be thoroughly familiar with w e l l s p e c i f i c a t i o n s , quality
a s s u r a n c e / q u a l i t y c o n t r o l p r o c e d u r e s , and s a f e t y p l a n s and r e q u i r e -
ments p r i o r t o i n s t a l l a t i o n o f m o n i t o r w e l l s .
Drilling. Common d r i l l r i g s a v a i l a b l e f o r m o n i t o r - w e l l i n s t a l l a t i o n
i n c l u d e c a b l e t o o l , a i r r o t a r y , mud rotary, reverse rotary, and
h o l l o w - s t e m auger. The c a b l e t o o l r i g r e p e a t e d l y l i f t s and drops a
d r i l l b i t , d r i l l stem, d r i l l i n g j a r s , and rope s o c k e t . The d r i l l b i t
c r u s h e s h a r d r o c k o r l o o s e n s u n c o n s o l i d a t e d m a t e r i a l and mixes the
l o o s e n e d p a r t i c l e s w i t h water t o form a s l u r r y o r s l u d g e . The s l u d g e
i s removed a t i n t e r v a l s by a sand pump or a b a i l e r .
A mud r o t a r y r i g c u t s a b o r e h o l e by r o t a t i n g a b i t i n t o the
f o r m a t i o n m a t e r i a l s and removing the c u t t i n g s by c o n t i n u o u s c i r c u l a -
t i o n of a d r i l l i n g f l u i d . In a c o n v e n t i o n a l r o t a r y system, mud i s
pumped down t h r o u g h the d r i l l p i p e and out t h r o u g h n o z z l e s i n the
bit. The mud f l o w s upward i n the a n n u l a r space around the d r i l l p i p e
to the s u r f a c e , where i t i s c h a n n e l e d i n t o a s e t t l i n g p i t and a
storage b a s i n . Although the w a l l of the borehole i s e f f e c t i v e l y

s e a l e d w i t h t h e mud, l a r g e q u a n t i t i e s o f f l u i d c a n be l o s t t o t h e
formation p r i o r to s e a l i n g . In reverse r o t a r y , the d r i l l i n g f l u i d i s
water which f l o w s down t h e a n n u l a r space around t h e d r i l l rods and up
i n s i d e t h e d r i l l rods t o t h e s u r f a c e . To p r e v e n t c a v i n g , t h e f l u i d
l e v e l must always be kept a t ground l e v e l .
Hollow-stem auger rigs a r e commonly used for drilling i n
u n c o n s o l i d a t e d m a t e r i a l w i t h enough c l a y so t h a t t h e b o r e h o l e w i l l
stand without caving. An auger stem i s t u r n e d and pushed as t h e
auger f l i g h t s c a r r y m a t e r i a l t o the surface. A i r r o t a r y d r i l l r i g s
a r e used f o r c o n s o l i d a t e d m a t e r i a l s . A i r i s c i r c u l a t e d through t h e
d r i l l p i p e , o u t through p o r t s i n t h e d r i l l b i t , and upward i n t h e
a n n u l a r space around t h e d r i l l p i p e .
T a b l e I d e s c r i b e s t h e r e l a t i v e advantages and d i s a d v a n t a g e s o f
different d r i l l i n g rigs. F o r i n s t a n c e , a h o l l o w - s t e m auger i s v e r y
e c o n o m i c a l f o r d r i l l i n g i n u n c o n s o l i d a t e d m a t e r i a l s and p r o v i d e s good
s o i l samples, p a r t i c u l a r l y above t h e water t a b l e . Mud r o t a r y i s

u s e f u l f o r d r i l l i n g i n r u n n i n g sands and s i l t s , i s m o d e r a t e l y
e x p e n s i v e , b u t p r o v i d e s poor s o i l samples. A i r r o t a r y i s expensive
and p r o v i d e s poor s o i l and r o c k samples, b u t i s v e r y r a p i d ; r o c k
fragments c a n g e n e r a l l y be i d e n t i f i e d , b u t o t h e r c h a r a c t e r i s t i c s such
as f r a c t u r i n g cannot. S m a l l zones o f c o n t a m i n a t i o n c a n be m i s s e d .
C l e a r l y t h e type o f r i g c a n be chosen o n l y a f t e r c a r e f u l c o n s i d e r a
t i o n o f t h e f o r m a t i o n s t o be d r i l l e d , time and budget c o n s t r a i n t s ,
and sampling r e q u i r e m e n t s .
W e l l I n s t a l l a t i o n and Development. Once b o r e h o l e s a r e completed,

w e l l s s h o u l d be i n s t a l l e d a c c o r d i n g t o d e t a i l e d w e l l s p e c i f i c a t i o n s .
The f o l l o w i n g i s a s e t o f good p r a c t i c e s a p p l i c a b l e t o most w e l l
installations.
The g r a v e l pack s h o u l d be i n s t a l l e d by t h e t r e m i e method t o

a s s u r e p r o p e r placement,
A f i n e sand pack s h o u l d be i n s t a l l e d above t h e g r a v e l pack t o
p r e v e n t m i g r a t i o n of the o v e r l y i n g cement i n t o the g r a v e l pack,
I f s u r f a c e c a s i n g i s i n s t a l l e d f o r a bedrock w e l l , g r o u t s h o u l d
be emplaced by t h e p r e s s u r e t r e m i e method t o i n s u r e a complete
s e a l around t h e w e l l . Grout s h o u l d be a l l o w e d t o s e t f o r a t
l e a s t 24 h o u r s .
A m e t h o d s u c h a s t h e plumb bob m e t h o d s h o u l d be u s e d t o
determine i f t h e c a s i n g a n d b o r e h o l e a r e plumb a n d t r u e .
C e n t r a l i z e r s s h o u l d be a t t a c h e d t o w e l l s as n e c e s s a r y ,
A l l f l u i d and mud produced by t h e d r i l l i n g o p e r a t i o n s s h o u l d be
r e t a i n e d i n p o r t a b l e mud p i t s f o r p r o p e r d i s p o s a l ,
A l l equipment s h o u l d be c l e a n e d between each w e l l i n s t a l l a t i o n
to p r e v e n t c r o s s - c o n t a m i n a t i o n . S p e c i f i c c l e a n i n g procedures
s h o u l d be o u t l i n e d i n t h e w e l l s p e c i f i c a t i o n s ,
To the extent possible, drilling of the borehole and
i n s t a l l a t i o n o f t h e w e l l s h o u l d be a c c o m p l i s h e d i n a c o n t i n u o u s
manner. T h i s w i l l m i n i m i z e t h e r i s k o f c r o s s - c o n t a m i n a t i o n ,
A w a t e r - l e v e l measurement s h o u l d be t a k e n upon c o m p l e t i o n o f
well installation,
W e l l s s h o u l d be d e v e l o p e d u n t i l t h e pumped o r b a i l e d water i s
c l e a r o r u n t i l s u c c e s s i v e pH and s p e c i f i c conductance v a l u e s
remain s t a b l e .
ON
ON
Table I. Comparisons o f D r i l l i n g Methods
Mud R o t a r y Reverse Auger-

Cable Tool Air Rotary (Conventional) Rotary Hollow-Stem
Cost Moderate High Moderate t o H i g h Moderate Low
Drillable Most Unlimited Unlimited Unconsol Unconsolida

Formations Materials idated ted
Formations
Formations
Depth Unlimited Unlimited Unlimited Unlimited
About 100 f t
Restrictions
Unlimited Unlimited Unlimited Unlimited Up t o 1 2 - i n c h
Hole Size
Water None o r s m a l l Mud Water None $
Drilling Fluids amounts o f water r
c
I n s t a l l i n g Grout Easy Sometimes Difficult i f

Easy Easy
o r G r a v e l Pack Difficult a n n u l a r space i s
limited
*V
Poor Good Good Above m
Quality of
Excellent F a i r t o Poor H
Soil/Rock Water T a b l e

Samples 5
Drilling Rate Rapid Moderate Rapid m
Slow Slow

70

C
%
m

E l e v a t i o n s o f measuring p o i n t s on w e l l s s h o u l d be determined by
a q u a l i f i e d s u r v e y o r t o t h e n e a r e s t 0.01 f o o t .
Recordkeeping. Keeping complete, accurate drilling logs is a

c r i t i c a l a s p e c t o f w e l l d r i l l i n g and i n s t a l l a t i o n t e c h n i q u e s . Table
I I l i s t s items t h a t may be i n c l u d e d i n a w e l l l o g , depending on t h e
type o f w e l l and t h e s p e c i f i c a t i o n s f o r s a m p l i n g . This i s a d e t a i l e d
l i s t and i n many c a s e s , i t may n o t be n e c e s s a r y t o r e c o r d a l l t h e
items l i s t e d . G e n e r a l l y , as much d e t a i l as t h e d r i l l i n g technique
c a n p r o v i d e s h o u l d be r e c o r d e d by t h e f i e l d i n s p e c t o r . Some items
t h a t may n o t seem c r i t i c a l a t t h e t i m e o f d r i l l i n g may p r o v i d e
i n s i g h t t o unanswered q u e s t i o n s o r a m b i g u i t i e s t h a t may a r i s e d u r i n g
a n a l y s i s of the data. Items such as l e n g t h o f c a s i n g and number o f
c a s i n g l e n g t h s s h o u l d be checked by the f i e l d i n s p e c t o r . In some
c a s e s , samples may be numbered by a random numbering system; these
v a l u e s s h o u l d be r e c o r d e d i n f i e l d n o t e s . A record of f i e l d or t r i p
b l a n k s s h o u l d a l s o be k e p t . Any c h e c k i n g i n t h e f i e l d o f w a t e r -
q u a l i t y p a r a m e t e r s , i . e . , pH and c o n d u c t i v i t y , s h o u l d be r e c o r d e d .
In g e n e r a l , t h e f i e l d i n s p e c t o r s h o u l d u n d e r s t a n d t h e c r i t i c a l n a t u r e
of h i s o r h e r t a s k , and s p e c i f i c g u i d e l i n e s f o r r e c o r d i n g f i e l d n o t e s
s h o u l d be e s t a b l i s h e d p r i o r t o t h e d r i l l i n g program.
Table II. I n f o r m a t i o n t o I n c l u d e on D r i l l i n g Logs
Name o f c o n t r a c t o r , d r i l l e r , i n s p e c t o r
L o c a t i o n o f s i t e and s p e c i f i c b o r e h o l e l o c a t i o n
B o r e h o l e number
Date - s t a r t / f i n i s h
Soil Characteristics
depth
g r a i n s i z e and t e x t u r e
angularity
moisture content
D r i l l i n g operations
rate
- loss of c i r c u l a t i o n
use o f water/mud
c o r e diameter
c o l o r o f c i r c u l a t i n g water
core r e c o v e r y
- d i a m e t e r o f auger o r c o r e
- type c o r e b a r r e l
- s i z e o f d r i v e hammer and f r e e f a l l d i s t a n c e t o
d r i v e hammer
blows p e r f o o t t o d r i v e sample
- f o r c e t o push t h i n w a l l samples
Well m a t e r i a l s / c h a r a c t e r i s t i c s
casing - type, diameter, i n t e r v a l
screen - type, diameter, i n t e r v a l , s l o t s i z e
grout - type, i n t e r v a l
t o t a l d r i l l e d depth
open h o l e i n t e r v a l
- sand pack - t y p e , i n t e r v a l
p r o t e c t i v e c a s i n g - t y p e , diameter
Continued on next page
Table I I C o n t i n u e d
Samples - number, d e p t h , t y p e , s i z e
S t a b i l i z e d water l e v e l
Rock C h a r a c t e r i s t i c s
d e p t h u n i t / f o r m a t i o n and member names
color
hardness
fracturing
coatings or f i l l i n g s (or lack o f ) i n j o i n t s or
seams
angle of bedding, s c h i s t o s i t y , o r other p l a n a r
features
- luster
thickness of bedding planes
degree o f w e a t h e r i n g
- decomposition
strength
- weathering
r o c k a l t e r a t i o n o t h e r than by w e a t h e r i n g
induration
rock q u a l i t y
- c a v i t i e s or voids
Literature Cited
1. "Standard Operating Safety Guides." Office of Emergency and

Remedial Response, Hazardous Response Support Division, Environ
mental Response Team, November, 1984.
2. Miller, G.D. Proc. 2nd Natl. Sym. Aquifer Restoration and
Ground-Water Monitoring, 1982, p. 236.
3. Houghton, R.L.; Berger, M.E. Proc. 3rd Natl. Sym. Aquifer
Restoration and Ground-Water Monitoring, 1983; p. 203.
4. Barcelona, M.J.; Gibb, J.P.; Millar, R.A.; "A Guide to the
Selection of Materials for Monitor Well Construction and Ground
Water Sampling;" Illinois Water Survey; Champaign, Illinois;
1983; p. 39.
5. Briggs, G.F.; Fieldler, A.G., Eds.; In "Ground Water and Wells;"
Johnson Division, UOP, Inc.; St. Paul, Minnesota, 1980 edition;
p. 209.
6. Richter, H.R.; Collentine, M.G; Proc. 3rd Natl. Sym. Aquifer
Restoration and Ground-Water Monitoring, 1983, p. 194.
7. Minning, R.; Proc. 3rd Natl. Sym. Aquifer Restoration and
Ground-Water Monitoring, 1983, p. 194.

10
Monitoring Ground Water for Pesticides
S. Z. Cohen, C. Eiden, and M . N. Lorber
Office of Pesticide Programs (TS-769C), U.S. Environmental Protection Agency,

At least 17 pesticides have been found in ground

water in a total of 23 states as a result of
agricultural practice. These results have been
obtained through three different types of monitoring

studies: (1) large-scale retrospective, (2) small-
scale retrospective, and (3) small-scale prospective.
The first two types of studies survey areas where
the pesticide(s) in question has already been used.
The third type of study is an intensive field study
where the pesticide is applied and monitoring begins
at time zero. Often, soil core data are at least as
important as ground-water data. The ability to draw
meaningful conclusions from large-scale studies is
greatly diminished unless the studies have a statis-
tical, stratified design. The purpose of this paper
is threefold: to describe the three study types;
suggest guidelines for ground-water sampling, soil
sampling and well construction; and update the
data summary of pesticides in ground water from
agricultural practice.
In 1984, Cohen e t a l . r e v i e w e d l e a c h i n g and m o n i t o r i n g d a t a on 12
d i f f e r e n t p e s t i c i d e s found i n ground water i n a t o t a l o f 18
d i f f e r e n t s t a t e s as a r e s u l t o f a g r i c u l t u r a l p r a c t i c e (V) They
a l s o e s t a b l i s h e d c r i t e r i a f o r p r e d i c t i n g whether c e r t a i n p e s t i c i d e s
c o u l d l e a c h t o ground water as a r e s u l t o f normal use. In the l e s s
t h a n 2 y e a r s s i n c e t h a t paper was p u b l i s h e d , t h e numbers o f p e s t i -
c i d e s found i n ground water have i n c r e a s e d s i g n i f i c a n t l y as have
the number o f s t a t e s found t o have p e s t i c i d e s i n ground w a t e r .
Seventeen p e s t i c i d e s have now been found i n t h e ground water o f 23
s t a t e s as a r e s u l t o f a g r i c u l t u r a l p r a c t i c e ( F i g u r e 1, T a b l e I ) .
(As d e s c r i b e d i n t h e " O c c u r r e n c e " s e c t i o n a t t h e end o f t h i s paper,
many a d d i t i o n a l f i n d i n g s can be a t t r i b u t e d t o poor d i s p o s a l p r a c -
t i c e s , m i x i n g - l o a d i n g o p e r a t i o n s , e t c . and a r e n o t i n c l u d e d i n t h i s
c o u n t . ) T h i s s i g n i f i c a n t i n c r e a s e i s more l i k e l y due t o an i n c r e a s e
i n t h e q u a l i t y and q u a n t i t y o f s t u d i e s r a t h e r t h a n an i n c r e a s e i n

F i g u r e 1. Numbers o f p e s t i c i d e s found i n ground water

a result of a g r i c u l t u r a l practice.
Table I . T y p i c a l P o s i t i v e Results of P e s t i c i d e Ground-Water

M o n i t o r i n g i n t h e U.S.t
Pesticide Use* State(s) Typical

Positive,
ppb
Alachlor H MD, , NE, 0.1-10
Aldicarb I, AR, AZ, CA, F L , 1-50
(sulfoxide MA, ME, NC, NJ,
& sulfone) NY, OR, R I , TX,

VA, WA, WI
Atrazine , IA, NE, WI, MD 0.3-3
Bromacil FL 300
Carbofuran I, NY, WI, MD 1-50
Cyanazine , PA 0.1-1.0
DBCP AZ, CA, HI, MD, SC 0.02-20
DCPA (and a c i d NY 50-700
products)
1,2-Dichloro- CA, MD, NY, WA 1-50
propane
Dinoseb NY 1-5
Dyfonate I IA 0.1
EDB CA, F L , GA, SC, 0.05-20
WA, AZ, MA, CT
Metolachlor , PA 0.1-0.4
Metribuzin IA 1.0-4.3
Oxamyl I, NY, RI 5-65
Simazine CA, PA, MD 0.2-3.0
1,2,3-Trichlor- CA, HI 0.1-5.0
opropane (impurity)
t T o t a l o f 17 d i f f e r e n t p e s t i c i d e s i n a t o t a l o f 23 d i f f e r e n t states.
*H - h e r b i c i d e
I = insecticide
N = nematicide
10. C O H E N ET AL. Monitoring Ground Water for Pesticides 173
the problem. However, o u r knowledge o f t h e t r u e e x t e n t o f p e s t i c i d e

o c c u r r e n c e i n ground water has i n c r e a s e d o n l y s l i g h t l y . This i s
not t o s a y t h a t EPA has been i d l e i n the i n t e r i m . On t h e c o n t r a r y ,
t h e r e has been a tremendous i n c r e a s e i n a c t i v i t y i n t h i s a r e a . The
problem i s t h a t t h e t a s k i s enormous. The t a s k i s t o c h a r a c t e r i z e
the e x t e n t o f c o n t a m i n a t i o n o r e x t e n t o f p o t e n t i a l c o n t a m i n a t i o n ,
i n terms o f :
1. p e s t i c i d e s i n g e n e r a l and the n a t i o n as a whole;
2. s p e c i f i c p e s t i c i d e s and groups o f p e s t i c i d e s , e.g.,
nematicides;
3. s p e c i f i c crop growing a r e a s , e.g., c i t r u s ;
4. a r e a s a s d e f i n e d by s p e c i f i c f i e l d c o n d i t i o n s , e.g., soil
p e r m e a b i l i t y and ground-water depth;
5. a r e a s as d e f i n e d p o l i t i c a l l y , e.g., counties;
6. i n d i v i d u a l p e s t i c i d e s , t h e r e l a t i o n s h i p between t h e i r
p r o p e r t i e s , f i e l d c o n d i t i o n , and the mechanisms o f l e a c h -
ing.
These c h a r a c t e r i z a t i o n s are n e c e s s a r y i n o r d e r t o make b e t t e r
i n f o r m e d r e g u l a t o r y d e c i s i o n s on p e s t i c i d e r e g u l a t i o n and d r i n k i n g
w a t e r contaminant r e g u l a t i o n s . C l e a r l y , no s i n g l e m o n i t o r i n g o r
p r e d i c t i v e e x e r c i s e can address a l l of these i s s u e s . What needs
t o be done, i n the case of m o n i t o r i n g s t u d i e s , i s t o c l e a r l y s t a t e
and l i m i t t h e o b j e c t i v e s o f t h e s t u d i e s , and then d e s i g n t h e s e
s t u d i e s so t h a t they c o n t a i n c o n s i d e r a t i o n s f o r h y d r o g e o l o g y ,
p e s t i c i d e usage, and s t a t i s t i c s . T h i s paper w i l l d i s c u s s t h r e e
study t y p e s which, c o l l e c t i v e l y , c a n be used t o c h a r a c t e r i z e t h e
problem i n t h e s i x d i f f e r e n t ways d e s c r i b e d above. Large-scale
r e t r o s p e c t i v e p r o b a b i l i t y , s m a l l - s c a l e r e t r o s p e c t i v e , and s m a l l -
s c a l e p r o s p e c t i v e s u r v e y s a r e d e s c r i b e d below. The two o t h e r
p u r p o s e s o f t h i s paper a r e t o o f f e r some g u i d e l i n e s f o r t h e conduct
of t h e s e s t u d i e s and t o update t h e d a t a summary o f p e s t i c i d e s i n
ground w a t e r from a g r i c u l t u r a l p r a c t i c e . But f i r s t i t would
be h e l p f u l t o l i s t some o f t h e t o o l s a v a i l a b l e t o d e s i g n t h e s e
studies.
I t i s important to note that p o t e n t i a l p e s t i c i d e l e a c h e r s can
be and have been i d e n t i f i e d (^, 2 ) . C r i t e r i a are a v a i l a b l e t o
a s s e s s ground-water v u l n e r a b i l i t y f o r p e s t i c i d e a p p l i c a t i o n (J^,
_3, 4_) The acronym "DRASTIC" d e s c r i b e s a scheme f o r combining
w e i g h t e d e v a l u a t i o n s o f seven d i f f e r e n t h y d r o g e o l o g i c a l parameters
i n t o a s c o r e , which i s an i n d i c a t o r o f r e l a t i v e ground-water c o n -
t a m i n a t i o n p o t e n t i a l f o r a county o r subcounty r e g i o n ( 3 ) . Also,
r e g i o n a l p e s t i c i d e s a l e s d a t a (_5) and county l e v e l c r o p d a t a ( 6 )
a r e a v a i l a b l e t o t h e p u b l i c , w h i l e more s p e c i f i c and c o n f i d e n t i a l
s a l e s o r use d a t a c a n be p r o v i d e d t o the EPA by t h e p e s t i c i d e i n -
d u s t r y ( " r e g i s t r a n t s " ) . F i n a l l y , s t a t i s t i c a l s u r v e y methods a r e
a v a i l a b l e ( 7 - 1 1 ) . Thus v a r i o u s t o o l s a r e a v a i l a b l e which can be
i n t e g r a t e d i n t o s t u d i e s d e s i g n e d t o s a t i s f y c e r t a i n o b j e c t i v e s as
d e s c r i b e d above.
Large-Scale Retrospective Studies
The o b j e c t i v e o f l a r g e - s c a l e r e t r o s p e c t i v e ground-water s t u d i e s i s
co c h a r a c t e r i z e the e x t e n t o f o c c u r r e n c e o f p e s t i c i d e s i n w e l l s
over a l a r g e a r e a . These s t a t i s t i c a l s u r v e y s c o v e r m u l t i c o u n t y
o r m u l t i s t a t e a r e a s and t y p i c a l l y i n v o l v e sampling of more than

100 w e l l s . They a r e complex and e x p e n s i v e s u r v e y s and are u s u a l l y
done f o r s p e c i f i c p e s t i c i d e s a f t e r d e t e r m i n a t i o n of a human h a z a r d
c o n c e r n and a f t e r documented w e l l c o n t a m i n a t i o n . T h i s type of
s u r v e y can a l s o be u s e f u l t o s t a t e o r o t h e r a g e n c i e s who would
l i k e t o make e s t i m a t e s about p e r c e n t a g e s of w e l l s contaminated by
v a r i o u s c h e m i c a l s u s i n g m u l t i r e s i d u e methods. A b r i e f d i s c u s s i o n
of some p r i n c i p l e s of p r o b a b i l i t y s u r v e y s f o l l o w s . F u l l e r e x p l a n a
t i o n of the b a s i c methods and t h e o r i e s of survey s t a t i s t i c s a r e
given elsewhere (7-11).
P r o b a b i l i t y s u r v e y s a r e s u r v e y s where samples a r e s e l e c t e d by
a s p e c i f i e d random p r o c e s s . The p o p u l a t i o n from which the samples
w i l l be s e l e c t e d i s c a l l e d the u n i v e r s e or the t a r g e t p o p u l a t i o n .
The d a t a c o l l e c t e d from t h e s e s u r v e y s a r e used t o make i n f e r e n c e s
about the t a r g e t p o p u l a t i o n of w e l l s which may be c a t e g o r i z e d i n
v a r i o u s ways. Some examples o f t a r g e t p o p u l a t i o n s a r e w e l l s i n :
a l l corn-growing c o u n t i e s where p e s t i c i d e
X i s a p p l i e d t o >10% of the l a n d a r e a ;
c e r t a i n ground-water b a s i n s i n the s o u t h e a s t ;
the U n i t e d S t a t e s ;
the S t a t e of F l o r i d a ;
areas with h i g h l y vulnerable hydrogeologies
i n a certain state, etc.
Once the t a r g e t p o p u l a t i o n has been d e f i n e d , two p r i n c i p l e s s h o u l d
be c o n s i d e r e d . F i r s t , s t a t i s t i c a l c o n c l u s i o n s drawn from the
s t u d y a r e not r e l i a b l y a p p l i c a b l e o u t s i d e the t a r g e t p o p u l a t i o n .
Second, i f w e l l s are a r b i t r a r i l y e x c l u d e d from s a m p l i n g a t l a t e r
s t a g e s of the s u r v e y d e s i g n or e x e c u t i o n , the s t a t i s t i c a l v a l i d i t y
of the study s u f f e r s s i g n i f i c a n t l y . The c o n v e r s e i s t r u e - w e l l s
f
c a n t be a r b i t r a r i l y i n c l u d e d . T h i s i s a c o r o l l a r y of the s t a t e
ment t h a t a l l sampling u n i t s ( w e l l s , farm f i e l d s , e t c . ) must have
a non-zero p r o b a b i l i t y of s e l e c t i o n . O t h e r w i s e , water q u a l i t y
r e s u l t s from w e l l s s e l e c t i v e l y chosen may r e f l e c t a p a r t i c u l a r
w e l l - c o n s t r u c t i o n o r " a q u i f e r - m a t e r i a l e f f e c t , " and w i l l not be
r e p r e s e n t a t i v e of a l l the water i n the s p e c i f i c a q u i f e r t h a t i s
under study ( 1 2 ) . H e l s e l and Ragone make use of an example where
w e l l s from two a r e a s a r e s e l e c t i v e l y chosen, one s e t of w e l l s a r e
s c r e e n e d i n c o a r s e g r a v e l s , the second s e t b e i n g screened i n a
v a r i e t y of m a t e r i a l s . R e s i d u e c o n c e n t r a t i o n s may d i f f e r between
the two s e t s , r e f l e c t i n g the d i f f e r e n c e i n l i t h o l o g i e m a t e r i a l s
s u r r o u n d i n g the w e l l s c r e e n s , and not the d i f f e r e n c e s i n p e s t i c i d e
use p a t t e r n s .
A f t e r the sample p o p u l a t i o n has been d e t e r m i n e d and the
c o n s t r a i n t s u n d e r s t o o d , an o v e r a l l e x p e r i m e n t a l d e s i g n can be
constructed. The major p o s s i b i l i t i e s a r e simple random s a m p l i n g ,
random s a m p l i n g w i t h i n g e o g r a p h i c a l or s p a t i a l c l u s t e r s , and
s t r a t i f i e d random s a m p l i n g . ( I n t h i s paper, "random s a m p l i n g " i s
a c o n v e n i e n t term w h i c h means sampling of e q u a l o r p r o p o r t i o n a t e
p r o b a b i l i t y and w i t h o u t r e p l a c e m e n t . ) In a l l c a s e s , a c r i t i c a l
s t e p i s the d e t e r m i n a t i o n o f the sample s i z e . There a r e e s t a b
l i s h e d ways f o r c a l c u l a t i n g the r e q u i r e d numbers, (7_, 9-11); but
b a s i c a l l y i s a f u n c t i o n of the d e s i r e d p r e c i s i o n of the c o n c l u s i o n
(where p r e c i s i o n i m p l i e s a l i m i t on the p r o b a b i l i t y , say .05, t h a t
the c o n c l u s i o n s d i f f e r from the t r u e answer by a t most a s p e c i f i e d
p e r c e n t a g e ( s a y 15%) o f t h e t r u e answer, t h e t a r g e t p o p u l a t i o n
s i z e , and t h e c o s t p e r sample.
Often, p r o b a b i l i t y surveys are designed i n stages. This i s
e s p e c i a l l y t h e case when the t a r g e t p o p u l a t i o n i s l a r g e and
s u c c e s s i v e s t a g e s a r e n e c e s s a r y t o reduce t h e p o t e n t i a l number o f
w e l l s , f a r m s , e t c . , t o be sampled. Once t h e t a r g e t p o p u l a t i o n has
been i d e n t i f i e d , i t i s c a r v e d up i n t o c o n v e n i e n t p o p u l a t i o n s e g
ments such as c o u n t i e s , e n u m e r a t i o n d i s t r i c t s , b a s i n s , e t c . These
segments a r e c a l l e d p r i m a r y sampling u n i t s ( P S U ' s ) . The next s t e p
i n s t a g e d d e s i g n i s t o randomly s e l e c t some PSU's f o r f u r t h e r
study. T h i s s u b p o p u l a t i o n o f randomly s e l e c t e d PSU's i s r e f e r r e d
t o as t h e f i r s t s t a g e sample. I n a two-stage d e s i g n , w e l l s a r e
then randomly s e l e c t e d from the sample frame f o r f i e l d s a m p l i n g ,
i . e . , water a n a l y s i s .
B e f o r e t h e s p e c i f i c s u r v e y types a r e d i s c u s s e d , some advantages
of p r o b a b i l i t y s u r v e y s s h o u l d be mentioned. Such s u r v e y s a r e e f f i
c i e n t i n t h a t r e s u l t s from a r e l a t i v e l y s m a l l number o f samples

can be used t o draw r e l i a b l e c o n c l u s i o n s about a l a r g e t a r g e t popu
lation. The p r o b a b i l i t y approach a l s o r e d u c e s p o s s i b l e s e l e c
t i o n b i a s r e s u l t i n g from the ' l e t ' s g r a b a sample here because i t
l o o k s good' p h i l o s o p h y . P u t i n d i f f e r e n t words, "the major ob
s t a c l e t o random s e l e c t i o n i s c o n v e n i e n c e - i f i t i s more c o n v e n i e n t
t o s e l e c t sampling p o i n t s i n a p a r t i c u l a r f a s h i o n , the p r o c e s s i s
p r o b a b l y not random and s h o u l d be a v o i d e d " (12)
In simple random s a m p l i n g , samples a r e randomly s e l e c t e d from
the t a r g e t p o p u l a t i o n , where t h e t a r g e t p o p u l a t i o n i s u s u a l l y
w e l l s , but may be the ground water under farms, g o l f c o u r s e s , e t c .
T h i s d e s i g n s t r a t e g y i s g e n e r a l l y o n l y recommended i n l i m i t e d
c i r c u m s t a n c e s f o r s t u d i e s o f p e s t i c i d e s i n ground water because o f
e x p e c t e d h i g h v a r i a n c e s i n t h e s t a t i s t i c a l c o n c l u s i o n s and t h e f a c t
t h a t i t does n o t a l l o w one t o i n c o r p o r a t e knowledge o f f i e l d con
d i t i o n s i n t o the design. One example where t h i s approach makes
sense i s when the p o p u l a t i o n t o be sampled i s v e r y n a r r o w l y d e f i n e d
and i s known t o be r e l a t i v e l y homogeneous. For example, a t a r g e t
p o p u l a t i o n c o u l d be w e l l s o f s i m i l a r c o n s t r u c t i o n i n a k a r s t l i m e
stone r e g i o n o f a two county a r e a dominated by one s o i l t e x t u r e ,
e.g., a loamy sand. I n t h i s c a s e , e s t i m a t e s r e s u l t i n g from s i m p l e
random s a m p l i n g would l i k e l y have a lower v a r i a n c e compared t o
o t h e r r e g i o n s c o n t a i n i n g w i d e l y v a r y i n g types o f s o i l and s u b s u r
f a c e h y d r o g e o l o g y . Thus knowledge o f ground-water v u l n e r a b i l i t y
was used t o l i m i t t h e t a r g e t p o p u l a t i o n , b u t was n o t a p a r t o f t h e
s t a t i s t i c a l design.
The second type o f random s a m p l i n g , which has some s p a t i a l
c o n t r o l on t h e sample d i s t r i b u t i o n , i s a s p e c i a l case o f s t r a t i f i e d
random s a m p l i n g . No examples o f t h i s type c o u l d be found i n t h e
l i t e r a t u r e p e r t a i n i n g t o w e l l sampling d e s i g n ; however, an example
of t h i s second type o f random s a m p l i n g p e r t a i n i n g t o s o i l core
s a m p l i n g was found and i s d i s c u s s e d i n t h e s e c t i o n on s o i l s a m p l i n g
under s m a l l - s c a l e r e t r o s p e c t i v e s t u d i e s . As r e g a r d s w e l l sampling
d e s i g n a p o s s i b l e d e s i g n s t r a t e g y i s as f o l l o w s : The w e l l s o f t h e
e a s t e r n shore o f a m i d - A t l a n t i c s t a t e a r e i d e n t i f i e d as t h e t a r g e t
population. G r i d s c o r r e s p o n d i n g t o 5 mi 5 mi a r e a s a r e l a i d
o v e r a map o f t h a t r e g i o n o f t h e s t a t e . One o r more w e l l s a r e
then randomly sampled w i t h i n each g r i d s e c t i o n . T h i s study type
may have l i m i t e d a p p l i c a t i o n t o a r e a s which c o n t a i n l a r g e h y d r o -

g e o l o g y and human a c t i v i t y ( e . g . , d i s p o s a l s i t e s ) d a t a gaps and
i n the s i t u a t i o n s when the time r e q u i r e d f o r an a p p r o p r i a t e
r e c o n n a i s s a n c e a n a l y s i s i s too l o n g . In such a s i t u a t i o n , t h i s
may be c o n s i d e r e d a p r e l i m i n a r y study which would l e a d t o the
g e n e r a t i o n of h y p o t h e s e s and the i n i t i a t i o n of a d d i t i o n a l s t u d i e s .
The t h i r d type of random sampling d i s c u s s e d i n t h i s paper i s
s t r a t i f i e d random s a m p l i n g . The p r i n c i p a l weakness of s i m p l e r a n -
dom sampling i s t h a t i t does not use r e l e v a n t i n f o r m a t i o n or j u d g e -
ment t h a t we have about the environment, i . e . , about p e s t i c i d e s
l e a c h i n g t o ground w a t e r . F o r example, i t would i n c o r p o r a t e our
knowledge t h a t a r e a s w i t h loamy sands o v e r l y i n g s o l u t i o n l i m e s t o n e
a q u i f e r s are p a r t i c u l a r l y v u l n e r a b l e to p e s t i c i d e p o l l u t i o n . This
knowledge can be used i n s t r a t i f i e d random s a m p l i n g . In t h i s
s u r v e y approach, the t a r g e t p o p u l a t i o n i s d i v i d e d i n t o s u b p o p u l a -
t i o n s o r s t r a t a t h a t a r e i n t e r n a l l y more homogeneous than the
t a r g e t p o p u l a t i o n as a whole ( 1 1 ) . Then s p e c i f i e d numbers of

samples a r e randomly s e l e c t e d from each s t r a t u m . Recommended
s t r a t i f i c a t i o n v a r i a b l e s a r e ground-water v u l n e r a b i l i t y and p e s t i -
c i d e usage. Human o r w e l l p o p u l a t i o n d e n s i t y may be used or i t
1
may be used as a ' s i z e m e a s u r e , a w e i g h t i n g f a c t o r t o i n c r e a s e
the p r o b a b i l i t y t h a t c e r t a i n a r e a s may be s e l e c t e d . The s t r a t a
s h o u l d be c o n s t r u c t e d so t h a t they a r e m u t u a l l y e x c l u s i v e and
a c c o u n t t o t a l l y f o r the t a r g e t p o p u l a t i o n .
F o l l o w i n g i s an example of a s t r a t i f i e d random s u r v e y . EPA's
O f f i c e o f D r i n k i n g Water and O f f i c e of P e s t i c i d e Programs (OPP) a r e
j o i n t l y d e s i g n i n g a n a t i o n a l s t r a t i f i e d random s u r v e y w i t h the h e l p
of s t a t i s t i c a l and h y d r o g e o l o g y c o n t r a c t o r s . The s u r v e y i s b e i n g
d e s i g n e d i n t h r e e s t a g e s - s e l e c t c o u n t i e s , s e l e c t county segments,
s e l e c t w e l l s . As of t h i s w r i t i n g , the d e s i g n of the second and
t h i r d s t a g e s i s u n c e r t a i n . However, i n the f i r s t stage the s t r a t i -
f i c a t i o n v a r i a b l e s a r e p e s t i c i d e usage ( 5 , 6) and ground-water
v u l n e r a b i l i t y ( 3 ) . A l l c o u n t i e s i n the U.S. a r e b e i n g c a t e g o r i z e d
a c c o r d i n g t o whether they have h i g h , medium, low o r uncommon p e s t i -
c i d e usage and h i g h , medium, o r low ground-water v u l n e r a b i l i t y .
Thus a l l c o u n t i e s i n the U.S. w i l l be p l a c e d i n t o one of the 12
(3x4) strata. The number of c o u n t i e s w i l l p r o b a b l y be near 200
and w i l l be d e t e r m i n e d u s i n g the c r i t e r i a d e s c r i b e d above ( d e s i r e d
precision, etc.)
T h e r e a r e t h r e e advantages of s t r a t i f i e d random sampling f o r
l a r g e t a r g e t p o p u l a t i o n s , when p r o p e r l y done, r e l a t i v e to s i m p l e
random s a m p l i n g . The o v e r a l l v a r i a n c e f o r the e s t i m a t e s s h o u l d be
s i g n i f i c a n t l y l o w e r . T h e o r e t i c a l l y , t h e r e i s an i n v e r s e square
r e l a t i o n s h i p between the number of s t r a t a and the v a r i a n c e ,
a l t h o u g h p r a c t i c a l l y the r e s u l t s a r e u s u a l l y l e s s d r a m a t i c (_7,
pp. 133-5).
The second advantage i s t h a t e s t i m a t e s can be p r o v i d e d f o r
c e r t a i n s u b d i v i s i o n s of the p o p u l a t i o n . F o r example, EPA s t a f f
d e s i r e s to draw m e a n i n g f u l c o n c l u s i o n s about the h i g h - h i g h s t r a t u m
i n the n a t i o n a l s u r v e y - the c o u n t i e s w i t h h i g h p e s t i c i d e use and
h i g h ground-water v u l n e r a b i l i t y . The t h i r d advantage i s t h a t the
p o s s i b i l i t y t h a t c e r t a i n segments of the t a r g e t p o p u l a t i o n may n o t
be sampled a t a l l can be e l i m i n a t e d . F o r example, i f t h e r e i s a
s m a l l but s i g n i f i c a n t c o t t o n - g r o w i n g a r e a i n a s t a t e , which i s of
i n t e r e s t , t h a t a r e a c a n be made i n t o i t s own s t r a t u m , w i t h s i m i l a r
treatments to other crop areas.
T h i s d i s c u s s i o n has emphasized t h e t h e o r y and b a s i c p r i n c i p l e s
of p r o b a b i l i t y sampling o f w e l l s i n a l a r g e a r e a . The next two
s e c t i o n s a d d r e s s s t u d i e s o f a r e a s of a few a c r e s o r l e s s . The
g u i d e l i n e s f o r w e l l sampling i n those s e c t i o n s a r e a p p r o p r i a t e f o r
t h i s s e c t i o n as w e l l .
Small-Scale Retrospective Studies
F o r a s m a l l - s c a l e r e t r o s p e c t i v e s t u d y , p a r t i c i p a n t s e n t e r and s t u d y
a f i e l d i n which a p e s t i c i d e has been used over a p e r i o d o f t i m e .
The purposes of s m a l l - s c a l e r e t r o s p e c t i v e s t u d i e s a r e t o d e t e r m i n e
whether t h e p e s t i c i d e ( s ) i n q u e s t i o n has l e a c h e d t o ground water
i n c e r t a i n f i e l d s , and t o c h a r a c t e r i z e t h e l e a c h i n g p a t t e r n i n t h e
s o i l p r o f i l e a t a given point i n time. This s e c t i o n contains d i s -
c u s s i o n s on s i t e s e l e c t i o n , s i t e c h a r a c t e r i z a t i o n , t h e number and
l o c a t i o n o f o b s e r v a t i o n w e l l s , w e l l c o n s t r u c t i o n and s a m p l i n g , and
s o i l sampling.
Site Selection. The f o l l o w i n g c r i t e r i a a r e i m p o r t a n t i n choosing

a site ( 2 2 , 14)
1) There s h o u l d be documented p r i o r usage of t h e p e s t i c i d e i n

the f i e l d s i t e , p r e f e r a b l y f o r s e v e r a l p r e v i o u s y e a r s . I f
p o s s i b l e , t h e f i e l d s h o u l d be s e p a r a t e h y d r o g e o l o g i c a l l y and
p h y s i c a l l y from o t h e r f i e l d s where t h e p e s t i c i d e under s t u d y
has been p r e v i o u s l y u s e d . T h i s a v o i d s t h e p o s s i b i l i t y o f r u n o f f
from o t h e r f i e l d s c o n t a m i n a t i n g t h e s t u d y f i e l d s and l e a c h i n g
from o t h e r f i e l d s c o n t a m i n a t i n g t h e u n d e r l y i n g a q u i f e r .
2) Land owner/farmer c o o p e r a t i o n i s e s s e n t i a l s i n c e he/she will

be c l o s e l y i n v o l v e d i n the study.
3) I t i s preferable to i n s t a l l observation wells s p e c i f i c a l l y

d e s i g n e d f o r the purposes o f t h e s t u d y . G u i d e l i n e s f o r w e l l
c o n s t r u c t i o n a r e g i v e n i n t h e w e l l c o n s t r u c t i o n s e c t i o n . How-
e v e r , e x i s t i n g w e l l s c a n be used i f s u f f i c i e n t i n f o r m a t i o n i s
a v a i l a b l e to c h a r a c t e r i z e the w e l l s . I f e x i s t i n g wells are
u s e d , t h e h i s t o r y o f t h e w e l l - c o n s t r u c t i o n w i l l be n e c e s s a r y .
The w e l l s h o u l d be r e j e c t e d from t h e s t u d y i f t h e s e d a t a a r e
not complete. Some p e r t i n e n t q u e s t i o n s t o a s k a r e : What i s t h e
w e l l depth? A t what d e p t h i s i t screened? W i t h what m a t e r i a l
i s t h e w e l l annulus f i l l e d , i . e . , g r a v e l , cement? Was t h e w e l l
sealed properly? Does t h e w e l l have a d e v i c e t o p r e v e n t back-
s i p h o n i n g i n s t a l l e d i n i t ? Of what m a t e r i a l i s t h e w e l l c a s i n g
constructed? There s h o u l d be o n l y one s h o r t s c r e e n o r p e r f o r a -
t i o n i n the c a s i n g . Well casings with several screens or per-
f o r a t i o n s a t d i f f e r e n t depths s h o u l d be r e j e c t e d from the s t u d y .
The w e l l c a s i n g may be i n a d e q u a t e f o r m o n i t o r i n g c e r t a i n
o r g a n i c s i f i t i s c o n s t r u c t e d w i t h any type o f p l a s t i c s o r
p l a s t i c i z e r s known t o a d s o r b o r g a n i c s .
4) Uniform s o i l c h a r a c t e r i s t i c s on t h e f i e l d are d e s i r a b l e .
U n i f o r m i t y i n t h i s c o n t e x t r e f e r s t o s l o p e and t e x t u r e . I d e a l l y ,
the f i e l d s h o u l d have a s l o p e o f l e s s than 2%, and i f p o s s i b l e ,
t h e r e s h o u l d be o n l y one s o i l s e r i e s on t h e f i e l d . I f more
than one s o i l s e r i e s i s on t h e f i e l d , a l l t h e s e r i e s s h o u l d be
of the same t e x t u r e , i . e . , a l l s h o u l d be sandy loams. This
c r i t e r i o n does n o t p r e c l u d e the p o s s i b i l i t y o f l a y e r e d s o i l s
( s o i l s w i t h d i s t i n c t h o r i z o n s ) as l o n g as the e n t i r e f i e l d i s
c h a r a c t e r i z e d by t h i s l a y e r e d s o i l . The more u n i f o r m the f i e l d ,
the e a s i e r w i l l be t h e i n t e r p r e t a t i o n o f r e s u l t s . Soil
Conservation Service s o i l surveys give s u f f i c i e n t l y d e t a i l e d
information to characterize a f i e l d .
Characterizing a Site. The s o i l i n the f i e l d must be c h a r a c t e r

ized. A minimum o f the f o l l o w i n g k i n d s of i n f o r m a t i o n s h o u l d be
recorded:
p e r m e a b i l i t y o f the i n d i v i d u a l s o i l l a y e r s as a f u n c t i o n o f d e p t h
down t o t h e water t a b l e ;
o r g a n i c matter;
bulk d e n s i t y ;
p a r t i c l e s i z e d i s t r i b u t i o n of sand, s i l t , and c l a y as a f u n c t i o n
of d e p t h , i f d i s t i n c t l y d i f f e r e n t h o r i z o n s e x i s t i n the s o i l
column down t o t h e water t a b l e ;
a v a i l a b l e water h o l d i n g c a p a c i t y , as d e f i n e d by the d i f f e r e n c e of
f i e l d c a p a c i t y and w i l t i n g p o i n t , b o t h o f which s h o u l d a l s o be
a s c e r t a i n e d f o r the s o i l ;
SCS s o i l s e r i e s c l a s s i f i c a t i o n f o r the s o i l s of t h e study s i t e ,
i f information i s a v a i l a b l e .
The h y d r o g e o l o g y o f t h e f i e l d must be c h a r a c t e r i z e d . I n many

cases, only semiquantitative analyses are necessary. Some p o i n t s
to consider a r e :
t y p e s , d e p t h s , and e x t e n t of l a y e r s of reduced p e r m e a b i l i t y such

as c l a y pans and s i l t - c l a y l e n s e s ;
w a t e r t a b l e d e p t h below t h e s u r f a c e as a f u n c t i o n of time; t h e
water t a b l e may f l u c t u a t e s e a s o n a l l y w i t h r a i n f a l l / r u n o f f e v e n t s
and snowmelt;
t h e d i r e c t i o n of ground-water f l o w ( c o n s t r u c t i o n of a f l o w - n e t ) ;
type of a q u i f e r ( c o n f i n e d , u n c o n f i n e d , a r t e s i a n ) ;
g e o l o g i c m a t e r i a l s c o m p r i s i n g t h e a q u i f e r (sand and g r a v e l ,
g l a c i a l t i l l , carbonates, e t c . ) ;
2
h y d r a u l i c c o n d u c t i v i t y ( s ) (K m /day) - whether t h e l o c a l p o r t i o n
o f t h e a q u i f e r i s c h a r a c t e r i z e d by one ( i s o t r o p i c ) o r s e v e r a l
values ( a n i s o t r o p i c ) ;
transmissivity;
whether t h e a q u i f e r has r e c h a r g i n g o r d i s c h a r g i n g c h a r a c t e r i s t i c s ;
any man-made a c t i v i t i e s t h a t may a f f e c t t h e water l e v e l o f t h e
a q u i f e r such as ground-water pumpage.
C l i m a t o l o g i c a l i n f o r m a t i o n f o r the s i t e w i l l be n e c e s s a r y .
P r e c i p i t a t i o n d a t a , a i r temperature and pan e v a p o r a t i o n d a t a , and
any use o f i r r i g a t i o n water must be c a r e f u l l y r e c o r d e d . Irrigation
and n a t u r a l r e c h a r g e i s a c r i t i c a l a s p e c t of p e s t i c i d e l e a c h i n g .
A water b a l a n c e d e t a i l i n g t h e water i n p u t s and o u t p u t s from t h e

f i e l d c a n be used t o e s t i m a t e r e c h a r g e . I n p u t s t o t h i s b a l a n c e
i n c l u d e p r e c i p i t a t i o n and i r r i g a t i o n . The o u t p u t s w h i c h can be
e s t i m a t e d a r e r u n o f f and vapotranspiration, and t h e remainder
can be assumed t o be r e c h a r g e .
Number and L o c a t i o n o f O b s e r v a t i o n W e l l s . The p r e c i s e amount o f

p e s t i c i d e which was a p p l i e d t o t h e s o i l s u r f a c e and i s a v a i l a b l e
f o r l e a c h i n g i s known as t h e s o u r c e term. F o r p e s t i c i d e s which
a r e a p p l i e d d i r e c t l y t o t h e s o i l , such as g r a n u l e s o r l i q u i d formu-
l a t i o n s s p r a y e d o n l y onto t h e s o i l s u r f a c e , t h e s o u r c e term c a n be
assumed t o be e q u a l t o t h e t o t a l amount o f a p p l i c a t i o n .
However, i f the p e s t i c i d e i s s p r a y e d onto a d e v e l o p i n g canopy,
then some o f t h e p e s t i c i d e w i l l be i n t e r c e p t e d by t h e p l a n t and
w i l l be u n a v a i l a b l e f o r l e a c h i n g . The s o u r c e term o b v i o u s l y cannot
be e s t i m a t e d a c c u r a t e l y w i t h o u t p o s t - a p p l i c a t i o n s a m p l i n g , which
i s why landowner r e c o r d s a r e i m p o r t a n t . E s t i m a t i o n of the source

term i s c r i t i c a l f o r t h e i n t e r p r e t a t i o n o f a l l subsequent d a t a
c o l l e c t i o n e f f o r t s , a s w e l l as f o r m o d e l i n g purposes ( i f t h a t w i l l
be p a r t o f the use o f f i e l d d a t a ) .
A n o t h e r c r i t i c a l i n f o r m a t i o n need f o r e i t h e r a r e t r o s p e c t i v e
o r a p r o s p e c t i v e s t u d y i s the d i r e c t i o n o f ground-water f l o w . I f
i t can be d e t e r m i n e d from p r e e x i s t i n g h y d r o g e o l o g i c a l i n f o r m a t i o n
on the s t u d y s i t e , t h e n the d e s i g n and placement o f the m o n i t o r i n g
w e l l s c a n be d e t e r m i n e d . I f the d i r e c t i o n o f ground-water f l o w
cannot be d e t e r m i n e d from e x i s t i n g d a t a , and p r e v i o u s l y i n s t a l l e d
w e l l s a r e p r e s e n t on the p r o p e r t y , they c a n be used t o t r y t o
e s t a b l i s h the ground-water f l o w n e t .
U n d e r s t a n d i n g the d i r e c t i o n o f ground water f l o w i s n e c e s s a r y
to d e t e r m i n e t h e l o c a t i o n o f m o n i t o r i n g w e l l s . The minimum number
of w e l l s i t e s i s suggested t o be 4 f o r one study s i t e . (Federal
R e g u l a t i o n s i n 40 CFR P a r t 256, s u b p a r t F o f the Resource C o n s e r -
v a t i o n and Recovery A c t s u g g e s t a t l e a s t f o u r m o n i t o r i n g w e l l s as
the minimum number f o r l a n d f i l l s . ) A " w e l l s i t e " c a n be d e f i n e d
as a c l u s t e r o f t h r e e w e l l s , l o c a t e d v e r y n e a r each o t h e r , which
p e n e t r a t e t h r e e depths o f the a q u i f e r , i . e . , each w e l l i s s c r e e n e d
a t a d i f f e r e n t d e p t h t o o b t a i n 3 d i m e n s i o n a l sampling o f the a q u i -
f e r a t each w e l l s i t e . The f i r s t w e l l i s p l a c e d c e n t r a l l y w i t h
r e s p e c t t o t h e s t u d y s i t e u p - g r a d i e n t and o u t s i d e o f t h e s t u d y
s i t e boundary; t h e second w e l l i s p l a c e d c e n t r a l l y w i t h r e s p e c t t o
the study s i t e and down-gradient and o u t s i d e o f t h e s t u d y s i t e
boundary; and t h e t h i r d and f o u r t h on e i t h e r s i d e o f t h e c e n t e r o f
the study s i t e w i t h i n t h e t h e s t u d y s i t e b o u n d a r i e s .
Once the w e l l s a r e i n p l a c e , ground-water samples c a n be t a k e n
f o r water q u a l i t y measurements. Assuming t h e f i e l d has had s e v e r a l
y e a r s o f s e a s o n a l p e s t i c i d e use, p e s t i c i d e s may be d e t e c t e d i n
w e l l samples any time of the y e a r . However, t h e two o p t i m a l times
f o r sampling beneath and j u s t down-gradient o f t h e f i e l d a r e n o t
l o n g f o l l o w i n g a p p l i c a t i o n i n l a t e s p r i n g and e a r l y summer, and
d u r i n g the w i n t e r - s p r i n g snowmelt p e r i o d ( c a . M a r c h ) . Experience
has shown t h a t l e a c h i n g p e s t i c i d e s t y p i c a l l y contaminate v e r y
s h a l l o w ground water beneath the f i e l d w i t h the f i r s t major p e r i o d
of r e c h a r g e f o l l o w i n g a p p l i c a t i o n ; i . e . , w i t h s p r i n g r e c h a r g e
f o l l o w i n g a p p l i c a t i o n i n t h e s p r i n g f o r p e s t i c i d e s i n the N o r t h e a s t ,
o r w i t h summer r a i n f o r s p r i n g a p p l i e d p e s t i c i d e s i n the S o u t h e a s t ,
Because of the temporal changes i n ground-water q u a l i t y ( 1 5 - 1 7 ) ,
w e l l s s h o u l d be sampled b e g i n n i n g a t the o n s e t of the sampling
program and c o n t i n u i n g t h r o u g h the w i n t e r and i n t o the next s e a s o n .
W e l l C o n s t r u c t i o n . The s e l e c t i o n of a d r i l l i n g method f o r t h i s
phase of work s h o u l d be based on the a b i l i t y of a p a r t i c u l a r method
t o a c h i e v e the o b j e c t i v e s of a d r i l l i n g program, which i n c l u d e
the f o l l o w i n g p o i n t s from L u h d o r f f and S c a l m a n i n i ( 1 8 ) :
1) t h e a b i l i t y t o p e n e t r a t e a l l a n t i c i p a t e d f o r m a t i o n s and
m a t e r i a l s , t o p e n e t r a t e a t a d e s i r e d r a t e , and t o c o n s t r u c t
a b o r e h o l e of d e s i r e d d i a m e t e r f o r the a n t i c i p a t e d w e l l , as
w e l l as f o r the placement of a g r a v e l o r sand pack and
n e c e s s a r y f o r m a t i o n s e a l i n g m a t e r i a l such as b e n t o n i t e o r
cement;
2) i d e n t i f i c a t i o n of l i t h o l o g y o r development of a g e o l o g i c l o g
of a l l f o r m a t i o n s and m a t e r i a l s p e n e t r a t e d , i n c l u d i n g p h y s i c a l
c h a r a c t e r i s t i c s and v i s u a l d e s c r i p t i o n of c o l o r , t e x t u r e , e t c . ;
3) c o l l e c t i o n of samples of a q u i f e r f l u i d s d u r i n g the d r i l l i n g
p r o c e s s and p r i o r t o w e l l c o n s t r u c t i o n , w h i l e a t the same time
minimizing p o t e n t i a l f o r cross-contamination ("cleanliness" i s
a key i s s u e i n d r i l l i n g - t h e r e s h o u l d be no c o n t a m i n a t i o n from
s u r f a c e s o i l s and w a t e r , i n a d d i t i o n t o c r o s s - c o n t a m i n a t i o n
between l a y e r s ) ;
4) c o l l e c t i o n of " u n d i s t u r b e d " s o i l samples from the c e n t e r l i n e

or s i d e w a l l of the b o r e h o l e ( t h i s o b j e c t i v e o f t e n r e q u i r e s the
d r i l l i n g t o be h a l t e d w h i l e s o i l samples a r e t a k e n from the
bottom of the i n c o m p l e t e b o r e h o l e ) ;
5a) c o m p l e t i o n of the b o r e h o l e i n t o a m o n i t o r i n g w e l l d u r i n g the

i n i t i a l c o n s t r u c t i o n p r o c e s s , i . e . , c o n s t r u c t i n g a w e l l as the
b o r e h o l e i s d r i l l e d o r c o n s t r u c t i n g a w e l l i n the b o r e h o l e
i m m e d i a t e l y a f t e r the d r i l l i n g t o o l s a r e removed;
or
5b) c o m p l e t i o n of a m o n i t o r i n g w e l l i n the b o r e h o l e f o l l o w i n g a
time l a p s e f o r i n t e r p r e t a t i o n of g e o l o g i c o r g e o p h y s i c a l d a t a
from the b o r e h o l e .
Though g e o p h y s i c a l l o g g i n g of the b o r e h o l e i s d e s i r a b l e i n
many s i t u a t i o n s , the a d d i t i o n a l expense and equipment n e c e s s a r y
may be p r o h i b i t i v e . F o r the s m a l l e r , more s h a l l o w w e l l s used i n
s m a l l - s c a l e ground-water s t u d i e s t h i s i s not n e c e s s a r y .
There a r e many d r i l l i n g t e c h n i q u e s a v a i l a b l e f o r w e l l
construction: h o l l o w stem; f l i g h t auger; d i r e c t c i r c u l a t i o n
rotary d r i l l i n g ; cable tool d r i l l i n g ; reverse c i r c u l a t i o n rotary
d r i l l i n g ; and a i r r o t a r y d r i l l i n g . B a r c e l o n a , Gibb and M i l l e r
(1983) p r o v i d e a more d e t a i l e d d i s c u s s i o n of each ( 1 9 ) .
10. COHEN ET AL. Monitoring Ground Water for Pesticides 181
F o r the purposes of a s m a l l - s c a l e r e t r o s p e c t i v e o r p r o s p e c t i v e
s t u d y , t h e h o l l o w stem, c o n t i n u o u s - f l i g h t auger i s recommended.
The h o l l o w - s t e m auger i s m o b i l e and i n e x p e n s i v e t o o p e r a t e . I t
i s c a p a b l e o f d r i l l i n g a p p r o x i m a t e l y 150 f e e t i n t o u n c o n s o l i d a t e d
material. ( P r a c t i c a l e x p e r i e n c e i n d i c a t e s t h a t 100 f e e t may be
successfully drilled.) The r i g i s equipped w i t h a removable p l u g
t h a t h e l p s i n the d r i l l i n g p r o c e s s , but t h a t i s i n s e r t e d i n s i d e
the h o l l o w stem of t h e auger and i s , t h e r e f o r e , e a s i l y removable.
The d r i l l i n g p r o c e d u r e uses no d r i l l i n g f l u i d s , t h e r e b y m i n i m i z i n g
c o n t a m i n a t i o n problems between the b o r e h o l e m a t e r i a l s and t h e
d r i l l i n g p r o c e s s ( 2 0 ) . Once the b o r e h o l e has been d r i l l e d t o t h e
d e s i r e d d e p t h , t h e p l u g i s removed from i n s i d e the h o l l o w stem and
a s m a l l - d i a m e t e r w e l l c a s i n g , 1 l / 4 " - 2 " , (3-5 cm) can be i n s e r t e d
i n s i d e t h e h o l l o w stem. The hollow-stem auger c a n then be p u l l e d
out o f the b o r e h o l e l e a v i n g the w e l l c a s i n g i n p l a c e , which c a n
then be e a s i l y g r o u t e d i n . S o i l c o r e samples c a n a l s o be o b t a i n e d
d u r i n g t h e d r i l l i n g p r o c e s s b y i n s e r t i n g a Shelby Tube o r a s p l i t
spoon ( s p l i t b a r r e l ) sampler i n s i d e the h o l l o w stem, l o w e r i n g t h e
assembly t o the bottom o f the h o l e and d r i v i n g t h e sampling tube
i n t o t h e u n d i s t u r b e d p r o f i l e ( 2 1 ) . These c o r e samples w i l l be
used f o r l i t h o l o g i e i d e n t i f i c a t i o n .
C r o s s - c o n t a m i n a t i o n o f d r i l l e d m a t e r i a l s and s o i l samples
c o l l e c t e d f o r l i t h o l o g i e i d e n t i f i c a t i o n c a n be m i n i m i z e d d u r i n g
d r i l l i n g by i n s t a l l i n g temporary c a s i n g as t h e d r i l l i n g p r o c e e d s ,
and r e v e r s i n g t h e d r i l l s p i n i n p l a c e . A f t e r t h e f i r s t w e l l h a s
been d r i l l e d from the s o i l s u r f a c e t o the d e s i r e d d e p t h , u s u a l l y
the water t a b l e and below, t h e s o i l c o r e s from t h i s s i t e may be
used f o r l i t h o l o g i e i d e n t i f i c a t i o n , as mentioned. F o r any o t h e r
w e l l s d r i l l e d o n the same p l o t , i n which a Shelby Tube o r s p l i t
spoon sampler a r e n o t u s e d , t h e f i r s t 18" o f e a r t h c a n be removed
w i t h a s h o v e l r e d u c i n g t h e p o s s i b i l i t y o f s o i l from t h e s e upper
zones from c o n t a m i n a t i n g the lower d r i l l i n g d e p t h s . This i s
d e s i r a b l e f o r r e t r o s p e c t i v e s t u d i e s as t h e f i r s t 18" o f s o i l o f t e n
c o n t a i n s the h i g h e r c o n c e n t r a t i o n s o f p e s t i c i d e s .
In most c a s e s the h o l l o w - s t e m auger w i l l produce a s u f f i c i e n t l y
deep b o r e h o l e f o r a s m a l l - s c a l e ground-water s t u d y d e s i g n e d t o
d e t e c t the l e a c h i n g o f p e s t i c i d e s from normal a g r i c u l t u r a l u s e .
Where deeper w e l l s a r e needed o r where c o n s o l i d a t e d f o r m a t i o n s a r e
encountered o t h e r t e c h n i q u e s may be r e s e a r c h e d f o r t h e i r a p p l i c a -
bility.
Once a new w e l l i s i n p l a c e i t needs t o be d e v e l o p e d . Well
development r e f e r s t o t h e procedure used t o c l e a r the w e l l - s c r e e n
of f i n e s i l t s and c l a y s produced d u r i n g d r i l l i n g . Pumping t h e
w e l l u n t i l sediment f r e e - f l o w i s e s t a b l i s h e d o r by u s i n g a surge
b l o c k t o l o o s e n c l o g g e d m a t e r i a l a r e recommended ( 2 1 ) . F o r t h e
purposes of s m a l l and l a r g e s c a l e ground-water s t u d i e s , a l l w e l l s
s h o u l d be c o n s t r u c t e d w i t h a s i n g l e , s h o r t s c r e e n a t a known depth
(12).
Once a s c r e e n e d c a s i n g h a s been lowered i n t o the b o r e h o l e t o
the depth of i n t e r e s t , q u a r t z sand, f r a c sand o r pea g r a v e l s h o u l d
be f i l l e d i n around and a few i n c h e s above t h e s c r e e n e d i n t e r v a l .
Expandable g r o u t s h o u l d be used t o f i l l i n the annulus above t h e
s c r e e n t o t h e s u r f a c e around the w e l l . The e n t i r e l e n g t h o f t h e
c a s i n g from s u r f a c e t o t h e s c r e e n e d i n t e r v a l s h o u l d be g r o u t e d i n
t o p r e v e n t seepage from the s u r f a c e down a l o n g the c a s i n g ( 2 1 ) .

The p e r m e a b i l i t y of g r o u t s e a l s i s f u r t h e r d i s c u s s e d by Kurt and
Johnson (1982) ( 2 2 ) . I t i s recommended t h a t cement s e a l s be used,
and b e n t o n i t e s e a l s be a v o i d e d .
The recommended m o n i t o r i n g w e l l d i a m e t e r i s 2 i n c h e s (5 cm)
(23). The type of w e l l c a s i n g i s i m p o r t a n t , and w i l l be d e t e r m i n e d
by the types of compounds sampled f o r . The f o l l o w i n g m a t e r i a l s
were ranked by the U.S. G e o l o g i c a l Survey (USGS) as t o t h e i r i n e r t -
n e s s and s u i t a b i l i t y as c a s i n g m a t e r i a l s : g l a s s , T e f l o n , s t a i n l e s s
s t e e l , g a l v a n i z e d s t e e l , PVC, b l a c k p i p e , f i b e r g l a s s . From the
a f o r e m e n t i o n e d USGS memorandum a c o m b i n a t i o n of m a t e r i a l s f o r w e l l
c a s i n g i s recommended, s p e c i f i c a l l y , "a T e f l o n or s t a i n l e s s s t e e l
s c r e e n and c a s i n g i n the water b e a r i n g zone and PVC c a s i n g f o r the
remainder of the h o l e . " T h i s p r o c e d u r e i s recommended f o r b o t h
v o l a t i l e and n o n - v o l a t i l e p e s t i c i d e s of expected low c o n c e n t r a t i o n
l e v e l s i n a n o n - c o r r o s i v e environment, i . e . , pH g r e a t e r than 5, no
i r o n p r e c i p i t a t i o n , and low c o n c e n t r a t i o n s of o r g a n i c s o l v e n t s .
Whenever PVC i s u s e d , no o r g a n i c - b a s e d s o l v e n t s or s e a l e r s s h o u l d
be used because of the p o s s i b i l i t y of c o n t a m i n a t i o n . J o i n t s of
c a s i n g s h o u l d be threaded and screwed t o g e t h e r , not g l u e d t o g e t h e r .
As w i t h w e l l c o n s t r u c t i o n and d r i l l i n g method p r e c a u t i o n s ,
a l l sampling d e v i c e s s h o u l d be c a r e f u l l y c l e a n e d p r i o r t o u s e .
T h e r e a r e many suggested methods. C u r r e n t p r a c t i c e a t the U.S.
G e o l o g i c a l Survey recommends a hot d e t e r g e n t s c r u b w i t h an i n -
organic detergent, p r e f e r a b l y a sulfonated detergent, followed
by a d i s t i l l e d water r i n s e f o r p l a s t i c and T e f l o n p a r t s and an
o r g a n i c s o l v e n t r i n s e f o r m e t a l p a r t s ( 2 4 ) . A l l sampling d e v i c e s
s h o u l d be p r e - r i n s e d w i t h the w e l l water to be sampled.
W e l l Sampling. B e f o r e a w e l l i s sampled, i t must be purged of i t s

s t a n d i n g water or s t o r a g e water u n t i l the w e l l y i e l d s r e p r e s e n t a -
t i v e a q u i f e r water upon pumping. Storage water i s water t h a t
"does not come i n t o c o n t a c t w i t h the f l o w i n g ground w a t e r " (25,
26). In the p a s t , the most common method used t o o b t a i n a r e p r e -
s e n t a t i v e a q u i f e r sample was t o f l u s h the w e l l - b o r e by pumping a
s p e c i f i e d number of w e l l - b o r e volumes of w a t e r . T h i s p r o c e d u r e i s
c o n s i d e r e d o u t d a t e d , and i s not a d v i s e d . The f o l l o w i n g e x c e r p t i s
a c o m p i l a t i o n of the i n f o r m a t i o n compiled by Gibbs and o t h e r s o u t -
l i n i n g recommendations f o r the c o l l e c t i o n of ground-water samples
(25).
1) A two or t h r e e hour pumping t e s t s h o u l d be conducted on each

m o n i t o r i n g w e l l t o be sampled. A n a l y s i s of the pump t e s t d a t a
and o t h e r h y d r o l o g i e i n f o r m a t i o n s h o u l d be used t o d e t e r m i n e
the f r e q u e n c y a t which samples w i l l be c o l l e c t e d and the r a t e
and p e r i o d of time each w e l l s h o u l d be pumped p r i o r t o c o l l e c t -
i n g the sample. I f pumping t e s t s cannot be c o n d u c t e d , s l u g
t e s t s may be s u b s t i t u t e d t o p r o v i d e the needed h y d r o l o g i e i n f o r -
mation.
2) In g e n e r a l , p e r i s t a l t i c and T e f l o n pumps are recommended f o r

s m a l l d i a m e t e r , 2" (5 cm) w e l l s . The p e r i s t a l t i c pump i s used
t o h e l p e v a c u a t e the c a s i n g .
The U.S. G e o l o g i c a l Survey r e q u i r e s t h a t t h e s p e c i f i c conductance

and temperature s t a b i l i z e b e f o r e t a k i n g a water sample t h a t i s
c o n s i d e r e d r e p r e s e n t a t i v e o f t h e a q u i f e r ; t h i s i s t h e OPP/EPA
p o l i c y , as w e l l . The pH o f t h e sample s h o u l d be r e c o r d e d t o +
0.1. There a r e no s e t number o f w e l l c a s i n g volumes t o be
pumped
These s m a l l 2" w e l l s s h o u l d n o t be overpumped t o t h e p o i n t

of d r y n e s s . A pumping r a t e slow enough t o a l l o w t h e w e l l t o
r e c h a r g e o r r e c o v e r i s recommended. Overpumping c a n cause
e x c e s s i v e s i l t and c l a y f i n e s t o be drawn from t h e w e l l ( 2 7 ) *
Measurement of c h e m i c a l parameters i s b e s t a c c o m p l i s h e d w i t h an
i n - l i n e c l o s e d measurement c e l l ( 2 5 ) . When t h e v a l u e s of t h e
i n d i c a t o r parameters a r e observed t o v a r y l e s s than +_ 10% o v e r
t h r e e c o n s e c u t i v e w e l l - b o r e s t o r a g e volumes, t h e w e l l may be
presumed t o have been a d e q u a t e l y f l u s h e d f o r r e p r e s e n t a t i v e

sampling. When i n - l i n e measurement c e l l s a r e n o t p r a c t i c a l ,
s t a n d a r d pH and c o n d u c t i v i t y meters and thermometers a r e u s e d .
A l l c o n t a i n e r s used f o r measurements must be r i n s e d 3 times w i t h
r e p r e s e n t a t i v e w e l l water.
3) Once t h e water has been determined t o be r e p r e s e n t a t i v e o f t h e

a q u i f e r , t h e p e r i s t a l t i c pump s h o u l d be removed. A T e f l o n
b l a d d e r pump o r p o s i t i v e d i s p l a c e m e n t pump s h o u l d be used t o
c o l l e c t t h e a c t u a l water samples. A t l e a s t 1 l i t e r o f r e p r e -
s e n t a t i v e w e l l w a t e r s h o u l d be pumped through t h e b l a d d e r pump
before sampling. The b l a d d e r pump (3 f e e t l o n g ) i s i n s e r t e d
i n t o t h e w e l l and f i l l s p a s s i v e l y w i t h w a t e r . The T e f l o n
b l a d d e r i n s i d e o f t h e pump i n f l a t e s w i t h N2 gas and d i s p l a c e s
the water sample up a T e f l o n tube and i n t o t h e sample c o n t a i n e r .
I t i s important t h a t t h e r e i s enough water t o c o m p l e t e l y c o v e r

the pump i n o r d e r t o p r e v e n t t h e i n t r o d u c t i o n o f a i r i n t o
the water sample. Sampling d e v i c e s s h o u l d be s e l e c t e d t h a t
m i n i m i z e t h e i n t r o d u c t i o n o f a i r and gas bubbles i n t o t h e sample
(28, 2 9 ) . F o r w e l l s w i t h o u t enough water t o c o v e r t h e b l a d d e r ,
a T e f l o n o r s t a i n l e s s s t e e l b a i l e r r e s e m b l i n g a l o n g , narrow
bucket may be used ( 2 7 ) . A l l c o l l e c t i o n c o n t a i n e r s s h o u l d
be r i n s e d 3 times w i t h r e p r e s e n t a t i v e w e l l water p r i o r t o
collection.
Most p e s t i c i d e s s t i l l i n u s e a r e n o t v o l a t i l e o r g a n i c s .
However, f o r v o l a t i l e o r g a n i c s , t h e f o l l o w i n g p r o c e d u r e s a r e
recommended (30)
1) A s i l i c o n / T e f l o n septum capped v i a l i s recommended f o r t h e

c o l l e c t i o n o f v o l a t i l e o r g a n i c compounds. T h i s a l l o w s t h e
l a b o r a t o r y c o n d u c t i n g t h e c h e m i c a l a n a l y s e s t o withdraw a sample
t h r o u g h t h e septum t o p , m i n i m i z i n g t h e sample's exposure t o
air.
2) F i l l t h e v i a l u n t i l a p o s i t i v e meniscus forms a t t h e t o p . Avoid

a e r a t i n g t h e sample w h i l e s e a l i n g t h e c o n t a i n e r .
3) Look f o r a i r b u b b l e s by t u r n i n g the c o n t a i n e r u p s i d e down. Any

bubbles a r e an i n d i c a t i o n of t r a p p e d a i r and the sample s h o u l d
be d i s c a r d e d and a new sample c o l l e c t e d .
Because p e s t i c i d e s may degrade a f t e r c o l l e c t i o n , the f o l l o w i n g

s t e p s may be c o n s i d e r e d t o m i n i m i z e t h a t breakdown. 1) F o l l o w
c o l l e c t i o n p r o c e d u r e s o u t l i n e d above. 2) Wrap the g l a s s sample c o n -
t a i n e r i n aluminum f o i l o r use amber g l a s s b o t t l e s o r use T e f l o n
sample c o n t a i n e r s t o s h i e l d p e s t i c i d e s from the e f f e c t s of s u n l i g h t .
3) D e a e r a t e samples w i t h N 2 , He or A r gas when they a r r i v e i n the
lab. 4) S t o r e samples a t 4C u n t i l a n a l y s i s , o r i f samples a r e
c o l l e c t e d i n T e f l o n b o t t l e s they can be f r o z e n u n t i l a n a l y s i s . 5)
E x t r a c t the samples as soon as p o s s i b l e , p r e f e r a b l y w i t h i n 2 weeks.
DO NOT f r e e z e samples i n g l a s s c o n t a i n e r s . F r e e z i n g may c r a c k
g l a s s c o n t a i n e r s . A l t h o u g h T e f l o n c o n t a i n e r s can be s h i p p e d w i t h
f r o z e n samples, f r e e z i n g and thawing p r o c e d u r e s may d i s t u r b the
c h e m i c a l e q u i l i b r i a of s o l u t e s i n s o l u t i o n , and i s t h e r e f o r e not
recommended ( 3 1 ) .
S o i l Sampling. S o i l s a m p l i n g p r o v i d e s i n f o r m a t i o n on u n s a t u r a t e d
zone p e s t i c i d e m i g r a t i o n , and as s u c h , i s a c r i t i c a l component
of r e t r o s p e c t i v e and p r o s p e c t i v e s t u d i e s . F o r t h i s r e a s o n , s o i l
s a m p l i n g f o r a r e t r o s p e c t i v e f i e l d study s h o u l d a d e q u a t e l y d e s c r i b e
p e s t i c i d e f a t e h o r i z o n t a l l y ( o v e r the e n t i r e f i e l d s u r f a c e ) and
v e r t i c a l l y ( t h r o u g h the v a r i o u s s o i l h o r i z o n s t o the ground w a t e r ) .
U n l i k e water s a m p l i n g , t h i s can be a c c o m p l i s h e d w i t h o n l y a s i n g l e
sampling date. This requirement r e s u l t s i n a s i g n i f i c a n t savings
of r e s o u r c e s i n c o n t r a s t t o a p r o s p e c t i v e f i e l d s t u d y , which r e -
q u i r e s s e v e r a l s o i l s a m p l i n g d a t e s over t i m e . O b v i o u s l y , the
t i m i n g of t h i s s o i l sampling d a t e i s c r i t i c a l . I t should occur
f o l l o w i n g a time p e r i o d when the p r e v i o u s a p p l i c a t i o n would have
s p r e a d out i n the p r o f i l e and l e a c h e d , i f t h a t i s what i t would
do. F o r a s p r i n g a p p l i c a t i o n , t h i s i s u s u a l l y i n the f a l l , f o r
example.
Few examples of e x p e r i m e n t a l d e s i g n s f o r s o i l sampling were

found i n the l i t e r a t u r e . T o u r t e l o t and M i e s c h (32) d i s c u s s the
e s t i m a t i o n of the t o t a l g e o c h e m i c a l v a r i a t i o n of a s h a l e u n i t
u s i n g a d e s i g n a p p r o a c h c a l l e d a " h i e r a r c h i a l a n a l y s i s of v a r i a n c e . "
T h i s i s one approach which c o u l d be a p p l i e d t o the v a r i a n c e of
p e s t i c i d e r e s i d u e s i n a s o i l p l o t s t u d y i n the f o l l o w i n g manner.
F o r a p l o t of v a r i a b l e s o i l c h a r a c t e r i s t i c s :
a) d e t e r m i n e a r e a s of v a r i a b l e s o i l types ( t e x t u r e s , % o r g a n i c
m a t t e r ) on the f i e l d , and c o n s i d e r these d i f f e r e n t " a r e a s " l e v e l 1
of the h i e r a r c h i a l a n a l y s i s of v a r i a n c e ;
b) d e t e r m i n e , by g r i d placement, s e c t i o n s w i t h i n each " a r e a " t o be

sampled, and c o n s i d e r t h e s e " s e c t i o n s " l e v e l 2 of the d e s i g n ; and
c) d e t e r m i n e , randomly, the number of samples per g r i d s e c t i o n to

be t a k e n , and c o n s i d e r t h i s l e v e l 3 of the d e s i g n .
S e v e r a l p r o c e d u r e s may be used as t o where t o take samples w i t h i n

a g r i d placement: a t i n t e r s e c t i o n p o i n t s o f the g r i d , i n t h e c e n t e r
of the g r i d s e c t i o n s , and a t o p p o s i t e c o r n e r s o f the g r i d s e c t i o n s .
The number o f samples t a k e n per g r i d s e c t i o n s h o u l d be a t l e a s t two
f o r t h e purposes o f sample comparison w i t h i n a g i v e n g r i d s e c t i o n .
L e v e l s 1, 2, and 3 a l l o w f o r comparison o f the v a r i a n c e i n t h e
parameter i n q u e s t i o n ( h e r e , p e s t i c i d e r e s i d u e c o n c e n t r a t i o n s i n
s o i l ) as a f f e c t e d by d i f f e r e n c e s between samples from " a r e a s " o f
d i f f e r e n t s o i l c h a r a c t e r i s t i c s , d i f f e r e n c e s between samples from
g r i d " s e c t i o n s " o f t h e same s o i l c h a r a c t e r i s t i c s , and d i f f e r e n c e s
between samples from the same g r i d " s e c t i o n " . The p e r c e n t a g e o f
v a r i a n c e c o n t r i b u t e d by each l e v e l o f the d e s i g n f o r the p e s t i c i d e
r e s i d u e i n v o l v e d o f i n t e r e s t c a n be d e t e r m i n e d (32) Krumbein and
S l a c k (33) i l l u s t r a t e d e t a i l s o f t h e c a l c u l a t i o n s i n v o l v e d i n
computing t h e v a r i a n c e components. The sample v a r i a n c e c o n t r i b u t e d
by a n a l y t i c a l t e c h n i q u e , l e v e l 4, c a n be e s t i m a t e d by d u p l i c a t e
a n a l y s e s of t h e samples.
T h e r e are then 4 l e v e l s o f v a r i a n c e which a r e a d d i t i v e and
t h e i r sum i s e q u a l t o t h e t o t a l v a r i a n c e o f t h e s o i l p l o t as a
whole, i f sampling and a n a l y s e s b i a s e s a r e absent t h r o u g h o u t t h e
experimental design procedure (32).
For a p l o t where a l l s o i l c h a r a c t e r i s t i c s a r e homogenous,
l e v e l 1, d e s c r i b e d above, would n o t be n e c e s s a r y , and t h e r e would
be 3 l e v e l s o f v a r i a n c e t o compare.
The use o f a g r i d t o s e l e c t s e c t i o n s t o be sampled has been
r e f e r r e d t o as " r e g u l a r l y spaced" s a m p l i n g , a s opposed t o random
s e l e c t i o n procedures, ( 3 2 ) . A systematic sampling procedure,
such as a g r i d i s recommended, (34, 3 5 ) .
The p r e c e d i n g d i s c u s s i o n i s i l l u s t r a t i v e and i s one s t r a t e g y
f o r s o i l c o r e s a m p l i n g . EPA c o n t i n u e s t o i n v e s t i g a t e t h i s i s s u e .
B a s i c a l l y , t h e g u i d a n c e which t h e a u t h o r s g i v e t o p e s t i c i d e
companies and o t h e r s i s 1) l o c a t e s o i l c o r i n g s i t e s i n an X p a t t e r n
or o t h e r r e g u l a r l y spaced p a t t e r n as d e s c r i b e d above, and 2) choose
a t l e a s t 5 s i t e s p e r 1 t o 3-acre p l o t .
G e n e r a l l y , s o i l probes and hand augers a r e used t o c o l l e c t
s o i l c o r e s from depths near t h e s u r f a c e . Probes a r e s t a i n l e s s
s t e e l t u b e s , a p p r o x i m a t e l y 2.5 cm i n d i a m e t e r sharpened and
b e v e l l e d on one end, and f i t t e d w i t h a h a n d l e t h a t i s used t o
push the probe i n t o t h e s o i l . Augers a r e used where probes w i l l
not p e n e t r a t e t h e s o i l . Augers a r e t w i s t e d o r screwed i n t o t h e
ground. They a r e 3-20 cm i n d i a m e t e r . Augers c o l l e c t a d i s t u r b e d
sample by v i r t u e o f t h e t w i s t i n g motion used t o i n s e r t t h e tube
i n t o the s o i l . Probes and hand augers a r e d e s i g n e d t o sample t h e
upper 2 meters o f s o i l ( 3 6 ) .
S h e l b y tubes and s p l i t b a r r e l samplers a r e used f o r deeper
s o i l c o r e sampling as mentioned e a r l i e r under w e l l c o n s t r u c t i o n .
Cross contamination of s o i l l a y e r s during the coring process
s h o u l d be a v o i d e d . T h i s c a n be a c c o m p l i s h e d e i t h e r by i n s t a l l i n g
temporary c a s i n g as d r i l l i n g p r o c e e d s , o r by d r i l l i n g t o a p o i n t ,
r e v e r s i n g t h e s p i n o f t h e auger f l i g h t t o c a r r y l o o s e s o i l out o f
the h o l e , and e n s u r i n g t h a t t h e s o i l a t t h e s u r f a c e i s stamped
down.
S o i l samples s h o u l d be t a k e n t o the d e p t h o f p e s t i c i d e pene
t r a t i o n a t each sampling e v e n t , and then a l i t t l e f u r t h e r t o e n s u r e
t h a t a l l t h e p e s t i c i d e i s a c c o u n t e d f o r . T h i s d e p t h can be e s t i -
mated w i t h a computer s i m u l a t i o n model, by judgement and e x p e r i e n c e ,
o r t h e sampling can be t o a c e r t a i n d e p t h , t h r e e f e e t f o r example.
When t h e p e s t i c i d e n e a r s t h a t l e v e l , the sampling d e p t h can be
i n c r e a s e d by i n c r e m e n t s such as a f o o t a t a t i m e . The l o c a t i o n o f
the ground water s h o u l d be c o n s i d e r e d when d e t e r m i n i n g the t o t a l
d e p t h of s o i l s a m p l i n g , w i t h deeper sampling f o r a deeper g r o u n d -
water l e v e l . Sampling s h o u l 4 be done i n 6 - i n c h i n c r e m e n t s .
Each i n d i v i d u a l sample s h o u l d o r i g i n a t e from a c o n t i n u o u s core
w h i c h has been t a k e n t o t h e p r e d e t e r m i n e d t o t a l d e p t h o f s a m p l i n g .
R e s o u r c e s p e r m i t t i n g , t h e r e s h o u l d a l s o be a t l e a s t one s e t o f
deep c o r e s t o c h a r a c t e r i z e t h e p r o f i l e t o the ground water, i f
the s o i l p r o f i l e has n o t a l r e a d y been e s t a b l i s h e d from p a s t o r
current well d r i l l i n g procedures.
Small Scale P r o s p e c t i v e Studies

These s t u d i e s a r e done by p e s t i c i d e r e g i s t r a n t s and o t h e r s c i e n t i f i c

r e s e a r c h e r s , and a r e u s u a l l y a s s o c i a t e d w i t h t h e p e s t i c i d e - u s e
r e g i s t r a t i o n process. The p r i m a r y o b j e c t i v e o f t h i s study type i s
to c h a r a c t e r i z e the subsurface f a t e of a p a r t i c u l a r p e s t i c i d e ,
i . e . , e s t a b l i s h the l e a c h i n g p o t e n t i a l i n a c o n t r o l l e d study. A
p r o s p e c t i v e s t u d y d e s i g n attempts t o f o l l o w t h e p e s t i c i d e from t h e
time i t i s a p p l i e d t o t h e s u r f a c e and u n t i l i t has degraded, r e a c h e d
the s a t u r a t e d zone, o r r e a c h e d a d e p t h s i g n i f i c a n t l y g r e a t e r than
the r o o t zone. As such, p a r t i c u l a r emphasis i s p l a c e d on s o i l
coring.
S i n c e many o f the d e t a i l s of r e t r o s p e c t i v e and p r o s p e c t i v e
s t u d i e s a r e s i m i l a r , such as c o n s t r u c t i n g w e l l s and e x t r a c t i n g
samples, o n l y the d i f f e r e n c e s between t h e two w i l l be c o v e r e d i n
the f o l l o w i n g s e c t i o n s .
S i t e S e l e c t i o n and C h a r a c t e r i z a t i o n . The most i m p o r t a n t c r i t e r i a

f o r s i t e s e l e c t i o n i s t h a t t h e r e s h o u l d be no p r i o r use o f t h e
p e s t i c i d e i n q u e s t i o n on t h e f i e l d s i t e . T h i s demands a landowner/
f a r m e r who keeps c a r e f u l r e c o r d s o f h i s f i e l d and method o f a p p l i -
c a t i o n f o r the p e s t i c i d e of i n t e r e s t . A l l other c r i t e r i a , i n c l u d i n g
h y d r o g e o l o g i c c o n s i d e r a t i o n s , s o i l homogeneity, e x i s t i n g w e l l i n f o r -
m a t i o n , and new w e l l c o n s t r u c t i o n a r e s i m i l a r i n t h e p r o s p e c t i v e
and r e t r o s p e c t i v e s t u d y . C h a r a c t e r i z a t i o n of a p r o s p e c t i v e f i e l d
s i t e i s similar to retrospective f i e l d s i t e characterization.
C o l l e c t i o n o f S o i l and Water Samples. S o i l sampling p r o v i d e s i n f o r -

m a t i o n on u n s a t u r a t e d zone p e s t i c i d e m i g r a t i o n , and as such, i s
the most c r i t i c a l d a t a t h a t w i l l come out of a p r o s p e c t i v e f i e l d
s t u d y . F o r t h i s r e a s o n , s o i l sampling programs s h o u l d a d e q u a t e l y
d e s c r i b e p e s t i c i d e f a t e h o r i z o n t a l l y , v e r t i c a l l y , and t e m p o r a l l y
(over time).
One s e t of s o i l samples s h o u l d be t a k e n p r i o r t o p e s t i c i d e
a p p l i c a t i o n , t o ensure that the f i e l d i s f r e e of r e s i d u e s . Another
s e t of samples s h o u l d be t a k e n on t h e same day as p e s t i c i d e a p p l i -
c a t i o n o r on t h e day a f t e r a p p l i c a t i o n . Three t o f o u r more s e t s
of samples s h o u l d be taken o v e r the c o u r s e of the season, p a r t i c u -
l a r l y a f t e r r a i n f a l l e v e n t s t o demonstrate the e f f e c t s of water
i n f i l t r a t i o n on p e s t i c i d e l e a c h i n g . One s e t s h o u l d be t a k e n a f t e r
the w i n t e r f a l l o w p e r i o d a t s p r i n g t i m e d u r i n g snowmelt. S o i l c o r e s
w i l l need t o be timed w i t h i r r i g a t i o n e v e n t s i n f i e l d s u s i n g i r r i -
gation practices.
One s e t o f w e l l samples s h o u l d be t a k e n p r i o r t o p e s t i c i d e
a p p l i c a t i o n t o e n s u r e t h a t the w e l l water i s f r e e o f r e s i d u e .
Water sampling s h o u l d then o c c u r f o l l o w i n g major r e c h a r g e e v e n t s ,
i . e . , major storms p r o d u c i n g r e c h a r g e . Placement and number o f
well s i t e s i ss i m i l a r to retrospective f i e l d s i t e s .
One i m p o r t a n t d i f f e r e n c e between a p r o s p e c t i v e and r e t r o s p e c -
t i v e study i s the a p p l i c a t i o n and a n a l y s i s o f t r a c e r s . Davis
(1980) d i s c u s s e d t y p e s o f t r a c e r s t h a t a r e a v a i l a b l e ( 3 7 ) . The
a d d i t i o n o f t r a c e r s a l o n g w i t h the p e s t i c i d e i s v a l u a b l e f o r t h e
following reasons:
1) t r a c e r s allow the researcher t o track t h e "water f r o n t " a s i t

moves down the s o i l p r o f i l e .
2) t r a c e r s a l l o w f o r the d e t e r m i n a t i o n o f t h e " r e t a r d a t i o n f a c t o r " ,

R, o f the p e s t i c i d e as i t t r a v e r s e s down the u n s a t u r a t e d zone.
R i s d e f i n e d as a r a t i o o f the d i s t a n c e o f t r a v e l o f the water
front t o the distance of t r a v e l of the p e s t i c i d e f r o n t .
3) t r a c e r s a l l o w f o r the d e t e r m i n a t i o n o f a phenomena known as

"macropore f l o w " , which i s t h e r a p i d f l o w o f a s m a l l p o r t i o n o f
water through macropores, e.g. worm h o l e s , r a p i d l y through t h e
s o i l p r o f i l e a t t h e o n s e t o f a storm, d i r e c t l y t o t h e a q u i f e r .
T r a c e r s a p p e a r i n g a t the w e l l f o l l o w i n g a storm c a n a l l o w f o r
macropore f l o w a n a l y s i s .
4) t r a c e r s a l l o w f o r the d e t e r m i n a t i o n o f the hydraulic conductivity

(K) i n t h e s a t u r a t e d zone.
C h l o r i d e and bromide a r e t h e t r a c e r s o f c h o i c e . T r a c e r s must be

a p p l i e d a t t h e time o f p e s t i c i d e a p p l i c a t i o n , so t h a t the movement
of t h e t r a c e r can be d i r e c t l y c o r r e l a t e d t o the movement o f p e s t i -
cide. However, i n a more d e t a i l e d s t u d y , Tennyson and S e t t e r g r e n
(38) found t h a t bromide moved more r a p i d l y i n s o i l - w a t e r than
would be e x p e c t e d from the l a b o r a t o r y d e t e r m i n e d s o i l h y d r a u l i c
conductivity (K). R a d i o a c t i v e m a t e r i a l s , o r g a n i c dyes, g a s e s ,
and f l u o r o c a r b o n s are n o t recommended f o r use as t r a c e r s . The
f l u o r o c a r b o n s have been used s u c c e s s f u l l y , though they have n o t
been used e x t e n s i v e l y t o d a t e (39) A f t e r the a p p l i c a t i o n o f
p e s t i c i d e and t r a c e r , t h e p r o c e d u r e s p r e v i o u s l y o u t l i n e d s h o u l d be
f o l l o w e d f o r m o n i t o r i n g s o i l and ground w a t e r .
Occurrence of P e s t i c i d e s i n Ground Water
At l e a s t 17 p e s t i c i d e s have been found i n ground water i n a t o t a l

of 23 s t a t e s as a r e s u l t of a g r i c u l t u r a l p r a c t i c e . These d a t a are
summarized i n T a b l e I and F i g u r e 1 as w e l l as i n the d i s c u s s i o n
below. Two o f t h e s e p e s t i c i d e s , 1,2-D and 1,2,3-TCP, a r e n o t
u s u a l l y c o n s i d e r e d t o be p a r t o f t h e a c t i v e i n g r e d i e n t s but a r e
s y n t h e t i c by p r o d u c t s of the a c t i v e i n g r e d i e n t s . U n l i k e t h e 1984
summary (_1), the term " a t l e a s t " has t o be used. T h i s i s because

of the s i g n i f i c a n t i n c r e a s e i n the number of d a t a g e n e r a t o r s as
w e l l as i n the d a t a g e n e r a t e d . I t i s d i f f i c u l t t o keep t r a c k of
so much knowledge. The n e x t update of t h i s s t a t i s t i c w i l l r e q u i r e
e i t h e r a d d i t i o n a l c o a u t h o r s o r a q u a l i f i e r such as "...many more
than X p e s t i c i d e s . . . " . H o p e f u l l y , the next update w i l l be more
c o n c l u s i v e as a r e s u l t of more s y s t e m a t i c and r i g o r o u s l y d e s i g n e d
surveys.
At p r e s e n t , we cannot y e t determine the e x t e n t of the p r o b l e m .
The EPA i s d e s i g n i n g a n a t i o n a l s t a t i s t i c a l s u r v e y which w i l l
attempt t o answer t h i s q u e s t i o n ( d e s c r i b e d b e l o w ) . In a d d i t i o n ,
EPA's O f f i c e o f P e s t i c i d e Programs (OPP) c o n t i n u e s t o i n v o l v e
i t s e l f i n v a r i o u s f i e l d p r o j e c t s around the U.S. i n c o l l a b o r a t i o n
w i t h s t a t e , c o u n t y , and USGS s t a f f . These s t u d i e s and o t h e r s which
a r e b e i n g done o r have been done s i n c e 1984 a r e v e r y i n t e r e s t i n g
and a r e worth h i g h - l i g h t i n g below. The a u t h o r s r e g r e t i f key,
c u r r e n t s t u d i e s a r e not mentioned i n the s y n o p s i s below. The

i n t e n t was t o l i s t o n l y the most r e c e n t and e x c i t i n g s t u d i e s of
w h i c h the a u t h o r s have p e r s o n a l knowledge. They a r e l i s t e d i n no
p a r t i c u l a r o r d e r by c h e m i c a l , s t a t e and agency. F o l l o w i n g t h i s
summary o f r e c e n t p r o j e c t h i g h l i g h t s i s a more complete summary of
m o n i t o r i n g r e s u l t s o r g a n i z e d by c h e m i c a l .
Aldicarb. Union Carbide C o r p o r a t i o n continues to monitor f o r

a l d i c a r b around the U.S. w i t h the a s s i s t a n c e of l o c a l government
officials. As w e l l , more m e c h a n i s t i c s t u d i e s c o n t i n u e on i t s
s u b s u r f a c e p e r s i s t e n c e and m o b i l i t y i n Long I s l a n d and F l o r i d a
(40-43). OPP i s i n the m i d s t of a r e g u l a t o r y d e c i s i o n on t h i s
c h e m i c a l , a p u b l i c use-by-use r i s k - b e n e f i t a n a l y s i s .
R e g i o n a l A s s e s s m e n t s . OPP i s c o l l a b o r a t i n g w i t h the Water

R e s o u r c e s D i v i s i o n o f USGS and l o c a l u n i v e r s i t i e s on a m u l t i - y e a r
study of c e r t a i n a r e a s of the High P l a i n s o r O g a l a l l a A q u i f e r as
w e l l as c e r t a i n a r e a s i n the San J o a q u i n V a l l e y . The o b j e c t i v e i s
t o study the r e l a t i o n s h i p between a g r i c u l t u r a l l a n d use on ground-
water q u a l i t y i n t h e s e a r e a s .
1
N a t i o n a l Survey. E P A s O f f i c e of D r i n k i n g Water and OPP a r e
d e s i g n i n g a n a t i o n a l s t a t i s t i c a l s u r v e y of p e s t i c i d e s i n e x i s t i n g
d r i n k i n g w a t e r w e l l s . The g o a l s are t o make s t a t i s t i c a l e s t i m a t e s
about n a t i o n w i d e o c c u r r e n c e , t o r e l a t e the o c c u r r e n c e t o f i e l d
c o n d i t i o n s ( p e s t i c i d e usage and h y d r o g e o l o g y ) , and t o make broad
e s t i m a t e s of the p o p u l a t i o n exposed. T e c h n i c a l d e t a i l s were de-
s c r i b e d above under " L a r g e - S c a l e R e t r o s p e c t i v e S t u d i e s . " A f i n a l
r e p o r t i s e x p e c t e d i n 1989.
D i b r o m o c h l o r o p r o p a n e (DBCP) i n C a l i f o r n i a and H a w a i i . DBCP has now

been found i n 2500 p r i v a t e d o m e s t i c , p u b l i c , and i r r i g a t i o n w e l l s
i n C a l i f o r n i a , and was r e c e n t l y found t o have l e a c h e d 400 f e e t
downward through the u n s a t u r a t e d or vadose zone ( 4 4 ) . California
S t a t e Assembly B i l l 1803, passed i n 1984, r e q u i r e s the s t a t e
h e a l t h department t o m o n i t o r 40 p r i o r i t y p e s t i c i d e s and o t h e r
organics. The r e m a i n i n g use of DBCP on p i n e a p p l e s i n H a w a i i was
c a n c e l l e d ( 4 5 ) . In a c o l l a b o r a t i v e e f f o r t between EPA and USGS,
a f i e l d by f i e l d ground-water v u l n e r a b i l i t y r e c o n n a i s s a n c e analysis
was performed on Maui ( 4 6 ) .
Iowa. The S t a t e o f Iowa G e o l o g i c a l Survey and the Department o f

Water, A i r , and Waste Management c o n t i n u e t o a g g r e s s i v e l y m o n i t o r
f o r p e s t i c i d e s i n ground w a t e r i n many a r e a s o f t h e s t a t e (47-50)
EPA/OPP i s c o l l a b o r a t i n g w i t h the U n i v e r s i t y o f Iowa and t h e IGS
i n a two-year s t r a t i f i e d random s u r v e y o f w e l l s and farm f i e l d s i n
f o u r types o f h y d r o g e o l o g i c e n v i r o n m e n t s .
E t h y l e n e Dibromide (EDB). R e s u l t s o f a c o l l a b o r a t i v e study o f

EDB between USGS and EPA/OPP i n southwest G e o r g i a were r e c e n t l y
p u b l i s h e d ( 5 1 ) . A f o l l o w up p r o j e c t i s c o n t i n u i n g . The S t a t e o f
F l o r i d a has been s u c c e s s f u l l y s t r u g g l i n g w i t h d e t e c t i o n s o f EDB i n
a p p r o x i m a t e l y 1000 p r i v a t e and p u b l i c w e l l s (11% p o s i t i v e s ) , r e s u l t -
i n g i n exposure t o g r e a t e r than 50,000 p e o p l e ( 5 2 ) . L a b o r a t o r y
r e s e a r c h on the s u b s u r f a c e f a t e o f EDB c o n t i n u e s (53, 5 4 ) .
Cape Cod. EPA/OPP i s c o l l a b o r a t i n g w i t h the Cape Cod P l a n n i n g and

Economic Development Commission and the USGS t o d e s i g n and conduct
a s m a l l - s c a l e r e t r o s p e c t i v e s t u d y o f ground-water q u a l i t y under
g o l f courses t r e a t e d w i t h p e s t i c i d e s . The USGS d i s t r i c t o f f i c e i s
a l s o l e n d i n g some t e c h n i c a l s u p p o r t t o t h i s e f f o r t .
Two o t h e r r e c e n t C a l i f o r n i a r e p o r t s a r e worth h i g h l i g h t i n g .
The C a l i f o r n i a Department o f Food and A g r i c u l t u r e r e c e n t l y completed
and r e p o r t e d on a u s e f u l c o m p u t e r i z e d w e l l i n v e n t o r y d a t a base f o r
a g r i c u l t u r a l p e s t i c i d e s i n ground water from n o n p o i n t s o u r c e s (55)
A 1983 r e p o r t by R a m l i t A s s o c . showed t h a t the number o f p e s t i c i d e s
found i n ground water as a r e s u l t o f p o i n t s o u r c e p o l l u t i o n g r e a t l y
outnumbered t h o s e from n o n p o i n t s o u r c e s ( 5 6 ) * This l a t t e r report
u n d e r s c o r e s the need t o determine c o n t a m i n a t i o n s o u r c e s so t h a t
p r o p e r r e m e d i a l and r e g u l a t o r y a c t i o n s a r e t a k e n .
F o l l o w i n g i s a c h e m i c a l - s p e c i f i c summary o f ground-water
monitoring r e s u l t s . T h i s i s an update o f t h e 1984 t a b u l a t i o n ,
which a l s o c o n t a i n e d e n v i r o n m e n t a l c h e m i s t r y d a t a (I) In order
f o r a p e s t i c i d e t o be i n c l u d e d on t h i s l i s t , t h e r e must be a n a l y t i -
c a l c o n f i r m a t i o n , t h e r e must be l a b and/or c o n t r o l l e d f i e l d d a t a
w h i c h demonstrate some l e a c h i n g p o t e n t i a l i n c e r t a i n environments,
and t h e f i n d i n g s must be t i e d t o a g r i c u l t u r a l p r a c t i c e . The same
c r i t e r i a a p p l i e d t o t h e 1984 t a b u l a t i o n . The c h e m i c a l s a r e l i s t e d
i n a l p h a b e t i c a l o r d e r . The d a t a a r e summarized by c h e m i c a l and by
s t a t e i n T a b l e I and F i g u r e 1, r e s p e c t i v e l y . There a r e a d d i t i o n a l
r e p o r t s o f p e s t i c i d e s i n ground water, b u t t h e r e p o r t s o n l y s a t i s f y
two o f t h e t h r e e c r i t e r i a f o r i n c l u s i o n on t h e l i s t . The t h r e e
p e s t i c i d e s i n q u e s t i o n a r e a r s e n i c i n Texas and EDB and a t r a z i n e
i n Hawaii.
These r e p o r t s a l l f o c u s on n o n p o i n t s o u r c e s o f p e s t i c i d e s
l e a c h i n g t o ground w a t e r . However, t h e e x t e n t o f o c c u r r e n c e o f
p e s t i c i d e s i n ground water from a g r i c u l t u r a l and i n d u s t r i a l p o i n t
s o u r c e s i s a l s o n o t known. A s e p a r a t e i n v e s t i g a t i o n i n t o t h i s
t o p i c would be w a r r a n t e d .
Alachlor. A l a c h l o r has been found r e c e n t l y i n Iowa (47-50),

P e n n s y l v a n i a ( 5 7 ) , and Maryland ( 5 8 ) . The s t u d i e s would a l l be
c l a s s i f i e d as l a r g e - s c a l e r e t r o s p e c t i v e . A l l s t u d y d e s i g n s had
s t r o n g h y d r o g e o l o g i c a l components, but had l i t t l e , i f any,
p r o b a b i l i s t i c components. I n the more l o c a l i z e d a r e a s the l a t t e r
components would not be n e c e s s a r y . The Iowa f i n d i n g s have been i n
p r i v a t e w e l l s , p u b l i c w e l l s , and o b s e r v a t i o n w e l l s i n v a r i o u s a r e a s
around the s t a t e and h y d r o g e o l o g i c environments r a n g i n g from
a l l u v i a l to k a r s t l i m e s t o n e . I n P e n n s y l a v a n i a , the USGS r e p o r t e d
s i x p o s i t i v e s i n a network of a p p r o x i m a t e l y 82 o b s e r v a t i o n and
r e s i d e n t i a l w e l l s i n c e n t r a l P e n n s y l v a n i a sampled f o r p e s t i c i d e s .
L i k e w i s e , i t was found i n f o u r p u b l i c and p r i v a t e w e l l s out o f 30
w e l l s sampled i n v a r i o u s l o c a t i o n s on M a r y l a n d ' s E a s t e r n S h o r e .
Most p o s i t i v e s f a l l i n the 0.1-10 ppb range. A l a c h l o r has now
been found i n f o u r s t a t e s ' ground w a t e r .
Aldicarb. As n o t e d p r e v i o u s l y (JL), the a l d i c a r b s p e c i e s u s u a l l y

found a r e the b i o o x i d i z e d m e t a b o l i t e s , a l d i c a r b s u l f o x i d e and
a l d i c a r b s u l f o n e . The o n l y new s t a t e w i t h a r e p o r t o f a l d i c a r b i n
ground water i s Rhode I s l a n d . The f i n d i n g r e s u l t e d from a water
q u a l i t y i n v e s t i g a t i o n by the USGS i n the v i c i n i t y o f p o t a t o f i e l d s
(59). The w e l l s c r e e n s g e n e r a l l y ranged between 15 and 50 f e e t
(4.6 - 15.2 m) deep. As T a b l e I i n d i c a t e s , a l d i c a r b has now been
found i n the ground water o f 15 s t a t e s . The f i n d i n g s have been i n
o b s e r v a t i o n , i r r i g a t i o n , and p r i v a t e domestic w e l l s but a p p a r e n t l y
not i n p u b l i c w e l l s . Based on work c i t e d p r e v i o u s l y (1) and o t h e r
more r e c e n t work (42, 6 0 ) , r o u g h l y 2000 w e l l s n a t i o n w i d e have been
found t o c o n t a i n a l d i c a r b r e s i d u e s , a t l e v e l s t y p i c a l l y r a n g i n g
from 1 t o 50 ppb t o t a l a l d i c a r b r e s i d u e s . These s t u d y d e s i g n s
would be c l a s s i f i e d under a l l t h r e e s t u d y t y p e s . The s i t e s e l e c t i o n
p r o c e s s has been p u r p o s i v e i n n a t u r e w i t h a heavy emphasis on s o i l
t y p e , w e l l d e p t h , and p e s t i c i d e a p p l i c a t i o n t i m i n g w i t h r e s p e c t
to r e c h a r g e events and c r o p growth.
A t r a z i n e . A t r a z i n e was found i n the same P e n n s y l v a n i a s u r v e y

mentioned i n the a l a c h l o r d i s c u s s i o n above. A t r a z i n e was r e p o r t e d
i n 21 of t h o s e w e l l s . I t was a l s o r e p o r t e d i n t h r e e p u b l i c w e l l s
i n the M a r y l a n d s u r v e y mentioned i n the a l a c h l o r d i s c u s s i o n . I t
has now been r e p o r t e d i n f i v e s t a t e s ' ground water a t l e v e l s t y p i -
c a l l y r a n g i n g between 0.3 and 3.0 ppb.
B r o m a c i l . There a r e no new p o s i t i v e s o f b r o m a c i l t o r e p o r t ,
a l t h o u g h i t i s seldom a n a l y z e d f o r i n w e l l s u r v e y s .
Carbofuran. The o n l y new s t a t e w i t h a r e p o r t o f c a r b o f u r a n i n

ground water i s M a r y l a n d . The f i n d i n g was beneath t e s t p l o t s on
M a r y l a n d ' s E a s t e r n Shore i n a s m a l l - s c a l e p r o s p e c t i v e s t u d y , and
p o s i t i v e s t y p i c a l l y exceeded 5 ppb. A t r a c e r was a p p l i e d . More
d e t a i l s cannot be g i v e n due t o the f a c t t h a t the i n f o r m a t i o n i s
c o n s i d e r e d by the r e g i s t r a n t , FMC, to be c o n f i d e n t i a l b u s i n e s s i n -
f o r m a t i o n ( 6 0 ) . C a r b o f u r a n has now been r e p o r t e d i n t h r e e s t a t e s '
ground water, a t l e v e l s t y p i c a l l y r a n g i n g between 1 and 50 ppb.
I t s h o u l d be noted t h a t c a r b o f u r a n ground-water m o n i t o r i n g has
r a r e l y attempted t o d e t e c t the t o x i c m e t a b o l i t e s , 3-OH and 3-keto
carbofuran. T h i s i s a d e f i c i e n c y which s h o u l d be a d d r e s s e d i n
future monitoring.
C y a n a z i n e . T h i s c h e m i c a l had n o t been found i n ground water as o f

the time t h e 1984 l i s t (1_) was w r i t t e n . The new f i n d i n g s a r e i n
n o r t h e a s t e r n Iowa (47-49) and c e n t r a l P e n n s y l v a n i a ( 5 7 ) . In the
Iowa s t u d i e s , c y a n a z i n e was found a t low l e v e l s i n t h r e e w e l l s and
a s p r i n g i n i n c i p i e n t k a r s t and k a r s t a r e a s . Cyanazine was r e p o r t e d
at 1.1 ppb i n one o f t h e 82 w e l l s i n t h e c e n t r a l P e n n s y l v a n i a s t u d y
where t h e water l e v e l i n t h e w e l l was a p p r o x i m a t e l y 75 f e e t below
land surface.
DBCP. No a d d i t i o n a l s t a t e s have r e p o r t e d DBCP f i n d i n g s . I n 1984,

DBCP was r e p o r t e d i n w e l l s o f f i v e s t a t e s ( 1 ) .
DCPA (and a c i d p r o d u c t s ) . No a d d i t i o n a l s t a t e s have r e p o r t e d DCPA

findings. I t was r e p o r t e d i n New York ground water ( 1 ) . These

c h e m i c a l s a r e n o t u s u a l l y i n c l u d e d i n ground-water m o n i t o r i n g
programs.
1,2-Dichloropropane. 1,2-D was r e c e n t l y r e p o r t e d i n a t l e a s t seven

s h a l l o w w e l l s i n w e s t e r n Washington i n a s s o c i a t i o n w i t h s o i l
i n j e c t i o n i n strawberry f i e l d s (61). The p u r p o s i v e w e l l s e l e c t i o n s
i n t h i s r e t r o s p e c t i v e s t u d y were done w i t h s t r o n g bases i n h y d r o -
g e o l o g y and p e s t i c i d e usage i n f o r m a t i o n . 1,2-D has now been r e -
1
p o r t e d i n f o u r s t a t e s ground water a t l e v e l s g e n e r a l l y r a n g i n g
between 1 and 50 ppb.
D i n o s e b . No a d d i t i o n a l s t a t e s have r e p o r t e d d i n o s e b f i n d i n g s . I t
had been found i n New York ground water ( 1_). This chemical i s not
u s u a l l y i n c l u d e d i n ground-water m o n i t o r i n g programs.
D y f o n a t e . T h i s c h e m i c a l was n o t on t h e 1984 l i s t . I t was found a t

0.11 ppb i n a s p r i n g d r a i n i n g a s o l u t i o n l i m e s t o n e a q u i f e r i n
n o r t h e a s t Iowa ( 4 9 ) . I t i s a marginal leacher; i . e . , i t s p e r s i s t -
ence and m o b i l i t y a r e l e s s than most o f t h e o t h e r ground-water
contaminants (,2).
EDB. Four a d d i t i o n a l s t a t e s have r e p o r t e d EDB i n ground water.

EDB was found i n 14 p u b l i c , p r i v a t e , and o b s e r v a t i o n w e l l s , o u t
of 95 w e l l s sampled, t a p p i n g s h a l l o w u n c o n f i n e d and deeper c o n f i n e d
a q u i f e r s i n w e s t e r n Washington (6^2, 6 3 ) . EDB has been found i n
s e v e r a l w e l l s i n southwest A r i z o n a a t sub-ppb l e v e l s , i n c l u d i n g
community w e l l s i n Phoenix ( 6 4 ) . C o n t a m i n a t i o n o f over 220 p u b l i c
and p r i v a t e w e l l s was r e p o r t e d i n w e s t e r n M a s s a c h u s e t t s and w e s t e r n
C o n n e c t i c u t where i t had been used i n t h e C o n n e c t i c u t R i v e r V a l l e y
(65, 6 6 ) . I n many c a s e s t h e s e l a r g e - s c a l e r e t r o s p e c t i v e s t u d i e s
have i n v o l v e d s a t u r a t i o n s a m p l i n g . That i s , e v e r y p o s s i b l e
t h r e a t e n e d w e l l was sampled. I n such s i t u a t i o n s , a s t a t i s t i c a l /
p r o b a b i l i s t i c d e s i g n i s m e a n i n g l e s s and n o t r e q u i r e d . EDB has
been found i n t h e ground water o f e i g h t s t a t e s a t w i d e l y v a r y i n g
l e v e l s which u s u a l l y range between 0.05 and 20 ppb.
Metolachlor. Both s t a t e r e p o r t s of m e t o l a c h l o r a r e new. I t was

found i n 4 out o f 82 w e l l s sampled i n the USGS c e n t r a l P e n n s y l v a n i a
study ( 5 7 ) . M e t o l a c h l o r was a l s o found i n a w e l l i n an i n c i p i e n t
k a r s t a r e a and two s p r i n g s d r a i n i n g a s o l u t i o n l i m e s t o n e a q u i f e r
i n n o r t h e r n Iowa (^8, 4 9 ) . C o n c e n t r a t i o n s t y p i c a l l y range between
0.1 and 0.5 ppb.
Metribuzin. T h i s p e s t i c i d e i s a r e c e n t a d d i t i o n t o the l i s t . It
was found i n t h r e e o b s e r v a t i o n w e l l s i n n o r t h e r n Iowa a t l e v e l s
r a n g i n g from 0.09 to 4.35 ppb ( 4 8 ) .
Oxamyl. The o n l y new s t a t e r e p o r t i n g oxamyl i n ground water i s

Rhode I s l a n d ( 5 9 ) . I t was found i n a t l e a s t f o u r o b s e r v a t i o n
w e l l s out o f 11 sampled. T y p i c a l l e v e l s o f oxamyl i n ground water
range from 1 to 60 ppb, w i t h the Rhode I s l a n d r e s u l t s c l o s e r t o 1
ppb. Oxamyl has now been found i n the ground water of two s t a t e s .
Simazine. Simazine was r e c e n t l y found i n e i g h t out of 82 w e l l s

sampled i n c e n t r a l P e n n s y l v a n i a ( 5 7 ) . I t was a l s o found i n one
w e l l a t the d e t e c t i o n l i m i t i n the p r e v i o u s l y mentioned Maryland
study (58). Simazine has been found i n the ground water of t h r e e
s t a t e s a t l e v e l s t y p i c a l l y r a n g i n g between 0.2 and 3.0 ppb.
Trichloropropane. 1 , 2 , 3 - T r i c h l o r o p r o p a n e (TCP) had been a by-

p r o d u c t of the m a n u f a c t u r e of d i c h l o r o p r o p e n e / d i c h l o r o p r o p a n e
nematicides. I t i s u n c e r t a i n whether t h i s p e r s i s t e n t and m o b i l e
i m p u r i t y i s s t i l l p r e s e n t i n p e s t i c i d e f o r m u l a t i o n s . TCP has
been found i n s m a l l - s c a l e and l a r g e - s c a l e r e t r o s p e c t i v e s t u d i e s i n
C a l i f o r n i a and Hawaii s o i l and ground water (67, 68). I t was found
a t l e a s t 10 f e e t down i n the s o i l p r o f i l e s i n H a w a i i , and i n
w e l l s i n Oahu and the C e n t r a l V a l l e y o f C a l i f o r n i a . Positives
t y p i c a l l y range between 0.2 and 2 ppb i n the s o i l and i n ground
water.
Concluding Remarks
The e x t e n t of the problem o f p e s t i c i d e s i n ground water i s not

known. What we have i s a c o l l e c t i o n of m o n i t o r i n g s t u d i e s , con-
c e i v e d w i t h d i f f e r e n t o b j e c t i v e s and u s i n g d i f f e r e n t d e s i g n s t r a t e -
g i e s , a l t h o u g h most a r e v a r i o u s s c a l e s o f r e t r o s p e c t i v e s t u d i e s .
(Most of these have e i t h e r been c i t e d i n the p r e s e n t work o r p r e -
v i o u s l y (1)) T h e r e f o r e the r e a d e r i s c a u t i o n e d about making
g e n e r a l i z a t i o n s about the r e s u l t s so f a r . F o r example, i t would
be easy to l o o k a t F i g u r e 1 and c o n c l u d e t h a t Iowa has a worse
ground-water p r o b l e m t h a n , s a y , M i s s o u r i . However, F i g u r e 1 may
o n l y r e f l e c t the f a c t t h a t the Iowa S t a t e government has a v e r y
a c t i v e m o n i t o r i n g program, e s p e c i a l l y when one c o n s i d e r s t h a t
M i s s o u r i has a p o t e n t i a l h i g h use of n e m a t i c i d e s i n permeable
s o i l s over s o l u t i o n limestone a q u i f e r s . Perhaps the next update
of t h i s g e n e r a l assessment w i l l be more c o n c l u s i v e and w i l l c i t e
a d d i t i o n a l good m o n i t o r i n g s t u d i e s which c o n t a i n s e v e r a l of the
key elements d e s c r i b e d e a r l i e r i n t h i s paper. L i k e w i s e , improve-
ments i n our p r e d i c t i v e c a p a b i l i t i e s s h o u l d enable us to be more
c o n c l u s i v e i n our assessments.
Acknowledgment s
The a u t h o r s g r a t e f u l l y acknowledge t h e a s s i s t a n c e o f t h e
S t a t i s t i c s Team o f OPP's T o x i c o l o g y Branch f o r s e v e r a l h e l p f u l
suggestions. L i k e w i s e , George DeBuchananne o f DeBuchananne &
A s s o c i a t e s and L e s M c M i l l i o n o f EPA-Las Vegas were i n v a l u a b l e
s o u r c e s o f i n f o r m a t i o n on w e l l c o n s t r u c t i o n and h y d r o g e o l o g y .
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50. Kelly, R., Iowa Department of Water and Waste Management, Des
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Jovanovich, A.P. "Investigation of Ethylene Dibromide (EDB)
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personal communication, 1985.
11
Field, Laboratory, and Modeling Studies
on the Degradation and Transport of Aldicarb Residues
in Soil and Ground Water
Russell L. Jones
Union Carbide Agricultural Products Company, Inc., Research Triangle Park, NC 27709
Research conducted on the movement and degradation of

aldicarb residues in the unsaturated and saturated zones

has shown that it is a complex process affected by soil and
hydrogeological properties, climatic conditions, and
agricultural practices. This paper presents the results of
unsaturated and saturated zone field studies conducted in
16 states over a period of six years in which approximately
20,000 soil and water samples have been collected. Results
from laboratory degradation studies are also included.
Computer modeling has been used to illustrate the effects
of variables such as soil field capacity, soil organic
matter, pesticide application timing, and climatic
conditions on the potential for aldicarb residues to reach
groundwater. These experimental and modeling studies show
that in most areas aldicarb residues degrade in the upper
portion of the unsaturated zone. In the relatively few
areas where aldicarb residues reach groundwater, the
primarily lateral movement of groundwater and the
continuing degradation usually limit the presence of
aldicarb residues to shallow groundwater near treated
fields.
The development o f modem a n a l y t i c a l methodology h a s made
p o s s i b l e t h e d e t e c t i o n and q u a n t i f i c a t i o n o f e x t r e m e l y low
concentrations o f chemicals. The a p p l i c a t i o n o f t h i s t e c h n o l o g y t o
groundwater a n a l y s e s made p o s s i b l e t h e d e t e c t i o n o f t r a c e l e v e l s o f
a l d i c a r b r e s i d u e s i n Long I s l a n d groundwater i n 1979 ( 1 ) . This
f i n d i n g prompted r e s e a r c h on t h e e n v i r o n m e n t a l f a t e o f w a t e r - s o l u b l e
p e s t i c i d e s b y s c i e n t i s t s i n u n i v e r s i t i e s , r e g u l a t o r y a g e n c i e s , and
a g r i c u l t u r a l c h e m i c a l m a n u f a c t u r e r s . Much o f t h i s r e s e a r c h f o c u s e d
on a l d i c a r b and two o f i t s m e t a b o l i t i e s ( a l d i c a r b s u l f o x i d e and
a l d i c a r b s u l f o n e ) . A l t h o u g h much i n d e p e n d e n t r e s e a r c h , e s p e c i a l l y
l a b o r a t o r y s t u d i e s , h a s been p e r f o r m e d (samples o f s u c h work a r e
i n c l u d e d i n r e f e r e n c e s 2-7), t h i s p a p e r w i l l f o c u s on l a b o r a t o r y and
f i e l d r e s e a r c h work i n w h i c h U n i o n C a r b i d e s c i e n t i s t s h a v e
p a r t i c i p a t e d o f t e n i n c o o p e r a t i o n w i t h s c i e n t i s t s from u n i v e r s i t i e s
or regulatory agencies.
0097-6156/86/0315-0197$06.50/0
Summary o f E x p e r i m e n t a l Methodology
U n s a t u r a t e d Zone S t u d i e s . These e x p e r i m e n t s began i n 1980 a t

s p e c i a l i n t e r e s t a r e a s i n t h e U n i t e d S t a t e s . I n e a c h a r e a , two t o
f i v e l o c a t i o n s , w h i c h were g r o w e r - t r e a t e d f i e l d s , were sampled once
or twice a f t e r a p p l i c a t i o n . S o i l c o r e s were t a k e n by hand auger a t
t h r e e s i t e s p e r l o c a t i o n w i t h s a m p l i n g o f s t r a t a from 0-0.3,
0.3-0.6, 0.6-1.2, 1.2-1.8, and 1.8-2.4 m. I n 1981, t h e number o f
s a m p l i n g i n t e r v a l s a t e a c h l o c a t i o n was i n c r e a s e d t o p r o v i d e a
b e t t e r e s t i m a t e o f d e g r a d a t i o n and movement. To r e d u c e t h e e f f e c t s
of the i n h e r e n t v a r i a b i l i t y a s s o c i a t e d w i t h f i e l d s t u d i e s , s e v e r a l
s a m p l i n g changes were made b e g i n n i n g i n 1982. T e s t f i e l d s were
c a r e f u l l y s e l e c t e d i n h i g h use o r p o t e n t i a l use a r e a s . Application
was s u p e r v i s e d by u n i v e r s i t y o r company p e r s o n n e l . E a c h t r e a t m e n t
was r e p l i c a t e d i n f o u r s u b p l o t s and f o u r c o r e s were t a k e n i n each
s u b p l o t by a s p e c i a l b u c k e t auger t e c h n i q u e d e s i g n e d t o r e d u c e
c o n t a m i n a t i o n between s o i l s t r a t a . I n a t y p i c a l s t u d y , about 100

s o i l samples would be t a k e n a t a g i v e n s a m p l i n g i n t e r v a l i n each
p l o t r e p r e s e n t i n g a s i n g l e treatment. F i e l d s t u d i e s i n c l u d e d from
t h r e e t o seven s a m p l i n g i n t e r v a l s a f t e r a p p l i c a t i o n . On t h e
a v e r a g e , one a r e a would i n c l u d e two t r e a t m e n t s and y i e l d 800 s o i l
samples p e r y e a r t o p r o v i d e s u f f i c i e n t i n f o r m a t i o n f o r e s t i m a t i o n o f
d e g r a d a t i o n and movement p a r a m e t e r s . However, i n 1984 a s t u d y was
conducted t o a s s e s s t h e e f f e c t o f s p a t i a l v a r i a b i l i t y on measurement
of d e g r a d a t i o n and movement. T h i s s t u d y i n v o l v e d 64 c o r e s p e r
i n t e r v a l and t h e c o l l e c t i o n and a n a l y s i s o f o v e r 3,100 s o i l samples.
S a t u r a t e d Zone S t u d i e s . B e g i n n i n g i n 1983, s a t u r a t e d zone s t u d i e s

were c o n d u c t e d u s i n g s e v e r a l c l u s t e r s o f t e s t w e l l s s c r e e n e d a t
v a r i o u s depths and l o c a t e d u p g r a d i e n t , w i t h i n , and downgradient o f
t h e t r e a t e d a r e a . A minimum o f f i v e c l u s t e r s o f t h r e e w e l l s e a c h i s
needed a t any one s t u d y a r e a t o e f f e c t i v e l y a s s e s s movement and
d e g r a d a t i o n o f r e s i d u e s i n t h e groundwater. A t one t e s t s i t e i n
F l o r i d a , a p p r o x i m a t e l y 160 t e s t w e l l s were i n s t a l l e d and have been
sampled on a m o n t h l y b a s i s . Two l i m i t e d s a t u r a t e d zone s t u d i e s have
a l s o been p e r f o r m e d by a n a l y z i n g water t a k e n from t h e o u t l e t o f
t i l e s draining treated f i e l d s .
I n a d d i t i o n t o s a t u r a t e d zone r e s e a r c h s t u d i e s , about 30,000
p o t a b l e w e l l w a t e r samples f r o m 32 s t a t e s have been c o l l e c t e d .
A l t h o u g h n o t s p e c i f i c a l l y c o v e r e d by t h i s p a p e r , i n s i g h t s g a i n e d
from these a n a l y s e s are i n c l u d e d i n the d i s c u s s i o n s e c t i o n s .
L a b o r a t o r y S t u d i e s . A v a r i e t y o f l a b o r a t o r y s t u d i e s have been
p e r f o r m e d i n c l u d i n g d e g r a d a t i o n r a t e s t u d i e s w i t h a c t u a l samples
f r o m t h e s a t u r a t e d and u n s a t u r a t e d zones, o x i d a t i o n mechanism
s t u d i e s , s a t u r a t e d zone d e g r a d a t i o n mechanism s t u d i e s , p o t e n t i a l f o r
s u l f o x i d e o r s u l f o n e r e d u c t i o n s t u d i e s , and d i s t i l l e d water
hydrolysis studies. The e x p e r i m e n t a l methodology i n t h e s e
experiments v a r i e d a c c o r d i n g t o the study o b j e c t i v e s .
Degradation
D e g r a d a t i o n Pathway. The d e g r a d a t i o n pathway o f a l d i c a r b ( F i g u r e 1)

i s t h e same i n p l a n t s , a n i m a l s , and s o i l . First, aldicarb i s
oxidized to a l d i c a r b sulfoxide. A p o r t i o n of the a l d i c a r b s u l f o x i d e
11. JONES Degradation and Transport of Aldicarb Residues 199
CH 3
0 CH3 CH 3
1 II 1
il 1 I
CH - S - C - CH - 0 NH - C H
3
-c- 3
CH 3 - S - C - CH NOH CH 3 - S- C- C=N
1 J I
CH 3 (=> CH 3 CH 3
Aldicarb Aldicarb oxime Aldicarb nitrile

[0.9 mg/kg] [2380 mg/kg] [570 mg/kg]
0 CH 3 0 0 CH 3 0 CH 3
II 1 H Il 1 Il I
II I II Il 1 Il I
C H - S - C - C H = - -
3 C - NH - C H 3 CH 3 - S - C - CH NOH CH 3 - S- C-
J
J I
CH 3
|=j> CH 3
CH
3
Aldicarb sulfoxide Aldicarb sulfoxide oxime Aldicarb sulfoxide nitrile

[0.9 mg/kg] [8060 mg/kg] [4000 mg/kg]
0 CH 3 0 0 CH 3 CH 3
II 1 II Il 1 Il I
II 1 II II 1 Il I
CH 3 - S - C - CH = - 0 - C - NH - C H 3 CZ> C H - S - C - CH = N - OH
3
CH 3 - S- C- C=N
II 1 Il I
II 1 Il 1 Il I
0 CH 3 0 CH 3 O CH 3
Aldicarb sulfone Aldicarb sulfone oxime Aldicarb sulfone nitrile

[24 mg/kg] [1590 mg/kg] [350 mg/kg]
Figure 1. D e g r a d a t i o n pathway for aldicarb (values i n parentheses

T
are acute oral LD,- s n for rats).
i s f u r t h e r o x i d i z e d t o a l d i c a r b s u l f o n e . Both a l d i c a r b s u l f o x i d e
and a l d i c a r b s u l f o n e , b i o l o g i c a l l y a c t i v e carbamates, a r e
c o n c u r r e n t l y degraded t o low t o x i c i t y (non-carbamate) compounds.
A l t h o u g h r e d u c t i o n o f a l d i c a r b s u l f o x i d e h a s been d e m o n s t r a t e d u n d e r
l a b o r a t o r y c o n d i t i o n s ( 8 ) , f i e l d data demonstrate t h a t n e i t h e r t h e
s u l f o x i d e n o r t h e s u l f o n e a r e reduced back t o parent a l d i c a r b o r t o
s u l f o x i d e i n t h e s a t u r a t e d o r u n s a t u r a t e d zones. I n t h i s paper, t h e
term a l d i c a r b r e s i d u e s r e f e r s t o t h e sum o f a l d i c a r b , a l d i c a r b
s u l f o x i d e , and a l d i c a r b s u l f o n e .
Many f a c t o r s i n f l u e n c e t h e d e g r a d a t i o n o f a l d i c a r b r e s i d u e s t o
b i o l o g i c a l l y i n a c t i v e compounds. Some o f t h e more i m p o r t a n t i n c l u d e
t e m p e r a t u r e and pH, and t h e p r e s e n c e o f m o i s t u r e and m i c r o b i a l
populations. The f o l l o w i n g p a r a g r a p h s d i s c u s s t h e s e i n more d e t a i l
f o r d e g r a d a t i o n o c c u r r i n g i n b o t h t h e u n s a t u r a t e d and s a t u r a t e d
zones.
u n s a t u r a t e d Zone Dgradation. A f t e r a p p l i c a t i o n , s o i l m o i s t u r e
r a p i d l y dissolves aldicarb i n the granule. Once i n s o l u t i o n , t h e
d e g r a d a t i o n processes b e g i n immediately. The o x i d a t i o n p r o c e s s i s
r e l a t i v e l y r a p i d and l i t t l e o r no p a r e n t a l d i c a r b e x i s t s a month
after application. The d e g r a d a t i o n o f a l d i c a r b s u l f o x i d e and
a l d i c a r b s u l f o n e i s t h e r e s u l t o f b o t h m i c r o b i a l and c h e m i c a l
action. E s p e c i a l l y i n a c i d i c s o i l s , m i c r o b i a l degradation i s
b e l i e v e d t o be t h e most i m p o r t a n t mechanism i n t h e r o o t zone, o r t h e
u p p e r s t r a t a o f t h e u n s a t u r a t e d zone. F a c t o r s w h i c h t e n d t o
increase the degradation rate of a l d i c a r b residues include m i c r o b i a l
p o p u l a t i o n s , h i g h t e m p e r a t u r e s , h i g h s o i l pH and h i g h s o i l m o i s t u r e
content.
The d e g r a d a t i o n r a t e o f a l d i c a r b r e s i d u e s i n t h e u n s a t u r a t e d
zone h a s been d e t e r m i n e d from f i e l d s t u d i e s conducted s i n c e 1982 i n
t e n d i f f e r e n t s t a t e s (9-15) ( T a b l e I ) where h a l f - l i f e ranged between
two weeks and t h r e e months. D a t a from t h e s e s i t e s i n d i c a t e t h a t
s o i l t e m p e r a t u r e appears t o b e t h e most dominant v a r i a b l e a f f e c t i n g
h a l f - l i f e o f a l d i c a r b r e s i d u e s under normal a g r i c u l t u r a l c o n d i t i o n s
i n t h e u n s a t u r a t e d zone, w i t h i n c r e a s i n g temperatures r e s u l t i n g i n
f a s t e r degradation. Once below t h e r o o t zone, no d e c r e a s e i n t h e
d e g r a d a t i o n r a t e w i t h d e p t h was o b s e r v e d e x c e p t i n a c i d i c , sand
subsoils. Because o f t h e d e c r e a s e i n m i c r o b i a l p o p u l a t i o n w i t h
d e p t h , t h i s r e l a t i v e l y c o n s t a n t d e g r a d a t i o n r a t e as a f u n c t i o n o f
d e p t h i n d i c a t e s t h a t s o i l c a t a l y z e d c h e m i c a l h y d r o l y s i s may b e an
i m p o r t a n t d e g r a d a t i o n mechanism even i n t h e r o o t zone o f many s o i l s .
S a t u r a t e d Zone Dgradtion. Because o f t h e r a p i d o x i d a t i o n p r o c e s s

i n t h e r o o t zone, p a r e n t a l d i c a r b i s r a r e l y d e t e c t e d i n t h e
s a t u r a t e d zone. I n r a r e i n s t a n c e s where t r a n s p o r t from t h e s o i l
s u r f a c e i s r a p i d , a l d i c a r b may be p r e s e n t a t l e s s t h a n f i v e p e r c e n t
o f t h e t o t a l r e s i d u e s found. I n t h e s a t u r a t e d zone, r e s i d u e s a r e
u s u a l l y a m i x t u r e o f a l d i c a r b s u l f o x i d e and a l d i c a r b s u l f o n e i n an
average r a t i o o f 3:2.
I f a l d i c a r b r e s i d u e s l e a c h i n t o t h e s a t u r a t e d zone, o r
groundwater, d e g r a d a t i o n o f t h e r e s i d u e s c o n t i n u e s , m a i n l y b y
c h e m i c a l h y d r o l y s i s i n c o l d a r e a s and b y b o t h c h e m i c a l h y d r o l y s i s
and m i c r o b i a l d e g r a d a t i o n i n warm a r e a s . F a c t o r s which tend t o
i n c r e a s e t h e d e g r a d a t i o n r a t e a r e h i g h temperature and h i g h pH.
M i c r o b i a l p o p u l a t i o n s may p r o v i d e a s i g n i f i c a n t c o n t r i b u t i o n t o
s a t u r a t e d zone d e g r a d a t i o n , e s p e c i a l l y i n s h a l l o w groundwater i n
warm a r e a s . H a l f - l i f e d e g r a d a t i o n r a t e s i n t h e s a t u r a t e d zone, as
measured i n t h e l a b o r a t o r y ( T a b l e I I ) , r a n g e f r o m about t h r e e days
f o r e a s t c o a s t a l F l o r i d a t o s e v e r a l y e a r s f o r e a s t e r n Long I s l a n d ,
New Y o r k . I n t h e s e e x p e r i m e n t s , t h e measured d e g r a d a t i o n r a t e s a r e
3 t o 40 t i m e s f a s t e r t h a n would b e p r e d i c t e d on t h e b a s i s o f
d i s t i l l e d water h y d r o l y s i s . ( 1 6 ) T h i s i n d i c a t e s t h a t even i n d e e p e r
groundwater some c a t a l y t i c f a c t o r s ( m i c r o b e s , m e t a l s , s u r f a c e
sorption e f f e c t s ) are present. P r e l i m i n a r y d a t a f r o m an o n g o i n g
mechanism s t u d y i n d i c a t e t h a t t h e r a t e i n c r e a s e i s m o s t l y due t o t h e
p r e s e n c e o f s o i l r a t h e r t h a n m i c r o b e s . Work b y t h e U n i v e r s i t y o f
W i s c o n s i n h a s i n d i c a t e d a h a l f - l i f e o f s i x months t o one y e a r i n
W i s c o n s i n groundwater (5-10C) w h i c h a g r e e s w i t h t e m p e r a t u r e -
e x t r a p o l a t e d l a b o r a t o r y d a t a u s i n g a c t u a l f i e l d samples.
Movement
The d r i v i n g f o r c e f o r movement o f a l d i c a r b r e s i d u e s i s t h e movement

of water. T h e r e f o r e , t h e movement o f w a t e r must be d e f i n e d b e f o r e
t h e movement o f a l d i c a r b r e s i d u e s c a n b e q u a n t i f i e d . F a c t o r s
i n f l u e n c i n g t h e movement o f w a t e r i n c l u d e r a i n f a l l , i r r i g a t i o n ,
vapotranspiration and s o i l f i e l d c a p a c i t y i n t h e u n s a t u r a t e d zone.
The amount o f o r g a n i c m a t t e r d e t e r m i n e s t h e r a t e o f a l d i c a r b
movement r e l a t i v e t o water movement i n b o t h t h e u n s a t u r a t e d and
s a t u r a t e d zones.
Movement o f A l d i c a r b f r o m t h e G r a n u l e . A l d i c a r b i s r e l e a s e d from
t h e a p p l i e d g r a n u l e s upon c o n t a c t w i t h s o i l m o i s t u r e . I f t h e ground
i s e x t r e m e l y d r y , no a l d i c a r b w i l l be r e l e a s e d u n t i l t h e ground i s
moistened by r a i n f a l l o r i r r i g a t i o n . In arid climates, i r r i g a t i o n
a f t e r a l d i c a r b a p p l i c a t i o n i s recommended. Under most a g r i c u l t u r a l
c o n d i t i o n s , a l d i c a r b i s r e l e a s e d from t h e granule w i t h i n hours by
normal s o i l moisture.
U n s a t u r a t e d Zone Movement. Because a l d i c a r b , a l d i c a r b s u l f o x i d e ,

and a l d i c a r b s u l f o n e do n o t s i g n i f i c a n t l y b i n d t o i n o r g a n i c s o i l
(10,17,18) and a r e s o l u b l e i n w a t e r , a l d i c a r b r e s i d u e s move w i t h
s o i l w a t e r i n b o t h t h e u n s a t u r a t e d and s a t u r a t e d z o n e s . Surface
s o i l , t h e u p p e r l a y e r o f t h e u n s a t u r a t e d zone, 0.3 t o 1.5 m deep
d e p e n d i n g on t h e c r o p , i s o f t e n termed t h e r o o t zone. In the root
zone, a l d i c a r b r e s i d u e s move downward w i t h w a t e r f r o m r a i n o r
irrigation. Conversely, p l a n t t r a n s p i r a t i o n o f water w i l l tend t o
r e t a i n r e s i d u e s i n t h e r o o t zone. E v a p o r a t i o n o f s o i l m o i s t u r e from
t h e l a n d s u r f a c e w i l l draw s o i l m o i s t u r e and a l d i c a r b r e s i d u e s f r o m
t h e r o o t zone toward t h e s u r f a c e . Movement o f a l d i c a r b r e s i d u e s i n
t h e l o w e r s t r a t a o f t h e u n s a t u r a t e d zone i s g e n e r a l l y i n a v e r t i c a l
direction. However, s o i l s t r u c t u r e s s u c h as c l a y l e n s e s o r hardpans
may r e s u l t i n some h o r i z o n t a l movement. A l d i c a r b r e s i d u e s do s o r b
t o o r g a n i c m a t t e r and i n some h i g h o r g a n i c m a t t e r s o i l s t h e r a t e o f
r e s i d u e movement may be up t o a f a c t o r o f t e n s l o w e r t h a n t h e r a t e
o f w a t e r movement. F a c t o r s w h i c h i n c r e a s e downward movement a r e a
h i g h r e c h a r g e r a t e ( r a i n f a l l p l u s i r r i g a t i o n minus
v a p o t r a n s p i r a t i o n ) , low s o i l f i e l d c a p a c i t y , and low s o i l o r g a n i c
matter. I n many c a s e s , movement i n t h e u n s a t u r a t e d zone i s t h e
r e s u l t o f a few r e l a t i v e l y heavy r a i n s .
Table I . A l d i c a r b and A l d i c a r b S u l f o n e
Crop
Arizona
1982 M a r i c o p a Cotton
Aldicarb a t Emergence
Aldicarb a t P l a n t i n g and Emergence
Aldicarb Sulfone at Planting
Aldicarb S u l f o n e a t Emergence
California
1980 E x p l o r a t o r y S t u d i e s a t Two S i t e s ( A l d i c a r b ) Cotton

1984 Manteca ( A l d i c a r b ) Tomatoes
Livingston (Aldicarb) Grapes
Fresno ( A l d i c a r b ) Grapes
Colorado
1984 E x p l o r a t o r y S t u d i e s a t Three S i t e s ( A l d i c a r b ) Potatoes
Florida
1980Exploratory Studies at Five S i t e s (Aldicarb) Citrus

1981Exploratory Studies at Five S i t e s (Aldicarb)
1982Indlantown ( A l d i c a r b )
1983Lake H a m i l t o n ( A l d i c a r b )
Ovledo ( A l d i c a r b )
Alcoma ( A l d i c a r b )
Indlantown ( A l d i c a r b )
Lutz ( A l d i c a r b )
Lake Buena V i s t a ( A l d i c a r b )
DeLeon S p r i n g s ( A l d i c a r b )
Fort Pierce (Aldicarb) Tomatoes
1984 Oavenport ( A l d i c a r b ) Citrus
Lake Hamilton ( A l d i c a r b
Alcoma ( A l d i c a r b )
Monitoring Wells ( A l d i c a r b )
1985 Lake H a m i l t o n ( A l d i c a r b )
Monitoring Wells ( A l d i c a r b )
Average c o n c e n t r a t i o n 1n s o i l c o r e s o r water samples

11. JONES Degradation and Transport of Aldicarb Residues
F i e l d Research Programs - 1 9 8 0 - J u l y , 1985.
Unsaturated Zone
No. of Samples A p p l i c a t i o n Rate Half-Life Maximum Leaching
Soi 1 Water kg/ha (months) Depth (m)*
1176
2.24 0.5 1.8
1.12,2.24 0.3, 0.8 1.8
3.36 0.5 1.8
2.24 0.3 1.8
28 4 0.61-2.5 1.2
584 3.36 1.5 1.8
351 247 4.48 1.5 1.2
759 4.48 1.5 3.0
40 3 3.36 1.2
141 23 5.6-11.2 2.4

445 88 5.6-11.2 2.4
31 7.56
575 298 11.2 0.6 3.0
354 171 11.2 0.6 1.2
146
91 7.56
55
18
50 --
224 20 3.36 0.6
3127 5.6 6.0
1187
212
49
29
44 5.6
820
12
13 __
73 5.6
1s l e s s than 5 ppb below t h i s d e p t h .

Table I . A l d i c a r b and A l d i c a r b S u l f o n e
Crop
Indiana
1983 B l u e c a s t ( A l d i c a r b ) Corn
Maine
1983 Presque I s l e ( A l d i c a r b ) Potatoes

Planting Application
Emergence A p p l i c a t i o n
Michigan
1983 B l 1 s s f 1 e l d (Aldicarb) Corn
Nebraska
1985 B a r t l e t t (Aldicarb) Corn
New York
1983 Phelps ( A l d i c a r b ) Potatoes

North C a r o l i n a
1983 H a r r e l l s v l l l e Tobacco
Aldicarb at Transplanting
A l d i c a r b Sulfone at Transplanting
Oregon
1980 E x p l o r a t o r y S t u d i e s a t One S i t e (Aldicarb) Potatoes
South C a r o l i n a
1985 E d l s t o (Aldicarb) Soybeans

Bare P l o t
Texas
1980 E x p l o r a t o r y S t u d i e s a t Three S i t e s (Aldicarb) Citrus
Average c o n c e n t r a t i o n 1n s o i l c o r e s or water
F i e l d Research Programs - 1 9 8 0 - J u l y , 1985 (continued).
U n s a t u r a t e d Zone
No. of Samples A p p l i c a t i o n Rate Half-Life Maximum Leaching
Soil Water kg/ha (months) Depth ( m ) *
208 20 1.68 1.1 0.6
1440
3.36 3.3 1.5
2.24 2.8 1.2
192 16 1.68 0.7 0.6
111 51 1.7
456
3.36 1.0 0.3
2.24 0.9 0.3
656
3.36 1.3 0.6
3.36 0.9 0.6
15 1 3.36 1.2
135 3.4
136 143 3.4
41 7 5.6 - 1.8
samples 1s l e s s than 5 ppb below t h i s d e p t h .

Table ! A l d i c a r b and A l d i c a r b S u l f o n e Field
Crop
Virginia
1980 E x p l o r a t o r y S t u d i e s a t Two S i t e s ( A l d i c a r b ) Potatoes

1981 E x p l o r a t o r y S t u d i e s a t Three S i t e s ( A l d i c a r b ) Potatoes
1983 B l a c k s t o n e Tobacco
Aldicarb at Transplanting
A l d i c a r b Sulfone at Transplanting
Washington
1980 E x p l o r a t o r y S t u d i e s a t Two S i t e s ( A l d i c a r b ) Potatoes

1983 Pasco ( A l d i c a r b )
Wisconsin
1980 E x p l o r a t o r y S t u d i e s a t F i v e S i t e s ( A l d i c a r b ) Potatoes
1981 E x p l o r a t o r y S t u d i e s a t S i x S i t e s ( A l d i c a r b )
1982 Hancock ( A l d i c a r b )
Emergence A p p l i c a t i o n w i t h Moderate I r r i g a t i o n
P l a n t i n g A p p l i c a t i o n w i t h Moderate I r r i g a t i o n
Emergence A p p l i c a t i o n w i t h Heavy I r r i g a t i o n
P l a n t i n g A p p l i c a t i o n w i t h Heavy I r r i g a t i o n
Cameron ( A l d i c a r b )
1983 Hancock
A l d i c a r b a t Emergence
Aldicarb at Planting
A l d i c a r b Sulfone at Planting
Average c o n c e n t r a t i o n 1n s o i l c o r e s or water samples

Research Programs 1980 - J u l y , 1985
U n s a t u r a t e d Zone
No. of Samples A p p l i c a t i o n Rate Half-Life Maximum L e a c h i n g
Soi 1 Water kg/ha (months) Depth ( m ) *
39 3 3.36 1.2
118 27 3.36
664
3.36 1.1 0.6
3.36 1.3 0.6
24 5 3.36 0.6
448 6.72 1.7 1.8
127 31 3.36 2.4

505 65 3.36 2.4
1230 10
2.24 1.2 1.8
3.36 1.7 2.4
2.24 1.8
3.36 3.0
338
2.24 1.5 1.2
3.36 2.0 1.2
1094 21
2.24 1.3 1.8
3.36 0.9 0.6
3.36 1.1 2.4
1s l e s s than 5 ppb below t h i s d e p t h .

TABLE I I . R e s u l t s of Laboratory Studies Measuring Degradation
Rates of A l d i c a r b Residues i n S a t u r a t e d Zone Samples
Sample Compounds Approximate pH Study Calculated Half-

1
Location Studied o f Sample Temp.C L i f e i n Days
New Y o r k
2
Long I s l a n d Sulfoxide & 6 13 800
2
Sulfone 25 360(243-704)
Wisconsin Sulfoxide & 7 25 14 ( 12,16)

C e n t r a l Sands S u l f o n e
Sulfone only 7 25 13 ( 10,16)
2
North C a r o l i n a Sulfoxide & 5 25 137(117,165)
Coastal P l a i n Sulfone
2
Sulfone only 5 25 108(63,368)
Florida
Lutz Sulfoxide & 6 25 49 (41,61)
Sulfone
Lake H a m i l t o n S u l f o x i d e & 6 25 47 (40,55)
Sulfone
Alcoma Sulfoxide & 6 25 49 (38,63)
Sulfone
Oveido Sulfoxide & 7 25 3 (1,5)
Sulfone
Fort Pierce Sulfone only 7 25 52 (40,74)
California Sulfoxide & 7 25 8 (7-10)

Livingston Sulfone
Colorado Sulfoxide &

San L u i s V a l l e y S u l f o n e 8 25 23 (17,35)
(1) Numbers i n p a r e n t h e s i s are the 95% c o n f i d e n c e limits.
(2) V a r i a t i o n i n l a t e r sampling i n t e r v a l s makes e s t i m a t i o n o f t h e s e values

difficult.
The amount, i f any, o f a l d i c a r b r e s i d u e s l e a c h i n g t o a s p e c i f i e d

d e p t h depends b o t h on t h e r a t e o f d e g r a d a t i o n and movement. F o r
example, t h e same amount o f l e a c h i n g c o u l d o c c u r i n a s i t u a t i o n
where t h e d e g r a d a t i o n r a t e and t h e r a t e o f movement a r e r e l a t i v e l y
slow, as i n a s i t u a t i o n where b o t h r a t e s a r e r e l a t i v e l y r a p i d . As
discussed e a r l i e r , the rate of degradation of aldicarb residues i n
t h e u n s a t u r a t e d zone i s r e l a t i v e l y f a s t ( h a l f - l i f e o f 0.5 t o 3
months). T h e r e f o r e , l e a c h i n g o f r e s i d u e s t h r o u g h t h e u n s a t u r a t e d
zone t o groundwater o c c u r s o n l y o c c a s i o n a l l y and t h e n o n l y i n a r e a s
w i t h r e l a t i v e l y s h a l l o w w a t e r t a b l e s (where t r a n s p o r t t o t h e water
t a b l e may b e a c c o m p l i s h e d q u i c k l y ) o r i n a r e a s w i t h a c i d i c sand
s u b s o i l s where d e g r a d a t i o n r a t e s a r e s l o w e r ( s u c h as p o r t i o n s o f
Long I s l a n d o r c e n t r a l F l o r i d a w i t h r e l a t i v e l y deep w a t e r t a b l e s ) .
The d e p t h t o w h i c h d e t e c t a b l e l e a c h i n g o f a l d i c a r b r e s i d u e s
o c c u r r e d i n f i e l d s t u d i e s i s l i s t e d i n T a b l e I . L e a c h i n g beyond
t h r e e meters o c c u r r e d i n t h e r i d g e a r e a o f F l o r i d a ( s p e c i f i c a l l y
Lake H a m i l t o n , Alcoma, D a v e n p o r t ) and w i t h p l a n t i n g a p p l i c a t i o n s i n

t h e C e n t r a l Sands o f W i s c o n s i n (Hancock). O t h e r work h a s shown
l e a c h i n g below t h r e e meters on Long I s l a n d . (16.19) The d e p t h t o
w h i c h a l d i c a r b r e s i d u e s may l e a c h i n a g i v e n s i t e may v a r y from y e a r
t o y e a r depending on t h e amount and d i s t r i b u t i o n o f r a i n f a l l and
irrigation. The t i m i n g o f an a p p l i c a t i o n r e l a t i v e t o weather
( r a i n f a l l and s o i l t e m p e r a t u r e ) may a f f e c t b o t h t h e r a t e o f movement
and t h e d e g r a d a t i o n r a t e , as d e m o n s t r a t e d i n W i s c o n s i n ( 9 ) , F l o r i d a
( 2 0 ) , and t h e n o r t h e a s t e r n U n i t e d S t a t e s (11.12).
S a t u r a t e d Zone Movement. The movement o f a l d i c a r b r e s i d u e s i n t h e

s a t u r a t e d zone i s i n t h e same d i r e c t i o n as groundwater movement. I n
most a r e a s , t h i s means t h a t i f a l d i c a r b r e s i d u e s r e a c h t h e s a t u r a t e d
zone, t h e y w i l l move p r i m a r i l y i n a h o r i z o n t a l d i r e c t i o n . Since
t h e r e i s u s u a l l y l i t t l e o r g a n i c m a t t e r i n t h e s a t u r a t e d zone,
a l d i c a r b r e s i d u e s t r a v e l a t t h e same speed as t h e groundwater,
g e n e r a l l y 0.03 t o 0.5 m p e r day. The r e s i d u e s t e n d t o r e m a i n n e a r
t h e t o p o f t h e s a t u r a t e d zone and v e r t i c a l movement i s slow.
I n o n l y a few a r e a s where a l d i c a r b i s u s e d have r e s i d u e s
a c t u a l l y been found t o move t h r o u g h t h e u n s a t u r a t e d zone b e f o r e
b e i n g c o m p l e t e l y degraded. I n these areas, the p o t e n t i a l f o r
p r e s e n c e o f r e s i d u e s i n d r i n k i n g water w e l l s depends on t h e amount
o f r e s i d u e s e n t e r i n g groundwater, t h e d e g r a d a t i o n r a t e i n
groundwater, t h e r a t e o f groundwater movement and t h e l o c a t i o n ,
c a s i n g d e p t h and i n t e g r i t y o f d r i n k i n g w a t e r w e l l s n e a r t r e a t e d
fields. I n most a r e a s , c o n t i n u e d d e g r a d a t i o n i n t h e s a t u r a t e d zone
and t h e slow h o r i z o n t a l movement accompanied by d i s p e r s i o n t e n d t o
r e s u l t i n a l d i c a r b r e s i d u e s b e i n g c o n s t r a i n e d t o s h a l l o w groundwater
near t r e a t e d areas.
Model S i m u l a t i o n
U n s a t u r a t e d Zone M o d e l s . V a r i o u s models e x i s t f o r e s t i m a t i n g t h e
movement and d e g r a d a t i o n o f p e s t i c i d e r e s i d u e s i n t h e u n s a t u r a t e d
zone ( 2 0 ) . Perhaps t h e b e s t model a v a i l a b l e i s PRZM d e v e l o p e d b y
t h e U.S. EPA ( 2 1 ) . The a p p l i c a b i l i t y o f PRZM t o t h e m o d e l i n g o f
a l d i c a r b r e s i d u e s h a s been d e m o n s t r a t e d u s i n g d a t a from Long I s l a n d
( 2 2 ) , F l o r i d a ( 2 0 ) , W i s c o n s i n (23.23.24). and N o r t h C a r o l i n a (24)
One o f t h e most i m p o r t a n t u s e s o f an u n s a t u r a t e d zone model i s

to i l l u s t r a t e the e f f e c t s of v a r i a b l e s . I n F i g u r e 2, PRZM has been
used to i l l u s t r a t e the e f f e c t of o r g a n i c matter, s o i l h y d r a u l i c
p r o p e r t i e s , and d e g r a d a t i o n r a t e on t h e amount o f l e a c h i n g . The
i n p u t p a r a m e t e r s l i s t e d i n T a b l e I I I have been used as a b a s i s f o r
t h e s e s i m u l a t i o n s . The e n v i r o n m e n t a l c o n d i t i o n s o f t h i s example a r e
s i m i l a r t o t h o s e o f t h e r i d g e c i t r u s growing a r e a i n c e n t r a l
Florida. The b a s e c a s e i l l u s t r a t i o n chosen was one where p o t e n t i a l
f o r movement t o t h e water t a b l e i s h i g h . Downward movement i s r a p i d
due t o h i g h r a i n f a l l , e x t r e m e l y low f i e l d c a p a c i t y f o r t h e s o i l , and
low s o r p t i o n t o s o i l . As F i g u r e 2 shows, even s m a l l changes i n
percent organic matter or f i e l d c a p a c i t y w i l l s i g n i f i c a n t l y a f f e c t
t h e d i s t a n c e r e s i d u e s move b e f o r e b e i n g decomposed. S m a l l changes
i n d e g r a d a t i o n r a t e have a s i g n i f i c a n t impact as w e l l .
These t y p e s o f s i m u l a t i o n s h e l p e x p l a i n t h e d i f f e r e n c e s seen i n
F l o r i d a f i e l d s t u d i e s i n t h e magnitude o f r e s i d u e s found i n s h a l l o w
groundwater u n d e r t r e a t e d c i t r u s g r o v e s i n c o a s t a l and r i d g e a r e a s .
The h i g h e r s o i l f i e l d c a p a c i t y and h i g h e r o r g a n i c m a t t e r c o n t e n t
t y p i c a l o f e a s t e r n c o a s t a l a r e a s r e s u l t s i n much lower r e s i d u e s
e n t e r i n g s h a l l o w groundwater compared t o t h e r i d g e a r e a .
S i m u l a t i o n s u s i n g t h e a c t u a l p a r a m e t e r s f o r c o a s t a l c i t r u s (and
other southeastern l o c a t i o n s ) coupled with experimental data confirm
t h a t t h e c e n t r a l F l o r i d a r i d g e a r e a i s more s e n s i t i v e t o l e a c h i n g o f
a l d i c a r b r e s i d u e s t o groundwater compared t o o t h e r s o u t h e a s t e r n
a g r i c u l t u r a l areas.
Because b o t h t h e amount and d i s t r i b u t i o n o f r a i n f a l l and
vapotranspiration change from y e a r t o y e a r a t a s p e c i f i c s i t e ,
m o d e l i n g can h e l p g e n e r a l i z e e x p e r i m e n t a l r e s u l t s . One method f o r
i l l u s t r a t i n g t h e e f f e c t o f y e a r - t o - y e a r weather v a r i a t i o n s i s t o
perform a s i m u l a t i o n with s e v e r a l consecutive years of r a i n f a l l .
The r e s u l t s o f t h i s s i m u l a t i o n can t h e n be summarized i n a
cumulative p r o b a b i l i t y d i s t r i b u t i o n curve. The r e s u l t s o f a
1 7 - y e a r s i m u l a t i o n (1965-1982 w i t h 1978 e x c l u d e d b e c a u s e o f m i s s i n g
weather d a t a ) f o r t h e Lake H a m i l t o n , F l o r i d a , l o c a t i o n u s i n g t h e
i n p u t p a r a m e t e r s i n T a b l e I I I a r e shown i n F i g u r e 3. This figure
shows t h a t 50 p e r c e n t o f t h e t i m e t h e amount o f a l d i c a r b r e s i d u e s
l e a c h i n g b e l o w 450 cm i s l e s s t h a n 7 p e r c e n t o f t h a t a p p l i e d when
t h e a p p l i c a t i o n d a t e was F e b r u a r y 15. When t h e a p l i c a t i o n d a t a was
June 15, 30 p e r c e n t o f t h e a p p l i e d r e s i d u e s l e a c h e d below 450 cm.
These d i f f e r e n c e s a r e a r e s u l t o f t h e uneven d i s t r i b u t i o n o f
r a i n f a l l during the year. T h e r e f o r e , an a p p l i c a t i o n on F e b r u a r y 15
( d u r i n g t h e l e s s r a i n y p o r t i o n o f t h e y e a r ) w i l l , on t h e a v e r a g e ,
r e s u l t i n l e s s r e s i d u e l e a c h i n g below a s p e c i f i e d d e p t h , t h a n a June
15 a p p l i c a t i o n ( d u r i n g t h e r a i n y p o r t i o n o f t h e y e a r ) .
S a t u r a t e d Zone Models. R e s u l t s from u n s a t u r a t e d zone s i m u l a t i o n s

can be used as i n p u t s t o s a t u r a t e d zone models t o p r e d i c t
c o n c e n t r a t i o n s o f a l d i c a r b r e s i d u e s i n groundwater. The s a t u r a t e d
zone model u s e d by t h e a u t h o r t a k e s t h e p e s t i c i d e i n p u t s i n t o
groundwater, as p r e d i c t e d by PRZM, and c a l c u l a t e s t h e c o n c e n t r a t i o n
and movement o f a l d i c a r b r e s i d u e s i n t h e u p p e r p o r t i o n o f t h e
s a t u r a t e d zone. The c o r e o f t h e s a t u r a t e d zone model i s a f i n i t e
element s o l u t e t r a n s p o r t c a l c u l a t i o n p r o c e d u r e d e v e l o p e d a t t h e
U n i v e r s i t y o f W i s c o n s i n ( 2 5 ) . The a c c u r a c y o f t h i s model i n
e s t i m a t i n g p e s t i c i d e movement i n groundwater i s (as w i t h o t h e r
JONES Degradation and Transport of Aldicarb Residues
F i g u r e 2(A,B). S i m u l a t e d e f f e c t o f o r g a n i c m a t t e r (A) and s o i l

h y d r a u l i c p r o p e r t i e s (B) on t h e l e a c h i n g o f a l d i c a r b r e s i d u e s
under F l o r i d a Ridge c o n d i t i o n s . C o n t i n u e d on n e x t page.
E V A L U A T I O N O F P E S T I C I D E S IN G R O U N D WATER
15 - 30 DAYS HALF LIFE

A_ J ^ Y S HALF LIFE
60 - 120 DAYS HALF LIFE
150 300 450

DEPTH IN CM
F i g u r e 2 ( C ) . S i m u l a t e d e f f e c t o f d e h y d r a t i o n r a t e on the
l e a c h i n g o f a l d i c a r b r e s i d u e s under F l o r i d a Ridge c o n d i t i o n s .
TABLE I I I . PRZM Base Case U s i n g F l o r i d a R i d g e C o n d i t i o n s
D a i l y R a i n f a l l Data: 1983 Lake A l f r e d Station
D a i l y E v a p o r a t i o n Data: 1983 Lake A l f r e d S t a t i o n

(Pan F a c t o r o f 1.0)
S o i l Hydraulic Properties:
Field Capacity Wilting Point

S o i l S t r a t a (cm) (vol. percent) (vol. percent)
0-15 6.7 1.8

15-30 5.3 1.3
30-45 6.6 1.2
45-60 4.3 0.9
60-75 4.9 0.9
75-90 4.1 0.6
90-450 3.8 0.8
SCS Curve Numbers: 47, 67, 83, 59, 77, 89, 40, 60,78
Root Zone Depth (cm): 150
P e s t i c i d e D e g r a d a t i o n Rate ( h a l f l i f e i n days):
0-150 cm 30
150-300 cm 30-60 ( i n t e r p o l a t e w i t h depth)
Below 300 cm 60
Pesticide S o i l Sorption Coefficient:
0-15 cm 0.08
15-30 cm 0.08
30-60 cm 0.03
Below 60 cm 0.00
Plant Uptake o f P e s t i c i d e : Not considered
Pesticide Application: 11.21 kg/ha on F e b r u a r y 16, 1983

214 E V A L U A T I O N O F P E S T I C I D E S IN G R O U N D WATER
F i g u r e 3. S i m u l a t e d c u m u l a t i v e p r o b a b i l i t y d i s t r i b u t i o n s showing
the e f f e c t o f weather (as a f u n c t i o n on depth) and a p p l i c a t i o n
t i m i n g on the l e a c h i n g o f a l d i c a r b r e s i d u e s .
s a t u r a t e d zone models) l a r g e l y dependent on t h e a c c u r a c y o f t h e

input parameters.
A s i m p l i f i e d example i s p r e s e n t e d i n F i g u r e 4 w h i c h h e l p s
i l l u s t r a t e how a s a t u r a t e d zone model c a n be u s e d i n s i m u l a t i n g
a l d i c a r b r e s i d u e c o n c e n t r a t i o n s . T h i s c a s e assumes a s t a r t i n g
c o n c e n t r a t i o n o f 100 ppb i n groundwater u n d e r a t r e a t e d a r e a , a
groundwater f l o w r a t e o f 0.15 m/day, and a d e g r a d a t i o n r a t e
c o r r e s p o n d i n g t o a h a l f - l i f e o f s i x months. These c o n d i t i o n s a r e
s i m i l a r t o t h o s e e n c o u n t e r e d i n much o f t h e r i d g e a r e a o f F l o r i d a .
Under t h e s e c o n d i t i o n s , 18 months l a t e r , a l d i c a r b r e s i d u e s w i l l be
p r e s e n t up t o 82 m downstream o f t h e t r e a t e d a r e a a t a c o n c e n t r a t i o n
o f about 12 ppb.
The r e s u l t s o f t h e s e model s i m u l a t i o n p r o j e c t i o n s a r e c o n s i s t e n t
w i t h r e s u l t s o b t a i n e d from f i e l d e x p e r i m e n t a l s t u d i e s n o t o n l y i n
F l o r i d a , but at other l o c a t i o n s . F o r example, i n t h e F l o r i d a r i d g e
c i t r u s r e g i o n , a l d i c a r b r e s i d u e s have n o t been d e t e c t e d i n s h a l l o w
groundwater a t d i s t a n c e s o f more t h a n 200-300 m downgradient o f

t r e a t e d groves. Experimental r e s u l t s a l s o demonstrate t h a t under
these c o n d i t i o n s , the a l d i c a r b r e s i d u e s are c o n s t r a i n e d t o the upper
3-6 m o f groundwater due t o d e g r a d a t i o n and l a t e r a l groundwater
flow. I n the c o a s t a l r e g i o n s of F l o r i d a , a l d i c a r b r e s i d u e s are
c o n s t r a i n e d t o t h e s h a l l o w groundwater w i t h i n t h e p e r i m e t e r o f t h e
t r e a t e d f i e l d s o r g r o v e s due t o t h e more r a p i d r a t e o f
degradation.(10,26) The r e s u l t s o f t h e s e e x p e r i m e n t a l and model
s i m u l a t i o n s t u d i e s h e l p e d p r o v i d e a b a s i s f o r s t a t e r e g u l a t i o n s on
the use of a l d i c a r b i n F l o r i d a .
Conclusions
The e n v i r o n m e n t a l d a t a b a s e f o r a l d i c a r b i s q u i t e e x t e n s i v e ,
c o n s i s t i n g o f about 20,000 s o i l and w a t e r samples from 38 r e s e a r c h
s t u d i e s and 30,000 p o t a b l e w e l l a n a l y s e s . These d a t a i n d i c a t e t h a t
a l d i c a r b r e s i d u e s degrade i n b o t h t h e u n s a t u r a t e d and s a t u r a t e d
zones w i t h t h e r a t e dependent on a v a r i e t y o f e n v i r o n m e n t a l
parameters. I n t h e u n s a t u r a t e d zone, t h e d e g r a d a t i o n r a t e
c o r r e s p o n d s t o a h a l f - l i f e o f about two weeks t o t h r e e months w i t h
the slower degradation r a t e s o c c u r r i n g i n c o l d e r areas. The
d e g r a d a t i o n r a t e i n t h e s a t u r a t e d zone c o r r e s p o n d s t o h a l f - l i v e s
r a n g i n g from a few days t o a few y e a r s . D e g r a d a t i o n r a t e s a r e most
r a p i d i n warm, a l k a l i n e groundwater.
The movement o f a l d i c a r b r e s i d u e s i s q u i t e complex, d e p e n d i n g on
a number o f i n t e r a c t i n g f a c t o r s . I n most a l d i c a r b u s e a r e a s ,
r e s i d u e s degrade c o m p l e t e l y b e f o r e moving t h r o u g h t h e u n s a t u r a t e d
zone and i n t o t h e s a t u r a t e d zone. I n t h e few a r e a s where a l d i c a r b
r e s i d u e s have e n t e r e d t h e s a t u r a t e d zone, r e s i d u e s a r e u s u a l l y
l o c a t e d i n s h a l l o w groundwater n e a r t r e a t e d f i e l d s .
When r e q u i r e d i n p u t p a r a m e t e r s a r e a v a i l a b l e , u n s a t u r a t e d and
s a t u r a t e d zone models a r e good t o o l s f o r i l l u s t r a t i n g t h e e f f e c t s o f
v a r i o u s combinations of v a r i a b l e s , a p p l y i n g experimental data t o
f i e l d s i t u a t i o n s , s e l e c t i n g p o t e n t i a l worst case s i t u a t i o n s f o r
f u r t h e r assessment, and d e t e r m i n i n g t h e e f f e c t o f management
p r a c t i c e s ( s u c h as changes i n a p p l i c a t i o n t i m i n g ) on r e s i d u e
movement. The a p p l i c a b i l i t y o f t h e u n s a t u r a t e d zone model t o
s i t u a t i o n s i n v o l v i n g a l d i c a r b has been d e m o n s t r a t e d o v e r a wide
Q_ OJjme _
6 Months
12 Months
18 Months
25-r
12.5
Treated
Area Distance From Treated Area (m)
F i g u r e 4. I l l u s t r a t i o n of saturated zone m o d e l i n g under F l o r i d a

ridge conditions.
range o f c o n d i t i o n s and t h e a c c u r a c y o f b o t h u n s a t u r a t e d and

s a t u r a t e d zone models p r e d i c t i o n s i s enhanced by t h e a v a i l a b i l i t y o f
e x t e n s i v e d a t a on s o r p t i o n and d e g r a d a t i o n r a t e s .
Acknowledgments
Many s c i e n t i s t s f r o m u n i v e r s i t i e s and r e g u l a t o r y a g e n c i e s have

c o n t r i b u t e d t o r e s e a r c h programs t h a t have been d e s c r i b e d i n t h i s
paper. I would l i k e t o s p e c i f i c a l l y acknowledge t h e c o n t r i b u t i o n s
of: . P. Anderson, R. F. C a r s e l , K. S. P o r t e r , P. S. C. Rao, J . A.
Wyman, D. Curwin, J . M. H a r k i n , G. C h e s t e r s , A. G. H o m s b y , W. B.
Wheeler, P. N k e d i - K i z z a , J . McNeal, R. J . Wagenet, H. B. Hughes, R.
V. Rourke, E. N. L i g h t f o o t , P. S. T h o m e , A. P. Lemley, D. A. Komm,
D. P o w e l l , R. 0. Hegg, and P. S t o f f e l a . I would a l s o l i k e t o
acknowledge t h e work o f t h e many p e o p l e a t U n i o n C a r b i d e who
p a r t i c i p a t e d i n these s t u d i e s .
References
1. Zaki, M. H., D. Moran, D. Harris, Am. J. Public Health 1982, 72,

1391-1395.
2. Smelt, J. ., M. Leistra, W. H. Houx, A. Dekker, Pestic. Sci.
1982, 13, 475-483.
3. Nicholls, P. H., R. H. Bromilow, T. M. Addiscott, Pestic. Sci.
1982, 13, 475-483.
4. Pacenka, S., K. S. Porter, "Preliminary Assessment of the
Environmental Fate of Potato Pesticide, Aldicarb, in Soil and
Ground Water" Eastern Long Island, New York, U.S. EPA Contract
8006876-02.
5. Lemley, A. J., W. Z. Zhong, J. Environ. Sci. Health 1983, 18
(2), 189-206.
6. Rothschild, E. R., R. J. Manser, M. P. Anderson, Ground Water
1982, 20, 437-445.
7. Dierberg, F. ., "Aldicarb Studies in Groundwaters from Citrus
Groves in Indian River County, Florida," Florida Water Resources
Research Center Publication No. 76, 1984.
8. Miles, C. J., J. J. Delfino, J. Agric. Food Chem.. 1985, 33,
455-460.
9. Wyman, J. ., J. O. Jensen, D. Curwen, R. L. Jones, T. E.
Marquardt, "Effects of Application Procedures and Irrigation on
Degradation and Movement of Aldicarb Residues in Soil."
Accepted for publication, 1985.
10. Hornsby, A. G., P.S. C. Rao, W., B. Wheeler, P. Nkedi-Kizza, R.
L. Jones, "Fate of Aldicarb in Florida Citrus Soils: 1. Field
and Laboratory Studies," presented at Characterization and
Monitoring of the Vadose (Unsaturated) Zone, Las Vegas, December
8-10, 1983.
11. Jones, R. L., R. V. Rourke, J. L. Hansen, "Effect of Application
Methods on Movement and Degradation of Aldicarb Residues in
Maine Potato Fields." Accepted for publication, 1985.
12. Wagenet, R. J., K. S. Porter, R. L. Jones, T. E. Marquardt,
"Aldicarb Movement in the Field Soil of Upstate New York."
Submitted for publication, 1985.
13. Wyman, J. ., J. Medina, D. Curwen, J. L. Hansen, R. L. Jones,

"Movement of Aldicarb and Aldoxycarb Residues in Soil."
Submitted for publication, 1985.
14. Jones, R. L., J. L. Hansen, R. R. Romine, T. E. Marquardt,
"Unsaturated Zone Studies on the Degradation and Movement of
Aldicarb and Aldoxycarb Residues." Submitted for publication,
1985.
15. Jones, R. L., "Central California Studies on the Degradation and
Movement of Aldicarb Residues," July, 1985 (to be submitted for
publication).
16. Porter, K. S., A. T. Lemley, . B. Hughes, R. L. Jones,
"Developing Information on Aldicarb Levels in Long Island
Groundwater," paper presented at the Second International
Conference on Groundwater Quality Research, Tulsa, March 26-29,
1984.
17. Supak, J. R., A. R. Swoboda, J. B. Dixon, Soil Sci. Soc. Am. J.,
1978 42, 244-247.
18. Bromilow, R. ., Ann. Appl. Biol. 1973, 75, 473-479.

19. Martin, J. ., "Long Island Deep Soil Boring for Aldicarb
Residues," Suffolk County Department of Health, 1981.
20. Jones, R. L., P.S.C. Rao, A. G. Hornsby, "Fate of Aldicarb in
Florida Citrus Soil: 2. Model Evaluation," paper presented at
Characterization and Monitoring of the Vadose (Unsaturated)
Zone, Las Vegas, December 8-10, 1983.
21. Carsel, R. F., C. N. Smith, L. A. Mulkey, J. D. Dean, P. Jowise,
"Users Manual for the Pesticide Root Zone Model (PRZM) Release
1", -60013-84-109, December 1984.
22. Carsel, R. F., L. A. Mulkey, M. N. Lorber, L. B. Baskin, "The
Pesticide Root Zone Model (PRZM): A Procedure for Evaluating
Pesticide Leaching Threats to Groundwater," accepted for
publication, Ecological Modeling 1985.
23. Jones, R. L., "Movement and Degradation of Aldicarb Residues in
Soil and Groundwater," presented at the Environmental Toxicology
and Chemistry Conference on Multidisciplinary Aproaches to
Environmental Problems, Crystal City, VA. 1983.
24. Lorber, . ., "A Method for the Assessment of Groundwater
Contamination Potential Utilizing PRZM - A Pesticide Root Zone
Model for the Unsaturated Zone, presented at the ACS Symposium
on Evaluation of Pesticides in Groundwater, Miami, April, 1985.
25. Wang, H. F., . P. Anderson, "Introduction to Groundwater
Modeling," W. H. Freeman, San Francisco, 1982.
26. Union Carbide, unpublished Florida unsaturated and saturated
zone monitoring data, 1983 - 1985.
12
Fate of Aldicarb in Wisconsin Ground Water
John M . Harkin, Frank A . Jones, Riyadh N. Fathulla, E. Kudjo Dzantor, and

David G. Kroll
Department of Soil Science, University of Wisconsin-Madison, Madison, WI 53706
Small amounts of aldicarb sulfoxide and sulfone leach

through sandy soils to shallow groundwater in Central
Wisconsin fields where aldicarb is applied to irrigated
potatoes. Leachate residue concentrations decrease

with application rates and later application time. The
pattern of leaching through soil and the levels detect-
able in groundwater are invariably highly erratic.
Leaching occurs mainly during the late summer and fall
of years of application; highest residue concentrations
in groundwater occur later in a zone near the water
table. These levels dissipate as this zone is overlain
with uncontaminated leachate, but residues disappear at
rates faster than can be ascribed to dilution and
dispersion due to natural groundwater movement. The
latter is complicated by water table fluctuations and
flow perturbation caused by water extraction for
irrigation. Residue attenuation is apparently accele-
rated by hydrolysis in the alkaline groundwater and
degradation by a variety of groundwater-inhabiting
bacteria. The groundwater alkalinity increases with
depth and fluctuates seasonally, rising in summer with
CO in the water, which dissolves dolomitic limestone
2
in the aquifer sediments. Rates of breakdown presum-
ably vary with the groundwater temperature, which
ranges from 3-4C in February-March to 20-21C in
August near the water table but remains at 12-14C 10 m
deep in the aquifer. This complex interplay of factors
prevents accurate prediction of the fate of aldicarb
residues in groundwater by mathematical modeling on the
basis of available data. Sensitivity analysis indi-
cates that degradation rates are the crucial determi-
nant of occurrence and persistence in groundwater.
f
The i n t r o d u c t i o n i n t h e e a r l y 1 9 7 0 s o f t h e s o i l - i n c o r p o r a t e d ,
w a t e r - s o l u b l e s y s t e m i c i n s e c t i c i d e / n e m a t i c i d e a l d i c a r b was r e g a r d e d
as a major advance i n t h e t e c h n o l o g y o f p e s t c o n t r o l . It elimi-
nated t h e once p r e v a l e n t h a z a r d o f i n a d v e r t e n t exposure o f a p p l i c a -
tors or inhabitants o f nearby d w e l l i n g s , wildlife, and u s e f u l
i n s e c t s to t o x i c chemicals during spraying or a e r i a l a p p l i c a t i o n o f
pesticides.
0097-6156/86/0315-0219$10.25/0
It was 1979 before i n t r u s i o n of a l d i c a r b residues into a

d o m e s t i c w e l l l o c a t e d c l o s e to i r r i g a t e d p o t a t o f i e l d s i n S u f f o l k
County on Long I s l a n d , New York was r e p o r t e d i n August, 1979 (1).
T h i s d i s c o v e r y p r e c i p i t a t e d an e x t e n s i v e s u r v e y o f o t h e r w e l l s i n
t h e v i c i n i t y (1_,2^ and r e g u l a t o r y a c t i o n s which e l i m i n a t e d the use
o f the i n s e c t i c i d e on Long I s l a n d . A l d i c a r b was b e i n g used on a
v a r i e t y of c r o p s i n s e v e r a l s t a t e s , and c o n c e r n a r o s e whether
residues of the p e s t i c i d e might a l s o be encountered in other
areas. On the b a s i s of i n f o r m a t i o n t h e n a v a i l a b l e , t h i s was deemed
u n l i k e l y , because of the s p e c i a l c i r c u m s t a n c e s of a l d i c a r b use on
Long I s l a n d . F i r s t , a p p l i c a t i o n r a t e s were h i g h : 5-7 pounds of
a c t i v e i n g r e d i e n t per a c r e ( l b a . i . / A 5.6-7.8 kg/ha) to e n s u r e
adequate c o n t r o l of two major p o t a t o p e s t s , the C o l o r a d o p o t a t o
beetle (Leptinotarsa deeemtineata) and the golden nematode
(Hetevodeva rostoehiensis); i n other areas such as Wisconsin
a p p l i c a t i o n r a t e s of o n l y 2-3 l b a . i . / A (2.2-3.4 kg/ha) were b e i n g
used on p o t a t o e s . S e c o n d l y , on Long I s l a n d , p o t a t o e s are grown on

irrigated sandy s o i l s over high water t a b l e s . While s i m i l a r
c o n d i t i o n s e x i s t i n o t h e r a r e a s , such as the C e n t r a l Sands r e g i o n
o f W i s c o n s i n , the a v e r a g e a n n u a l p r e c i p i t a t i o n r a t e i s much h i g h e r

f o r Long I s l a n d (50 v e r s u s 30 i n c h e s 127 v. 76 cm per y e a r ) .
T h i r d , the c o n t a m i n a t e d Long I s l a n d a q u i f e r i s l a r g e l y a s h a l l o w
c o n f i n e d a q u i f e r , and the pH and a l k a l i n i t y of the water a r e low.
In W i s c o n s i n , i n c o n t r a s t , much o f the uppermost a q u i f e r i n the
p o t a t o - g r o w i n g a r e a i s c l o s e to d i s c h a r g e a r e a s , e i t h e r d r a i n a g e
d i t c h e s or the W i s c o n s i n R i v e r and i t s t r i b u t a r i e s , and the pH and
a l k a l i n i t y o f the water are h i g h I t was known t h a t
a l d i c a r b r e s i d u e s have o n l y b r i e f p e r s i s t e n c e i n s u r f a c e water, and
a r e more s t a b l e under a c i d than a l k a l i n e c o n d i t i o n s . Indeed, on
the b a s i s o f a g e o g r a p h i c s c a l e model ( c f . 6) p r o j e c t i o n s were made
u s i n g a n u m e r i c a l r a t i n g system which a t the time ranked the Long
Island aquifer first in sensitivity toward aldicarb residue
c o n t a m i n a t i o n , W i s c o n s i n ' s C e n t r a l Sand P l a i n a d i s t a n t second, and
all other areas of aldicarb useespecially those i n warmer
southern statesas relatively safe, regardless of a p p l i c a t i o n
rates.
However, f o l l o w i n g p r e s s r e p o r t s c l a i m i n g t h a t e v i d e n c e f o r
the o c c u r r e n c e of s e v e r a l p e s t i c i d e s , i n c l u d i n g a l d i c a r b , had been
found by gas c h r o m a t o g r a p h i c a n a l y s i s o f s i x W i s c o n s i n groundwater
samples, the m a n u f a c t u r e r and the S t a t e o f W i s c o n s i n examined f r e s h
samples from the same w e l l s . The S t a t e t e s t s i n d i c a t e d no contam
i n a t i o n by any of 70 p e s t i c i d e s f o r which a n a l y s e s were c o n d u c t e d .
However a t the t i m e , no l a b o r a t o r y i n W i s c o n s i n had f a c i l i t i e s f o r
conducting aldicarb residue analyses i n the p a r t s - p e r - b i l l i o n
range. U n i o n C a r b i d e ' s a n a l y s e s i n d i c a t e d the p r e s e n c e of a l d i c a r b
residues in one sample from a monitoring well at a potato
processing p l a n t wastewater d i s p o s a l a r e a . This provoked the
company to examine samples from s e v e r a l d o e m s t i c w e l l s , and to
r e p o r t i n J a n u a r y 1981 t h a t a l d i c a r b r e s i d u e s had been found i n 12
samples. As more w e l l w a t e r samples were a n a l y z e d , f u r t h e r contam
i n a t e d s i t e s were d e t e c t e d . O b v i o u s l y , the g e o g r a p h i c s c a l e model
was i n a d e q u a t e to p r e d i c t p o l l u t i o n i n c i d e n t s f o r W i s c o n s i n .
As a r e s u l t of the i n i t i a l p r e s s r e p o r t s , r e s e a r c h was begun
by the U n i v e r s i t y of W i s c o n s i n i n the Central Sands a r e a of
W i s c o n s i n t o examine groundwater f o r the p r e s e n c e of p e s t i c i d e
12. HARKIN ET AL. Fate of Aldicarb in Wisconsin Ground Water 221
residues. Because o f r e s t r i c t e d f u n d i n g , e f f o r t s were c o n c e n t r a t e d

e x c l u s i v e l y on a l d i c a r b , as r e p r e s e n t i n g a w o r s t - c a s e s i t u a t i o n ,
because t h i s was t h e o n l y m a t e r i a l f o r which t h e p r e s e n c e o f
residues at levels o f c o n c e r n had been c o n f i r m e d by r e l i a b l e
analyses.
The major g o a l o f t h e r e s e a r c h was t o determine which f a c t o r s
a f f e c t e d t h e amount o f i n t r u s i o n o f p e s t i c i d e r e s i d u e s i n t o t h e
groundwater and t h e i r p e r s i s t e n c e and d i s t r i b u t i o n i n t h e ground-
water. Such i n f o r m a t i o n c o u l d e n a b l e t h e m a n u f a c t u r e r and s t a t e
and f e d e r a l r e g u l a t o r y agencies t o d e c i d e whether the m a t e r i a l
could be used safely, and i f s o , under what conditions i n
Wisconsin. A f u r t h e r g o a l was t o p r e d i c t how l o n g t h e r e s i d u e
concentrations a l r e a d y i n t h e water would remain a t l e v e l s o f
c o n c e r n and whether t h e i r movement t o domestic w e l l s c o u l d be
forecast.
The f i r s t s t e p toward a t t a i n i n g these g o a l s was to c o l l e c t
a l d i c a r b r e s i d u e c o n c e n t r a t i o n s and o t h e r water q u a l i t y p a r a m e t e r s
f o r water samples withdrawn from v a r i o u s depths i n t h e a q u i f e r i n
and around s e v e r a l f i e l d s i n which i r r i g a t e d p o t a t o e s had been
t r e a t e d a t d i f f e r i n g times w i t h a l d i c a r b . The next s t e p was t o
d e s c r i b e t h e mechanisms o f a l d i c a r b d i s p o s i t i o n f o l l o w i n g a p p l i c a -
t i o n and t o c a l i b r a t e and t e s t a model u s i n g d a t a f o r a l d i c a r b and
other chemical s p e c i e s accumulated from t h e l i t e r a t u r e and from
recent f i e l d analyses. I t was hoped t h i s approach would permit
s a t i s f a c t o r y p r e d i c t i o n o f t h e d i s t r i b u t i o n and f a t e o f a l d i c a r b
applied at a f i e l d - s i z e s c a l e , and t h e p o t e n t i a l f o r e n t e r i n g
d o m e s t i c w e l l s w i t h i n 0.5-5 m i l e s (0.8-8.0 km) a t l e v e l s above t h e
recommended s a f e t y l e v e l o f 10 yg/L. T y p i c a l 160-acre (65-ha)
i r r i g a t e d p o t a t o f i e l d s i n W i s c o n s i n a r e square and have s i d e s 0.5
m i l e (0.8 km) l o n g , and p r i v a t e w e l l s s e r v i n g farmhouses o r r u r a l
homes a r e o f t e n l o c a t e d i n t h e c o r n e r s o f o r i m m e d i a t e l y a d j a c e n t
to such f i e l d s o r among a s e r i e s o f such f i e l d s .
Procedures
Site Selection. N i n e 160-acre (65-ha) i r r i g a t e d f i e l d s i n two o f

the main potato-growing counties o f Wisconsin (Portage and
Waushara, 6.4 and 2.2 m i l l i o n cwt. o r 3.2 and 1.1 m i l l i o n q u i n t a l s
i n 1981) were s e l e c t e d f o r s t u d y . S o i l s i n each f i e l d were w e l l
drained sands o r loamy sands, m a i n l y o f the P l a i n f i e l d s e r i e s
( T y p i c Udipsamments), c o n t a i n i n g 1-2% o r g a n i c matter i n the A
horizon. Seven f i e l d s had p r e v i o u s l y been examined (5_,7_).
The eighth f i e l d was l o c a t e d i m m e d i a t e l y southwest o f one
f i e l d a l r e a d y b e i n g m o n i t o r e d i n Waushara County, t h e n i n t h f i e l d
was d i r e c t l y northwest o f t h e e i g h t h f i e l d . A l l f i e l d s had known
h i s t o r i e s o f a l d i c a r b t r e a t m e n t s ( T a b l e I ) . The d i r e c t i o n o f
undisturbed groundwater f l o w i n t h e a r e a i s a p p r o x i m a t e l y west-
northwest and t h e r a t e i s a p p r o x i m a t e l y 1 f o o t (30 cm) p e r day
(8,9_). When c e n t r a l - p i v o t i r r i g a t o r s a r e i n u s e , groundwater f l o w
i s p e r t u r b e d by t h e cone o f d e p r e s s i o n c r e a t e d by water w i t h d r a w a l
through h i g h - c a p a c i t y irrigation pumps (5J0L>2) T N E C O N E O F
d e p r e s s i o n does n o t extend t o the edge o f t h e f i e l d and r e c o v e r y i s
r a p i d once pumping c e a s e s .
Table I. A l d i c a r b A p p l i c a t i o n Rates and Frequencies i n the

9 F i e l d s under Study
A p p l i c a t i o n r a t e i n pounds o f
Field a c t i v e i n g r e d i e n t per a c r e (kg/ha) Years treated
1 3.0 (3.4) 1977, 1979, 1981
2 3.0 (3.4) 1976, 1978, 1980
3 2.4 (2.7) 1976, 1977
2.5 (2.8) 1978
2.7 (3.0) 1979
3.0 (3.4) 1980
4 3.0 (3.4) 30 rows west of
center p i v o t ,
1982 (5 a c r e s )
5 3.0 (3.4) 1979
3.0 (3.4) E a s t h a l f , 1980
6 2.25 (2.5) 1981*
7 3.0 (3.4) 1980

1.95 (2.1) 1982*
1.8 (2.0) 1984*
8 2.7 (3.0) 1978, 1980, 1981
9 3.0 (3.4) 1979, 1980
Treated at plant emergence; a l l o t h e r t r e a t m e n t s were a t planting.
The f i e l d s were o r i g i n a l l y s e l e c t e d to a l l o w comparison o f

aldicarb residue movement and persistence under the conditions
pertinent to i t s p r e s c r i b e d ( l a b e l ) use and p r e - and post-1982
maximum a p p l i c a t i o n r a t e s [3 v e r s u s 2 l b a . i . / A (3.4 v. 2.2
kg/ha)]. At the s t a r t of the s t u d y :
1. F i e l d s 3, 8 and 9 had received a l d i c a r b a p p l i c a t i o n s at

p l a n t i n g s e v e r a l y e a r s i n sequence;
2. Fields 1 and 2 had received aldicarb applications at
p l a n t i n g i n a l t e r n a t e years;
3. F i e l d 5 had r e c e i v e d a l d i c a r b a t p l a n t i n g o n l y once;
4. Field 4 had never been t r e a t e d w i t h a l d i c a r b and was
downgradient i n the water t a b l e from a t r e a t e d f i e l d ;
5. F i e l d 6 had been t r e a t e d o n l y once a t p l a n t emergence 1 y e a r
before monitoring;
6. F i e l d 7 had been t r e a t e d once at p l a n t i n g , then 2 y e a r s
later at plant emergence during the first year of
monitoring.
Well Installation. In seven fields, monitoring wells were

i n s t a l l e d a t e i g h t o r more p o s i t i o n s around the p e r i m e t e r o f the
f i e l d and one or more l o c a t i o n s c l o s e to the c e n t e r p i v o t . Only
two p e r i m e t e r w e l l s i t e s were chosen i n the o t h e r two f i e l d s ( t o
comply w i t h the owner's w i s h e s ) . The w e l l s were p l a c e d as c l o s e as
p o s s i b l e to the t r e a t e d a r e a s . The w e l l c a s i n g s were Schedule 40
p o l y v i n y l c h l o r i d e (PVC) p i p e ; the w e l l p o i n t s were made of PVC
w i t h 1 o r 3 f e e t (30 o r 91 cm) o f 0.006 i n c h (0.15 mm) s l i t s (Timco
Mfg., Sauk C i t y , WT 53578). S h a l l o w w e l l s were i n s t a l l e d by hand-
a u g e r i n g t h r o u g h the s o i l t o o r s l i g h t l y below the water t a b l e
using a 4-inch (102 mm) diameter Soil Conservation Service
s t a i n l e s s s t e e l bucket auger ( A r t ' s Machine Shop, American F a l l s ,

OR 83211) The d r i l l i n g s were s t o r e d i n sequence on a s h e e t o f
p l a s t i c a l o n g s i d e the h o l e . A d r i v i n g cap was p l a c e d i n t h e end o f
the p i p e and t h e w e l l d r i v e n t o t h e d e s i r e d depth u s i n g a p o s t
driver o r sledgehammer. The emergent p i p e was c u t o f f a t a
s u i t a b l e e l e v a t i o n above ground and a r u b b e r vacuum pump hose
inserted into the w e l l . Water pumped from t h e w e l l u s i n g a
b a t t e r y - d r i v e n p e r i s t a l t i c pump (ISCO Model 1680 Wastewater Sampler
Superspeed Pump, ISCO, L i n c o l n , NB 68528) was s q u i r t e d down the
o u t s i d e o f t h e c a s i n g as t h e d r i l l i n g s from t h e h o l e were r e t u r n e d
i n the r e v e r s e o f t h e sequence i n which they had been removed.
This r e c o n s t i t u t e s the o r i g i n a l s o i l p r o f i l e without channeling o r
arching. The t o p 1 m o f t h e d r i l l e d h o l e was s e a l e d w i t h d r y ,
p u l v e r i z e d b e n t o n i t e c l a y ( Q u i c k - J e l l , N.L. B a r o i d I n d u s t r i e s , P.O.
Box 4350, Houston, TX 77210). A f t e r i n s t a l l a t i o n , t h e w e l l was
d e v e l o p e d by pumping u n t i l t h e withdrawn water c o n t a i n e d no v i s i b l e
s e d i m e n t s . Each w e l l was capped w i t h a screw-on t o p s e c u r e d w i t h a

long-shank b i c y c l e p a d l o c k i n s e r t e d t h r o u g h h o l e s d r i l l e d d i a g o -
n a l l y t h r o u g h t h e cap and p i p e f i t t i n g .
A commercial truck-mounted well d r i l l i n g r i g was used t o
i n s t a l l deeper w e l l s . D r i l l i n g was performed u s i n g h o l l o w - s t e m
c o n t i n u o u s f l i g h t a u g e r s , which were l e f t i n p l a c e w h i l e a p r e a s -
sembled PVC w e l l was d r i v e n by hand t o embed i t i n t h e a q u i f e r
sediments a t t h e p r e s e l e c t e d d e p t h . The h o l l o w - s t e m auger was t h e n
removed, t h e d r i l l i n g s washed i n as b e f o r e and t h e w e l l s e a l e d w i t h
b e n t o n i t e a t t h e t o p and d e v e l o p e d by pumping.
I n each f i e l d , a r a i n - g a u g e was a t t a c h e d t o one m o n i t o r i n g
w e l l t o c o l l e c t r a i n f a l l and i r r i g a t i o n w a t e r . The l o c a t i o n o f t h e
w e l l s and samplers i n F i e l d s 1-7 a r e shown i n F i g u r e s 1 and 2.
M o n i t o r i n g w e l l s were a l s o p l a c e d i n f o u r t e s t p l o t s sown t o
p o t a t o e s a t the U n i v e r s i t y o f W i s c o n s i n - M a d i s o n E x p e r i m e n t a l Farm,
near Hancock, W i s c o n s i n . These p l o t s were t r e a t e d w i t h a l d i c a r b a t
a r a t e o f 2 l b . a . i . / A (2.24 kg/ha) a t p l a n t i n g and a t p l a n t emer-
gence. One s e t o f p l o t s was i r r i g a t e d a t a r a t e c o r r e s p o n d i n g t o
the measured vapotranspiration r a t e f o r t h e r e g i o n , t h e second s e t
a t 1.6 times t h e vapotranspiration r a t e ( 2 1 ) .
M u l t i l e v e l Samplers. M u l t i l e v e l samplers (10) assembled i n the

l a b o r a t o r y were i n s t a l l e d a t s e l e c t e d p o s i t i o n s i n f i v e f i e l d s . A
b u n d l e o f 0 . 5 - i n c h (12.7 mm) o.d. h i g h - d e n s i t y l i n e a r p o l y e t h y l e n e
tubes (Central Plastics Distributors, Madison, WI 53703) were
c l u s t e r e d around a c e n t r a l 0 . 7 5 - i n c h (19.1 mm) d i a m e t e r PVC p i p e a t
d i s t a n c e s 18 i n c h e s (45.7 cm) a p a r t . The ends o f each sampler were
s u r r o u n d e d by a s c r e e n o f S t y l e 3401 Typar spunbonded p o l y p r o p y l e n e
(DuPont de Nemours Chemicals Corp., W i l m i n g t o n , DE 19898) t a p e d t o
the t u b i n g . The bundle o f tubes was s e c u r e d around t h e c e n t r a l PVC
p i p e u s i n g duct tape and i n s t a l l e d t h r o u g h a h o l e d r i l l e d t o t h e
d e s i r e d depth w i t h t h e d r i l l r i g . The bottom end o f t h e h o l l o w -
stem auger was c l o s e d w i t h a l a r g e r u b b e r s t o p p e r t o p r e v e n t sand
from f i l l i n g t h e c e n t e r o f the auger d u r i n g d r i l l i n g . With the
auger i n p l a c e a t a depth such t h a t t h e uppermost s a m p l i n g p o r t
would be a t o r a l i t t l e below t h e water t a b l e , t h e i n s i d e o f t h e
auger stem was f i l l e d w i t h water t o a l e v e l above t h e water
table. The m u l t i l e v e l - s a m p l e r bundle was i n s e r t e d t h r o u g h the
auger's h o l l o w stem and a l l o w e d t o s i t u n t i l t h e tubes had f i l l e d
w i t h water. The r u b b e r s t o p p e r was then d i s l o d g e d from t h e end o f

the auger by t a p p i n g s h a r p l y on t h e end o f t h e c e n t r a l PVC p i p e .
Unless t h e auger stem i s f i l l e d w i t h water b e f o r e t h e rubber
s t o p p e r i s d i s p l a c e d , sand i s swept up i n t o t h e h o l l o w stem when
the s t o p p e r i s d i s l o d g e d . T h i s jams t h e m u l t i l e v e l sampler i n t h e
h o l l o w - s t e m auger when i t i s removed from t h e h o l e . By f i l l i n g t h e
h o l l o w stem w i t h water t h e auger c a n be withdrawn l e a v i n g the
m u l t i l e v e l sampler i n p l a c e a t t h e d e s i r e d d e p t h . After position-
i n g t h e s a m p l e r s , t h e d r i l l h o l e around t h e bundle was r e f i l l e d by
washing i n removed m a t e r i a l and s e a l i n g t h e s u r f a c e w i t h b e n t o n i t e .
Each sampler was d e v e l o p e d u s i n g t h e p e r i s t a l t i c pump u n t i l t h e
water d e l i v e r e d c o n t a i n e d no sediment. The ends o f t h e tubes and
c e n t r a l p i p e emerging from t h e ground were c o v e r e d w i t h a capped
PVC p i p e which was l o c k e d t o t h e c e n t r a l PVC p i p e w i t h a b i c y c l e
padlock.
F i e l d Lysimeters. I n a d d i t i o n , p o t a t o e s were p l a n t e d i n each o f

two f i e l d l y s i m e t e r s (11,12) and t r e a t e d w i t h a l d i c a r b a t p l a n t
emergence a t a r a t e o f 3 (1982) and 2 (1983-5) l b a . i . / A (3.36 and
2.24 k g / h a ) . Each l y s i m e t e r was s p r a y - i r r i g a t e d w i t h 0.75 i n c h
(19.3 mm) o f water t w i c e a week throughout t h e growing season. The
s o i l i n each l y s i m e t e r was m a i n t a i n e d under a c o n s t a n t s u c t i o n
u s i n g an e l e c t r i c pump ( G a s t , Benton Harbor, MI 49022) w i t h a
bleed. D r a i n a g e from each l y s i m e t e r was passed t h r o u g h a s e p a r a t e
water meter f i t t e d w i t h an a u t o m a t i c c o u n t e r and p r i n t e r t o measure
incremental and c u m u l a t i v e f l o w . Portions o f d r a i n a g e were
d i v e r t e d p e r i o d i c a l l y from each l y s i m e t e r t o a p l e x i g l a s s sampler
in parallel t o t h e d r a i n a g e system and b o t t l e d and f r o z e n f o r
future analysis.
Sampling. Water samples were c o l l e c t e d p e r i o d i c a l l y from each

m o n i t o r i n g w e l l , each s a m p l i n g tube on t h e m u l t i l e v e l s a m p l e r s , and
from the i r r i g a t i o n w e l l s i n the f i e l d s under s t u d y . Before
s a m p l i n g , water was pumped from each m o n i t o r i n g w e l l o r s a m p l i n g
tube u n t i l a c l e a r sample c o u l d be o b t a i n e d o r u n t i l 3 t o 5 times
the volume o f t h e w e l l had been removed, t o a s s u r e t h a t t h e sample
came from t h e groundwater around the w e l l and not from s t a g n a n t
water i n t h e w e l l . D u p l i c a t e o r t r i p l i c a t e samples were c o l l e c t e d
i n new 500-ml Nalgene b o t t l e s o r 5 - l i t e r brown g l a s s b o t t l e s w i t h
T e f l o n - l i n e d c a p s , each p r e v i o u s l y washed w i t h a c e t o n e , d i s t i l l e d
water, and r i n s e d t h r e e times w i t h water from t h e w e l l o r sampler
b e i n g sampled. The temperature o f each sample was measured t o t h e
n e a r e s t 0.1C and the pH measured w i t h a D i g i - S e n s e d i g i t a l pH
meter ( C o l e - P a l m e r Instrument Co., C h i c a g o , I L 60648), p r e v i o u s l y
c a l i b r a t e d i n the l a b o r a t o r y a g a i n s t a C o r n i n g Model 130 pH meter
( C o r n i n g M e d i c a l , M e d f i e l d , MA 02052). Each sample was c h i l l e d i n
i c e water i n an i n s u l a t e d p i c n i c c o o l e r and l a t e r frozen u n t i l
analysis.
B e f o r e each m o n i t o r i n g w e l l was sampled, t h e e l e v a t i o n o f t h e
groundwater t a b l e was measured u s i n g a "popper" ( a p l a s t i c c y l i n d e r
w i t h a concave base which e m i t s a popping sound when i t impinges on
a water s u r f a c e ) suspended a t the end o f a s t e e l measuring t a p e .
T h i s d e v i c e gave a c c u r a t e measurements o f water t a b l e depths w i t h -
out c o n t a m i n a t i n g t h e w e l l w a t e r .
I n A p r i l 1982, b e f o r e c r o p s were p l a n t e d , the d r i l l r i g was

used to c o l l e c t water samples from s p o t s d i r e c t l y beneath the
growing a r e a of F i e l d 5. A 30-cm m e t a l w e l l p o i n t w i t h s t a i n l e s s -
s t e e l s c r e e n welded to the end of a s e c t i o n o f h o l l o w - s t e m auger
was d r i l l e d t o v a r i o u s depths below t r e a t e d a r e a s . Water samples
were withdrawn t h r o u g h T e f l o n t u b i n g i n s e r t e d down the h o l l o w stem
i n t o the p o i n t u s i n g the p e r i s t a l t i c pump. S e d i m e n t - f r e e samples
were b o t t l e d and s t o r e d f o r a n a l y s i s as p r e v i o u s l y d e s c r i b e d .
P e r i o d i c a l l y , b a t c h e s o f samples were removed from the f r e e z e r
and thawed f o r a n a l y s i s . Parameters examined i n c l u d e d l a b o r a t o r y
pH, conductivity, total a l k a l i n i t y , c a l c i u m , magnesium, sodium,
p o t a s s i u m , n i t r a t e , c h l o r i d e , s u l f a t e , and a l d i c a r b r e s i d u e s .
The pH was determined u s i n g a C o r n i n g Model 130 d i g i t a l pH
meter; carbonate and bicarbonate a l k a l i n i t i e s were determined
t i t r i m e t r i c a l l y , a c c o r d i n g to Method 403; n i t r a t e - n i t r i t e by the
automated cadmium r e d u c t i o n method (Method 418 F) and s u l f a t e by
the t u r b i d i m e t r i c method (Method 426c) of Standard Methods f o r the

E x a m i n a t i o n o f Water and Wastewater ( 1 3 ) ; and c h l o r i d e u s i n g a
B u c h l e r - C o t l o v e Model #4-2000 C h l o r i d o m e t e r t i t r a t o r ( 1 4 ) . Na and
were d e t e r m i n e d by flame photometry on a Coleman Model 21 i n s t r u
ment a c c o r d i n g to Methods 322B and 325B ( 1 3 ) ; Mg and Ca were
determined by atomic a b s o r p t i o n on a Perkin-Elmer Model 306
i n s t r u m e n t a c c o r d i n g t o Method 303A ( 1 3 ) .
A l d i c a r b Residue A n a l y s i s . For a n a l y s i s o f a l d i c a r b r e s i d u e s , a
100-ml a l i q u o t o f each thawed sample was o x i d i z e d w i t h 1 ml of 40%
p e r o x y a c e t i c a c i d , the e x c e s s a c i d n e u t r a l i z e d w i t h 25 ml of 10%
sodium b i c a r b o n a t e , and the a l d i c a r b s u l f o n e produced by the
oxidation extracted with two 100-ml portions of methylene
chloride. The e x t r a c t was d r i e d over 100 g of sodium s u l f a t e ,
e v a p o r a t e d to d r y n e s s , r e d i s s o l v e d i n 1 ml o f a c e t o n e : e t h e r and
chromatographed on a column 12.5 mm d i a m e t e r 10 cm of f l o r o s i l
( F l o r o d i n Co., B e r k e l y S p r i n g s , WV 25411) u s i n g 1:1 a c e t o n e : e t h e r
as e l u e n t . The p u r i f i e d s u l f o n e f r a c t i o n was a g a i n e v a p o r a t e d to
dryness, dissolved i n 1 ml of acetone and s u b j e c t e d to gas
chromatography i n an H-P 5880 i n s t r u m e n t ( H e w l e t t - P a c k a r d , P a l o
A l t o , CA 94304) on a 2 meter 2 mm i . d . column packed w i t h 10% SP-
1000 on 80-100 mesh S u p e l c o p o r t ( S c i e n t i f i c P r o d u c t s , McGraw Park,
IL 60085) u s i n g a Tracor flame photometric detector (Tracor
Instruments, Austin, TX 78721) o r an H-P nitrogen/phosphorus
specific detector.
The i n j e c t o r temperature was 260C, the d e t e c t o r temperature
300C. A n a l y s e s were r u n i s o t h e r m a l l y a t 180 o r 200C u s i n g h e l i u m
as c a r r i e r gas a t a f l o w r a t e of 25 ml/min. The hydrogen f l o w r a t e
f o r the d e t e c t o r was 3 ml/min and the a i r f l o w r a t e 60 ml/min u s i n g
an a t t e n u a t o r s e t t i n g of 2 . The l i m i t of d e t e c t i o n by this
m e t h o d a s s t a t i s t i c a l l y d e f i n e d by the American C h e m i c a l S o c i e t y ' s
Committee on E n v i r o n m e n t a l Improvement ( 1 4 ) w a s below 1 u g / l i t e r
o r ppb but v a l u e s below 1 ppb p r i n t e d out by the i n s t r u m e n t
p r o c e s s o r were r e p o r t e d as n o n - d e t e c t s (ND). For q u a l i t y c o n t r o l ,
s t a n d a r d s were a n a l y z e d f o l l o w i n g e v e r y t e n t h sample. Samples o f
pure a l d i c a r b , a l d i c a r b s u l f o x i d e and a l d i c a r b s u l f o n e were donated
by Union-Carbide Agricultural Products Company, Raleigh, NC.
R e c o v e r i e s of over 90% were c o n s i s t e n t l y o b t a i n e d w i t h 1, 10, and
100 ppb l e v e l s o f the i n d i v i d u a l compounds o r m i x t u r e s of the pure
s t a n d a r d s o l u t i o n s s p i k e d i n t o d i s t i l l e d o r Madison w e l l water or
field samples and subjected to the extraction, cleanup and
analysis. U n l e s s recommended c r i t e r i a f o r r e c o v e r i e s from f o r t i -
f i e d samples (16) and b l a n k s were met, d a t a were d i s c a r d e d and a l l
reagents, solvents and p r o c e d u r e s were r e v i e w e d . As a further
q u a l i t y c o n t r o l measure, some d u p l i c a t e samples were sent f r o z e n i n
i n s u l a t e d c o n t a i n e r s to U n i o n C a r b i d e f o r a n a l y s i s f o r i n t e r l a b o r a -
t o r y comparison.
Water samples from r u r a l r e s i d e n c e s c l o s e to the e x p e r i m e n t a l
s i t e s were a l s o a n a l y z e d . Three s h a l l o w d o m e s t i c w e l l s c o n t a m i -
n a t e d by a l d i c a r b r e s i d u e s above the s u g g e s t e d no a d v e r s e r e s p o n s e
l e v e l o f 10 ppb were deepened to examine whether the water q u a l i t y
would be Improved.
Bacterial Analysis. Groundwater and a q u i f e r sediments samples were

c o l l e c t e d a s e p t i c a l l y f o r b a c t e r i a l a n a l y s i s ; the sediments were
o b t a i n e d u s i n g h o l l o w - s t e m augers ( 1 7 ) . W i t h the augers i n p o s i -

t i o n i n the s o i l or groundwater a t a p r e s e l e c t e d d e p t h , samples
were c o l l e c t e d i n s i d e a r i g i d , c l e a r p l a s t i c tube ( A c k e r D r i l l Co.,
S c r a n t o n , PE) p r e v i o u s l y s t e r i l i z e d u s i n g u l t r a v i o l e t l i g h t p a s s e d
t h r o u g h the lumen. T h i s tube was inserted inside a split-spoon
sampler sterilized by d o u s i n g w i t h e t h a n o l and flaming. The
sampler was f e d t h r o u g h the h o l l o w stem w i t h an e x t e n d e r rod and
f o r c e d i n t o the u n d i s t u r b e d s o i l / g r o u n d w a t e r below the bore h o l e .
A f t e r removal from the s p l i t - s p o o n sampler, the ends of the p l a s t i c
c y l i n d e r were c u t o f f w i t h a s t e r i l i z e d k n i f e and capped w i t h
s t e r i l i z e d p l a s t i c caps. Subsamples removed under s t e r i l e l a b o r a -
tory conditions from the c e n t e r s of the s o i l c o r e s were examined
for bacteria.
Samples of [S-^^CH^] a l d i c a r b , a l d i c a r b s u l f o x i d e and a l d i c a r b
sulfone were i n c u b a t e d w i t h samples of groundwater and aquifer
s e d i m e n t s to examine the p o t e n t i a l f o r m i c r o b i a l degradation in
situ i n groundwater. The 1
[S- CH3] a l d i c a r b was p r o v i d e d by U n i o n
C a r b i d e A g r i c u l t u r a l P r o d u c t s Company; the l a b e l e d s u l f o x i d e was
p r e p a r e d from t h i s by o x i d a t i o n w i t h hydrogen p e r o x i d e , the sulfone
f r o m the aldicarb by oxidation with peroxyacetic a c i d . These
oxidants afforded better y i e l d s of c l e a n e r p r o d u c t than t h e rrr
c h l o r o p e r o x y b e n z o i c a c i d p r e v i o u s l y used ( 1 8 ) .
Results
The r e s u l t s of the m o n i t o r i n g c l e a r l y i n d i c a t e t h a t regardless

of a p p l i c a t i o n r a t e , t i m i n g and f r e q u e n c y , r e s i d u e s o f a l d i c a r b a r e
l e a c h e d beyond the rooting zone of p o t a t o e s grown i n i r r i g a t e d
sandy s o i l s i n t o u n d e r l y i n g groundwater. The water t a b l e d e p t h i s
not the critical significant factor in restraining aldicarb
leaching: r e s i d u e s were found where the water t a b l e was o n l y 3.9
feet (1.2 m) or as deep as 17.3 feet (5.3 m) below the soil
surface. T h i s i s not s u r p r i s i n g , s i n c e n e i t h e r a l d i c a r b nor i t s
sulfoxide or sulfone i s strongly absorbed by s o i l s , especially
coarse-textured s o i l s (19,20). The groundwater t a b l e i n the a r e a
is subject to s e a s o n a l and long-term f l u c t u a t i o n s . The water
t a b l e s i n the f i e l d s s t u d i e d dropped by 2-4 f e e t (61-122 cm) d u r i n g
the growing season due to water removal for irrigation but
r e c o v e r e d to more o r l e s s the o r i g i n a l l e v e l by the s t a r t of the
next season. The water t a b l e a t t h e U.W.-Madison E x p e r i m e n t a l Farm

near Hancock, WI f l u c t u a t e d by 5 f e e t (152 cm) around a mean
v a l u e d u r i n g t h e y e a r s 1951-1984.
E r r a t i c Residue D i s t r i b u t i o n . However, t h e p a t t e r n o f a l d i c a r b
r e s i d u e c o n c e n t r a t i o n s e n c o u n t e r e d were a s t o u n d i n g l y v a r i a b l e g i v e n
a uniform a p p l i c a t i o n r a t e a c r o s s t h e 127-acre (51-ha) t r e a t e d
c e n t r a l p o r t i o n o f each 160-acre (65-ha) f i e l d . The water l o a d i n g s
from i r r i g a t i o n p l u s p r e c i p i t a t i o n may be assumed t o be u n i f o r m
over t h i s r e l a t i v e l y s m a l l a r e a , and t h e s o i l s a r e r e l a t i v e l y
uniform. Consequently, a l d i c a r b residue penetration t o the
groundwater should be u n i f o r m . The s a n d - a n d - g r a v e l a q u i f e r i s
r e l a t i v e l y homogeneous and l a r g e l y s t r a t i f i e d (8^9) > so t h a t m a i n l y
l a t e r a l movement o f r e s i d u e s w i t h l i t t l e v e r t i c a l m i x i n g might be
expected. I t was t h e r e f o r e s u r p r i s i n g t h a t i n each f i e l d no
aldicarb residues were found i n some w e l l s downgradient from
t r e a t e d a r e a s , low l e v e l s i n o t h e r s , and h i g h l e v e l s i n o t h e r s , a l l
at approximately t h e same d e p t h (Table II). O c c u r r e n c e s and
c o n c e n t r a t i o n s were a l s o e r r a t i c i n t h e m u l t i l e v e l samplers ( T a b l e
III). Concentrations of a l d i c a r b r e s i d u e s i n the s o i l s o l u t i o n ,
i . e . v a l u e s based on the water c o n t e n t o f s o i l samples t a k e n from
the vadose zone, were a l s o e r r a t i c ( T a b l e I V ) and c o n c e n t r a t i o n s i n
l e a c h a t e from the l y s i m e t e r s a l s o v a r i e d w i d e l y over l a r g e ranges
(Table V ) . Aldicarb residues apparently do n o t p e n e t r a t e t o
groundwater by b l e e d i n g t h r o u g h t h e vadose zone a t a c o n s t a n t r a t e ,
but r a t h e r i n p u l s e s o f v a r y i n g c o n c e n t r a t i o n . Peak c o n c e n t r a t i o n s
appear t o be a s s o c i a t e d w i t h minor w e t t i n g f r o n t s p a s s i n g t h r o u g h
the s o i l . So f a r we have been u n a b l e t o d e t e r m i n e c l e a r l y whether
h i g h e s t l o a d i n g s (volume c o n c e n t r a t i o n ) p e n e t r a t e w i t h sharp o r
d i f f u s e w e t t i n g f r o n t s under c o n d i t i o n s o f u n s a t u r a t e d f l o w t h r o u g h
t h e vadose zone, i . e . whether t h e l o a d i n g i s p r o p o r t i o n a l t o t h e
flow.
T a b l e I I r e c o r d s t h e c o n c e n t r a t i o n s o f a l d i c a r b r e s i d u e s found
in water samples from m o n i t o r i n g wells which had d e t e c t a b l e
residues present a t some time d u r i n g t h e s a m p l i n g p e r i o d . No
s i g n i f i c a n t r e s i d u e s were d e t e c t e d a t any time i n any o t h e r w e l l s
(12 more w e l l s i n F i e l d s 1 and 2, 13 i n F i e l d 3, 16 i n F i e l d s 4 and
5, 10 i n F i e l d 6, 11 i n F i e l d 7, and 1 i n each o f F i e l d s 8 and
9). Well depths i n t h e groundwater i n c r e a s e i n t h e sequence
i n d i c a t e d by t h e d e s i g n a t i o n A, o r C a s s o c i a t e d w i t h t h e l o c a t i o n
number f o r any f i e l d . The w e l l s which i n i t i a l l y c o n t a i n e d contam
i n a t e d o r uncontaminated water i n any f i e l d were a t s i m i l a r d e p t h s
i n t h e water t a b l e ; t h u s , t h e p a t t e r n o f r e s i d u e o c c u r r e n c e s cannot
be a s c r i b e d t o i n a p p r o p r i a t e w e l l placement o r d e p t h .
These d a t a g i v e some i d e a o f t h e e r r a t i c a r e a l d i s t r i b u t i o n o f
a l d i c a r b residue contamination even w i t h i n a s i n g l e f i e l d . For
example, on F i e l d 5, t r e a t e d i n i t s e n t i r e t y i n 1979 and i n t h e
e a s t e r n h a l f i n 1980, s i g n i f i c a n t c o n c e n t r a t i o n s o f r e s i d u e s were
i n i t i a l l y e n c o u n t e r e d o n l y a t two s p o t s a t and d i r e c t l y n o r t h o f
the c e n t e r p i v o t ( s i t e s 7 and 2, F i g . 1 ) . S u r p r i s i n g l y , no r e s i
dues were i n i t i a l l y e n c o u n t e r e d i n water from w e l l s a t p o s i t i o n s 3,
4 o r 5, o r a t any time i n samples from t h e n e i g h b o r i n g F i e l d 4, a l l
directly downgradient i n the a q u i f e r from the t r e a t e d area.
R e s i d u e s (12 ppb) were found i n June 1981 i n water from t h e i r r i g a
t i o n w e l l which was cased t o a depth o f 36 f e e t (11 m), o r 28 f e e t
T a b l e II. A l d i c a r b Residue C o n c e n t r a t i o n s (ppb) In Water Samples from M o n i t o r i n g Wells (In which Residues were
S t a t i s t i c a l l y Quantifiable (15).
Mean
Wei 1 water Date ( y e a r , month)
Wei 1 depth table 1980 1981 1982 1983 1984 1985
No. (cm) (cm) 12 2 3 4 5 8 11 3 6 8 9 10 12 2 3 5 6 7 8 9 10 11 2 3 5 6 7 9
c
l e l d s 1 ,2
19 754 478 ND 1 2 2 1 6 7 7 6 4 9 12 11 8 17 24 8 21 19 11 5 19 16 16
23 549 480 49 70 10 4 2 30 115 6 121 118 63 58 36 11 13 9 2 ND 1 ND 11 6 ND
2C 1072 476 ND 1 2 5 ND ND ND 1 8 1 6 10 ND 4 ND 1 4 4 13 ND 19 6 17 28 ND
38 572 424 6 11 48 47 11 23 7 10 8 4 3 ND ND ND 1 1 ND ND ND ND 1 ND
4A 552 333 4 26 42 65 8 49 22 81 29 90 36 2 ND 88 100 64 51 25 5 ND 7 -
7C 1052 459 ND 1 ND ND ND ND ND 3 ND 3 ND 2 9 1 6 7 2 3 3 3 ND 8 6 2
8A 531 420 15 30 9 10 2 18 9 3 7 7 11 24 21 6 11 20 14 5 13 10 18 ND 10 15 -
9C 1069 344 22 17 3 10 12 8 6 2 1 1 7 7 9 21 18 8 15 32 14 23 14 17 19 8 19 29 15
1 OB 526 342 47 30 68 40 55 30 35 40 39 36 24 24 16 18 15 7 6 7 7 4 4 8 -
13A 541 338 69 103 69 53 37 14 24 6 6 116 116 91 70 48 48 67 85 72 55 40 33 17 10 ND
c
leld 3
_

3A 365 225 ND ND ND ND 6 6 13 3 3 4 4 ND ND 2 13 16 13 18 9 9 14 9 11 13

4A 399 221 30 72 67 88 13 ND 2 3 ND ND 13 3 ND ND ND ND 2 5 5 ND 2 2
4B 562 226 18
- -
12 3 1 21 15 7 21 20 33 8 18 ND ND ND 6 ND 2 ND 1 2 - -a
5A 373 212 73 10 21 23 ND ND ND ND ND m
5B 508 215 ND ND ND 18 ND 3 1 ND 3 4 2 5 1 ND ND ND ND ND ND ND H
6A
- -
348 180 116 157 153 100 82 3 3 13 17 48 44 38 5 8 ND ND ND 2 ND ND 2 1 1
-
6B 549 181 2 4 2 1 24 11 19 6 ND 3 ND ND ND 7 15 8 2 ND 1 ND 1 ND -
7A 338 174 35 69 86 180 39 30 ND 4 8 10 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
7B 531 1 71 22 16 28 39 37 88 80 39 22 24 7 7 7 7 11 24 6 ND 4 3 4 3
9A 553 189
-
191 7 150 123 83 ND ND 4 1 3 5 6 5 2 ND ND ND ND ND ND ND 1 ND ND 1

F i e l d s 4, 5
28 292 128 195 150 171 142 140 66 64 1 13 9 6 ND ND ND ND ND ND ND
C
ND ND ND ND ND ND ND ND
2C 427 131 10 12 21 1 ND ND ND 3 11 2 ND ND ND ND ND ND ND ND ND ND ND ND
40 338 206 5 ND 27 8 23 13 28 11 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
7B 323 295 110 79 77 83 86 26 44 78 8 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND i
7C 427 270 3 2 18 3 1 3 1 1 2 2 3 ND ND ND ND ND ND ND ND ND ND ND ND
m

12. HARKIN ET AL. Fate of Aldicarb in Wisconsin Ground Water
ZzZzZZ^ZZzZ
Q Q Q Q < M Q C 1 Q Q
z z z z z z

Q < Q Q

Q | <-
-
ZZZZ<NCM-*
^
Q CM
i

0~ 00 < (
>
\

\
- ,- ^ | ^
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ci ^
T a b l e III. A l d i c a r b Residue Concentrations (ppb) In Groundwater Samples Withdrawn through M u l t i l e v e l Samplers
Depth below Date (year, month)

water t a b l e 1981 1982 1983 1984
Site (cm) 11 3 6 8 9 10 12 2 3 5 6 7 8 9 10 1 2 3 5 6 7
Field 3 15 173 138 55 24 17 8 27 36 8 3 ND ND ND ND 2 ND 1 ND ND ND

61 193 130 45 36 21 49 46 28 3 4 ND ND 1 1 ND 2 ND ND ND
107 158 181 160 81 31 17 18 12 3 16 10 5 5 ND ND 1 ND ND 1
11 152 77 25 24 47 9 17 25 16 13 12 9 ND ND ND ND ND ND ND 1
198 38 19 17 24 16 10 24 20 5 2 ND 4 ND ND ND 3 ND ND 2
244 14 14 37 7 12 18 18 4 10 ND 14 ND 3 ND 2 ND 1 1 tn
290 12 13 ND 23 10 12 9 19 12 7 5 7 5 ND ND ND ND ND ND
15 133 170 54 11 1 ND 6 ND ND 3 1 ND ND 1 ND 1 ND ND ND
61 78 221 49 17 54 13 8 8 4 3 4 ND ND ND 1 ND 1 ND ND ND
107 45 45 19 54 46 64 35 30 10 5 3 ND ND ND ND ND 1 ND ND 1
12 152 26 68 22 49 34 34 69 29 9 13 3 2 6 3 ND 3 2 ND 2
198 16 18 29 19 30 12 31 30 49 17 14 4 5 ND ND ND 2 ND ND 3
244 12 15 17 22 30 19 13 11 17 14 5 4 ND 2 ND ND ND ND ND 2
290 10 29 20 23 19 13 14 5 6 11 5 1 ND ND ND ND ND 1
15 36 118 162 82 36 11 ND ND ND ND 4 ND ND ND 2 ND 1 ND ND 1
61 100 128 24 52 46 30 7 ND 1 9 ND ND ND ND ND 1 ND ND ND
107 94 16 22 50 23 78 62 38 18 8 ND 5 4 2 ND 1 ND ND ND
13 152 29 16 21 40 16 24 34 33 14 8 3 2 ND 2 ND ND 2 ND 2
198 10 10 17 35 7 14 15 5 17 5 7 3 1 5 ND ND 3 ND 2
244 8 14 7 15 17 9 3 4 3 5 1 ND ND 4 ND ND 1
290 5 10 4 1 15 21 10 12 7 15 5 5 ND ND ND ND ND 2
F i e l d s 4,5 46, 91 , 135 (all ND's)

183, 226, 274

318 ND ND ND ND 2 5 ND ND 2 2 ND ND ND 1 ND ND ND ND ND ND >
7 4 2 ND ND
70
366 ND ND ND 2 3 6 5 2 4 5 ND ND ND ND 7*
m
46 2 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND H
>
91 ND ND 1 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND r
135 ND ND 3.8 8 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
183 ND 7 2 33 10 5 1 2 ND ND ND ND ND ND ND ND ND ND ND ND
226 30 20 54 59 55 6 1 4 6 ND ND ND ND ND ND ND ND ND ND ND
274 12 69 45 20 34 29 20 5 17 11 15 7 12 ND ND ND ND ND ND ND ND
318 ND 14 12 22 29 25 16 34 27 22 22 20 24 8 ND 1 ND ND ND ND ND s,
366 ND 17 11 4 18 34 18 22 19 12 2 10 8 7 13 3 ND ND ND ND ND
53 122 ND ND ND ND 2 ND ND ND ND ND ND ND ND ND ND ND ND ND
91 1 46 36 1 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND S'
244 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
488 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND W
s
S'
91 ND 1 ND 2 1 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
135 44 2 11 ND ND ND ND ND ND 4 ND ND ND ND ND ND ND ND
183 193 45 41 53 12 ND ND ND ND ND ND ND ND 1 ND ND ND ND ND ND
13 226 136 13 10 36 57 11 5 2 ND ND ND ND ND ND ND ND ND ND ND ND ND
274 97 ND 9 140 80 ND 8 16 3 ND ND 8 3 ND ND ND ND ND ND ND
318 67 ND 5 10 7 8 3 5 4 6 5 5 1 ND ND ND ND ND ND
366 ND ND ND ND
-
ND 2 6 7 4 1 3 2 1 ND ND ND ND ND ND ND
411 ND ND ND 3 ND ND ND 3 3 3 2 2 2 ND ND ND ND ND ND ND

Table IIIContinued
Field 6
2 None detected a t any depth (high SOM)
15 ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
61 ND ND 1 ND ND ND ND ND ND ND ND ND ND ND ND ND ND
m
107 1 20 18 16 ND ND ND ND ND 1 ND 1 ND ND ND ND ND ND
152 3 104 64 55 9 3 5 ND ND 7 ND ND ND ND ND ND ND ND r
c
198 14 20 2 7 28 49 37 ND 2 ND ND ND ND ND ND ND ND ND
244 2 1 1 13 3 34 15 3 ND 1 ND ND ND ND ND ND ND
290 ND ND ND ND ND ND 25 23 5 ND ND ND 3 ND ND ND ND ND

335 ND ND ND ND ND ND 11 14 7 ND ND 2 5 ND 2 ND ND ND
378 ND ND ND ND ND ND ND 12 4 ND ND , 1 4 ND 2 ND ND ND
Field 7

m
81 64 23 29 45 7 ND ND ND ND ND ND ND ND GO
46 2 150 59
91 ND ND 57 59 48 77 55 27 23 6 13 7 ND ND ND ND ND ND

135 2 ND 47 8 21 22 39 22 31 27 28 20 2 ND ND ND ND ND
73
183 10 6 7 13 42 38 32 38 18 44 8 14 3 9 4 6 ND
- 26 5 ND 1 ND 1 16 46 39 37 15 9 G
226 16 50 26 24 26 1
D
274 50 118 33 23 26 16 ND ND ND ND 2 21 31 27 27 10 8
318 85 85 3 14 30 40 14 16 5 ND ND 8 4 2 5 6 6 9
366 6 7 6 6 14 36 6 18 6 11 13 7 14 ND 9 5 5 2

m
73
12. HARKIN ET AL. Fate of Aldicarb in Wisconsin Ground Water
ON CM CM KN
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-
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-
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CM CM CM Q CM CM
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198
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12
T a b l e IV. Texture, Alkalinity and M o i s t u r e Contents o f S o i l Samples

(Oct. 27-28, 1981) from the Vadose Zone In Potato F i e l d s and
A l d l c a r b Residue Concentrations (ppb) In t h e S o i l and
S o i l S o l u t i o n <"H 0" In L a s t Oolumn).
2
SampIIng CaC0 3
Soil separates, % % Aldlcarb In
Field depth (cm) pH equlv. {%) Sand SI It CI ay H02 Soil H0 2
1 0-30 6.1 0.46 86.4 10.4 5.0 6.8 5 70

30-60 6.0 0.38 95.3 2.3 2.4 4.0 ND 0
60-120 5.4 0.41 98.3 0.6 0.1 1.8 ND 0
120-180 5.3 0.65 99.9 0.1 0 3.5 ND 0
180-240 5.2 0.43 100 0 0 7.0 ND 0
1 0-30 6.0 0.42 88.5 7.5 4.0 7.8 11 141

30-60 5.4 0.37 95.3 3.4 1.3 3.5 ND 0
60-120 5.2 0.40 98.1 1 .5 0.4 4.0 ND 0
120-180 5.2 0.39 99.3 0.5 0.2 4.0 7 175
1 0-30 6.2 0.48 88.5 7.5 3.0 7.1 11 155

30-60 5.8 0.30 97.2 2.1 0.7 4.3 ND 0
60-120 5.3 0.36 98.7 0.9 0.4 3.0 ND 0
120-180 5.0 0.33 98.9 1.1 0 3.9 ND 0
3 0-30 6.9 0.61 93.8 3.5 2.7 4.3 7 163

30-60 6.3 0.83 91.8 6.2 2.0 4.5 ND 0
60-120 5.1 1.02 94.2 4.1 1 .7 4.0 ND 0
120-180 5.0 0.64 95.0 3.0 2.0 6.8 ND 0
3 0-30 6.4 0.59 90.7 4.7 4.6 6.7 7 104

30-60 6.0 0.45 93.3 5.3 1.4 3.9 ND 0
60-120 5.1 0.40 92.9 5.3 1 .8 3.5 15 429
120-180 5.0 0.42 97.2 0.9 1.9 6.4 ND 0
3 0-30 6.4 0.66 87.5 9.4 3.1 7.1 11 155

30-60 5.3 1.47 94.7 3.3 2.0 4.3 ND 0
60-120 5.0 0.38 98.0 1 .3 0.7 3.0 ND 0
120-180 5.1 0.40 95.1 3.4 1.5 3.9 ND 0
H A R K I N ET A L . Fate of Aldicarb in Wisconsin Ground Water
Tab! IV. (Continued)
SamplIng CaC0 3 Sol 1 s e p a r a t e s , % % A l d i c a r b In

Field depth (cm) PH equv. (%) Sand Slit Clay H02 Soil H 0
2
10* 0-30 6.3 0.74 88.9 7.4 3.7 8.9 5 56

30-60 5.3 0.40 90.1 6.7 3.2 6.3 ND 0
60-120 5.5 0.46 95.2 2.5 2.3 4.8 ND 0
120-180 5.5 0.46 96.2 2.5 1.3 4.3 ND 0
180-240 5.5 0.39 98.1 1 .0 0.9 5.4 ND 0
10 0-30 6.8 0.67 87.3 9.1 3.6 8.7 5 57

30-60 5.8 0.47 92.1 5.4 2.5 5.9 ND 0
60-120 5.5 0.86 97.2 1.9 0.9 4.7 ND 0
120-180 5.0 0.64 93.6 3.6 2.8 6.0 10 166
180-240 5.1 0.49 96.8 1.7 1.5 5.1 ND 0
10 0-30 6.0 0.55 85.8 10.0 4.2 8.1 ND 0

30-60 5.0 0.47 89.6 7.4 3.4 5.6 ND 0
60-120 5.4 0.54 97.6 1 .8 0.6 3.7 ND 0
120-180 5.2 0.44 97.4 1.5 1.1 4.4 ND 0
180-240 5.2 0.46 99.6 0.4 0 5.3 11 207
10 0-30 5.8 0.60 84.6 10.6 4.8 8.9 25 281

30-60 5.6 0.44 88.3 6.6 5.1 6.5 21 323
60-120 5.2 0.51 88.1 8.5 3.4 6.2 50 806
120-180 5.2 0.49 85.6 14.4 0.4 7.9 79 1000
180-240 5.4 0.44 99.2 0.6 0.2 7,.6 18 237
10 0-30 6.1 0.90 83.8 10.9 5.3 10.6 17 160

30-60 5.2 0.48 85.4 6.9 7.7 8.4 ND 0
60-120 4.7 0.47 88.8 5.7 5.5 7.2 9 125
120-1 80 5.0 0.41 96.7 1.2 1.1 4.2 16 381
180-240 5.3 0.46 88.6 0.5 0.9 11 .7 15 128
F i e l d 10 In Portage County was t r e a t e d with 3 lb a . I . / A (3.36 kg/ha) a t

p l a n t i n g In 1979 and 1981.
ON
Table V. Concentrations Ippb, Mean/Range (No. of Samples)! of A l d l c a r b Residues In Lyslmeter Leachate;

A p p l i c a t i o n Rates: 3 lb a . I . / A 3.36 kg/ha In 1982, 2 lb a . I . / A 2.24 kg/ha In 1983, 1984, at P l a n t i n g
1982 1983 1984

Month Rectangular Round Rectangular Round Rectangular Round
June N D / - (1) 3/0-7 (3) ND/- (4) ND/-4 5/ND-6 (7) ND/ND-2 (7)
July 434/149-693 (6) 414/148-670 (11) 140/ND-162 (9) 100/2-250 (9) 64/5-148 (14) 19/3-71 (18)
Aug. 146/40-400 (40) 430/80-751 (40) 311/178-434 (11) 425/290-546 (11) 145/142-148 (2) 101/64-162 (6)
Sept. 87/64-143 (6) 210/115-316 (6) 1 1 / - (1) 3/- (1)
Oct. 31/ND-127 (5) 21/ND-123 (4) ?

-
m
H

5
m
3

c

?
m

HARKIN E T A L . Fate of Aldicarb in Wisconsin Ground Water
0 0.25 mi
0 0.5km
(A) May 18, 1981

F i g u r e 1. Maps showing w a t e r - t a b l e c o n t o u r s f o r F i e l d s 1-5 and

l o c a t i o n s o f m o n i t o r i n g w e l l s , i r r i g a t i o n w e l l s , and m u l t i l e v e l
samplers
(8.5 m) below the water t a b l e (5). S i m i l a r l y , no c o n t a m i n a t i o n was

i n i t i a l l y observed a t s i t e s 1, 11 and 12 i n F i e l d s 1 and 2, which
had each been t r e a t e d t h r e e t i m e s , a l t h o u g h the m o n i t o r i n g w e l l s
were i n the p a t h o f groundwater f l o w . L i k e w i s e , no r e s i d u e s were
d e t e c t e d i n one w e l l a t p o s i t i o n 3 i n F i e l d 3 o r w e l l s a t p o s i t i o n s
2 and 4 i n F i e l d 6 ( F i g . 2 ) .
No a l d i c a r b r e s i d u e s were ever d e t e c t e d i n water taken from
w e l l s i n s t a l l e d i n t e s t p l o t s a t the U.W.-Madison E x p e r i m e n t a l Farm
n e a r Hancock, WI, even though one s e t o f p l o t s was i r r i g a t e d a t 1.6
times the measured s o i l m o i s t u r e vapotranspiration r a t e ( c f . 2 1 ) .
A r e a s o n t h a t no a l d i c a r b r e s i d u e s were d e t e c t e d a t many p o s i -
t i o n s c o u l d be t h a t the w e l l depths s e l e c t e d were above o r below a
narrow plume of a l d i c a r b c o n t a m i n a t i o n . However, the results
observed w i t h the m u l t i l e v e l samplers, w i t h the 45 cm depth i n t e r -
v a l s between sampling p o r t s ( T a b l e I I I ) , i n d i c a t e t h a t t h i s i s not
likely: where c o n t a m i n a t i o n o c c u r s , the plume i s u s u a l l y s p r e a d
out over a depth of s e v e r a l sampling l e v e l s . A l s o , no s i g n i f i c a n t

aldicarb residues were e n c o u n t e r e d at a l l i n some multilevel
samplers ( e . g . a t l o c a t i o n s 3 and 7 i n F i e l d 5; l o c a t i o n 2 i n F i e l d
6).
One explanation for the paradoxical residue distribution
a p p a r e n t l y l i e s i n the uneven p e n e t r a t i o n o f a l d i c a r b r e s i d u e s t o
the groundwater and t h e i r d i s t r i b u t i o n w i t h depth i n the a q u i f e r .
Water samples withdrawn from p o s i t i o n s d i r e c t l y below the t r e a t e d
a r e a i n F i e l d 5 showed a v a r i e t y o f c o n c e n t r a t i o n p r o f i l e s w i t h
depth ( F i g u r e 3 ) , w i t h maximum c o n c e n t r a t i o n s r a n g i n g from 18 ppb
at p o s i t i o n "a" to 108 ppb a t p o s i t i o n "e". At p o s i t i o n "b",
r e s i d u e s were found o n l y a t a depth o f 3 f e e t (91.5 cm) below the
water t a b l e (19 p p b ) .
Soil samples c o l l e c t e d from the vadose zone a l s o show a
v a r i e t y of a l d i c a r b r e s i d u e c o n c e n t r a t i o n p r o f i l e s (Table I V ) . In
v i e w o f the low Kd v a l u e f o r a l d i c a r b i n sandy s o i l s (22) i t can be
assumed t h a t any a l d i c a r b r e s i d u e s d e t e c t e d i n s o i l samples a r e
e n t i r e l y d i s s o l v e d i n the s o i l m o i s t u r e . I f s o i l residue values
are r e c a l c u l a t e d on a s o i l - m o i s t u r e b a s i s , the r e s u l t i n g peak
c o n c e n t r a t i o n s a r e c l o s e r to those observed i n the groundwater or
l e a c h a t e from the l y s i m e t e r s . However, the p a t t e r n o f r e s i d u e
c o n c e n t r a t i o n s i n the vadose zone i s a l s o h i g h l y e r r a t i c and b e a r s
no apparent relation to soil texture, moisture content or
a l k a l i n i t y (Table IV). Equally e r r a t i c concentration distributions
were observed f o r samples c o l l e c t e d on o t h e r d a t e s i n the same
year. S i m i l a r l y e r r a t i c r e s u l t s were o b t a i n e d f o r d i f f e r e n t s o i l
p r o f i l e s from Long I s l a n d p o t a t o f i e l d s ( 2 2 ) .
Residues i n Lysimeter Leachate. The 1982-84 l y s i m e t e r s t u d i e s

i n d i c a t e d t h a t b r e a k t h r o u g h o f a l d i c a r b r e s i d u e s began around mid-
J u l y , o r 30-40 days a f t e r treatment, peaked i n mid-August and
declined during September t h r o u g h mid-October to <10 ppb or
nondetectable l e v e l s . No r e s i d u e s were d e t e c t e d i n samples taken
a t any o t h e r time o f the y e a r . The growing season i s the p e r i o d o f
the y e a r when water a p p l i c a t i o n r a t e s a r e h i g h by c o m b i n a t i o n of
p r e c i p i t a t i o n and i r r i g a t i o n . The mean monthly p r e c i p i t a t i o n f o r
t h e y e a r s 1976 through 1984 i s shown i n F i g u r e 4. The p r e c i p i t a -
t i o n of 55.5, 61.1 and 60.2 cm f o r the months A p r i l through
September was supplemented by 19 i r r i g a t i o n a p p l i c a t i o n s t o t a l l i n g
HARKIN E T A L . Fate of Aldicarb in Wisconsin Ground Water
0.5 km
Irrigation well
Observation well
Multilevel sampler
2 10 3 *

11 :
*
112
1
*
Field 7
8 *:
7 5

6

F i g u r e 2. Map showing l o c a t i o n o f F i e l d s 6 and 7 r e l a t i v e t o

F i e l d 4, w a t e r - t a b l e c o n t o u r s and p o s i t i o n s o f m o n i t o r i n g
w e l l s , i r r i g a t i o n w e l l s and m u l t i l e v e l s a m p l e r s .

4

e f
Field 4
b Field 5
20 40 60 80
A l d i c a r b r e s i d u e , ppb
F i g u r e 3. L o c a t i o n s i n F i e l d 5 sampled t h r o u g h t h e h o l l o w - s t e m
auger ( A p r i l 19-21, 1982) and d i s t r i b u t i o n o f a l d i c a r b r e s i d u e s
v e r s u s depth below t h e water t a b l e .
0 "
J F M A M J J A S O N D
MONTH
L
-20
J F M A M J J A S O N D
MONTHS
A M J J A S
MONTHS
F i g u r e 4. Mean a i r and s o i l t e m p e r a t u r e s and p r e c i p i t a t i o n i n

s t u d y a r e a , 1976-84.
36.7, 32.8, and 22.5 cm f o r t h e y e a r s 1982, 1983 and 1984. I r r i g a -

t i o n water was a p p l i e d between t h e b e g i n n i n g o f June and m i d -
September. The average and range o f a l d i c a r b r e s i d u e c o n c e n t r a -
t i o n s f o r August, September and October i n 1982 when t h e a l d i c a r b
a p p l i c a t i o n r a t e was 3 l b / A (3.36 kg/ha) were s u b s t a n t i a l l y h i g h e r
than t h o s e f o r 1983 and 1984, when t h e r a t e was 2 l b / A (2.24
kg/ha). Treatment took p l a c e i n a l l c a s e s a t p l a n t emergence, s i x
weeks a f t e r p l a n t i n g . However, i n 1982, j u s t a f t e r t h e l y s i m e t e r s
were i r r i g a t e d immediately following aldicarb application, they
were drenched w i t h a heavy (1.9 cm) r a i n f a l l .
Because o f equipment f a i l u r e s , i t was not p o s s i b l e t o d e r i v e
an a c c u r a t e mass b a l a n c e f o r t h e amount o f a l d i c a r b leached.
However, by m u l t i p l y i n g the average o f the c o n c e n t r a t i o n s o f each
c o n s e c u t i v e p a i r o f samples by t h e i n t e r v e n i n g volume o f d r a i n a g e
f o r 1983, t h e y e a r w i t h t h e b e s t d a t a s e t , a rough e s t i m a t e o f t h e
f r a c t i o n o f a p p l i e d a l d i c a r b l e a c h e d was o b t a i n e d : 3.6% f o r t h e
r e c t a n g u l a r , 13.5% f o r the round l y s i m e t e r . C o n c e n t r a t i o n s were

h i g h e r f o r 1982, p r o b a b l y because o f t h e h i g h e r a p p l i c a t i o n r a t e ,
but t h e f r a c t i o n l e a c h e d f o r the p e r i o d measured was almost the
same as f o r 1982: 5.4 f o r the r e c t a n g u l a r v e r s u s 16.4 f o r t h e
round l y s i m e t e r . F o r 1983, when the amount o f i r r i g a t i o n water
a p p l i e d was lower, t h e p e r c e n t a g e s l e a c h e d and t h e c o n c e n t r a t i o n s
were s u p r i s i n g l y low: 3.2% f o r the r e c t a n g u l a r v e r s u s 1.6% f o r t h e
round l y s i m e t e r . The volumes o f l e a c h a t e c o l l e c t e d i n each c a s e
were s i m i l a r t o those o b t a i n e d d u r i n g p r e v i o u s s t u d i e s o f n i t r a t e
l e a c h i n g w i t h t h e l y s i m e t e r s when "improved" ( r e d u c e d ) irrigation
r a t e s were used ( 2 3 ) . Twenty-six samples o f l y s i m e t e r l e a c h a t e
a n a l y z e d by Union C a r b i d e u s i n g an HPLC method which determined
a l d i c a r b and i t s o x i d e s s e p a r a t e l y e s t a b l i s h e d t h a t no " p a r e n t "
a l d i c a r b l e a c h e d through t h e s o i l ; t h e r e s i d u e s were e x c l u s i v e l y
s u l f o x i d e and s u l f o n e i n a r a t i o o f 2.2 (range 1 t o 4 ) . R e s i d u e s
i n samples from m o n i t o r i n g and h o u s e h o l d w e l l s a n a l y z e d i n t h e same
way by U n i o n C a r b i d e showed that these too were exclusively
sulfoxide and s u l f o n e i n a r a t i o o f 1.3 ( 2 4 ) . A l t h o u g h t h e
l y s i m e t e r s l i e o n l y 30 m a p a r t , and both were t r e a t e d i d e n t i c a l l y
each y e a r , t h e d i f f e r e n c e each year i n t h e c o n c e n t r a t i o n s and
e s t i m a t e d f r a c t i o n s o f t h e r e s i d u e s l e a c h e d i s remarkable; t h i s may
reflect non-uniform i n f i l t r a t i o n observed under p o t a t o canopies
(25). Non-uniform l e a c h i n g i s a l s o i n d i c a t e d by t h e v a r i a b i l i t y i n
r e s i d u e c o n c e n t r a t i o n s i n t h e vadose zone ( T a b l e I V ) ; c f . ( 2 2 ) .
Residue D i s t r i b u t i o n w i t h Depth. Wherever p e r s i s t e n t aldicarb

residues occur i n wells or m u l t i l e v e l samplers t h e plume o f
c o n t a m i n a t i o n i s observed a t p r o g r e s s i v e l y deeper l e v e l s w i t h time
( T a b l e s I I , I I I ) . H i g h e s t l e v e l s a r e observed i n a l a y e r near t h e
water t a b l e i n y e a r s f o l l o w i n g a l d i c a r b use; peak c o n c e n t r a t i o n s
represent approximately averages of lysimeter leachate. If
a l d i c a r b i s not used i n the f o l l o w i n g y e a r , r e c h a r g e o f r e s i d u e -
f r e e water from p r e c i p i t a t i o n and i r r i g a t i o n i s g r a d u a l l y s u p e r -
imposed upon t h i s c o n t a m i n a t e d l a y e r , making i t appear t o s i n k . As
the plume " s i n k s , " the c o n c e n t r a t i o n s d e c r e a s e d r a m a t i c a l l y . A t
most l o c a t i o n s , abrupt changes and f l u c t u a t i o n s w i t h i n a few months
i n d i c a t e t h a t mechanisms o t h e r than p h y s i c a l d i l u t i o n and d i s p e r -
s i o n must be r e s p o n s i b l e f o r t h e c o n c e n t r a t i o n changes and d i s a p -
pearance o f d e t e c t a b l e r e s i d u e s . T h i s s u g g e s t s t h a t d e g r a d a t i o n o f
residues to non-toxic fragments, presumably by chemical or

m i c r o b i a l h y d r o l y s i s , i s o c c u r r i n g i n the groundwater. However, i n
some i n s t a n c e s , e.g. s i t e s 3 and 4 i n F i e l d 5, a zone of c o n t a m i n a -
t i o n remains and a p p a r e n t l y passes below the l o w e s t l e v e l i n t h e
multilevel samplers (Table III). However, no r e s i d u e s were
d e t e c t e d i n a m o n i t o r i n g w e l l 6.6 m below the water t a b l e a t s i t e 4
and no p e r s i s t e n t plume was o b s e r v e d a t s i t e 7 i n the same f i e l d .
The same t r e n d s were o b s e r v e d w i t h the 3 d o m e s t i c w e l l s which
were deepened. The f i r s t w e l l , a p p r o x i m a t e l y 1 km west a l o n g the
road between F i e l d s 1 and 2, was a sand p o i n t whose s c r e e n began a t
a depth o f o n l y 82 cm below the water t a b l e and y i e l d e d water w i t h
a l d i c a r b r e s i d u e c o n t e n t s o f 90-111 ppb i n 1981 and 1982. After
deepening t o 235 cm, r e s i d u e l e v e l s f e l l t o 26 ppb (12-82), but
g r a d u a l l y r o s e a g a i n i n 1983 [45 ( 6 - 8 3 ) , 63 ( 9 - 8 3 ) , 72 (12-83] and
a g a i n d e c l i n e d w i t h f l u c t u a t i o n s d u r i n g 1984-85 [53 ( 2 - 8 4 ) , 63
( 3 - 8 4 ) , 38 ( 4 - 8 4 ) , 46 (5-84, 51 ( 6 - 8 4 ) , 74 ( 7 - 8 4 ) , 59 ( 8 - 8 4 ) , 42
( 9 - 8 4 ) , 45 (12-84), 45 ( 3 - 8 5 ) , 39 ppb ( 6 - 8 5 ) ] . The second w e l l , a

sand point i n s t a l l e d i n the northwest corner of F i e l d 1, had
i n i t i a l l y s c r e e n s t a r t i n g 245 cm below the water t a b l e and y i e l d e d
water c o n t a i n i n g 12-16 ppb o f a l d i c a r b r e s i d u e s i n 1981 and 1982.
After deepening by 305 cm, the water was free from aldicarb
r e s i d u e s i n 1983 and showed o n l y t r a c e s i n 1984-85 [1 ( 1 - 8 4 ) , 2 ( 2 -
8 4 ) , 3 ( 3 - 8 4 ) , ND ( 5 - 8 4 ) , 4 ( 6 - 8 4 ) , 8 ( 7 - 8 4 ) , 9 ( 8 - 8 4 ) , ND ( 9 - 8 4 ) ,
1 (12-84), 5 ( 3 - 8 5 ) , 6 ( 6 - 8 5 ) ] . The t h i r d w e l l , a sand p o i n t w i t h
s c r e e n s t a r t i n g 250 cm below the water t a b l e , was l o c a t e d c l o s e to
F i e l d 4 and had r e s i d u e l e e l s o f 6-11 ppb i n 1981 and 1982.
F o l l o w i n g deepening, no f u r t h e r r e s i d u e s were d e t e c t e d .
Clearly, the persistence and resultant distribution of
a l d i c a r b r e s i d u e s i n groundwater a r e f a r from u n i f o r m , even under
uniformly treated, uniformly i r r i g a t e d f i e l d s . Residues seem t o
d i s s i p a t e t o l e v e l s of <10 yg/L o r d i s a p p e a r e d e n t i r e l y by the time
they r e a c h depths o f 3-4 m below the water t a b l e , but were more
p e r s i s t e n t i n some a r e a s than o t h e r s .
R e l a t i o n to A l k a l i n i t y . Some e x p l a n a t i o n s f o r t h i s b e h a v i o r can be
offered. P e r s i s t e n t l e v e l s appear t o be a s s o c i a t e d w i t h low pH
(4.5-6.5) and a l k a l i n i t y (<10 mg/L) i n the groundwater. Residues
d i s a p p e a r e d f a s t e r from F i e l d s 4 and 5, where pH and a l k a l i n i t i e s
were h i g h , e s p e c i a l l y a t deeper l e v e l s ( F i g u r e 5) than i n F i e l d s 1
and 2, where pH and a l k a l i n i t y were low ( F i g u r e 6 ) . R a t e s of
c h e m i c a l h y d r o l y s i s o f a l d i c a r b and i t s o x i d e s have been e x t e n -
s i v e l y s t u d i e d (26-29). A l k a l i n i t y and pH tend t o i n c r e a s e w i t h
depth i n the a q u i f e r under a l l f i e l d s . However, p r e d i c t i o n o f
r a t e s o f c h e m i c a l h y d r o l y s i s based on known r a t e c o n s t a n t s a r e
complicated by two phenomena: 1. f l u c t u a t i o n s i n groundwater
temperature; 2. h i g h e r in situ pH and alkalinity than those
measured i n the l a b o r a t o r y .
S h a l l o w groundwater i s c o l d e r i n F e b r u a r y and warmer i n August
than deep groundwater ( c f . F i g u r e 7 ) , a f f e c t i n g h y d r o l y s i s r a t e s .
T h i s r e f l e c t s the h i g h e r a i r and s o i l temperatures and p r e c i p i t a -
t i o n d u r i n g the summer months ( F i g u r e 4 ) . The s e a s o n a l d i f f e r e n c e s
in temperature w i t h depth a r e more pronounced a t the edges of
f i e l d s than i n the c e n t e r ( F i g u r e 7 ) . Presumably the cone o f
d e p r e s s i o n caused by irrigator pumps d u r i n g the summer causes
t u r b u l e n c e s which v e r t i c a l l y mix the water more a t the m i d d l e o f
HARK1N ET AL. Fate of Aldicarb in Wisconsin Ground Water
F i g u r e 5. p H / a l k a l i n i t i e s i n s h a l l o w (A/C) and deep (C/D)

groundwater under F i e l d s 4 and 5.
F i g u r e 6. p H / a l k a l i n i t i e s i n s h a l l o w (A/C) and deep (B/D)

groundwater under F i e l d s 1 and 2.
F i g u r e 7. V a r i a t i o n i n t e m p e r a t u r e w i t h depth ( i n c r e a s i n g i n
45-cm i n c r e m e n t s A-I) i n groundwater, a: F i e l d 6, P o s i t i o n 2;
b: F i e l d 7, P o s i t i o n 9; c: F i e l d 6, P o s i t i o n 4; d: F i e l d 7,
P o s i t i o n 12.
fields. I t i s not known whether d e n s i t y d i f f e r e n c e s a s s o c i a t e d

w i t h temperature d i f f e r e n c e s promote v e r t i c a l m i x i n g and a f f e c t
r e s i d u e c o n c e n t r a t i o n s a t a q u i f e r l o c a t i o n s beyond t h e i n f l u e n c e o f
pumping drawdown.
The p a r t i a l p r e s s u r e o f C(>2 (pCC^) i n groundwater in situ may
be many times h i g h e r t h a n t h a t o f e x t r a c t e d samples; t h i s i s t h e
case i n C e n t r a l Wisconsin. The e x c e s s CO2 i s " l o s t t o t h e atmos-
phere d u r i n g t i t r a t i o n " t o d e t e r m i n e l a b o r a t o r y a l k a l i n i t y (13, p .
263). The q u a n t i t y l o s t depends on t h e amount o f a g i t a t i o n d u r i n g
t i t r a t i o n and t h e degree o f s u p e r s a t u r a t i o n a t t a i n e d a t low pH
levels (30). If alkalinity were s o l e l y d e t e r m i n e d by pC02
according to the carbonate e q u i l i b r i u m , i . e .
[ A l k ] = [HCO3""] + 2 [ C 0 ~ ] + [OH"] - [ H ]
3
2 +
a h i g h e r pC02 would tend t o d e c r e a s e a l k a l i n i t y and pH. However,

i n the p r e s e n c e o f i n s o l u b l e d o l o m i t i c l i m e s t o n e (Ca,Mg)C03, a
h i g h e r pC02 tends t o d i s s o l v e more Ca and Mg as m o d e r a t e l y s o l u b l e
b i c a r b o n a t e s , a c t u a l l y i n c r e a s i n g pH and a l k a l i n i t y . If alkalinity
i s d e f i n e d as t h e e x c e s s o f c a t i o n s o f s t r o n g bases over a n i o n s o f
s t r o n g a c i d s , a c o r r e c t e d in situ a l k a l i n i t y c a n be c a l c u l a t e d by a
balance of a l l the h i g h l y d i s s o c i a t e d i o n species present i n the
groundwater ( 3 0 ) , i . e .
+ +
[ A l k ] - [ N a ] + [ K ] + 2 [Ca**] + 2 [Mg**] + ...
-[CI"] - 2 [ S 0 ] - [NO3-]
4
=
...
T a b l e VI shows examples o f l a b o r a t o r y - m e a s u r e d and the s u b s t a n -

t i a l l y h i g h e r c a l c u l a t e d in situ a l k a l i n i t i e s f o r 10 samples o f
groundwater from F i e l d 6. The v a l u e s shown i n F i g s . 5 and 6 a r e
l a b o r a t o r y , n o t in situ pH and a l k a l i n i t i e s . H i g h e r in situ pH and
a l k a l i n i t y would l e a d t o f a s t e r r a t e s o f a l d i c a r b r e s i d u e b r e a k -
down. P r o j e c t i o n s o f a l d i c a r b r e s i d u e d e g r a d a t i o n by a l k a l i n e
h y d r o l y s i s s h o u l d be based on in situ pH, a l k a l i n i t y and tempera-
ture. These, like the residue concentrations, vary widely,
s p a t i a l l y and t e m p o r a l l y .
Table VI. Measured and C a l c u l a t e d A l k a l i n i t i e s f o r 10

Groundwater Samples from F i e l d 6
Depth i n Aldicarb equivalents)

Date groundwater (cm) r e s i d u e s (yg/L) Measured Calculated
8-82 107 ND 8.9/64 -/161
8-82 107 1 8.5/36 -/267
10-82 107 18 7.7/33 -/58
10-82 152 64 8.1/50 -/149
7-82 174 ND 6.7/35 -/54
7-82 229 37 5.2/2 -/99
10-82 229 29 5.9/4 -/18
8-82 290 ND 8.8/26 -/257
10-82 290 ND 8.6/45 -/51
10-82 378 ND 8.0/23 -/204
R e l a t i o n to M i c r o b i a l A c t i v i t y . Breakdown of a l d i c a r b r e s i d u e s by
biodgradation is presumably superimposed upon chemical
hydrolysis. Results of e x a m i n a t i o n of s o i l and water samples
removed a s e p t i c a l l y from depths of 2 0 , 75 and 230 cm below the
water t a b l e i n F i e l d s 5, 6 and 7 f o r m i c r o b i a l c o n t e n t a r e shown i n
T a b l e s V I I and V I I I . Groundwater samples c o l l e c t e d i n s t e r i l i z e d
c o n t a i n e r s through s t e r i l i z e d equipment were supplemented w i t h the
s t e r i l i z e d y e a s t e x t r a c t n o r m a l l y used f o r i s o l a t i n g s o i l b a c t e r i a
and c o l o n i e s enumerated by the p o u r - p l a t e method. The same method
was used f o r a q u i f e r sediment a b s t r a c t e d a s e p t i c a l l y i n s t e r i l i z e d
p l a s t i c c y l i n d e r s u s i n g a s t e r i l i z e d s p l i t - s p o o n sampler ( 1 7 ) .
The b a c t e r i a a r e a s s o c i a t e d p r i m a r i l y w i t h sediment p a r t i c l e s .
The counts are s i m i l a r to those o b t a i n e d i n groundwater and
s a t u r a t e d sediments by o t h e r s ( 3 1 - 3 3 ) . About 36 s e p a r a t e s p e c i e s
o f b a c t e r i a have been i s o l a t e d ; n i n e of 18 s t u d i e d i n d e t a i l were
tentatively c l a s s i f i e d (Figure 8). A l l a r e b a c t e r i a ; no f u n g i were
encountered. A l l are f a c u l t a t i v e anaerobes, but t h e i r growth i n t o

the medium r a t h e r t h a n on the suface o f s e m i s o l i d agar deeps
suggests t h e i r preference f o r m i c r o a e r o p h i l i c c o n d i t i o n s , such as
those that occur i n Wisconsin groundwater (5 mg/L dissolved
oxygen). The w e l l - d r a i n e d sandy s o i l s c l e a r l y p e r m i t d i f f u s i o n of
a i r to s h a l l o w groundwater. S e v e r a l i s o l a t e s p r e f e r much lower
concentrations o f s u b s t r a t e s i n growth media than normal s u r f a c e
s o i l or wastewater b a c t e r i a . Some i s o l a t e s form p i n p o i n t c o l o n i e s
on a l d i c a r b or i t s o x i d e s as s o l e c a r b o n s o u r c e . A b i l i t y of a
b a c t e r i u m and f i v e s o i l f u n g i t o u t i l i z e a l d i c a r b as a s o l e c a r b o n
s o u r c e or degrade i t as a c o m e t a b o l i t e has been r e p o r t e d p r e v i o u s l y
(34).
i 4
T a b l e IX shows the m i c r o b i a l breakdown w i t h time of [ S - C H ] - 3
a l d i c a r b , a l d i c a r b s u l f o x i d e and a l d i c a r b sulfone to C02 in

groundwater samples. I n c u b a t i o n t e m p e r a t u r e s of 10C and 20C were
used to a p p r o x i m a t e the mean and h i g h e s t a n n u a l groundwater temper-
atures i n Central Wisconsin.
The slow r a t e o f a l d i c a r b breakdown i s u n i m p o r t a n t , s i n c e o n l y t h e

o x i d e s o c c u r i n W i s c o n s i n groundwater.
Evolution of CO2 from a l d i c a r b s u l f o x i d e showed a t y p i c a l
degradation pattern: a l a g ( a c c l i m a t i o n ) phase of 2 to 4 weeks
f o l l o w e d by r a p i d m i n e r a l i z a t i o n ; a l d i c a r b s u l f o n e showed no l a g
phase. With the sulfone at 20C, some radioactivity was
i n c o r p o r a t e d i n t o b a c t e r i a l c e l l s t r a p p e d on membrane f i l t e r s .
In s o i l s , a l d i c a r b and i t s o x i d e s l a b e l e d a t the tf-methyl
group were c o n v e r t e d more r a p i d l y t o C02 than [ S - CH3] 1
deriva-
tives (35). T o t a l m i n e r a l i z a t i o n of a l d i c a r b r e s i d u e s i s not
needed t o d e t o x i f y them; h y d r o l y s i s o f the carbamate e s t e r i s
enough. R a t e s of d e t o x i f i c a t i o n of a l d i c a r b o x i d e s by m i c r o b i a l
hydrolysis in groundwater may be faster than the rates of
m i n e r a l i z a t i o n t o C 0 o b s e r v e d i n the l a b o r a t o r y .
2
The l a r g e v a r i a b i l i t y i n t e m p e r a t u r e , pH, a l k a l i n i t y , n i t r a t e
content, etc. w i t h depth i n groundwater we have o b s e r v e d may

Library
1155 16th St. f N.W.
Washington, D.C 20036
Table VII. E n u m e r a t i o n o f Groundwater B a c t e r i a by Pour Plate

Counts on Groundwater-Yeast E x t r a c t Agar
Depth below B a c t e r i a l counts

groundwater Colony forming units/ml
3
Sampling d a t e Site/Field feet/cm mean ( s d ) 1 0 ~
11/82 4D/5 20.5/625 2.7 (0.3)
1/83 1A/6 1.4/43 7.4 (0.2)
IB/6 3.9/119 6.0 (0.7)
5A/6 1.8/55 8.4 (0.2)
5B/6 6.7/205 8.0 (0.3)
2/83 1A/6 1.4/45 4.6 (0.2)
IB/6 3.9/120 5.3 (0.1)
5A/6 1.8/55 3.0 (0.2)

5B/6 6.7/205 4.9 (0.1)
3/83 1A/6 3.4/104 4.8 (0.3)
IB/6 5.7/174 3.5 (0.2)
5A/6 3.6/110 5.1 (0.2)
5B/6 8.5/260 4.8 (0.2)
8/83 5A/7 1.9/58 3.7 (0.1)
9/83 5B/7 5.6/171 0.6 (0.3)
12/83 5A/7 2.4/73 0.9 (0.4)
5B/7 4.4/134 0.6 (0.4)
Table V I I I . Enumeration of B a c t e r i a i n A q u i f e r
Sediments by Pour P l a t e Counts on
Groundwater-Yeast E x t r a c t Agar
Sampling d e p t h Colony f o r m i n g u n i t s / g o f
m (ft) sediment (x 1 0 ~ ) 4
2.2 (7.5) 9.0

3.1 (10.0) 8.5
4.6 (15.0) 4.7
T a b l e IX. M i n e r a l i z a t i o n o f [ 5 - C H 3 ] A l d i c a r b and i t s O x i d e s
i n Groundwater Samples
Duration of % o f added r a d i o a c t i v i t y
incubation, e v o l v e d as C0 at 2
Compound days 10C 20C

Aldicarb 70 0.9 0.3
Aldicarb sulfoxide 63 3.6 5.9
Aldicarb sulfone 63 1.3 12.6
a f f e c t b o t h b a c t e r i a l numbers and r a t e s o f a l d i c a r b o x i d e s d e g r a d a
tion, accounting i n p a r t f o r the e r r a t i c pattern of residues
concentrations encountered. S i m i l a r l y , the decreases i n r e s i d u e
c o n c e n t r a t i o n s i n l y s i m e t e r l e a c h a t e from 1982-1984 ( T a b l e V) may
reflect adaptation o f vadose zone b a c t e r i a t o a l d i c a r b oxide
residues.
V a r i a b i l i t y o f Chemical P a r a m e t e r s . Patterns of concentrations of

i n o r g a n i c s p e c i e s d e r i v e d from f e r t i l i z e r l e a c h a t e , e.g. n i t r a t e ,
c h l o r i d e and potassium, i n m o n i t o r i n g w e l l s and m u l t i l e v e l samplers
were a l s o e r r a t i c , even though ammonium n i t r a t e and potassium
c h l o r i d e a r e a p p l i e d every year. H i g h l e v e l s o f N O 3 , C l , o r any
o t h e r parameter measured d i d n o t c o r r e l a t e w i t h h i g h l e v e l s o f
aldicarb residues. F o r i n s t a n c e , c o n c e n t r a t i o n s were o f t e n much
h i g h e r (10-30 mg/L) than Na c o n c e n t r a t i o n s (1-10 mg/L), e s p e c i a l l y
i n samples taken from F i e l d 3, r e g a r d l e s s o f whether the samples
c o n t a i n e d a l d i c a r b r e s i d u e s o r n o t . C o n c e n t r a t i o n s and d i s t r i b u
t i o n w i t h depth o f n i t r a t e were e q u a l l y e r r a t i c . I n extreme c a s e s
( W e l l 4, F i e l d 6) t h e average NO3 c o n t e n t was 77 mg/L, t h e range o f
c o n c e n t r a t i o n s 4-360 mg/L (n 1 9 ) . F o r w e l l s 5A and 5B ( F i e l d 6 ) ,
the average and ranges were 52 (28-96) and 49 (10-134) mg/L ( n -
19). S i m i l a r l y f o r w e l l s 9C, F i e l d 1 and 7A and 7B, F i e l d 5, t h e
a v e r a g e s and ranges were 21 (6-36, = 2 2 ) , 15 (4-44, = 18) and
35 (7-70, 2 0 ) . I n no i n s t a n c e d i d peaks i n NO3 l e v e l s
c o r r e s p o n d t o peaks i n a l d i c a r b r e s i d u e s . However, i n no case were
a l d i c a r b r e s i d u e s ever found i n samples t h a t c o n t a i n e d no o r o n l y
l i t t l e NO3.
Modelling E f f o r t s . Two d i f f e r e n t approaches a r e b e i n g used t o

e v a l u a t e the f i e l d d a t a : c o n t o u r i n g p l o t s w i t h r e a l d a t a and
p r e d i c t i v e m o d e l i n g i n e f f o r t s t o match t h e f i e l d d a t a .
Contour p l o t s c o u l d be p r e p a r e d s u c c e s s f u l l y f o r groundwater
e l e v a t i o n s and groundwater c h e m i s t r y d a t a ( e . g . pH, a l k a l i n i t y , NO3
Cl, K) because real values were a v a i l a b l e f o r every sample
analyzed. The d e n s i t y o f sampling l o c a t i o n s was i n s u f f i c i e n t t o
c o n t o u r t h e a l d i c a r b r e s i d u e plume because many o f t h e samples d i d
not c o n t a i n d e t e c t a b l e l e v e l s .
The contour p l o t s were c o n s t r u c t e d u s i n g t h r e e Madison Area
Computing Center (MACC) s u b r o u t i n e s . The f i r s t s u b r o u t i n e runs an
interpolation o f the d a t a provided to create a uniform grid
network. R e f i n i n g and smoothing s u b r o u t i n e s a r e then used t o
reduce l a r g e numerical v a r i a t i o n s . The smoothed n u m e r i c a l m a t r i x
i s s u b j e c t e d t o t h e c o n t o u r i n g s u b r o u t i n e which p l o t s i s o p l e t h s
from the n u m e r i c a l d a t a . The d a t a e n t e r e d i n t o the s u b r o u t i n e s
i n c l u d e two numbers t o g i v e a l o c a t i o n i n t h e g r i d network and a
t h i r d v a l u e r e p r e s e n t i n g the parameter b e i n g p l o t t e d . Variations
of d e p t h i n t h e groundwater a r e p l o t t e d on d i f f e r e n t maps, so t h a t
each c o n t o u r r e p r e s e n t s a s p e c i f i e d depth i n the a q u i f e r . The
p l o t s o f pH and a l k a l i n i t y f o r s h a l l o w and deep w e l l s ( F i g s . 6 and
7) were o b t a i n e d i n t h i s way. S i m i l a r diagrams f o r N O 3 , C I , Na and
FIRST STAGE TESTS IN IDENTIFYING BACTERIAL ISOLATES

Gram + 4
Shape R R
Size
Width, 1.0-1.5 1.0 0.8 0.5-1.0
Length, pm 2.0-4.0 2.0-3.0 1-5 1.5-2.0
Spores +
Motility
Catalase - +
Oxidase

Growth In air + + + +
Growth anaeroblcally
+ M +(?)
Glucose O/F
Bacillus
m .
Corynebacterlum
Cytophaga
Flavobacterlum
Unidentified
Unidentified
R = Rods
b
v s varies
F i g u r e 8. C h a r a c t e r i s t i c s o f some f a c u l a t i v e a n a e r o b i c
b a c t e r i a i s o l a t e d from W i s c o n s i n groundwater. The boxed
numbers i n d i c a t e the number of s p e c i e s t e n t a t i v e l y i d e n t i f i e d .
c o n c e n t r a t i o n s were p r e p a r e d but b o r e no o b v i o u s r e l a t i o n t o
observed a l d i c a r b r e s i d u e l e v e l s .
To t r y t o p r e d i c t a l d i c a r b movement t o and i n the groundwater,
e f f o r t s a r e b e i n g made t o combine two models, the U.S. Environ
m e n t a l P r o t e c t i o n Agency's P e s t i c i d e Root Zone Model (36) and the
Random Walk Model ( 3 7 ) . The g o a l i s to match t h e o u t p u t o f t h e
c o m b i n a t i o n o f t h e s e models w i t h the o b s e r v e d a l d i c a r b residue
c o n c e n t r a t i o n s l i s t e d i n T a b l e s I I and I I I .
The P e s t i c i d e Root Zone Model (PRZM) i s b e i n g u t i l i z e d to
c a l c u l a t e a d a i l y concentration of a l d i c a r b l e a c h i n g i n t o the
groundwater. D a i l y m e t e o r o l o g i c a l r e c o r d s and i r r i g a t i o n s c h e d u l e s
are i n p u t i n t o the model. Other i m p o r t a n t i n p u t parameters i n c l u d e
T a b l e . E f f e c t s o f V a r y i n g S o i l O r g a n i c M a t t e r (SOM) and t h e H a l f - L i f e o f
A l d l c a r b on the Output o f t h e PRZM Model, w i t h i n Ranges i n t h e F i e l d s S t u d i e d
Unsaturated s o i l P e r c e n t SOM i n Percent H a l f - l i f e (days) i n Percent

a
column l e n g t h ( c m / f t ) r o o t i n g / v a d o s e zones change r o o t i n g / v a d o s e zones change
122/4 2/0.1 6 14/180 11
3/0.1 11 14/365 21
5/0.1 19 30/365 44
60/365 61
305/10 2/0.1 7 14/180 39

3/0.1 12 14/365 71
5/0.1 21 30/365 106
60/365 127
488/10 2/0.1 8 14/180 148

3/0.1 14 14/365 327
5/0.1 24 30/365 436
60/365 496
Compared t o " s t a n d a r d " c o n d i t i o n s ( 1 % SOM i n r o o t i n g zone, 0.1% SOM i n vadose

z o n e ) , a l d i c a r b c o n c e n t r a t i o n s i n groundwater would be d e c r e a s e d by t h i s
percentage.
'Compared t o " s t a n d a r d " c o n d i t i o n s ( h a l f - l i f e 14 days i n r o o t i n g zone, 90 days i n
vadose z o n e ) , a l d i c a r b c o n c e n t r a t i o n s i n groundwater would be i n c r e a s e d by t h i s
percentage.
s e v e r a l s o i l and p e s t i c i d e p r o p e r t i e s . PRZM i s a c o m p a r t m e n t a l i z e d
mass-balance type model and downward movement o f water and s o l u t e s
i n t h e s o i l column i s assumed t o o c c u r whenever t h e s o i l m o i s t u r e
c o n t e n t exceeds t h e f i e l d c a p a c i t y . The f i e l d c a p a c i t y and w i l t i n g
point i n o u r s i m u l a t i o n s were 11.2% and 4.8% ( 2 1 ) . The s o i l
o r g a n i c m a t t e r c o n t e n t was e s t i m a t e d from county summaries (38) and
c o r e samples ( 3 9 ) . The s o i l o r g a n i c m a t t e r c o n t e n t (OM) i s used t o
c a l c u l a t e t h e s o i l b u l k d e n s i t y (BD) by t h e f o l l o w i n g e q u a t i o n
(40):
1 0 0
BD = -
% OM 100.Q-% OM
OMBD MBD
where OMBD and MBD a r e the b u l k d e n s i t i e s o f the o r g a n i c m a t t e r and

mineral f r a c t i o n s of the s o i l . The s o i l o r g a n i c m a t t e r c o n t e n t i s
a l s o used t o c a l c u l a t e t h e s o i l d i s t r i b u t i o n c o e f f i c i e n t (K^) from
the r e l a t i o n s h i p between t h e p a r t i t i o n c o e f f i c i e n t s between water

and o c t a n o l ( K ) > and water and s o i l o r g a n i c c a r b o n ( K ) :
Q W Q C
log K o c = 1.00 l o g K Q w - 0.21
u s i n g the e q u a t i o n (41):
d oc 100
An octanol/water partition coefficient, l o g K , o f 0.69

Q W for
a l d i c a r b (42) g i v e s a K Q C o f 3.1, so t h a t t h e c a l c u l a t e d s o i l
distribution coefficient o f 0.0155 i n d i c a t e s very little
adsorption of aldicarb. Values for f o r the a l d i c a r b oxides
would be presumably much lower, i . e . these compounds would be
s o r b e d even l e s s by s o i l .
The f i n a l s i g n i f i c a n t paramater i s decay r a t e . A sensitivity
analysis of h a l f - l i v e s (T-^) r a n g i n g from 14 t o 365 days was
conducted (Table X). A v e r y s i g n i f i c a n t (>400%) change was seen i n
the r e s i d u e l e a c h i n g as a l d i c a r b below 488 cm (16 f e e t ) . The h i g h
v a r i a b i l i t y o f decay r a t e s i n the u n s a t u r a t e d zone (43-6) makes the
choice of a single value or single range o f decay r a t e s o f
questionable value. A number o f s i m u l a t i o n s u t i l i z i n g b e s t and
worst case decay r a t e ranges i s b e i n g used t o d e t e r m i n e the c o n c e n
t r a t i o n o f a l d i c a r b t h a t c o u l d l e a c h i n t o the groundwater. The
o u t p u t o f t h e s e s i m u l a t i o n s w i l l be f e d i n t o the Random-Walk Model;
movement o f a l d i c a r b r e s i d u e s through t h e s a t u r a t e d zone i s b e i n g
simulated u t i l i z i n g t h i s model ( 3 7 ) . Residue c o n c e n t r a t i o n s a r e
i n p u t i n t o the model d a i l y and a r e assumed t o a c t as a c o n s e r v a t i v e
s o l u t e showing v e r y l i t t l e r e t a r d a t i o n . The movement o f a l d i c a r b
r e s i d u e s i s assumed t o be governed by the d i r e c t i o n and v e l o c i t y o f
the groundwater f l o w . S i m u l a t i o n o f h y d r o g e o l o g i c a l parameters
such as h y d r a u l i c c o n d u c t i v i t y ( ) , s t o r a g e c o e f f i c i e n t s , d i s p e r
s i o n c o e f f i c i e n t s a r e s i m i l a r t o those used i n an e a r l i e r m o d e l i n g
study ( 9 ) . The t h i c k n e s s o f t h e a q u i f e r and the decay r a t e a r e
i n i t i a l l y b e i n g s e t a t 6.1 m and 900 d a y s . These two parameters
a r e q u i t e s i g n i f i c a n t and no s i n g l e v a l u e may perhaps a d e q u a t e l y
s i m u l a t e even a f i e l d - s i z e model. C o n s e q u e n t l y , ranges o f v a l u e s

are being u t i l i z e d i n a s e n s i t i v i t y a n a l y s i s .
Our e f f o r t s t o c a l i b r a t e t h e models w i t h t h e f i e l d d a t a have
been u n s u c c e s s f u l . Even u s i n g the value f o r a l d i c a r b w h i c h i s
l e s s w a t e r - s o l u b l e and more s t r o n g l y sorbed than t h e s u l f o x i d e and
s u l f o n e , t h e forms which a c t u a l l y l e a c h t h e PRZM model o v e r e s t i -
mates t h e amount o f r e s i d u e l e a c h i n g , compared w i t h measured v a l u e s
( c f . 39); the i n p u t s i n t o t h e Random Walk Model a r e t h e r e f o r e t o o
h i g h and t h e o u t p u t s do not c o r r e s p o n d t o observed d a t a . This
suggests t h a t t h e d e g r a d a t i o n o f r e s i d u e s by a l k a l i n e h y d r o l y s i s
and m i c r o b i a l m e t a b o l i s m i n b o t h t h e vadose zone and groundwater i s
s u b s t a n t i a l l y h i g h e r than has been assumed on t h e b a s i s o f r a t e
c o n s t a n t s d e r i v e d from l a b o r a t o r y s t u d i e s (26-9, 4 3 - 6 ) .
Conclusions
Regardless o f a p p l i c a t i o n r a t e s and d a t e s , some r e s i d u e s o f

a l d i c a r b , a p p a r e n t l y e x c l u s i v e l y t h e s u l f o x i d e and s u l f o n e , l e a c h
t h r o u g h sands/sandy loams i n i r r i g a t e d p o t a t o f i e l d s i n C e n t r a l
W i s c o n s i n and i n t o s h a l l o w groundwater. However, t h e p e n e t r a t i o n
p a t t e r n s a r e h i g h l y e r r a t i c i n time and space, j u d g i n g from l e v e l s
measured i n s o i l samples from the vadose zone, l y s i m e t e r l e a c h a t e
and shallow monitoring w e l l s . Other contaminants being leached
from a g r i c u l t u r a l c h e m i c a l s a p p l i e d t o s u r f a c e s o i l s , e.g. n i t r a t e ,
chloride and p o t a s s i u m , exhibit equally erratic concentration
distributions. A l d i c a r b r e s i d u e s e n c o u n t e r e d i n t h e groundwater
tend t o be i n i t i a l l y more c o n c e n t r a t e d i n a zone near t h e water
table. As t h i s zone i s o v e r l a i n by f u r t h e r d r a i n a g e , t h e contam-
i n a t e d zone " s i n k s " t o lower depths i n t h e a q u i f e r , and r e s i d u e
concentrations decrease. The r e d u c t i o n i n c o n c e n t r a t i o n i s g r e a t e r
than can be a s c r i b e d t o s t r a i g h t f o r w a r d d i l u t i o n and d i s p e r s i o n
processes. Superimposed upon t h e normal c o n c e n t r a t i o n r e d u c t i o n s
due t o c l a s s i c a l d i l u t i o n / d i s p e r s i o n mechanisms a s s o c i a t e d w i t h
groundwater f l o w i s t h e s e a s o n a l f l u c t u a t i o n i n water t a b l e and t h e
l o c a l f l u c t u a t i o n s and p e r t u r b a t i o n s i n f l o w p a t t e r n s caused by
water a b s t r a c t i o n by h i g h c a p a c i t y i r r i g a t i o n w e l l s . Groundwater
t e m p e r a t u r e s i n c r e a s e w i t h depth i n w i n t e r and d e c r e a s e i n summer;
c o r r e s p o n d i n g d e n s i t y d i f f e r e n c e s may promote v e r t i c a l m i x i n g and
a c c e l e r a t e r e s i d u e d i s p e r s i o n by c o n v e c t i o n .
Residue p e r s i s t e n c e i n groundwater appears t o be a s s o c i a t e d
w i t h low pH and a l k a l i n i t y . Groundwater pH and a l k a l i n i t y i n c r e a s e
w i t h depth i n t h e a q u i f e r . High CO2 c o n t e n t s i n t h e groundwater,
e s p e c i a l l y i n summer, tend t o i n c r e a s e water c o n t e n t s o f Ca and Mg
by d i s s o l u t i o n o f d o l o m i t i c l i m e s t o n e r e s i d u e s from t h e a q u i f e r
s e d i m e n t s , i n c r e a s i n g pH and a l k a l i n i t y above l a b o r a t o r y - d e t e r m i n e d
values. Such c o n d i t i o n s a p p a r e n t l y promote c h e m i c a l h y d r o l y s i s o f
a l d i c a r b r e s i d u e s , r e d u c i n g t h e i r p e r s i s t e n c e i n deeper ground-
water.
The a b i l i t y o f b a c t e r i a found i n t h e groundwater and a q u i f e r
sediments t o m e t a b o l i z e a l d i c a r b o x i d e s suggests that m i c r o b i a l
degradation i s r e s p o n s i b l e i n part f o r disappearance of residues
from groundwater.
The complex interplay of this multiplicity of physical,
chemical and b i o l o g i c a l f a c t o r s which a f f e c t aldicarb residue
concentrations i n the groundwater a t any p l a c e and time makes
e f f o r t s t o d e s c r i b e the f a t e o f a l d i c a r b i n W i s c o n s i n p o t a t o fields
by m a t h e m a t i c a l models an e x t r e m e l y arduous, perhaps f u t i l e , task.
Literature Cited
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72, 1391-5.
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Hist. Survey, Madison, WI. 1981, 39 pp.
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Madison, WI, 1982.
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Wastewater," American Public Health Association, American
Water Works Association, Water Pollution Control Federation,
15th Edit. 1981.
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Med. 1958, 50, 358-71.
15. American Chemical Society, Committee on Environmental
Improvement, "Principles of Environmental Analysis," Anal.
Chem. 1983, 55, 2210-8.
16. Horwitz, W.; Kamps, R. L . ; Boyer, K. W. J. Assoc. Off. Anal.
Chem. 1980, 63, 1344-54.
17. Dzantor, . K.; Harkin, J. M. Submitted to J. Envir. Qual.
1985.
18. Coppedge, J. R.; Lindquist, D. .; Bull, D. L . ; Dorough, H.
W. J. Agr. Food Chem. 1967, 15, 902-10.
19. Smelt, J. H.; Schut, C. J.; Dekker, .; Leistra, M. Neth. J.
Plant Path. 1981, 87, 177-91.
20. Smelt, J. H.; Schut, C. J . ; Leistra, M. J . Environ. Sci.
Health Bd. 1983, 18, 643-65.
21. Wyman, J. .; Jensen, J. O.; Curwen, D.; Jones, R. L . ;
Marquardt. Environ. Toxicol. Chem. 1985, 5 pp.
22. Enfield, C. G.; Carsel, R. F.; Cohen, S. Z.; Phan, T.;

Walters, D. M. Ground Water 1982, 20, 711-22.
23. Saffigna, P. G.; Keeney, D. R.; Tanner, C. B. Agron. J. 1977,
69, 251-7
24. Romine, R. R. Union Carbide Agricultural Products Co.,
Research Triangle, NC. 1985. Personal comunications.
25. Saffigna, P. G.; Tanner, C. B.; Keeney, D. R. Agron. J. 1976,
337-42.
26. Chapman, R. .; Cole, C. M. J. Environ. Sci. Health 1982,
B17, 487-504.
27. Lemley, A. T.; Zhong, W. Z. J. Environ. Sci. Health 1983,
B18, 189-206.
28. Hansen, J. L.; Spiegel, M. L. Environ. Toxicol Chem. 1983, 2,
147-53.
29. Miles, C. J.; Delfino, J. J. J. Agric. Food Chem. 1985, 33,
455-60.
30. Stumm, W.; Morgan J. "Aquatic Chemistry;" John Wiley and

Sons, New York, 1981.
31. Ghiorse, W. C.; Balkwill, D. L. Dev. Industr.Microbiol. 1983,
24, 213-24.
32. Hirsch, P.; Rades-Rohkohl, E. Dev. Industr. Microbiol. 1983,
24, 183-200.
33. Wilson, J. T.; McNabb, J. F.; Wilson, B. H.; Noonan, M. J.
Dev. Industr. Microbiol. 1983, 24, 225-33.
34. Spurr, H. W.; Sousa, A. A. J. Environ. Qual. 1965, 3, 130-3.
35. Heywood, D. L. Environ. Qual. Saf. 1975, 4, 128-33.
36. Carsel, R. F.; Smith, C. N.; Mulkey, L. .; Dean, J. D.;
Jowise, P. "Users Manual for the Pesticide Root Zone Model
(PRZM). 1984, EPA-600/3-84-109. U.S. Environmental
Protection Agency, Washington, D.C.
37. Prickett, T. .; Maymik, T. G.; Lonnquist, C. G. "A Random-
Walk Solute Transport Model for Selected Groundwater Quality
Evaluation. 1981, Illinois State Water Survey Bull. 65, 103
pp.
38. Wisconsin State Soil Testing Laboratory. Summary Reports for
Portage and Washara Counties 1976-1980 and 1981-1984. Dept.
of Soil Science, University of Wisconsin-Madison, 1981, 1985.
39. Wyman, J. .; Medina, J.; Curwen, D.; Hansen, J. L.; Jones, R.
L. 1985, in the press.
40. Rawls, W. O. Soil Sci. 1983, 135, 123-5.
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1979, 13, 241-48.
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Nonpoint Source Pollution;" Overcash, M.R.; Davison, J.M.
Eds., Ann Arbor Science, 1980. p. 23-36.
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Sci. 1978, 9, p. 286-92.
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p. 271-82.
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p. 255-69.
13
Complexity of Contaminant Dispersal
in a Karst Geological System
1 2
David A . Kurtz and Richard R. Parizek
1
Department of Entomology, The Pennsylvania State University, University Park,
PA 16802
2
Department of Geosciences, The Pennsylvania State University, University Park,
PA 16802
The various means of dispersal of environmental con-

taminants within folded and faulted carbonate (karst)
rocks that define a complex karst aquifer system of
the Central Appalachian type include surface and sub-
surface pathways. Chemicals may be exchanged among
surface water, soilwater, and groundwater flow
systems. Concentrations of a marker compound found
in spring waters, Spring Creek surface waters, and
groundwater pumped from wells located adjacent to
Spring Creek illustrate these exchange processes.
Water from residential wells grouped near each other
and located downstream from a waste-disposal site
contained the marker compound at different levels
ranging from 5 to 22 ppt in 1984. Concentrations
found in 1977/78 were similar to those found in 1984
in some houses but were different in others. Evi-
dence is presented that show barriers to subsurface
water flow exist in the form of geological struc-
tures , of subsurface water table divides and gradient
directions, and of water flows within groundwater
basins of various sizes, all of which channel the
potential flow of contaminants and limit dispersion
possibilities. The contaminant may have entered the
more regional carbonate aquifers by natural streambed
leakage, by infiltration induced by groundwater
pumpage, or by nearby sewage sludge disposal.
C h e m i c a l c o n t a m i n a t i o n o f some groundwater and s u r f a c e - w a t e r s u p p l i e s

may have o c c u r r e d as a r e s u l t o f p o i n t - s o u r c e , waste d i s p o s a l p r a c -
t i c e s l o c a t e d near S t a t e C o l l e g e , PA and t h e P e n n s y l v a n i a State
University. The compound, u n i d e n t i f i e d , b u t h a v i n g a c o n s i s t e n t
r e t e n t i o n time f o r e l u t i o n i n the a n a l y t i c a l method used f o r t r a c i n g
and q u a n t i f i c a t i o n , w i l l be f u r t h e r d e s c r i b e d a s a marker compound i n
o r d e r t o p r o p e r l y f o c u s on t h e d i s p e r s a l a s p e c t s o f t h i s problem. I t
0097-6156/ 86/ 0315-0256S07.50/ 0

13. K U R T Z A N D PARIZEK Complexity of Contaminant Dispersal 257
was found i n water a r e a s and may have r e s u l t e d from p r o d u c t i o n from

any o f v a r i o u s compounds i n a l o c a l m a n u f a c t u r i n g p l a n t . Disposal of
waste m a t e r i a l s r e s u l t i n g from t h e manufacture o f v a r i o u s c h e m i c a l s
20-30 y e a r s ago was i n a c c o r d a n c e w i t h a c c e p t e d p r o c e d u r e s o f those
times i n o n - s i t e d i s p o s a l areas. These a r e a s a r e l o c a t e d on
g e o l o g i c a l l y transported and r e s i d u a l s o i l s up t o 60 f e e t t h i c k .
They o v e r l i e f o l d e d and f a u l t e d l i m e s t o n e and i n t e r s p e r s e d d o l o m i t i c
bedrock t h a t c o n t a i n s s e c o n d a r y s o l u t i o n o p e n i n g s . Unfortunately,
the p l a n t was s i t e d on a sequence o f t i l t e d l a y e r s o f l i m e s t o n e whose
s o l u t i o n c a v i t i e s extended d e e p l y from t h e s u r f a c e . The marker
compound was found f i r s t i n s u r f a c e and groundwater some y e a r s ago
and continues to the present day d e s p i t e more r e c e n t attempts t o
decontaminate t h i s d i s p o s a l s i t e . Contaminants a r e b e i n g released
s l o w l y f r o m u n s a t u r a t e d s o i l and b e d r o c k i m m e d i a t e l y below and
adjacent t o t h e p l a n t and a r e l i k e l y t o l i n g e r f o r some y e a r s t o
come.
L i n e d and u n l i n e d l a g o o n s were c o n s t r u c t e d on-site to store

l i q u i d wastes. These l e a k e d a t v a r i o u s times i n t h e p a s t thus c o n -
t r i b u t i n g t o groundwater p o l l u t i o n . A l a n d t r e a t m e n t o p e r a t i o n where
l i q u i d wastes were d i s p o s e d o f by f l o o d i r r i g a t i o n methods a l s o added
to the p o l l u t i o n . These o n - s i t e waste d i s p o s a l p r a c t i c e s have con-
t r i b u t e d t o s o i l w a t e r and groundwater c o n t a m i n a t i o n and a r e marked
"A" i n F i g u r e 1. This i s the p o t e n t i a l i n i t i a l d i s p o s a l point f o r
the marker compound and o t h e r c h e m i c a l s u b s t a n c e s r e l e a s e d w i t h p l a n t
e f f l u e n t s and s l u d g e s .
S u r f a c e and s u b s u r f a c e d r a i n a g e below t h e p l a n t f l o w s i n t o
Spring Creek, a stream known f o r i t s f i n e t r o u t f i s h i n g , scenic
b e a u t y , and t h e l o c a t i o n o f Benner S p r i n g s F i s h R e s e a r c h S t a t i o n ,
o p e r a t e d by t h e Commonwealth o f P e n n s y l v a n i a ( F i g u r e 1 ) . Water
samples i n t h i s stream n e a r t h e s o u r c e o f c o n t a m i n a t i o n have been
found t o c o n t a i n 20 t o 90 ng/kg ( p p t ) o f t h e marker compound d u r i n g
the p a s t 10 y e a r s (_1).
T h i s paper w i l l d i s c u s s the various means o f d i s p e r s a l o f

compounds d i s p o s e d i n a waste area located i n a region of diverse
hydrogeological s e t t i n g .
Chemical A n a l y s i s Methods
Sampling. Water samples were c o l l e c t e d i n g a l l o n g l a s s j u g s w i t h

t e f l o n - l i n e d stoppers. The j u g s had been p r e v i o u s l y c l e a n e d and
s i l a n i z e d w i t h d i m e t h y l d i c h l o r o s i l a n e and were e x t r a c t e d t o check f o r
r e s i d u e s o r a r t i f a c t s o f t h e marker compound p r i o r t o u s e .
W e l l water samples were c o l l e c t e d from r e s i d e n t i a l taps p r i o r t o

any i n - p l a c e water s o f t e n i n g u n i t s . Water samples t a k e n d u r i n g a
s p r i n g f l o o d water p e r i o d were c o l l e c t e d from i n s i d e taps a f t e r a
f u l l o p e n f l u s h o f 30 m i n u t e s . T h i s a s s u r e d t h a t t h e sample
c o l l e c t e d was groundwater withdrawn from t h e c a r b o n a t e a q u i f e r some
d i s t a n c e from t h e w e l l . Stream samples were t a k e n a t t h e c e n t e r o f
the c h a n n e l near t h e stream s u r f a c e . The c r o s s s e c t i o n a l s t r e a m
samples were t a k e n e q u i d i s t a n t a p a r t a t 1/3 t h e water d e p t h a t each
l a t e r a l p o s i t i o n . Water samples were s t o r e d l e s s than a week a t 5 C .
F i g u r e 1 T o p o g r a p h i c map showing the a r e a of c o n t a m i n a t i o n of

the marker compound i n groundwater and s u r f a c e water. Area
covers 5 x 6 km. D e s i g n a t e d p o i n t s a r e d e s c r i b e d i n the t e x t .
Extraction. A c c u r a t e l y measured samples, a p p r o x i m a t e l y 3 L i n s i z e ,

were e x t r a c t e d i n t h e i r o r i g i n a l c o n t a i n e r s f o u r times each w i t h 175
mL o f t o l u e n e ( B a k e r , R e s i - A n a l y z e d ) . Each l a y e r o f t o l u e n e was
s i p h o n e d o f f t h e water w i t h an a s p i r a t o r - d r i v e n t e f l o n tube a p p a r a
tus. The combined s o l u t i o n e x t r a c t was r o t o e v a p o r a t e d t o d r y n e s s i n
a s i l a n i z e d f l a s k and was t a k e n up w i t h t o l u e n e f o r c h r o m a t o g r a p h i c
analysis
Chromatography. Gas c h r o m a t o g r a p h i c a n a l y s i s ( T r a c o r , Model 220)

was performed w i t h a 1.8 m 4 mm i . d . "" column packed w i t h 1.5%
SP-2250/1.95% SP-2401 c o a t e d on S u p e l c o p o r t 100/120 s u p p o r t . The
oven temperature was 220C, and t h e i n l e t and d e t e c t o r temperatures
were 250 and 350C, r e s p e c t i v e l y . The gas f l o w was 60 ^ / m i n w i t h
95:5 argon:methane. D e t e c t i o n was a c c o m p l i s h e d w i t h a N i electron
c a p t u r e d e t e c t o r c o n t r o l l e d by a l i n e a r i z e d e l e c t r o m e t e r ( T r a c o r ) .
Output s i g n a l s were p r o c e s s e d e l e c t r o n i c a l l y ( V a r i a n CDS-401).
Samples were a l s o a n a l y z e d w i t h a 25 m f u s e d s i l i c a c a p i l l a r y
column, d i r e c t i n j e c t i o n , c o a t e d w i t h c r o s s l i n k e d 5% p h e n y l m e t h y l
s i l i c o n e (Hewlett Packard, u l t r a - p e r f o r m a n c e ) . The n i t r o g e n c a r r i e r
gas was 44 cm/sec. F o l l o w i n g i n j e c t i o n i n t o a 200C zone, t h e column
was h e l d a t 50C f o r 6 minutes and then programmed a t 3C/min t o
250C. P e a k s were i d e n t i f i e d r e l a t i v e t o a d i e l d r i n i n t e r n a l
standard
Quantification. Residue c o n c e n t r a t i o n s were c a l c u l a t e d by use o f

r e g r e s s i o n c a l i b r a t i o n graphs on l o g a r i t h m i c a l l y t r a n s f o r m e d data
(2). L a c k o f f i t p r o t o c o l was observed f o r the c a l i b r a t i o n g r a p h .
L a b o r a t o r y r e c o v e r i e s o f the marker compound were r u n a t a l l

times when unknown samples were a n a l y z e d ( T a b l e I ) . These were
always accompanied by a b l a n k r e c o v e r y o f t h e water used as a s p i k i n g
medium.
Hydrogeological Setting
The s t u d y a r e a i s l o c a t e d i n N i t t a n y V a l l e y i n t h e c e n t r a l p a r t o f
P e n n s y l v a n i a , an a r e a about 100 km l o n g and 10 km wide bounded by
N i t t a n y and Tussey M o u n t a i n s . I n t h i s l o c a l e t h e A l l e g h e n y Mountains
s t r e t c h southwest t o n o r t h e a s t and a r e n e s t l e d a g a i n s t t h e A l l e g h e n y
Front. B a l d E a g l e Creek f l o w s t o t h e n o r t h e a s t i n B a l d E a g l e V a l l e y
a g a i n s t t h e f r o n t and i s s e p a r a t e d from N i t t a n y V a l l e y by B a l d E a g l e
Mountain, From a p o s i t i o n t o t h e s o u t h o f N i t t a n y Mountain and
e x t e n d i n g 25 km n o r t h w a r d , S p r i n g Creek winds i t s way a c r o s s s h a l l o w
l i m e s t o n e and d o l o m i t e a q u i f e r s b e f o r e f l o w i n g i n t o B a l d E a g l e Creek
at Milesburg. F i g u r e 1 shows a g e n e r a l i z e d t o p o g r a p h i c a l map o f t h e
immediate a r e a o f s t u d y , and F i g u r e 2 a r e g i o n a l g e o l o g i c a l c r o s s
s e c t i o n of Nittany V a l l e y .
N i t t a n y Mountain i s a s y n c l i n a l m o u n t a i n . I t i s cored with

r e s i s t a n t s a n d s t o n e s , l e s s r e s i s t a n t s h a l e s and s i l t s t o n e s . Tilted
s h a l e beds make up the l o w e r , more g e n t l e s l o p e s o f N i t t a n y Mountain
which s t a n d s more than 900 f e e t above t h e g e n e r a l u p l a n d s u r f a c e o f
the v a l l e y . T h i s upland i s u n d e r l a i n by n e a r l y 8000 f e e t o f f o l d e d
and f a u l t e d c a r b o n a t e r o c k s which have been a r c h e d upward t o form a
Table I. Recovery of the Marker Compound from Spiked Tap Water
Date Samples Accompanying Spike Charge Marker Recovery

the Recovery T e s t s
ng % std. dev.
Aug. 1981 Single well 6 90

23 99 12 (n=4)
Jun. 1983 Spring Creek 150 107

109
Thornton Spring
240 92
Jun. 1984 Stream Cross Section 240 92 7 (n=10)
2 99
Jan. 1985 House Water Taps 104
15 92
100
Feb. 1985 S p r i n g Creek F l o o d 2.5 127*

House Water Taps 127*
5 121*
141*
* Peak h e i g h t s o f 1.3 and 2.3 cm, resp. contained unresolvable

s h o u l d e r peaks.
broad a n t i c l i n e w i t h minor s y n c l i n a l f o l d s . The r e g i o n has been

weathered to produce d i s t i n c t i v e k a r s t t e r r a i n . The r e f e r e n c e i n
t h i s d i s c u s s i o n t o k a r s t r e f e r s always to weathered c a r b o n a t e r o c k s .
I t has been c u t by a t l e a s t two zones of t h r u s t f a u l t s , one t h a t
s u r f a c e s near the p l a n t and one t h a t i s exposed to the west. Tear
f a u l t s a r e r e c o g n i z e d t h a t c r o s s c u t and d i s p l a c e t h e u p t u r n e d
k a r s t i f i e d r o c k s and a l s o i n c r e a s e t h e i r p e r m e a b i l i t y down v a l l e y
where marker compound has been d e t e c t e d i n groundwater.
Rocks r a n g i n g i n age from L a t e Cambrian t h r o u g h Lower Devonian

a r e t r a n s e c t e d by S p r i n g Creek between the m a n u f a c t u r i n g p l a n t s i t e
and i t s c o n f l u e n c e w i t h B a l d E a g l e Creek. L i m e s t o n e u n i t s of the
M i d d l e O r d o v i c i a n S e r i e s u n d e r l i e the p l a n t and extend u p s l o p e t o the
base of N i t t a n y M o u n t a i n . T o g e t h e r , t h e s e l i m e s t o n e u n i t s a r e n e a r l y
900 f e e t t h i c k and i n c l u d e the more s o l u b l e k a r s t i f i e d r o c k s t h a t
l o c a l i z e a l l o f the known caves i n c e n t r a l P e n n s y l v a n i a 3) These
s t r a t a c o n t a i n abundant s o l u t i o n c a v i t i e s b o t h above and below the
water t a b l e near the p l a n t and a r e r e s p o n s i b l e f o r c o n d u i t systems
t h a t d r a i n groundwater p a r a l l e l t o the s u r f a c e t r e n d of i n d i v i d u a l
r o c k l a y e r s to s p r i n g s l o c a t e d on S p r i n g Creek t o the southwest of
the p l a n t and t o the head waters of Logan Branch l o c a t e d n o r t h e a s t of
K U R T Z A N D PARIZEK Complexity of Contaminant Dispersal
AOiinition
s U0 Beliefonte Doioiite a: Tuscoror Forition

J Axeinn Luestone
jn Nittanv uoioiite
wlS atonenenqe mestone
Juniata Formation
JJ
o OSNCQO Snastoni
ur Reeoiviue Snaie
% uQI
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3 Liiestones

Figure 2. Regional g e o l o g i c a l cross section of Nittany Valley

(4).
the p l a n t ( F i g u r e s 3 and 4 ) . These c o n d u i t s a r e r e c h a r g e d by d i f f u s e

i n f i l t r a t i o n o f s u r f a c e water t h a t e n t e r s r e s i d u a l and t r a n s p o r t e d
s o i l s , by s u r f a c e water t h a t e n t e r s swallow h o l e s near t h e base o f
N i t t a n y Mountain l o c a t e d t o t h e e a s t o f t h e p l a n t , and by groundwater
t h a t d r a i n s i n t o these c o n d u i t s from a d j a c e n t , l e s s s o l u b l e beds o f
l i m e s t o n e and d o l o m i t e l o c a t e d b o t h e a s t and west o f t h e p l a n t .
The M i d d l e O r d o v i c i a n l i m e s t o n e u n i t s a r e , i n t u r n , t h r u s t above
a very fine-grained, r e l a t i v e l y insoluble dolomite. This thrust
f a u l t causes cavernous l i m e s t o n e u n i t s t o be exposed a l o n g a second
narrow b e l t t h a t i s p a r a l l e l t o the n o r t h e a s t - s o u t h w e s t t r e n d o f
Nittany Mountain and s e p a r a t e d from the main belt of Middle
O r d o v i c i a n S e r i e s l i m e s t o n e s by a t h i n , r e p e a t e d s e c t i o n of d o l o m i t e .
T h o r n t o n S p r i n g s emerges from t h e uppermost s e c t i o n o f t h i s same
dolomite.
The d o l o m i t e i s more r e s i s t a n t than t h e o v e r l y i n g M i d d l e O r d o v i -

c i a n S e r i e s l i m e s t o n e u n i t s and an u n d e r l y i n g l i m e s t o n e sequence t h a t
i s exposed f u r t h e r t o t h e n o r t h w e s t o f the p l a n t . The d o l o m i t e forms
a r i d g e o f low r e l i e f t h a t p a r a l l e l s Route 26 ( F i g u r e 3) and s i g n i f i -
c a n t l y i n f l u e n c e s l o c a l and more r e g i o n a l groundwater f l o w . A low
r e l i e f groundwater mound u n d e r l i e s t h i s r i d g e . Thin shale p a r t i n g s ,
the r a t h e r impure n a t u r e o f the d o l o m i t e , and i t s i n c l i n a t i o n toward
N i t t a n y Mountain r e s t r i c t groundwater f l o w a c r o s s t h e d i r e c t i o n o f
bedding. These f e a t u r e s a l s o h e l p t o s u p p o r t t h e groundwater mound
which s e r v e s as a h y d r a u l i c b a r r i e r t o groundwater f l o w . Water move-
ment a l o n g t h e s o u t h e a s t f l a n k of t h i s groundwater mound i s toward
the p l a n t and c o n d u i t d r a i n system. Along the mountain's n o r t h w e s t -
e r n s l o p e , f l o w i s northwestward toward S p r i n g C r e e k . Besides the
hydraulic barrier o f f e r e d by t h i s groundwater d i v i d e , a deep,
c o n f i n e d f l o w system a l s o i s p r e s e n t w i t h i n a t h i n sandstone bed t h a t
i s found near the t o p o f t h e d o l o m i t e and c r o p s o u t a l o n g the r i d g e
( F i g u r e 3) ( 4 0 . Groundwater t h a t c i r c u l a t e s t h r o u g h the c o r e o f
N i t t a n y Mountain appears t o be moving u p d i p t h r o u g h t h i s porous
sandstone and i s d i s c h a r g e d a t i t s o u t c r o p a l o n g t h e r i d g e c r e s t .
T h i s deep groundwater f l o w system a l s o r e s t r i c t s contaminant movement
from t h e p l a n t s i t e t h r o u g h t h e r i d g e toward S p r i n g Creek t o t h e
northwest. Contaminants f i r s t must e n t e r S p r i n g Creek near T h o r n t o n
S p r i n g s t o the southwest ( p o i n t B, F i g u r e 1) b e f o r e b e i n g d i s p e r s e d
w i t h i n s u r f a c e and g r o u n d w a t e r d o w n v a l l e y . A pumping c o n e o f
d e p r e s s i o n has d e p r e s s e d water l e v e l s a t one p o i n t i n t h i s mound
( F i g u r e 4) b u t t h e marker compound has n o t been d e t e c t e d i n any o f
the w e l l s r e s p o n s i b l e f o r t h i s d e p r e s s i o n (_1).
A t r a n s i e n t , groundwater d i v i d e s e p a r a t e s groundwater f l o w a l o n g
the c o n d u i t systems d e v e l o p e d i n the M i d d l e O r d o v i c i a n S e r i e s l i m e -
s t o n e s ( p o i n t A, F i g u r e 4 ) . Two groundwater s u b b a s i n s a r e r e c o g -
nized : one t h a t d r a i n s t o s p r i n g s a l o n g Logan Branch and t h a t i s
u n a f f e c t e d by p l a n t w a s t e s , a n d a s e c o n d b a s i n t h a t d r a i n s t o
Thornton Spring ( F i g u r e 4 ) . T h i s d i v i d e i s not f i x e d i n i t s l o c a t i o n
by r o c k s t r u c t u r e but r a t h e r can m i g r a t e n o r t h e a s t w a r d o r southwest-
ward i n r e s p o n s e t o changes i n r e c h a r g e , d i s c h a r g e , and groundwater
pumpage
Regional
Water
Table
Barriers to
Groundwater Flow
Groundwater Divide
Inclined Confining Beds
Artesian Aquifer
Figure 3. Geological cutaway showing possible entrance, disper-

sion pathways, and b a r r i e r s to groundwater flow near the plant
site.

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K a r s t a q u i f e r s downstream from T h o r n t o n S p r i n g and l o c a t e d near

H o u s e r v i l l e can be h i g h l y p r o d u c t i v e t o water w e l l s and a r e r e l i e d
upon f o r d o m e s t i c and farm water s u p p l i e s . Bathgate ( L ) and Thompson
S p r i n g s (M) ( F i g u r e 1) a l o n g S l a b Cabin Run and above the c o n f l u e n c e
o f S p r i n g Creek a r e used f o r p u b l i c water s u p p l i e s and Benner S p r i n g
(N) a l o n g S p r i n g Creek, f o r a s t a t e f i s h h a t c h e r y . Three t e s t w e l l s
d r i l l e d on t h e f l o o d p l a i n and v a l l e y s l o p e o f S p r i n g Creek n e a r
H o u s e r v i l l e penetrated c a v e r n o u s , c a r b o n a t e r o c k t h a t y i e l d e d more
than a 100 gpm i n one w e l l and i n e x c e s s o f 2500 gpm i n t h e two o t h e r
wells. These w e l l s were i n t e n t i o n a l l y l o c a t e d on f r a c t u r e - t r a c e
i n t e r s e c t i o n s as r e v e a l e d by a n a l y s i s o f a e r i a l p h o t o g r a p h y . Other
w e l l s a r e l e s s p r o d u c t i v e b u t , n e v e r t h e l e s s , an i m p o r t a n t aquifer
system has been shown t o e x i s t a l o n g S p r i n g Creek below T h o r n t o n
Spring.
The upland s u r f a c e d e v e l o p e d on k a r s t i f i e d r o c k s c o n t a i n s a
b l a n k e t o f r e s i d u a l s o i l d e r i v e d from t h e p r o l o n g e d c h e m i c a l weather
ing of s o l u b l e bedrock. I t v a r i e s i n t h i c k n e s s from l e s s than 1 t o
more than 100 f e e t near t h e p l a n t . I t i s h i g h l y v a r i a b l e having
formed from t h e d i f f e r e n t i a l s o l u t i o n a t t a c k on k a r s t r o c k s . Up t o
60 f e e t o f s o i l u n d e r l i e s t h e p l a n t s i t e l o c a l l y , b u t bedrock o u t
c r o p s a r e common a l o n g Route 26 j u s t beyond the p l a n t .
C o l l u v i u m a l s o makes up some o f t h e u n c o n s o l i d a t e d overburden

d e p o s i t s that o v e r l i e bedrock. These u n s o r t e d d e p o s i t s o f sand,
s i l t , c l a y , c o b b l e s , and b o u l d e r s were t r a n s p o r t e d down t h e s l o p e s o f
N i t t a n y Mountain under a f r e e z e - t h a w c l i m a t e . They v a r y i n t h i c k n e s s
from l e s s than 1 t o more than 60 f e e t where they were d e p o s i t e d
w i t h i n p r e - e x i s t i n g s i n k h o l e s near the base o f N i t t a n y M o u n t a i n .
P e r c h e d groundwater d e v e l o p s i n t h e s h a l l o w s o i l p r o f i l e o f
these s l o p i n g c o l l u v i a l d e p o s i t s which d i v e r t s s u r f a c e water and
s h a l l o w groundwater down t h e lower s l o p e s o f N i t t a n y Mountain out
over the r e g i o n a l water t a b l e ( F i g u r e 3 ) . Water may p e r c h above a
dense s h a l l o w soil h o r i z o n and near t h e c o l l u v i u m - r e s i d u a l soil
c o n t a c t where b o t h s o i l u n i t s a r e w e l l d e v e l o p e d .
S p r i n g Creek and i t s t r i b u t a r y , S l a b Cabin Creek, a r e perched

above t h e r e g i o n a l water t a b l e from Route 26 downstream towards
Houserville. Water l e v e l s i n w e l l J o f F i g u r e 1 d r i l l e d w i t h i n l e s s
than t e n f e e t o f S p r i n g Creek commonly s t a n d from 11 t o 13 f e e t below
the l e v e l o f t h e stream s u r f a c e as do water l e v e l s i n t e s t w e l l
l o c a t e d a l o n g i t s v a l l e y s l o p e o r w a l l ( F i g u r e s 1 and 5 ) . Both w e l l s
were cased i n t o bedrock and o b t a i n water from s o l u t i o n o p e n i n g s .
T e s t h o l e s d r i l l e d f o r t h e S t a t e C o l l e g e bypass a c r o s s t h e f l o o d
p l a i n o f S l a b C a b i n Creek j u s t upstream from i t s c o n f l u e n c e with
S p r i n g Creek show s o i l t h i c k n e s s e s r a n g i n g 5.5 t o 30 f e e t . These
r a t h e r p o o r l y permeable d e p o s i t s a r e composed o f s i l t , sand, c l a y ,
and g r a v e l . The water t a b l e ranged i n d e p t h from 3 t o more than 10
f e e t below l a n d s u r f a c e i n t e s t b o r i n g s l o c a t e d i n t h e f l o o d - p l a i n o f
Slab Cabin Creek i n d i c a t i n g t h a t water f l o w i s downward t h r o u g h
channel and f l o o d - p l a i n sediments i n t o the u n d e r l y i n g carbonate
aquifer (Figure 5 ) .
An e l e v e n f o o t deep t e s t p i t i n c h a n n e l sand and g r a v e l d e p o s i t s

w i t h i n 15 f e e t of the bank of S p r i n g Creek and n i n e f e e t below the
e l e v a t i o n of the stream s u r f a c e remained d r y u n t i l i t was b a c k f i l l e d
i n d i c a t i n g t h a t S p r i n g Creek i s perched a t t h i s l o c a t i o n ( p o i n t P,
F i g u r e 1) In the a r e a between the c o n f l u e n c e o f T h o r n t o n S p r i n g and
H o u s e r v i l l e , water l e v e l s measured i n p i e z o m e t e r s p l a c e d a t one f o o t
depths below S p r i n g Creek c h a n n e l a l s o showed t h a t s u r f a c e water f l o w
i s downward t h r o u g h f l o o d p l a i n d e p o s i t s .
A downward component of f l o w i s p r e s e n t d u r i n g p e r i o d s of h i g h
s e a s o n a l water t a b l e and when S p r i n g Creek and S l a b Cabin Run a r e i n
flood. D u r i n g p e r i o d s of f l o o d , s u r f a c e water comes i n t o c o n t a c t
with i s o l a t e d carbonate bedrock outcrops l o c a t e d a l o n g the v a l l e y
s l o p e s of these c r e e k s and p r o v i d e l o c a l pathways f o r c o n t a m i n a t e d
s u r f a c e waters t o e n t e r the k a r s t a q u i f e r . E l s e w h e r e , f l o o d waters
come i n c o n t a c t w i t h r e s i d u a l and t r a n s p o r t e d s o i l t h a t b l a n k e t s the
lower p o r t i o n of v a l l e y s l o p e s , hence, p r e v e n t i n g the d i r e c t e n t r y of

s u r f a c e water i n t o the l o c a l a q u i f e r .
T h i s p e r c h e d water system p r o v i d e s a p o t e n t i a l n a t u r a l pathway

for the m i g r a t i o n of c o n t a m i n a n t s i n t o the u n d e r l y i n g k a r s t a q u i f e r ,
but t h e s e c o n t a m i n a n t s f i r s t must t r a v e l t h r o u g h a v a r i a b l e t h i c k n e s s
of f l o o d - p l a i n s e d i m e n t s t h a t are r a t h e r p o o r l y p e r m e a b l e . No
swallow ( s i n k ) h o l e s have been r e c o g n i z e d a l o n g the c h a n n e l of S p r i n g
Creek between where T h o r n t o n S p r i n g j o i n s S p r i n g Creek and the v i c i n -
i t y of the d o w n v a l l e y water w e l l s t h a t c o n t a i n the marker compound.
Such o p e n i n g s , i f p r e s e n t , would p r o v i d e a d i r e c t c o n n e c t i o n between
the s u r f a c e - w a t e r and groundwater systems.
Man-made c o n n e c t i o n s between s u r f a c e and groundwater systems may

e x i s t a l o n g the f l o o d p l a i n of S p r i n g Creek where water w e l l s pene-
t r a t e f l o o d p l a i n sediments. The a n n u l a r space between d r i l l h o l e s
and w e l l c a s i n g s a r e not g r o u t e d i n t o b e d r o c k a t e v e r y home s i t e
a l o n g the v a l l e y and some s u r f a c e water may g a i n a c c e s s to bedrock
along these r o u t e s . Sewer mains c r o s s the f l o o d - p l a i n and c h a n n e l of
S p r i n g Creek a t s e v e r a l l o c a t i o n s below T h o r n t o n S p r i n g . The mains
and t h e i r l a t e r a l s are b u r i e d from 5 to more than 12 f e e t below l a n d
surface. These were p l a c e d i n t o t r e n c h e s t h a t were d r i l l e d and
b l a s t e d b e f o r e b e i n g e x c a v a t e d wherever b e d r o c k was p e n e t r a t e d and
b a c k f i l l e d w i t h permeable l i m e s t o n e a g g r e g a t e . Groundwater i s f r e e
to m i g r a t e a l o n g or t h r o u g h t h e s e g r a v e l e n v e l o p e s t h a t s u r r o u n d the
sewer mains p e r m i t t i n g movement i n t o the u n d e r l y i n g bedrock wherever
the r e g i o n a l water t a b l e i s below s u r f a c e water l e v e l s i n S p r i n g
Creek ( F i g u r e 6 ) . They may a l s o have a l l o w e d c o n t a m i n a t e d s u r f a c e
water t o e n t e r the u n d e r l y i n g k a r s t a q u i f e r .
P o s s i b l e D i s p e r s i o n Pathways of Land D i s p o s e d Wastes
T a b l e I I p r o v i d e s a l i s t o f the p o s s i b l e pathways i n which a l a n d

d i s p o s e d waste can be d i s p e r s e d and which a r e b e l i e v e d to be a v a i l a -
b l e a t the p l a n t s i t e .
Stream alluvium
I, jj Bedrock
F i g u r e 5. S p r i n g Creek p e r c h e d above t h e r e g i o n a l water t a b l e

near H o u s e r v i l l e as r e v e a l e d by water l e v e l s measured i n w e l l s
and p i e z o m e t e r s p l a c e d i n c h a n n e l bottom s e d i m e n t s .
F i g u r e 6. G e o l o g i c a l cutaway showing t h e u t i l i t y l i n e as a
c o n d u i t o f groundwater and p o s s i b l e i n c l u d e d c o n t a m i n a t i o n media.
Table I I . P o s s i b l e Pathways f o r Contaminant Dispersal
Pathway Marker Compound
S u r f a c e Water-Groundwater Flow (downward) known
Groundwater known
G r o u n d w a t e r - S u r f a c e Water Flow (upward) known
Surface Water known
S u r f a c e Runoff and S o i l Erosion known (1)

Buried U t i l i t y Lines suspected
Induced Groundwater Flow suspected
Sewage Sludge D i s p o s a l known (1)
Biota known (5)
Atmosphere uncertain
S u r f a c e Water t o Groundwater Flow. There a r e f o u r l o c a t i o n s i n the

s t u d y a r e a where a s u r f a c e water to groundwater f l o w of c o n t a m i n a n t s
c o u l d take p l a c e : (1) a t the b u r i a l s i t e where the wastes were
d i s p o s e d of w i t h i n s o i l , (2) a t v a r i o u s p l a c e s under the c h a n n e l and
f l o o d p l a i n o f S p r i n g Creek where i t i s perched above the r e g i o n a l
water t a b l e , (3) where s t o r m r u n o f f o c c u r r e d a t the p l a n t s i t e and
e n t e r e d a d r a i n a g e d i t c h a l o n g Route 26, and (4) where sewage s l u d g e
from the U n i v e r s i t y A r e a J o i n t A u t h o r i t y was d i s p o s e d of on a g r i c u l -
t u r a l l a n d s near H o u s e r v i l l e .
The s u r f a c e to groundwater pathway i s p r o b a b l y the most impor-

t a n t way i n which c o n t a m i n a n t s were i n i t i a l l y d i s p e r s e d i n t o the
l o c a l e n v i r o n m e n t . Groundwater was c o n t a m i n a t e d a t the p l a n t s i t e by
i n f i l t r a t i n g s u r f a c e water and p l a n t e f f l u e n t s , i n f i l t r a t i o n t h r o u g h
s o i l d e p o s i t s and u n s a t u r a t e d b e d r o c k , and r e c h a r g e to the water
table.
T h o r n t o n S p r i n g , which i s downgradient from the p l a n t , i s

c o n t a m i n a t e d as a r e waters o b t a i n e d i n i n t e r c e p t o r w e l l s d r i l l e d on
s i t e as p a r t o f an ongoing c l e a n u p program. The waters pumped from
the i n t e r c e p t o r w e l l s a r e t r e a t e d as p a r t of c l e a n u p o p e r a t i o n s ( 6 ) .
No t e s t i n g was done as p a r t of t h i s i n v e s t i g a t i o n of i n t e r c e p t o r
and m o n i t o r i n g w e l l s d r i l l e d o n - s i t e but a number o f t e s t s were made
on T h o r n t o n S p r i n g water samples 0.9 km below the p l a n t .
13. KURTZ AND PARIZEK Complexity of Contaminant Dispersal 269
Downvalley from T h o r n t o n S p r i n g , measurable concentrations of

the marker compound were found i n v a r i o u s w a t e r - s u p p l y w e l l s l o c a t e d
i m m e d i a t e l y a d j a c e n t t o S p r i n g Creek. I t i s concluded that s u r f a c e
water was the major s o u r c e and pathway o f t h e s e o r g a n i c s u b s t a n c e s
b e f o r e r e e n t e r i n g groundwater d o w n v a l l e y because o f t h e c h e m i c a l d a t a
c o l l e c t e d , t h e perched n a t u r e o f S p r i n g Creek, and t h e p r e s e n c e o f
c o n t a m i n a t e d f i s h and p l a n t s i n t h e Creek. I t i s n o t known, however,
i f t h e s e contaminants e n t e r e d t h e c a r b o n a t e a q u i f e r near H o u s e r v i l l e
t h r o u g h streambed and f l o o d p l a i n i n f i l t r a t i o n , l e a k a g e a l o n g w e l l
c a s i n g s , l e a k a g e t h r o u g h g r a v e l b a c k f i l l d e p o s i t s p l a c e d a l o n g sewer
mains, i n f i l t r a t i o n i n t o o u t c r o p s a l o n g t h e v a l l e y s l o p e o f S p r i n g
Creek, l e a c h i n g o f sewage s l u d g e d i s p o s e d o f on a d j a c e n t u p l a n d s ,
and/or w i t h i n groundwater t h a t may have m i g r a t e d beneath S p r i n g Creek
v a l l e y from the v i c i n i t y o f T h o r n t o n S p r i n g . A c o m b i n a t i o n of t h e s e
pathways most l i k e l y was i n v o l v e d .
A l t h o u g h i t has been shown t h a t s u r f a c e water f l o w s downward

t h r o u g h t h e f l o o d p l a i n o f S p r i n g Creek, f i n d i n g a c h e m i c a l example
of t h i s i n t e r a c t i o n i n a stream bed f o r t h e marker compound r e q u i r e s
e x t r e m e l y c a r e f u l work which has n o t y e t been completed.
Groundwater D i s p e r s a l . Once a contaminant has found i t s way i n t o

groundwater i n a k a r s t a q u i f e r system, i t i s d i f f i c u l t t o p r e d i c t i t s
e x a c t movement. I t depends upon t h e i n t e r c o n n e c t i o n o f openings
a f f o r d e d by j o i n t s , f r a c t u r e s , b e d d i n g - p l a n e p a r t i n g s , f a u l t p l a n e s ,
and r o c k l a y e r s w i t h i n t e r g r a n u l a r , p r i m a r y and s e c o n d a r y o p e n i n g s .
Any o r a l l o f t h e s e p l a n a r and i n t e r g r a n u l a r openings may be e n l a r g e d
to p r o v i d e an i n t e r c o n n e c t e d network o f s o l u t i o n v o i d s and c o n d u i t s .
These may be d e v e l o p e d as a maze o f s m a l l openings o r be c o n c e n t r a t e d
as a few d i s t i n c t l a r g e o p e n i n g s .
Contaminants may m i g r a t e w i t h i n s a t u r a t e d r e s i d u a l o r t r a n s -
p o r t e d s o i l s , w i t h i n s o i l macropores, o r w i t h i n s m a l l i n t e r c o n n e c t e d
pores where t h e y f i n d t h e i r way i n t o groundwater. In e i t h e r case
contaminant d i s p e r s a l w i l l be l i m i t e d t o d i s t i n c t groundwater s u b -
b a s i n s d e f i n e d by f i x e d o r t r a n s i e n t groundwater d i v i d e s , by t h e
h y d r a u l i c - h e a d d i s t r i b u t i o n w i t h i n t h e f l o w system, and by g e o l o g i c a l
b a r r i e r s which r e s t r i c t f l o w such as the p r e s e n c e o f p o o r l y permeable
s o i l o r bedrock u n i t s .
The r e g i o n a l water t a b l e shown i n F i g u r e 4 p r o v i d e s some i n s i g h t

i n t o t h e pathways a v a i l a b l e f o r s u b s u r f a c e f l o w . One groundwater
d i v i d e e x i s t s near t h e t o p o f N i t t a n y Mountain and a n o t h e r a l o n g t h e
groundwater r i d g e t h a t runs p a r a l l e l t o and n o r t h o f Route 26. These
d i v i d e s p r e c l u d e s h a l l o w groundwater f l o w from the p l a n t s i t e t o any
d i r e c t i o n e x c e p t downward, and t o t h e n o r t h e a s t toward s p r i n g s a t t h e
head o f Logan Branch o r southwest toward T h o r n t o n S p r i n g ( p o i n t B,
F i g u r e 1 ) . The s h o r t t r a n s i e n t d i v i d e s e p a r a t i n g t h e s e two ground-
water s u b b a s i n s ( T h o r n t o n S p r i n g and Logan Branch systems) i s l o c a t e d
near t h e Route 26-150 i n t e r s e c t i o n ( p o i n t A, F i g u r e 4 ) . To d a t e , no
marker compound i s known t o have been r e c o v e r e d from w e l l s n o r t h e a s t
o f t h i s d i v i d e , o n l y i n t h e T h o r n t o n S p r i n g s u b b a s i n and w e l l s
l o c a t e d down v a l l e y near H o u s e r v i l l e .
The marker compound was d e t e c t e d i n an u p l a n d w e l l l o c a t e d n o r t h

of t h e p l a n t and a c r o s s t h e w e s t e r n groundwater d i v i d e o f t h i s s u b -
basin. The s t a t i c water l e v e l i n t h i s w e l l s t a n d s above t h e e l e v a -
t i o n o f S p r i n g Creek and water l e v e l s near t h e p l a n t . It is unlikely
t h a t c o n t a m i n a t e d groundwater c r o s s e d beneath t h i s groundwater d i v i d e
t h r o u g h u p t u r n e d , somewhat p o o r l y permeable beds o f d o l o m i t e and t h e
t h i n , a r t e s i a n sandstone a q u i f e r .
The l a r g e s t amount o f i n i t i a l d i s p e r s a l had t o have been from

the p l a n t s i t e down groundwater g r a d i e n t t o T h o r n t o n S p r i n g ( p o i n t B,
Figure 1). T h i s s p r i n g , l o c a t e d 0.90 km down g r a d i e n t from t h e
b u r i a l s i t e , i s the most prominent l o c a t i o n o f r e s i d u e s o f the marker
compound i n t h e a r e a . I n 1977 c o n c e n t r a t i o n s o f i t ranged from
2000-4000 ng/L ( p p t ) (7 samples) and i n 1978 they were 3000 ppt (2
samples) 3 ) Measurements were made a t t h i s s i t e i n June o f 1983 as
p a r t o f t h e p r e s e n t i n v e s t i g a t i o n , f u l l y 20 y e a r s a f t e r waste b u r i a l ,
and t h e water was found i n a s i n g l e measurement t o c o n t a i n 6400 p p t

at that time.
One w e l l n e a r H o u s e r v i l l e d r i l l e d and c a s e d t o a d e p t h o f 200

f e e t i n August o f 1981 c o n t a i n e d 22 p p t o f marker compound ( a n a l y -
t i c a l l y confirmed). The c o n t i n u e d p r e s e n c e o f t h e compound i n t h i s
w e l l was n o t c o n f i r m e d w i t h a d d i t i o n a l s a m p l i n g .
O t h e r downstream a r e a s , however, have a l s o shown d i s p e r s a l o f

the marker compound w i t h i n t h e k a r s t a q u i f e r . C o n c e n t r a t i o n s have
been f o u n d i n numerous d o m e s t i c w e l l - w a t e r s u p p l i e s i n t e s t i n g
programs o f 1977/78 U_) and i n J a n u a r y o f 1985 i n t h e r e g i o n o f lower
t o p o g r a p h i c and water t a b l e e l e v a t i o n l o c a t e d about 4.0 t o 4 . 9 km
downstream o f t h e d i s p o s a l s i t e ( a s measured a l o n g S p r i n g Creek
drainage). F i g u r e 7 shows t h e c o n c e n t r a t i o n s o f t h e marker compound
found i n t h e s e home s u p p l i e s . A l l homes a r e l o c a t e d a d j a c e n t t o t h e
stream e x c e p t Number G-G which i s l o c a t e d 0.5 km u p g r a d i e n t from t h e
stream.
The c h e m i c a l d a t a show, f i r s t , t h a t t h e l e v e l s found i n 1984

g e n e r a l l y were comparable t o those found i n 1977-78 by t h e P e n n s y l -
v a n i a Department o f E n v i r o n m e n t a l Resources (1) The 1985 sampling
found more f o r Houses G-B and G-C b u t l e s s f o r Houses G-D and G-G.
T h i s i n d i c a t e s t h e l o n g term p e r s i s t e n c e o f the marker compound. The
d i f f e r e n c e s i n d i c a t e p o s s i b l e c h a n g i n g f l o w p a t t e r n s i n t h e ground-
water s y s t e m . The h i g h v a l u e f o r House G-C may i n d i c a t e changes i n
the h y d r a u l i c head o f t h e l o c a l groundwater s u p p l i e s o f t h e a r e a .
Heavy pumping o f groundwater s u p p l i e s f o r t h e U n i v e r s i t y community,
and l e s s e r amounts f o r f a r m s , and homes nearby may have caused t h e s e
c h a n g i n g p a t t e r n s i n groundwater movement. T h i s , i n t u r n , may have
a l s o d i v e r t e d away a l l o f t h e c o n t a m i n a t e d water as shown f o r House
G-G. A l t e r n a t e l y , i t may have been t h e r e s u l t o f l o n g term n a t u r a l
f l o w o f groundwater which has h e l p e d t o l o c a l l y f l u s h t h e a q u i f e r o f
the marker compound.
The c o m p l e x i t y o f t h e groundwater f l o w system i s a l s o seen by

comparing the p r i v a t e w e l l a n a l y s e s w i t h the p r i v a t e w e l l p r o f i l e s o f
Figure 8. T h i s f i g u r e shows t h e b e s t e s t i m a t e o f t h e d e p t h o f each
well with respect to land-surface elevation. The marker compound
G-A G-B G-C G-D G-E GF G-G

HOUSE
F i g u r e 7. C o n c e n t r a t i o n s o f t h e marker compound found i n home

water s u p p l i e s l o c a t e d a l o n g S p r i n g Creek f o r two d i f f e r e n t
s a m p l i n g t i m e s , 1977/78 i n open g r a p h and 1984 i n darkened g r a p h .
NR i s n o t r e p o r t e d ; ND i s n o t d e t e c t e d .
1000
LAND
STREAM
900
LAND I GA G-B G-C G-D G-E G-G

ELEVATION HOUSE LOCATION
ft.
F i g u r e 8. H e i g h t - o f - l a n d p r o f i l e of d o m e s t i c water s u p p l i e s
c o n t a i n i n g t h e marker compound showing r e l a t i v e depths o f w e l l s
below t h e s t r e a m bed o f S p r i n g Creek. The house l o c a t i o n a x i s i s
to s c a l e .
v a l u e s of 1984 showed l a r g e d i f f e r e n c e s i n c o n c e n t r a t i o n f o r house

w e l l s G-B and G-C even though they a r e i n c l o s e p r o x i m i t y and d r i l l e d
to a s i m i l a r d e p t h . In c o n t r a s t , house w e l l s G-B, G-E, and G-F con-
t a i n e d s i m i l a r c o n c e n t r a t i o n s of the marker compound but were d r i l l e d
to d i f f e r e n t depths. These c o n c l u s i o n s a r e o n l y t e n t a t i v e s i n c e the
w e l l depths a r e e s t i m a t e d and the c a s i n g depths a r e not known.
T h e t i m e f r a m e f o r c o m p a r i n g movement o f s u r f a c e w a t e r and
groundwater can be i l l u s t r a t e d i n the f o l l o w i n g example. During a
heavy r a i n f a l l i n F e b r u a r y o f 1985, samples were made of s u r f a c e
water c o n c e n t r a t i o n s a t p o i n t H and groundwater pumped from the w e l l s
i n the two homes l o c a t e d n e a r e s t to t h a t p o i n t , G-B and G-C ( F i g . 1 ) .
The t o t a l d i s t a n c e between these homes was o n l y 0.3 km a l o n g the
stream. F i g u r e 9 shows v i a l s of e x t r a c t e d water samples t a k e n a t
these t h r e e l o c a t i o n s and p l a c e d i n g r a p h form w i t h r e s p e c t to t i m e .
The sample of the s u r f a c e s t r e a m e x t r a c t i o n h a v i n g the d a r k e s t c o l o r ,
p r o b a b l y a r e s u l t of n a t u r a l l y o c c u r r i n g components, o c c u r r e d a t z e r o
hours. The d a r k e s t c o l o r o f the house G-B groundwater f l o w system
samples was found a t a d e l a y of 24 hours from the d a r k e s t c o l o r o f
the s u r f a c e samples. I t was a l s o n o t i c e d t h a t the w e l l water of
House G-C had no c o l o r to any of the v i a l s d e s p i t e i t s c l o s e l a t e r a l
and v e r t i c a l p r o x i m i t y .
C o n c e n t r a t i o n s of the marker compound ( F i g u r e 10) found d u r i n g

the h i g h water t a b l e c o n d i t i o n s f o r these t h r e e s i t e s d i s c u s s e d above
d i d not appear t o c o r r e l a t e w i t h e x t r a c t c o l o r . The marker compound
a n a l y t i c a l d a t a , however, c o n t a i n u n c e r t a i n t y due to apparent chroma-
tographic a r t i f a c t s . The p r e s e n c e o f c o l o r e d compounds i n t h e
e x t r a c t a n t , however, does p r o v i d e an independent assessment of the
p o s s i b l e i n t e r c o n n e c t i o n between s u r f a c e water and groundwater i n
this locale. The f a c t t h a t the c o l o r p a t t e r n s of the two houses
compared were d i f f e r e n t a l s o d e m o n s t r a t e s p o t e n t i a l l y d i f f e r e n t p a t h -
ways of f l o w t h a t a r e r e a c h i n g these two houses d e s p i t e the c l o s e
p r o x i m i t y of t h e i r w e l l s .
Groundwater t o S u r f a c e Water Flow. The p o s s i b i l i t y of b r i n g i n g xeno-

b i o t i c compounds t o the s u r f a c e from c o n t a m i n a t e d groundwater s o u r c e s
i s o b v i o u s t h r o u g h the mode of a s p r i n g , such as T h o r n t o n S p r i n g . It
i s not so o b v i o u s t h a t t h i s mode happens w i t h i n S p r i n g Creek immedi-
a t e l y below T h o r n t o n S p r i n g . D i r e c t exchange upward of groundwater
to the S p r i n g Creek c h a n n e l i s p r e c l u d e d wherever and whenever the
r e g i o n a l water t a b l e stands below stream l e v e l . Since t h i s hydro-
l o g i c a l c o n d i t i o n has p e r s i s t e d i n t h e f l o o d p l a i n r e g i o n n e a r
f
H o u s e r v i l l e a t l e a s t s i n c e the mid-1960 s when the f i r s t t e s t w e l l
was d r i l l e d t h e r e , no groundwater upward f l o w i s s u s p e c t e d i n t h i s
region.
O t h e r s p r i n g s i n the a r e a , a s i d e from T h o r n t o n S p r i n g , c o u l d
b r i n g groundwater to the s u r f a c e . A s p r i n g a t l o c a t i o n I i n F i g u r e 1
was t e s t e d i n A p r i l of 1985 f o r the marker compound but none was
d e t e c t e d a t the 1 ppt l e v e l .
Surface Water. The spreading of e n v i r o n m e n t a l contaminants v i a

s u r f a c e w a t e r i s p r o b a b l y t h e most o b v i o u s d i s p e r s i o n p a t h w a y .
Conclusions based on s t r e a m water s a m p l i n g must be c a r e f u l l y done
K U R T Z A N D PARIZEK Complexity of Contaminant Dispersal
F i g u r e 9. Photograph o f v i a l s c o n t a i n i n g water e x t r a c t i o n p r o -
d u c t s from stream and home s u p p l i e s as a f u n c t i o n o f time d u r i n g
f l o o d water stream c o n d i t i o n s .
401
201
<
ce
LU

24 48
HOURS
40
20
<
QC

LU

0 24 48
HOURS
Figure 10(a,b). The marker compound found i n water from f l o o d e d S p r i n g

Creek and two s e l e c t e d homes nearby: stream a n a l y s i s (a) a t p o i n t
i n F i g u r e 1, and home water a n a l y s i s (b) i n House G-B.
40
20 I
-
<
oc
I-
z
UJ

24 48
HOURS
Figure 10(c). The marker compound found i n water from f l o o d e d Spring

Creek a t House G-C.
s i n c e a t any p o i n t t h e r e may be a d d i t i o n s to o r s u b t r a c t i o n s from the

water f l o w . These exchanges can be from groundwater or s u r f a c e water
s u p p l i e s f o r water uses t o meet i n d u s t r i a l o r d o m e s t i c needs.
The marker compound was found i n s u r f a c e waters from the con-

f l u e n c e of T h o r n t o n S p r i n g t o a p o i n t some 30 km downstream i n June
of 1983 ( F i g u r e 11). Stream volumes were measured f o r t h i s e n t i r e
l e n g t h and the d a t a c o r r e l a t e d f a i r l y w e l l where w i t h l a r g e r down-
stream water volumes a t lower stream l o c a t i o n s t h e r e was o b t a i n e d the
e x p e c t e d lower c o n c e n t r a t i o n s .
To d e t e r m i n e the s a m p l i n g a c c u r a c y i n a stream c o n t a i n i n g s m a l l
contaminant i n f l u x from one bank, stream c r o s s - s e c t i o n a l sampling was
done i n June of 1984 a t v a r i o u s i n t e r v a l s below the c o n f l u e n c e . The
d a t a p r e s e n t e d i n T a b l e I I I show t h a t a t 60 meters downstream the
range of the c o n c e n t r a t i o n s of the marker compound was wide and the
v a r i a n c e of t h i s group of p o i n t s was l a r g e . At b o t h 200 and 1000 m

the d a t a a r e s i m i l a r w i t h a s m a l l v a r i a n c e i n d i c a t i n g complete m i x i n g
at 200 m e t e r s . Hence, f o r the t o t a l watershed s t u d y the stream
a n a l y s e s a r e r e p r e s e n t a t i v e of the whole stream body.
T a b l e I I I . C r o s s S e c t i o n Stream A n a l y s i s
f o r the Marker Compound, S p r i n g Creek, 1984
Distance Marker Compound Variance

Below Cross S e c t i o n Analyses
Confluence _
m ppt
60 145 40 11 4 0.1 3700
200 45 44 45 44 42 2.0
1000 loss 34 43 36 39 15
46 43 42 43 43 2.4
Stream w i d t h d i v i d e d i n t o 5 e q u a l segments.
S u r f a c e Runoff and S o i l E r o s i o n . Surface runoff i s overland flow

i m m e d i a t e l y f o l l o w i n g p e r i o d s of snow melt and r a i n f a l l . I t i s the
main p r o c e s s by which c o n t a m i n a t e d sediment i s eroded and t r a n s p o r t e d
from u p l a n d s e t t i n g s . L i q u i d s , a p p l i e d t o the l a n d or r e l e a s e d to
perched groundwater t h a t i s d i s c h a r g e d back to the s u r f a c e , and con-
t a m i n a t e d s o i l s may be t r a n s p o r t e d i n t o s u r f a c e streams i n t h i s
manner.
S h o r t l y a f t e r the p l a n t l a n d f i l l wastes were found t o be con-

t a m i n a t i n g o t h e r a r e a s , m i r e x , one of the p r o d u c t s manufactured a t
t h i s site> was found i n a d r a i n a g e d i t c h a l o n g Route 26 j u s t 0.18 km
1983-84
HIGH
LOW
f /
4 " 22 32
STREAM DISTANCE, kr
F i g u r e 11. S u r f a c e - w a t e r measurements of marker compound concen-

t r a t i o n s a t v a r i o u s d i s t a n c e s a l o n g S p r i n g Creek showing the
range of c o n c e n t r a t i o n s i n shaded t o n e .
away to the n o r t h w e s t . The m a t e r i a l most l i k e l y was d i s p e r s e d t h e r e

t h r o u g h the o v e r l a n d r o u t e . The d r a i n a g e d i t c h r a r e l y has f l o w i n g
water i n i t except d u r i n g p e r i o d s of r a i n f a l l or snowmelt. In l a t e r
t e s t s i t was found t h a t c o n c e n t r a t i o n s of m i r e x i n f i s h i n S p r i n g
Creek, i n t o which the d r a i n a g e d i t c h d i s c h a r g e s j u s t below T h o r n t o n
S p r i n g , were l e s s a f t e r the s u r f a c e s o i l was dug out and removed (I)
I t i s u n c e r t a i n i f t h e r e was a causal r e l a t i o n s h i p i n this case,
however
P l a n t e f f l u e n t s a p p l i e d to s u r f a c e farm l a n d l a t e i n the mid or

1
l a t e I960 s d i d run o f f from the s p r a y f i e l d . T e r r a c e s were l a t e r
b u i l t to c o n t a i n t h i s r u n o f f , but some sediment and e f f l u e n t s i n e v i -
t a b l y escaped from the s i t e . I t i s not known i f t h i s s u r f a c e r u n o f f
c o n t a i n s the marker compound.
U t i l i t y Lines. Sewer l i n e s a r e p r e s e n t a l o n g Route 26 near the p l a n t

and, as w e l l , a l o n g and i n S p r i n g Creek below T h o r n t o n S p r i n g . One

sewage l i n e f o l l o w s the stream f o r 6.0 km b e f o r e i t heads to a sewage
treatment p l a n t . Because of the d e p t h of c o n s t r u c t i o n of the mains,
t h i s pathway c o u l d v e r y w e l l be the main s o u r c e of f l o w i n t o the
p r i v a t e home w e l l s u p p l i e s a l o n g the s t r e a m . With manholes e v e r y 100
m t h e r e are numerous p o t e n t i a l s u r f a c e e n t r y p o i n t s of c o n t a c t . If
t h i s d i s p e r s a l method i s proven to be a v i a b l e one, then t h e r e i s a
good p r o b a b i l i t y t h a t c o n t a m i n a n t s would be t r a n s p o r t e d t h r o u g h the
sewer mains t o the t r e a t m e n t p l a n t and become i n c o r p o r a t e d i n the
sewage sludge. The Pennsylvania Department of Environmental
Resources has r e p o r t e d Q ) t h a t the s l u d g e d e r i v e d from the U n i v e r -
s i t y A r e a J o i n t A u t h o r i t y Sewage T r e a t m e n t P l a n t l o c a t e d b e l o w
H o u s e r v i l l e c o n t a i n e d the marker compound. The manner i n which t h i s
s l u d g e was contaminated has not been f u r t h e r e s t a b l i s h e d .
Induced Groundwater Flow. Groundwater can be i n d u c e d to f l o w from a

nearby stream wherever water l e v e l s i n the w e l l a r e drawn down below
stream l e v e l and the groundwater g r a d i e n t s l o p e s from the stream t o
the w e l l . Drawdown i s i l l u s t r a t e d by the f a c t t h a t i n the e a r l y
I960's heavy pumping from w e l l s completed by Penn S t a t e U n i v e r s i t y
moved a g i v e n water t a b l e e l e v a t i o n c o n t o u r outward from the w e l l
f i e l d almost 2 km over a two-year span. T h i s has r e s u l t e d i n a
pumping cone of d e p r e s s i o n i n the B i g Hollow a r e a . However, t h i s
w e l l f i e l d i s i s o l a t e d from the H o u s e r v i l l e a r e a by a groundwater
divide.
The a c t u a l waste b u r i a l s i t e f o r these marker compound r e s i d u e s

was l o c a t e d o n l y 0.35 km away from a n o t h e r t r a n s i e n t water t a b l e
d i v i d e ( p o i n t A, F i g u r e 4 ) . Heavy pumping from an i n d u s t r i a l s o u r c e
l o c a t e d a l o n g Route 26 to the n o r t h e a s t and on the o t h e r s i d e of the
d i v i d e c o u l d have e a s i l y s h i f t e d groundwater f l o w from southwest to
n o r t h e a s t a l o n g Route 26 ( F i g u r e 4 ) . In t h a t case b o t h ends of t h i s
groundwater f l o w system c o u l d have been a f f e c t e d by the marker com-
pound, i . e . , T h o r n t o n S p r i n g s i d e and Logan Branch s i d e .
D o m e s t i c w e l l s a l o n g S p r i n g Creek a l s o can i n d u c e streambed

i n f i l t r a t i o n f o r the same r e a s o n . Induced f l o w may be a s i g n i f i c a n t
pathway f o r f u r t h e r groundwater d i s p e r s a l i n the f u t u r e as more
groundwater i s pumped from e x i s t i n g well fields, or new well fields

a r e completed i n the r e g i o n .
Sewage Sludge D i s p o s a l . I f a c h e m i c a l l y p e r s i s t e n t contaminant works

i t s way i n t o a sewage l i n e and ends up i n the t r e a t m e n t p l a n t , an
a d d i t i o n a l mode o f d i s p e r s i o n w i l l become a v a i l a b l e : s l u d g e d i s p o s a l .
In many a r e a s the s l u d g e i s of such n u t r i e n t v a l u e t h a t i t i s s p r e a d
on farm f i e l d s f o r f e r t i l i z e r . A l t h o u g h t h e r e i s p r o b a b l y l e s s use
of s l u d g e as f e r t i l i z e r due t o the p r e s e n c e of h a r m f u l l e v e l s of
t o x i c m e t a l s , such as cadmium (7), and o r g a n i c s , such as PCB's (_7),
p r e s s u r e has been e x e r t e d by b o t h the sewer a u t h o r i t y and i n d i v i d u a l
farmers to r e c y c l e t h i s n u t r i t i v e waste. N o n e t h e l e s s , the marker
compound h a s b e e n f o u n d i n s l u d g e (_1 ) . Once on t h e f i e l d s t h e
m a t e r i a l s i n the s l u d g e can be d i s p e r s e d i n t o p l a n t s grown t h e r e , i t
can p e r c o l a t e back i n t o the groundwater, o r i t can be t r a n s p o r t e d as
o v e r l a n d f l o w d u r i n g p e r i o d s of storm f l o w , t h i s t i m e , perhaps, a t
some d i s t a n c e away from the o r i g i n a l s o u r c e s . T h i s water may e n t e r

streams o r s i n k h o l e s d u r i n g p e r i o d s of e x c e s s i v e r u n o f f . The l e a c h a t e
from t h i s s l u d g e c o u l d r e a c h home w e l l s u p p l i e s u p g r a d i e n t from the
c h e m i c a l o r sewage treatment p l a n t , or r e g i o n s w i t h known s u r f a c e o r
groundwater c o n t a m i n a t i o n . T h i s mechanism may account f o r the marker
compound found i n w e l l G-G.
Biota. B i o t a a r e a n o t h e r means of d i s p e r s a l of contaminants i n the

environment. When the m a t e r i a l i s b i o m a g n i f i e d , such as the case
f
w i t h m i r e x , DDT, and P C B s and to a l e s s e r e x t e n t w i t h more p o l a r
compounds, b o t a n i c a l and z o o l o g i c a l l i f e can be a f f e c t e d and, as
w e l l , s e r v e as a mode of d i s p e r s a l . Chemical r e s i d u e s from the
p r o d u c t i o n p l a n t have been found i n f i s h i n S p r i n g Creek r e s u l t i n g i n
a warning by PA DER t o a v o i d e a t i n g the f i s h .
A t m o s p h e r i c Route. To complete the d i s p e r s i o n system one cannot

l e a v e o u t t h e mode o f s p r e a d i n g v i a t h e a t m o s p h e r e . Volatile
materials can evaporate from land and water sources into the
atmosphere. The same i s t r u e about compounds t h a t a r e adsorbed o r
absorbed i n t o d u s t t h a t i s c a r r i e d i n t o the atmosphere by the wind o r
r e l e a s e d from s t a c k s . No d a t a e x i s t s f o r t h i s p o t e n t i a l pathway a t
the p l a n t .
Summary and C o n c l u s i o n s
From the range of t h i s s t u d y we c o n c l u d e t h a t the d i s p e r s a l of waste

c h e m i c a l c o n t a m i n a n t s , throughout a p o r t i o n of the k a r s t or c a r b o n a t e
r o c k a q u i f e r system i n N i t t a n y V a l l e y , has proceeded i n the f o l l o w i n g
manner: 1. At the d i s p o s a l s i t e c o n d u i t openings i n the l i m e s t o n e
p e r m i t t e d major e n t r a n c e t o the groundwater system. 2. The dense
c o l l u v i u m and r e s i d u a l s o i l perched the water system i n the d i s p o s a l
s i t e a r e a and c o n t r i b u t e d to o v e r l a n d f l o w i n times of h i g h w a t e r .
This resulted i n s m a l l amounts of contaminated sediment being
d e p o s i t e d i n d i t c h a r e a s down g r a d i e n t from the d i s p o s a l s i t e and,
p o s s i b l y , t r a n s p o r t of contaminants to the r e c e i v i n g stream, S p r i n g
Creek. 3. The groundwater mound a d j a c e n t t o the s h a l l o w v a l l e y of
the p l a n t j u s t t o the n o r t h e a s t p r o v i d e d a d i r e c t i o n a l b a r r i e r t o
flow i n that d i r e c t i o n . 4. The l e s s s o l u b l e d o l o m i t e r i d g e w i t h
accompanying groundwater mound p r e s s u r e d by a deep, c o n f i n e d a q u i f e r
s e r v e s as a d i r e c t i o n a l b a r r i e r to the n o r t h w e s t . 5. C h e m i c a l r e s i -
dues e n t e r i n g the groundwater r e g i o n s under the p l a n t r e e n t e r e d the
s u r f a c e water a t T h o r n t o n S p r i n g j u s t d o w n h i l l from the p l a n t and
have p e r s i s t e d t o the p r e s e n t . H i g h c o n c e n t r a t i o n s of the marker
compound, up t o 6400 p t , were found i n t h i s s p r i n g . The contaminant
e n t e r e d S p r i n g Creek a t t h i s p o i n t . 6. The p e r c h e d f l o w system of
S p r i n g Creek i n the a r e a below the c o n f l u e n c e w i t h T h o r n t o n S p r i n g
p r o v i d e s a n a t u r a l t r o u g h f o r water t o remain on the s u r f a c e . Only
s m a l l amounts of water, c o n t a i n i n g the marker compound c o u l d p e r c o -
l a t e t o the groundwater t h r o u g h t h i s l i m i t e d b a r r i e r . Concentrations
o f the marker compound were found a l l a l o n g t h i s stream i n d e c r e a s i n g
c o n c e n t r a t i o n s f r o m 145 t o 5 p p t f o r a d i s t a n c e o f 30 km. The
o c c a s i o n a l p r e s e n c e of r o c k o u t c r o p p i n g on the m a r g i n of the f l o o d
p l a i n i n s e g m e n t s o f S p r i n g C r e e k i n t h i s a r e a d o e s a l l o w some
downward f l o w o f s u r f a c e w a t e r and c o n t a m i n a n t s . 7. Man-made
connections between the s t r e a m bed and groundwater a r e a s below a r e
a l l o w e d v i a u t i l i t y sewer l i n e c o n s t r u c t i o n a l o n g the bed and f l o o d

p l a i n of S p r i n g C r e e k . M i n o r d i s p e r s i o n can o c c u r w i t h i n the sewer
l i n e t h r o u g h l e a k s i n the j o i n t s and manhole c o v e r s . 8. There a r e no
known swallow h o l e s i n the S p r i n g Creek bed between T h o r n t o n S p r i n g
and w e l l s c o n t a i n i n g the marker compound to a l l o w major downflow by
t h i s means.
Concentrations of the marker compound were found i n shallow

d o m e s t i c water s u p p l i e s up t o 22 ppt i n the r e g i o n of 4-4.8 km below
the T h o r n t o n S p r i n g c o n f l u e n c e . Major c o n t r i b u t i o n s to t h e s e con-
c e n t r a t i o n s c o u l d have o c c u r r e d t h r o u g h the u t i l i t y l i n e c o n s t r u c t i o n
or extensive groundwater f l o w emanating from under the Thornton
S p r i n g a r e a and f l o w i n g down v a l l e y below the f l o o d p l a i n of S p r i n g
Creek.
I n the s u b s u r f a c e system, however, t h e r e i s c o n c e r n about con-

c e n t r a t i o n s of contaminant compounds i n d r i n k i n g w a t e r . Both s h a l l o w
and deep w e l l s have been found t o c o n t a i n the marker compound i n t h i s
s y s t e m . More i n f o r m a t i o n i s needed to f u l l y a s s e s s the v a r i o u s a r e a s
of the a q u i f e r impacted t o d a t e and r a t e s of t r a n s f e r between them
especially because changes can occur in aquifer systems when
groundwater pumpage i n c r e a s e s . The t r a n s p o r t of r e s i d u a l s of these
s u b s t a n c e s i n f l o o d p l a i n and c h a n n e l bottom sediments must be b e t t e r
u n d e r s t o o d t o a s s e s s t h e n a t u r e o f t h e r e l e a s e i n t o g r o u n d and
s u r f a c e water i n the f u t u r e .
Acknowledgments
The a u t h o r s w i s h to e x t e n d t h e i r thanks f o r the c a r e f u l t e c h n i c a l

work done by two s t u d e n t s , C h r i s t o p h e r Zoky and R i c h a r d H o f f , who d i d
a l l of the a n a l y t i c a l work c i t e d i n t h i s p a p e r . T h i s paper i s
p u b l i s h e d as J o u r n a l S e r i e s p a p e r No. of the Pennsylvania
A g r i c u l t u r a l Experiment S t a t i o n .
References
1. Alters, D. personal communication, unpublished internal reports,

Department of Environmental Resources, Bureau of Water Quality
Management, Williamsport Regional Office, PA.
13. KURTZ A N D PARIZEK Complexity of Contaminant Dispersal 281
2. Kurtz, D. A. Anal. Chim. Acta 1983, 150, 105-114.

3. Parizek, R. R.; White, W. B. "Application of Quaternary and
Tertiary Geological Factors to Environmental Problems in Central
Pennsylvania. Guidebook of the 50th Annual Field Conference of
Pennsylvania Geologists: Central Pennsylvania Revisited";
Department of Environmental Resources, Bureau of Topographic and
Geological Survey, Harrisburg, PA, 1985.
Rauch, R. R.; White, W. B. Water Resources Res. J. 1970, 6,
1175-1192.
4. Parizek, R. R. In "Hydrogeology and Geochemistry of Folded and
Faulted Carbonate Rocks of the Central Appalachian Type and
Related Land Use Problems"; Parizek, R. R., White, W. ., and
Langmuir, D., Eds.; Mineral Conservation Series Circular 82,
Earth and Mineral Science Experiment Station, The Pennsylvania

State University, University Park, PA, 1971; pp. 9-65.
5. Hesser, R. "Contamination of Spring Creek and Foster Joseph
Sayers Lake," Environmental Contamination: Fish and Wildlife
Concensus; Meeting of PA Chapt. Wildlife Society and Central PA
Chapt. Am. Fisheries Society at The Penna. State Univ., Univ.
Park, PA, April 19, 1985.
6. Emrich, G. H., S. M. Martin, Inc., Valley Forge, PA, 1985,
personal communication.
7. Baker, D. E.; et al. "Criteria and Recommendations for Land
Application of Sludges in Northeastern Pennsylvania"; Penna.
Agric. Experiment Station, University Park, PA, 1985.
14
1,2-Dibromoethane (EDB) in Two Soil Profiles
D. W. Duncan and R. J. Oshima
California Department of Food and Agriculture, Environmental Hazards Assessment

Program, Sacramento, CA 95814
Soil properties and Ethylene Dibromide (EDB) concentra-

tions were measured at two locations with histories of
EDB applications. The objective was to explain the

presence of EDB residues in a well near one location and
the lack of residues in a well near the other location.
The soil profile was sampled at each location from the
surface to groundwater, and groundwater samples were
collected at the profile base. A combination of
statistical analyses (stepwise linear regression and
discriminant analyses) was applied to soil data to
interpret differences within each location. Maxm i um EDB
concentrations were found at location 1 between 0 and
0.98 meters and ranged from 0.3 to 12.5 ppb, correlating
with organic carbon. Location 1, composed of a silty
clay, contained a deeper band of EDB lying between 2.35
and 2.98 meters below the soil surface. Within the band,
EDB concentrations ranged from 0.2 to 0.6 ppb. The
presence of this deeper band was not correlated with any
measured variables, including organic carbon, and may
represent migrating EDB. The fumigant was found between
0 and 0.46 meters at location 2 and was correlated with
organic carbon. EDB was not found in deeper soil layers
of location 2, which was characterized as a more coarsely
textured soil than location 1. Depth to groundwater was
5.2 and 4.0 meters at locations 1 and 2 respectively, and
EDB was not detected in water sampled at the profile
bases.
In 1954, E t h y l e n e Dibromide (EDB) was i n t r o d u c e d as a p r o d u c t f o r t h e

p r e p l a n t treatment o f a g r i c u l t u r a l f i e l d s t o c o n t r o l nematodes and i t
i s s t i l l used worldwide. EDB i s a v o l a t i l e , h a l o g e n a t e d h y d r o c a r b o n
t h a t i s u s u a l l y marketed as a l i q u i d . The l i q u i d i s i n j e c t e d 15 t o
30 c e n t i m e t e r s beneath t h e s o i l s u r f a c e w i t h a t r a c t o r d r i v e n c h i s e l
t o o l where t h e v a p o r s permeate s o i l a i r spaces and k i l l t h e
0097-6156/ 86/ 0315-0282$06.00/ 0

14. D U N C A N A N D OSHIMA 1,2'Dibromoethane (EDB) in Two Soil Profiles 283
parasites. Amounts o f a p p l i e d a c t i v e i n g r e d i e n t range from 9 t o 73

k i l o g r a m s / h e c t a r e depending upon s o i l c h a r a c t e r i s t i c s and s e v e r i t y o f
the nematode problem. Because o f h i g h p r o d u c t c o s t , f u m i g a t i o n i s
c a r r i e d out on s o i l used t o grow c r o p s w i t h r e l a t i v e l y h i g h monetary
y i e l d s s u c h as t o b a c c o , v e g e t a b l e , v i n e y a r d and o r c h a r d c r o p s ()
D u r i n g 1983, EDB r e s i d u e s were i d e n t i f i e d i n w e l l water samples
c o l l e c t e d i n F l o r i d a , G e o r g i a , C a l i f o r n i a and South C a r o l i n a ( 2 ) .
I n a d d i t i o n , a s o i l c o r i n g s t u d y i n C a l i f o r n i a r e v e a l e d EDB r e s i d u e s
from t h e s o i l s u r f a c e t o a d e p t h of 12 meters ( 3 ) . As a r e s u l t o f
w a t e r m o n i t o r i n g and s o i l c o r i n g s t u d i e s , the Environmental
P r o t e c t i o n Agency (EPA) i s s u e d a s u s p e n s i o n o r d e r i n O c t o b e r , 1983 t o
d i s c o n t i n u e t h e use o f EDB as a p e s t i c i d e ( 2 ) .
As a r e g u l a t o r y agency, t h e C a l i f o r n i a Department o f Food and
A g r i c u l t u r e (CDFA) i s c o n c e r n e d w i t h c r e a t i n g a s t r a t e g y t o
s e l e c t i v e l y c o n t r o l t h e a p p l i c a t i o n o f p e s t i c i d e s used on s o i l t o
r e d u c e t h e p o t e n t i a l f o r groundwater c o n t a m i n a t i o n . Pesticides are
c u r r e n t l y r e g u l a t e d i n C a l i f o r n i a a t t h e county government l e v e l w i t h
a r e p o r t i n g system based on township, range and s e c t i o n c o o r d i n a t e s
(1 s e c t i o n = 1 square m i l e o r 2.59 square k i l o m e t e r s ) . A new
r e g u l a t o r y design should i n c o r p o r a t e r e s u l t s of l a b o r a t o r y , w e l l
s a m p l i n g , s o i l c o r i n g and computer m o d e l i n g s t u d i e s t o h e l p e s t i m a t e
the p o t e n t i a l f o r a p e s t i c i d e t o r e a c h groundwater w i t h i n a s e c t i o n .
A CDFA s t u d y i n p r o g r e s s (_4) i s s t a t i s t i c a l l y comparing w e l l sample
d a t a o f d i b r o m o c h l o r o p r o p a n e (DBCP) r e s i d u e s w i t h s o i l t y p e s .
P r e l i m i n a r y r e s u l t s i n d i c a t e a v e r y h i g h c o r r e l a t i o n between w e l l s
c o n t a i n i n g DBCP l e v e l s and h i g h l y permeable s o i l s . A l t h o u g h seeming
t o p o i n t out an o b v i o u s c o r r e l a t i o n , t h e d a t a a l l o w statistically
based p r e d i c t i o n s o f w e l l c o n t a m i n a t i o n as a r e s u l t o f a g r i c u l t u r a l
p e s t i c i d e use i n a r e a s as s m a l l as 1 s e c t i o n . T h i s use o f w e l l
s a m p l i n g d a t a , i n a d d i t i o n t o s o i l c o r i n g and v a r i a b l e s measured i n
the l a b o r a t o r y such as s o r p t i o n , s o l u b i l i t y i n water and v o l a t i l i t y
can s u p p o r t l o c a l p e s t i c i d e use d e c i s i o n s perhaps t o a r e s o l u t i o n o f
1 section.
S o i l core data can provide r e a l evidence of p e s t i c i d e s l e a c h i n g
t o groundwater. T h i s paper d e s c r i b e s a s o i l c o r i n g s t u d y d e s i g n e d t o
examine r e l a t i o n s h i p s between s o i l p r o p e r t i e s o f two a g r i c u l t u r a l
l o c a t i o n s and t h e p r e s e n c e o r absence o f EDB. Sampling l o c a t i o n s
were n e a r l y a m i l e a p a r t w i t h s i m i l a r s o i l s , EDB a p p l i c a t i o n
h i s t o r i e s , and a g r i c u l t u r a l p r a c t i c e s . One l o c a t i o n was n e a r a w e l l
where EDB r e s i d u e s had been f o u n d , and t h e o t h e r l o c a t i o n was n e a r a
w e l l where EDB r e s i d u e s were n o t f o u n d . S o i l c o r e s were taken a t
b o t h l o c a t i o n s from t h e s o i l s u r f a c e t o t h e p o i n t a t w h i c h
groundwater was f i r s t r e a c h e d . S o i l p r o p e r t i e s , s u c h as t e x t u r e ,
m o i s t u r e , o r g a n i c c a r b o n c o n t e n t , pH and e l e c t r i c a l c o n d u c t i v i t y were
measured. I n a d d i t i o n , c l a y t y p e s and r e l a t i v e amounts o f c l a y t y p e s
were measured. The s t u d y o b j e c t i v e was t o compare measured v a r i a b l e s
a t b o t h s i t e s and suggest an e x p l a n a t i o n f o r t h e p r e s e n c e o f EDB i n
w e l l w a t e r a t one l o c a t i o n and absence o f t h e c h e m i c a l i n w e l l water
at t h e o t h e r l o c a t i o n .
Materials and Methods
Sample S i t e D e s c r i p t i o n . Two s o i l c o r i n g s i t e s were s e l e c t e d i n t h e

w e s t e r n p o r t i o n o f S t a n i s l a u s County on t h e west s i d e o f t h e San
Joaquin V a l l e y , C a l i f o r n i a . S e l e c t i o n was based on w e l l sampling

s u r v e y r e s u l t s conducted d u r i n g the summer of 1983 ( 5 ) . Both s o i l
c o r i n g l o c a t i o n s c o n s i s t e d o f a g r i c u l t u r a l f i e l d s as c l o s e as
p o s s i b l e t o one of the p r e v i o u s l y sampled w e l l s . L o c a t i o n 1 was 62.0
meters from a d o m e s t i c w e l l 42.7 meters deep where EDB r e s i d u e s were
d e t e c t e d . The w e l l had a s a n i t a r y s e a l 6.0 meters deep and was
p e r f o r a t e d between 31.4 and 37.5 m e t e r s . L o c a t i o n 2 was 111 meters
from a d o m e s t i c w e l l 36.6 meters deep where EDB r e s i d u e s were not
detected. T h i s w e l l a l s o had a s a n i t a r y s e a l 6.0 meters deep and was
p e r f o r a t e d from 31.0 t o 34.0 m e t e r s .
F o r more than 10 y e a r s , EDB was a p p l i e d a t l o c a t i o n 1 i n 3 out of
e v e r y 4 y e a r s a t a r a t e of 2 t o 3 l i t e r s / h e c t a r e . EDB a t l o c a t i o n 2,
about 1 m i l e from l o c a t i o n 1, was a l s o a p p l i e d a t a r a t e of 2 t o 3
l i t e r s / h e c t a r e f o r o v e r 10 y e a r s i n 3 out of e v e r y 4 y e a r s . A
f o r m u l a t i o n of 86% a c t i v e i n g r e d i e n t was used most r e c e n t l y a t b o t h
l o c a t i o n s and a p p l i e d i n the s p r i n g of 1983 i n p r e p a r a t i o n f o r l i m a
bean c r o p s . The f i e l d s were h i s t o r i c a l l y used f o r v e g e t a b l e c r o p

p r o d u c t i o n w i t h water s u p p l i e d t h r o u g h f u r r o w i r r i g a t i o n . About 50
h e c t a r e - c e n t i m e t e r s were used i n 1983 t o i r r i g a t e l i m a bean c r o p s a t
l o c a t i o n 1 and 41 h e c t a r e - c e n t i m e t e r s were used t o i r r i g a t e the same
c r o p a t l o c a t i o n 2. The a v e r a g e p r e c i p i t a t i o n t o t a l i n the a r e a was
28.73, 36.40 and 52.10 c e n t i m e t e r s f o r 1980, 1981, and 1982,
respectively. A t o t a l of 51.00 c e n t i m e t e r s were r e c o r d e d i n the 9
months p r i o r t o s o i l c o r i n g ( 6 ) .
S o i l type a t l o c a t i o n 1 was Meyer's c l a y , d e s c r i b e d as a v e r y
deep, w e l l - d r a i n e d c l a y s o i l t h a t cracks when d r y t o a d e p t h of about
90 c e n t i m e t e r s p r o d u c i n g an a n g u l a r , b l o c k y s t r u c t u r e ( 7 ) . L o c a t i o n
2 was c h a r a c t e r i z e d i n the E l S o l y o S e r i e s w h i c h c o n s i s t s of
m o d e r a t e l y w e l l - d r a i n e d , f i n e t e x t u r e d s i l t y c l a y loams. Subsurface
s o i l s a r e d e s c r i b e d as compact and c o n s i s t i n g of c a l c a r e o u s heavy
s i l t y c l a y loams ( 7 ) .
S o i l Coring. S o i l c o r i n g o c c u r r e d i n O c t o b e r , 1983, and was

a c c o m p l i s h e d w i t h a truck-mounted M o b i l e D r i l l , model B-53 drilling
r i g and 20.3 c e n t i m e t e r (8 i n c h ) h o l l o w - s t e m a u g e r s . Segments of the
s o i l p r o f i l e were c o l l e c t e d w i t h a s p l i t b a r r e l sampler, 50.8
c e n t i m e t e r s l o n g and c o n t a i n i n g t h r e e s t a i n l e s s s t e e l c y l i n d e r s
s t a c k e d end t o end. E a c h 15.2x6.4 c e n t i m e t e r (6x2.5 i n c h ) c y l i n d e r
was numbered and weighed b e f o r e b e i n g p l a c e d i n t o the s p l i t b a r r e l .
The i n t e r i o r s of the c y l i n d e r s were r i n s e d w i t h e t h y l a c e t a t e , the
s o l v e n t used f o r EDB e x t r a c t i o n i n the l a b o r a t o r y , and the s p l i t
b a r r e l was a t t a c h e d t o a Moss W i r e l i n e sampler and lowered by a s t e e l
c a b l e i n t o the h o l l o w a u g e r . D r i l l i n g and s o i l sampling o c c u r r e d
s i m u l t a n e o u s l y but the s p l i t b a r r e l d i d not r o t a t e d u r i n g the
s a m p l i n g p r o c e s s and was p r e s s e d i n t o the s o i l ahead of the a u g e r .
A f t e r d r i l l i n g 50.8 c e n t i m e t e r s of s o i l , the sampler was withdrawn.
The c u t t i n g t i p of the s p l i t b a r r e l h e l d a 5 c e n t i m e t e r segment of
sampled s o i l w h i c h was d i s c a r d e d . Thus, 45.7 c e n t i m e t e r s of s o i l was
sampled f o r e v e r y 50.8 c e n t i m e t e r s d r i l l e d . S o i l samples remained
e n c a s e d i n the c y l i n d e r s when removed from the s p l i t b a r r e l . After
r e m o v a l , the c y l i n d e r ends were s e a l e d w i t h aluminum f o i l and t i g h t l y
f i t t i n g p l a s t i c caps. The c y l i n d e r s were weighed a g a i n t o o b t a i n
s o i l b u l k weight and t h e n f r o z e n on d r y i c e (-70 C ) .
14. DUNCAN A N D OSHIMA 1,2-Dibromoethane (EDB) in Two Soil Profiles 285
When w a t e r - s a t u r a t e d s o i l was reached d u r i n g t h e d r i l l i n g

process, s o i l sampling stopped. A 2 m i l t h i c k T e f l o n s h e e t , about
10x20 c e n t i m e t e r s , was a t t a c h e d i n s i d e t h e s p l i t b a r r e l w i t h a s t e e l
basket i n s e r t . The sampler was lowered t h r o u g h t h e auger and a l l o w e d
to sink i n t o the s a t u r a t e d l a y e r before being r a i s e d t o the s u r f a c e .
The T e f l o n s h e e t a l l o w e d water t o move i n t o t h e sampler, but when
r a i s e d , weight from t h e column o f water i n t h e b a r r e l caused t h e
T e f l o n t o c o l l a p s e and s e a l e d t h e o p e n i n g . The s p l i t b a r r e l was
removed and t h e water poured i n t o 1 l i t e r amber b o t t l e s . Two b o t t l e s
were f i l l e d t o c a p a c i t y and s e a l e d w i t h f o i l - l i n e d c a p s .
D u r i n g s o i l c o r i n g , water samples were c o l l e c t e d from t h e w e l l
a s s o c i a t e d w i t h t h e s o i l c o r e l o c a t i o n s . F r e s h r e c h a r g e water was
sampled a f t e r o p e r a t i n g t h e w e l l pump l o n g enough t o c o m p l e t e l y purge
and r e p l a c e water i n t h e c a s i n g , u s u a l l y about 30 m i n u t e s . A l l water
samples were c o l l e c t e d w h i l e t h e pumps were o p e r a t i n g . A T e f l o n tube
was a t t a c h e d t o a S c h r a d e r a e r a t i o n v a l v e , l o c a t e d between t h e pump
and s t o r a g e tank. W i t h t h e c o r e o f t h i s v a l v e removed, water from

the w e l l was d i r e c t e d i n t o 1 l i t e r amber g l a s s b o t t l e s t h a t were
f i l l e d t o c a p a c i t y and s e a l e d w i t h aluminum f o i l - l i n e d c a p s . I f the
w e l l was n o t e q u i p p e d w i t h a S c h r a d e r v a l v e , a f a u c e t between t h e
pump and s t o r a g e tank was used as a s a m p l i n g p o r t . A T e f l o n tube was
i n s e r t e d i n t o t h e f a u c e t o p e n i n g and pushed i n t o t h e p i p e t o reduce
a e r a t i o n b e f o r e t h e sample b o t t l e s were f i l l e d . One w e l l r e q u i r e d
water t o be sampled from a f a u c e t a f t e r i t had passed t h r o u g h a
s t o r a g e tank. The tank was emptied and f i l l e d t h r e e t i m e s b e f o r e t h e
sample was c o l l e c t e d . B o t t l e s c o n t a i n i n g w a t e r samples were s t o r e d
on wet i c e i m m e d i a t e l y a f t e r f i l l i n g .
S o i l Core S p l i t t i n g and A n a l y s i s . A m e c h a n i c a l sample s p l i t t e r was

c o n s t r u c t e d t o remove f r o z e n s o i l from t h e s t e e l c y l i n d e r s and d i v i d e
i t l o n g i t u d i n a l l y i n t o three portions. T h i s d e v i c e was an
e l e c t r o n i c a l l y c o n t r o l l e d h y d r a u l i c pump t h a t pushed t h e f r o z e n s o i l
p a s t two s t e e l b l a d e s and i n t o t h r e e s h o o t s w h i c h c h a n n e l e d t h e
samples i n t o c o l l e c t i o n c o n t a i n e r s : one f o r m o i s t u r e d e t e r m i n a t i o n ,
one f o r q u a n t i t a t i v e c h e m i c a l a n a l y s i s and one f o r p h y s i c a l a n a l y s e s .
S o i l samples were kept f r o z e n f o r about 2 weeks b e f o r e b e i n g s p l i t
and two weeks more were r e q u i r e d t o s p l i t t h e samples.
The sample p o r t i o n used f o r m o i s t u r e d e t e r m i n a t i o n was s p l i t i n t o
a h a l f - p i n t j a r . A p i n t j a r was used t o c o n t a i n t h e p o r t i o n o f s o i l
r e s e r v e d f o r c h e m i c a l a n a l y s i s and was i m m e d i a t e l y s e a l e d . The p i n t
j a r s were s t o r e d on d r y i c e and s h i p p e d w i t h i n 3 days t o t h e CDFA
C h e m i s t r y L a b o r a t o r y i n Sacramento, C a l i f o r n i a f o r a n a l y s i s . The
t h i r d p o r t i o n o f t h e sample was used t o d e t e r m i n e t e x t u r e , o r g a n i c
m a t t e r c o n t e n t , pH, e l e c t r i c a l c o n d u c t i v i t y and m o i s t u r e . T h i s
p o r t i o n was c o l l e c t e d i n a p l a s t i c bag and s t o r e d i n a r e f r i g e r a t e d
chamber a t 3 C.
T e x t u r a l a n a l y s i s was conducted u s i n g temperature-controlled
w a t e r b a t h s and t h e Bouyoucos hydrometer method (8) w i t h 2
modifications. F i r s t , s o i l samples were a g i t a t e d f o r 20 seconds w i t h
p l a s t i c p l u n g e r s i n s t e a d o f m i x i n g t h e s o i l by i n v e r t i n g t h e
c o n t a i n e r , and second, t h e c l a y s u s p e n s i o n was n o t washed and s i e v e d
to d e t e r m i n e f r a c t i o n a l s i z e s . O r g a n i c m a t t e r p e r c e n t a g e s were
d e t e r m i n e d w i t h a d i c h r o m a t e r e d u c t i o n method ( 9 ) . Electrical
c o n d u c t i v i t y ( e c ) and pH were measured from t h e s a t u r a t i o n e x t r a c t o f
a 100 gnu sample. A Beckman S o l u b r i d g e model SD26 was used f o r the

ec measurements and pH was d e t e r m i n e d w i t h a C o r n i n g model 125 and
s e p a r a t e pH and r e f e r e n c e e l e c t r o d e s . I n a d d i t i o n , the weight of the
s a t u r a t e d s o i l p a s t e was used t o e s t i m a t e w a t e r - h o l d i n g c a p a c i t y f o r
e a c h sample. X - r a y d i f f r a c t i o n a n a l y s i s was performed on the c l a y
f r a c t i o n , o b t a i n e d from t e x t u r a l a n a l y s i s , t o d e t e r m i n e c l a y t y p e s i n
e a c h sample. A q u a n t i t a t i v e a n a l y s i s was performed on each X - r a y e d
sample t o d e t e r m i n e p r o p o r t i o n s of c l a y t y p e s . Both a n a l y s e s were
performed by the Department o f Geology and P h y s i c a l S c i e n c e a t the
C a l i f o r n i a S t a t e U n i v e r s i t y i n C h i c o (_10). EDB i n b o t h s o i l and
w a t e r samples was e x t r a c t e d by r e f l u x i n g and c o - d i s t i l l a t i o n w i t h
e t h y l a c e t a t e f o l l o w e d by d r y i n g w i t h sodium s u l f a t e . An a l i q u o t of
the e x t r a c t was t h e n i n j e c t e d i n t o a P e r k i n - E l m e r gas chromatograph
6
equipped with a N i ^ e l e c t r o n capture d e t e c t o r (11).
Results
C h e m i c a l a n a l y s i s of the s o i l p r o f i l e segments a t l o c a t i o n 1 r e v e a l e d
EDB r e s i d u e s between 0 and 0.98 meters and between 2.35 and 2.98
meters below t h e s u r f a c e ( T a b l e I ) .
Table I. EDB Concentrations (ppb d r y wt.) in Soil Segments
Location Concentration* Depth ( c e n t i m e t e r s ) Meters

1 4.3 1.0
-15.2
6.1 15.2
-30.4
12.5 30.4
-45.7 0 - 0.97
0.8 66.0
-81.3
0.3 81.3
-97.0
0.6 280.4 - 298.7

0.3 304.8
- 323.1 2.35 - 2.98
0.3 323.1
- 341.4
0.2 341.4
- 359.7
2 5.4 1.0 - 15.2
1.3 15.2
- 45.7
30.4 0 - 0.46
0.3
* Minimum d e t e c t a b l e l e v e l = O.lppb
30.4
-
The c h e m i c a l was not d e t e c t e d i n the p r o f i l e b a s a l water o r i n

c o n c u r r e n t samples c o l l e c t e d from the d o m e s t i c w e l l 62 meters away.
C h e m i c a l a n a l y s i s of the s o i l p r o f i l e a t l o c a t i o n 2 ( T a b l e I )
d e t e c t e d EDB between 0 and 0.46 meters below the s o i l s u r f a c e w h i l e
water sampled a t the p r o f i l e base c o n t a i n e d no r e s i d u e s . However,
EDB was d e t e c t e d i n water sampled on the day of c o r i n g from the
d o m e s t i c w e l l 111 meters away. T a b l e I I summarizes water sample
data.
The r e s u l t s of measured s o i l p r o p e r t y v a r i a b l e s f o r b o t h c o r e
l o c a t i o n s appear i n F i g u r e s 1, 2 and 3. P o r t i o n s of the p r o f i l e s
were not sampled and appear as breaks i n the f i g u r e columns.
a
c
CORE MOISTURE ORGANIC
DEPTH SOIL EDB CONTENT SATURATION CONTENT SAND GRAVEL >
Cm) TYPES (ppb) % WEIGHT Cgm) X X >

0 T D

1 2
>
2
4

5 + 3 S-

13 0 40 0 61 0 1 100 0 100 0 100 0 100
SOIL TYPES LEGEND
ET71SAND (foolud. gr 1)
Ell] SILT
S I CLAY
I GROUND WATER
Figure 1. H i s t o g r a m s o f measured variables at l o c a t i o n 1,
00
CORE MOISTURE ORGANIC

DEPTH SOIL EDB CONTENT SATURATION CONTENT SAND SILT CLAY GRAVEL
(m) TYPES (ppb) X WEIGHT Cgm) X X X X X
4
40 0 51 100 0 I
5
SOIL TYPES LEGEND
LVJ SAND ( i n c l u d e s g r a v e l )
EM] SILT
~ CLAY
GROUND WATER
F i g u r e 2. H i s t o g r a m s of measured v a r i a b l e s a t l o c a t i o n 2.
F i g u r e 3* Histograms of e l e c t r i c a l c o n d u c t i v i t y and pH measured

at l o c a t i o n s 1 and 2.
14. DUNCAN AND OSHIMA 1,2-Dibromoethane (EDB) in Two Soil Profiles 289
O c c a s i o n a l l y t h e s p l i t b a r r e l sampler would n o t c o n t a i n a f u l l
a l l o t m e n t o f s o i l a l t h o u g h t h e auger d r i l l e d a complete 51
centimeters. Most o f t e n t h e s o i l was p r o b a b l y compressed, but a
p o r t i o n o f t h e sandy and s a t u r a t e d sample c o l l e c t e d near t h e p r o f i l e
base o f l o c a t i o n 2 dropped o u t as t h e sampler was r a i s e d . Another
p r o f i l e s e c t i o n a t l o c a t i o n 2, between 2 and 2.5 meters
was d r i l l e d out and n o t sampled because t h e s p l i t b a r r e l c o u l d n o t
penetrate.
X-ray a n a l y s i s r e v e a l e d m o n t m o r i l l o n i t e , i l l i t e and k a o l i n i t e i n
samples from both l o c a t i o n s . R e l a t i v e p r o p o r t i o n s a r e p r e s e n t e d i n
Table I I I .
Table II. EDB C o n c e n t r a t i o n s (ppb) i n Water Samples
Background W e l l s Core Water Wells

Month Jun, J u l , Aug Oct Oct
Location
1 N.D. a
N.D. N.D.
2 0.2 b
N.D. 0.2 C
a. None d e t e c t e d
b. Mean of 3 r e p l i c a t e d samples
c. Mean of 2 r e p l i c a t e d samples
Table III. C l a y Types and R e l a t i v e Proportions
Location Montmorillonite Kaolinite Illite

1 59.4 26.6 14.0
2 57.0 27.0 16.0
S t a t i s t i c a l A n a l y s i s . Stepwise m u l t i p l e l i n e a r r e g r e s s i o n a n a l y s i s
was used t o determine t h e measured s o i l p r o p e r t i e s most c o r r e l a t e d
w i t h EDB r e s i d u e s and t o f o r m u l a t e a p r e d i c t i v e e q u a t i o n t o e s t i m a t e
chemical concentration. The r e g r e s s i o n a n a l y s i s was performed on
r e s u l t s from l o c a t i o n 1 ( T a b l e IV) o n l y because t h e number o f
segments c o n t a i n i n g r e s i d u e s a t l o c a t i o n 2 were n o t s u f f i c i e n t t o
produce an a n a l y s i s .
Table IV. Regression Analysis for Location 1
F Ratio Variables R 2
76.23 Organic Matter 0.7840

y = -1.883 + 9.597 ( o r g a n i c m a t t e r )
The r e g r e s s i o n o f l o c a t i o n 1 r e v e a l e d o r g a n i c m a t t e r (p>.001) as
the s i n g l e and o n l y i m p o r t a n t v a r i a b l e i n p r e d i c t i n g EDB r e s i d u e s and
e x p l a i n e d 78% o f t h e v a r i a b i l i t y i n the data. The s t a n d a r d e r r o r o f
1.372 produced 95% c o n f i d e n c e i n t e r v a l s of 2.74 ppb EDB. An

a d d i t i o n a l r e g r e s s i o n a n a l y s i s was performed on d a t a from l o c a t i o n 1
( T a b l e V) t o d e t e r m i n e i f r e s i d u e s found i n the upper p o r t i o n of the
p r o f i l e were c o r r e l a t e d w i t h the same v a r i a b l e s as r e s i d u e s i n the
lower p r o f i l e p o r t i o n . The d i v i s i o n was made j u s t above the f o u r
lower segments c o n t a i n i n g r e s i d u e s . The a n a l y s i s e x c l u d e d any
samples t h a t d i d not have a measurement f o r each v a r i a b l e . Thus, the
low F r a t i o f o r the upper p o r t i o n was p r o b a b l y due to the s m a l l
sample s i z e , but o r g a n i c m a t t e r s t i l l a c c o u n t e d f o r a s i g n i f i c a n t
(p>.05) p o r t i o n of the v a r i a b i l i t y . The lower p o r t i o n , however,
produced no s i g n i f i c a n t F r a t i o , i n d i c a t i n g the p r e s e n c e of EDB
r e s i d u e s was a p p a r e n t l y u n a s s o c i a t e d w i t h o r g a n i c m a t t e r and a l l
o t h e r measured v a r i a b l e s .
T a b l e V. Regression Analysis f o r Location 1, Divided

2
F Ratio Variables R
Upper Core 14.5 Organic Matter 0.8286
Lower Core Nonsignificant
D i s c r i m i n a n t a n a l y s i s c r e a t e d a model t o p r e d i c t the p r e s e n c e or
absence of r e s i d u e s i n s o i l segments of l o c a t i o n 1 and was used to
v e r i f y the outcome of the d i v i d e d r e g r e s s i o n a n a l y s i s . The a n a l y s i s
used a s t e p w i s e l i n e a r r e g r e s s i o n to d e t e r m i n e w h i c h v a r i a b l e s were
important i n p r e d i c t i n g r e s i d u e s . As e x p e c t e d , o r g a n i c m a t t e r was
produced as the p r e d i c t i v e o r d i s c r i m i n a t i n g v a r i a b l e . The a n a l y s i s
a s s i g n e d p r o b a b i l i t y s c o r e s t o each sample based on the r e l a t i o n s h i p
between the d i s c r i m i n a t i n g v a r i a b l e and the p r e s e n c e or absence of
EDB i n each sample. The p r o b a b i l i t i e s were t h e n used to c l a s s i f y
e a c h sample as t h e o r e t i c a l l y c o n t a i n i n g o r not c o n t a i n i n g r e s i d u e s .
The r e s u l t s of t h i s h y p o t h e t i c a l c l a s s i f i c a t i o n were compared w i t h
e x p e r i m e n t a l r e s u l t s t o d e t e r m i n e the a c c u r a c y of the model ( T a b l e
VI). EDB i n the f o u r p r o f i l e segments n e a r the s o i l s u r f a c e a t
l o c a t i o n 1 was s t r o n g l y p r e d i c t e d by the model. However, the f o u r
p r o f i l e segments between 2.35 and 2.98 meters t h a t c o n t a i n e d EDB were
s t r o n g l y p r e d i c t e d t o c o n t a i n no r e s i d u e s . EDB r e s i d u e s i n the lower
p r o f i l e segments were not a s s o c i a t e d w i t h any of the measured
variables.
Table VI. Discriminant A n a l y s i s of L o c a t i o n 1
Classification Matrix
Correct No. of Cases C l a s s i f i e d

No Residues Residues
100.0 % No Residues 15 0
50.0 % Residues 4 4
Total 82.6 % 19 4
Discussion
The c o r r e l a t i o n between EDB r e s i d u e s and s o i l o r g a n i c m a t t e r as a

r e s u l t o f s o r p t i o n i s a w e l l documented a s s o c i a t i o n ( 1 2 , 1 3 ) . This
r e l a t i o n s h i p would a l s o be e x p e c t e d because t h e fumigant was a p p l i e d
n e a r t h e s o i l s u r f a c e where t h e g r e a t e s t amounts o f o r g a n i c m a t t e r
o c c u r . However, t h e deeper group o f segments a t l o c a t i o n 1
c o n t a i n i n g EDB r e s i d u e s were u n a s s o c i a t e d w i t h any v a r i a b l e s i n t h e
regression. The d i s c r i m i n a n t a n a l y s i s a l s o i n c o r r e c t l y p r e d i c t e d t h e
lower p o r t i o n as b e i n g f r e e o f r e s i d u e s . EDB i n t h e lower segments
may have l e a c h e d w i t h t h e water f l u x i n i t i a t e d by i r r i g a t i o n and
r a i n f a l l , o r accumulated as a r e s u l t o f l e a c h i n g . A s o i l core s t u d y
by Z a l k i n e t a l . ( 3 ) found o r g a n i c m a t t e r , m o i s t u r e and c l a y t o be
s i g n i f i c a n t p r e d i c t i v e v a r i a b l e s o f EDB r e s i d u e s above 2.40 meters i n
a sandy s o i l . I n t h i s s t u d y , core segments between 2.40 and 12.20
meters t h a t c o n t a i n e d EDB l e v e l s were g e n e r a l l y u n a s s o c i a t e d w i t h
measured s o i l p r o p e r t i e s i n a r e g r e s s i o n a n a l y s i s and t h e a u t h o r s
s u g g e s t e d t h e r e s i d u e s were a c c u m u l a t i n g o r l e a c h i n g . Again, the
l a c k o f s i g n i f i c a n t r e s i d u e p r e d i c t o r s i n t h e lower h a l f o f t h e h o l e
w i t h r e l a t i v e l y low o r g a n i c m a t t e r would suggest t h a t t h e EDB was
migrating. T h i s i s s p e c u l a t i o n , but i t appears t o f i t t h e a n a l y s i s .
C l a y type a t l o c a t i o n s 1 and 2 was n o t s i g n i f i c a n t i n p r e d i c t i n g
the p r e s e n c e o r absence o f EDB. A d s o r p t i o n o f a n o n i o n i c compound
l i k e EDB t o wet c l a y s would n o t be e x p e c t e d ( 1 2 ) .
The movement o f v o l a t i l e p e s t i c i d e s i n f i n e , m o i s t s o i l has been
s t u d i e d by McKenry and Thomason (_14) who found t h a t
1 , 3 - D i c h l o r o p r o p e n e (1,3-D) moved no more t h a n 4 5 . 7 c e n t i m e t e r s i n t o a
s i l t y c l a y loam w i t h 23% m o i s t u r e i n 20 d a y s . F o r comparison, a s o i l
c o r i n g s t u d y performed by t h e C a l i f o r n i a S t a t e Water R e s o u r c e s
C o n t r o l Board measured 1,3-D i n a f i n e sandy loam t o a d e p t h o f 198
c e n t i m e t e r s 45 days a f t e r a p p l i c a t i o n (JM5). The f i n e t e x t u r e and
g e n e r a l l y h i g h m o i s t u r e l e v e l s throughout t h e p r o f i l e a t l o c a t i o n 1
i n t h e p r e s e n t s t u d y would p r o b a b l y make t h e t r a n s p o r t o f EDB from
the s u r f a c e t o lower p r o f i l e l e v e l s a l e n g t h y p r o c e s s . Therefore i t
may be o f s i g n i f i c a n c e t h a t t h e w e l l a s s o c i a t e d w i t h l o c a t i o n 1 d i d
not have a h i s t o r y o f d e t e c t e d EDB r e s i d u e s d e s p i t e a 10 y e a r h i s t o r y
of EDB u s e on a nearby f i e l d .
I n c o n t r a s t t o l o c a t i o n 1, t h e p r o f i l e a t l o c a t i o n 2 was
s h a l l o w e r , c o n t a i n e d more sand, and below a d e p t h o f 0.60 meters
would be c o n s i d e r e d a loam. The sandy l a y e r s a t t h e p r o f i l e base
would t e n d t o a c c e l e r a t e movement o f t h e p e s t i c i d e a s s o c i a t e d w i t h
the b u l k f l o w o f water and perhaps would account f o r t h e l a c k of
r e s i d u e s i n t h e deeper l a y e r s o f t h e p r o f i l e and f o r c o n t a m i n a t e d
w e l l water n e a r b y . Based on t e x t u r e and m o i s t u r e a n a l y s e s , one would
expect a l o n g e r time r e q u i r e d f o r downward movement o f EDB a t
l o c a t i o n 1 compared w i t h l o c a t i o n 2.
I n summation, EDB may tend t o l e a c h more s l o w l y t h r o u g h t h e f i n e r
s o i l of l o c a t i o n 1 than through the r e l a t i v e l y coarse s o i l of
l o c a t i o n 2. T h i s i s a p o s s i b l e e x p l a n a t i o n f o r t h e p r e s e n c e o f EDB
i n w e l l water a t l o c a t i o n 2 and i t s absence i n w e l l water a t l o c a t i o n
1.
Comparisons between s o i l c o r e a n a l y s e s and t h e p r e s e n c e o r
absence o f p e s t i c i d e s i n n e a r b y w e l l s a r e s p e c u l a t i v e because o f w e l l
and p r o f i l e d e p t h d i f f e r e n c e s and because o f a l a c k o f i n f o r m a t i o n
about s t r a t a w i t h i n the s p e c i f i c groundwater r e g i o n o f the f i e l d and

w e l l sampled. However, c o r r e l a t i o n s between r e s i d u e s i n w e l l water
and s o i l p r o p e r t i e s can o f t e n be shown. Work i n p r o g r e s s by Teso and
Younglove ( 4 ) , shows t h a t a d i s c r i m i n a n t a n a l y s i s performed on w e l l
sample r e s u l t s f o r DBCP i n a s s o c i a t i o n w i t h s o i l t y p e c l a s s i f i c a t i o n s
c o r r e c t l y p r e d i c t s c o n t a m i n a t i o n o r no c o n t a m i n a t i o n 75% o f t h e t i m e .
A t o t a l o f 532 w e l l s were sampled i n a g r i c u l t u r a l a r e a s where DBCP
had been u s e d . The r e s u l t s were compared w i t h s o i l type d a t a on
township, range, s e c t i o n s u r v e y e d c o o r d i n a t e s . T h i s suggests t h a t
w e l l d a t a may be r e l a t e d s p a t i a l l y t o s o i l c o r e d a t a w i t h some degree
of c e r t a i n t y . The r e l a t i o n s h i p can be used t o h e l p f o c u s s o i l c o r e
r e s e a r c h on s p e c i f i c a r e a s where groundwater r e s i d u e s a r e found due
to a g r i c u l t u r a l usage. U l t i m a t e l y , t h e s e d a t a i n a d d i t i o n t o
l a b o r a t o r y r e s u l t s and p r e d i c t i o n s made from models w i l l be used t o
s u p p o r t t h e development o f measures t o r e f i n e r e g u l a t i o n o f p e s t i c i d e
use.
Acknowledgments
The a u t h o r s w i s h t o thank t h e C a l i f o r n i a S t a t e Water Resources

C o n t r o l Board (SWRCB) f o r s u p p o r t i n f u n d i n g t h i s work, and
Syed A l i (SWRCB) f o r a s s i s t a n c e i n p r e p a r a t i o n o f t h e s t u d y . We a r e
g r a t e f u l t o A. Hugh S i n c l a i r , S t a n i s l a u s County A g r i c u l t u r e
Commissioner, f o r a i d i n d e t e r m i n i n g s o i l c o r e l o c a t i o n s and t o N o l a n
P e t z and D a n i e l J . P e r e z f o r use of t h e i r l a n d .
Literature Cited
1. van Berkum, J, A. In "Soil Disinfestation"; Muller, D. ED.;

Elsevier: Amsterdam, 1979; pp. 58, 59, 82.
2. "Ethylene Dibromide (EDB) - Position Document 4," U.S
Environmental Protection Agency, Office of Pesticide Programs,
1983.
3. Zalkin, F.; Wilkerson, M.; Oshima, R. J. "Pesticide Movement
to Groundwater Volume II: Pesticide Contamination in the Soil
Profile at DBCP, EDB, Simazine and Carbofuran Application
Sites," California Department of Food and Agriculture, 1984.
4. Teso, R. R., Work in Progress, California Department of Food
and Agriculture at the University of California, Riverside.
5. Smith,C.;Margetich; S., Fredrickson, S.; "A Survey of Well
Water in Selected Counties of California for Contamination by
EDB in 1983," California Department of Food and Agriculture,
1983.
6. "Climatological Data, California Section" U.S. Dept. of
Commerce, National Oceanic and Atmospheric Administration,
1979-83.
7. McLaughlin, J.C.;Huntington, G. L. "Soils of Westside
Stanislaus Area California"; University of California, Davis,
1968; sheets 2,3.
8. Bouyoucos, G. J. Agronomy Journal 1962, 54, 464-5.
9. Quick, J. "California Soil Testing Procedures Manual";
California Fertilizer Association, 701 12th St. Suite 110,
Sacramento, CA 95814, Method S 18.0.
10. Duncan, D. W.; Oshima, R. J. "Ethylene Dibromide in Two Soil

Profiles" California Department of Food and Agriculture, 1985.
11. "Residues Determination of Dibromo-chloropropane in crops,
soil, water"; Shell Development Co., Biological Sciences
Research Center, Modesto, CA, Method #MMS-R-272-3, 1976.
12. Goring, C. A. I. Ann. Rev. Phytopath. 1967, 5, 285-318.
13. Bailey, G. W.; White, J. L. Res. Rev. 1970, 32, 29-92.
14. McKenry, M. V.; Thomason, I. J. Hilgardia 1974, 42, 393-438.
15. "1,2-Dichloropropane (1,2-D), 1,3-Dichloropropene (1,3-D)"
Toxic Substances Control Program, California State Water
Resources Control Board, Special Projects Report No. 83-8sp,
1983.
15
Chemical and Microbial Degradation
of 1,2-Dibromoethane (EDB) in Florida Ground Water,
Soil, and Sludge
R. A . Weintraub, G. W. Jex, and H . A . Moye
Pesticide Research Laboratory, University of Florida, Gainesville, F L 32611

The chemical and microbial degradation of 1,2-dibro-

moethane (EDB) in the subsurface environment was
studied in laboratory incubations of groundwater,
soil suspensions and sludge suspensions. EDB has
been determined to have a chemical half-life of 1.5
to 2 years in Florida groundwaters (22C). Rate con-
stants for degradation determined at elevated temper-
atures were used to obtain extrapolated values via
Arrhenius kinetics. Hydrolysis is the major mode of
degradation, giving ethylene glycol and bromide ion,
and is not pH-dependent between pH 4 and 9. Formal-
dehyde, an oxidation product of ethylene glycol, was
shown to be a degradation product during extended in-
cubation at elevated temperatures. Concentrations of
1 to 2 ppm of EDB were anaerobically degraded to eth-
ylene by either methanogenic or facultative sludge in
about 60 days, whereas Florida soils examined were
nearly incapable of degrading EDB under these condi-
tions.
1,2-Dibromoethane ( e t h y l e n e d i b r o m i d e ; EDB) i s used as a l e a d -

scavenger i n g a s o l i n e , a s o i l fumigant n e m a t i c i d e , a fumigant f o r
s t o r e d g r a i n s , as a treatment t o conform w i t h q u a r a n t i n e r e g u l a -
t i o n s f o r c e r t a i n f r u i t shipments and a s a means o f k e e p i n g m i l l i n g
m a c h i n e r y f r e e from i n s e c t s . By l a t e 1983, EDB r e c e i v e d g r e a t
n o t o r i e t y when i t was r e p o r t e d t h a t t r a c e amounts o f t h i s c h e m i c a l
were d e t e c t e d i n g r a i n s and g r a i n p r o d u c t s i n t h e U.S. and i n
groundwater i n F l o r i d a , G e o r g i a , C a l i f o r n i a , South C a r o l i n a , New
York, and H a w a i i (I). By March of 1984, a l l r e g i s t e r e d
a g r i c u l t u r a l u s e s o f EDB were phased o u t as a r e s u l t o f t h e U.S.
1
E n v i r o n m e n t a l P r o t e c t i o n Agency's (EPA) d e t e r m i n a t i o n t h a t E D B s
a g r i c u l t u r a l u s e s p r e s e n t e d an "imminent h a z a r d " t o t h e h e a l t h o f
humans. The c h e m i c a l had been shown t o have a h i g h a c u t e t o x i c i t y
i n a l l animals t e s t e d , o r a l L D 5 0 v a l u e s r a n g i n g from 50 mg/kg i n
t h e r a b b i t t o 420 mg/kg i n female mice (2) I t s mutagenicity
toward b a c t e r i a (3) and c a r c i n o g e n i c i t y i n r a t s and mice (4) have
0097-6156/86/0315-O294$06.00/0
1986 American Chemical Society
15. WEINTRAUB ET AL. Degradation of 1,2-Dibromoethane 295
been demonstrated and t h e mechanisms o f t o x i c i t y have been de

1
scribed i n p r o g r e s s i v e d e t a i l since the I960 s (5,6).
Consistent measurable levels o f EDB i n groundwater have
sparked c o n c e r n o v e r t h e p e r s i s t e n c e o f t h a t p o r t i o n o f c h e m i c a l
t h a t does n o t v o l a t i l i z e o r i s n o t r e a d i l y degraded. I t s chemical
p r o p e r t i e s make i t f a i r l y m o b i l e i n t h e s u b s u r f a c e environment,
h a v i n g a s o l u b i l i t y i n water o f 4300 ppm a t 30C (7) and a v a p o r
f
p r e s s u r e o f 11 mm Hg a t 25C ( 8 ) , g i v i n g i t a H e n r y s c o n s t a n t o f
k
a p p r o x i m a t e l y 6.3 I0~ 3
atm-m /mol. A v a l u e o f 58 i s o b t a i n e d
u s i n g t h e a p p r o p r i a t e p r e d i c t i v e model (9?Y A v a l u e o f 66 mL/g
has been e x p e r i m e n t a l l y o b t a i n e d i n two v a r y i n g s o i l s ( 1 0 ) . Such
c h e m i c a l and f i e l d characteristics p l a c e EDB on t h e l i s t o f
pesticides with the potential t o be groundwater contamination
h a z a r d s by t h e c r i t e r i a e s t a b l i s h e d by U.S. EPA O f f i c e o f P e s t i c i d e
Programs (1)
I n v e s t i g a t i o n s i n t h e p a s t have have f o c u s e d r e s i d u a l EDB on
c r o p s and on p r o c e s s e d o r s t o r e d p r o d u c t s (11-13). Values o f the

o r d e r o f 5-10 days (14) and 14 y e a r s (15) have been r e p o r t e d as t h e
h a l f - l i f e due t o h y d r o l y s i s i n n e u t r a l aqueous s o l u t i o n s a t ambient
temperature. The b i o l o g i c a l c o n v e r s i o n o f EDB t o e t h y l e n e and
bromide i o n by an a n a e r o b i c s o i l - w a t e r c u l t u r e h a s been r e p o r t e d t o
o c c u r i n two months ( 1 6 ) . In another study, b a c t e r i a l c u l t u r e s
under d e n i t r i f y i n g c o n d i t i o n s f a i l e d t o show any p o t e n t i a l f o r
d e g r a d i n g EDB ( 1 7 ) . F u r t h e r , i t was found t h a t under methanogenic
i n c u b a t i o n c o n d i t i o n s , EDB was t r a n s f o r m e d to a water-insoluble
non-halogenated g a s , which was thought t o be e t h y l e n e (18,19).
Recent a c c o u n t s of photodegradation showed EDB was c o m p l e t e l y
m i n e r a l i z e d t o HBr and C 0 by h e t e r o g e n e o u s p h o t o c a t a l y s i s (on
2
T1O2) i n aqueous s o l u t i o n (20),while i n another study, the

p h o t o r e a c t i o n was r e p o r t e d t o p r o c e e d v i a t h e c o n v e r s i o n o f EDB t o
bromoethanol f o l l o w e d by t h e c y c l i z a t i o n t o e t h y l e n e o x i d e w h i c h
was h y d r o l y z e d t o e t h y l e n e g l y c o l by a p r o c e s s n o t enhanced by
l i g h t (21).
Two y e a r s a f t e r t h e b a n on a g r i c u l t u r a l u s e o f EDB, c o n c e n t r a
t i o n s r a n g i n g from 0.02 t o about 600 ppb have been d e t e c t e d i n
well-water samples b e i n g t a k e n by t h e s t a t e o f F l o r i d a ' s EDB
monitoring program. Figure 1 gives a representation of the
l o c a t i o n s and f r e q u e n c y o f s t a t e - c o n t r o l l e d EDB a p p l i c a t i o n s and
water w e l l s i t e s found t o be contaminated w i t h EDB as o f March
1985. Estimated amounts of applied EDB i n Florida total
600-700,000 L / y e a r . G r e a t e r than one-half o f the contaminated w e l l
s i t e s have been below 0.20 ppb and most o f t h e r e m a i n i n g p o s i t i v e s
have been between 0.20 and 10 ppb. Depths o f t h e w e l l s sampled
v a r y w i d e l y from 3 t o 300 m ( 2 2 ) . F l o r i d a ' s c i t r u s , peanut, and
soybean farming a r e a s , where most o f t h e EDB u s e h a s been
c o n c e n t r a t e d f o r 40 t o 50 y e a r s , a r e l o c a t e d on p r e d o m i n a n t l y sandy
s o i l s w i t h r e l a t i v e l y low o r g a n i c c o n t e n t ( i . e . <1%). The s o i l s
a r e m o s t l y e n t i s o l , s p o d o s o l , a l f i s o l and u l t i s o l t y p e s ( 2 3 ) . The
f a t e o f s u b s u r f a c e r e s i d u a l EDB i s o f g r e a t c o n c e r n i n l i g h t o f t h e
f a c t t h a t t h e groundwater i s t h e s o u r c e o f p o t a b l e w a t e r f o r about
88 p e r c e n t o f F l o r i d a ' s h o u s e h o l d s ( n a t i o n a l l y , about one h a l f t h e
p o p u l a t i o n ' s p o t a b l e w a t e r i s d e r i v e d from groundwater sources)
(23).
T h i s study i n v e s t i g a t e s t h e d e g r a d a t i o n o f EDB by h y d r o l y s i s
i n groundwater samples and by m i c r o b i a l a c t i v i t y i n s o i l samples
c o l l e c t e d from n o r t h c e n t r a l and n o r t h w e s t e r n r e g i o n s o f F l o r i d a .
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L a b o r a t o r y experiments were performed w i t h n a t u r a l samples i n o r d e r

to make q u a l i f i e d e s t i m a t e s o f t h e p e r s i s t e n c e o f EDB i n t h e
s u b s u r f a c e environment and t o i d e n t i f y t h e p r o d u c t s o f d e g r a d a t i o n .
The p o t e n t i a l f o r b i o t r a n s f o r m a t i o n o f t h e c h e m i c a l by two d i f f e r
ent s l u d g e p r e p a r a t i o n s was a l s o i n v e s t i g a t e d .
MATERIALS AND METHODS
Groundwater D e g r a d a t i o n K i n e t i c s .
Groundwater o b t a i n e d from s h a l l o w w e l l s i n t h r e e n o r t h c e n t r a l and
northwest F l o r i d a c o u n t i e s ( P o l k ( ) , H i g h l a n d s ( ) , and J a c k s o n
(J) and l a b o r a t o r y d e i o n i z e d water (DW) were f o r t i f i e d w i t h EDB
(EPA a n a l y t i c a l s t a n d a r d , 99%+ p u r i t y ) t o c o n c e n t r a t i o n s o f 10 o r
100 ppb. G l a s s serum b o t t l e s (100 mL Wheaton, M i l l v i l l e , NJ) were
f i l l e d w i t h t h e s o l u t i o n s , t h e headspace purged w i t h N 2 and t h e
b o t t l e s t i g h t l y capped w i t h T e f l o n - c o a t e d rubber septum s e a l crimp
caps ( S u p e l c o , B e l i e f o n t e , P A ) . B e f o r e sample p r e p a r a t i o n , t h e
serum b o t t l e s , s e a l s , and caps were a u t o c l a v e d (121C, 15 p s i , 20
m i n u t e s ) and the w a t e r s were e i t h e r a u t o c l a v e d (same c o n d i t i o n s ) o r
filtered (0.20 ym f i l t e r , M i l l i p o r e , B e d f o r d , MA) t o e l i m i n a t e
microbial activity. S e t s o f p r e p a r e d samples i n d u p l i c a t e were
i n c u b a t e d i n an i n v e r t e d p o s i t i o n i n a darkened water b a t h . Due t o
the r e l a t i v e s t a b i l i t y o f EDB a t ambient temperatures o b s e r v e d i n
p r e l i m i n a r y e x p e r i m e n t s , i n c u b a t i o n s were performed a t 40, 50, 60,
70, and 80C 0.5C. Serum b o t t l e s were p e r i o d i c a l l y t a k e n o u t o f
the water b a t h and a l l o w e d t o e q u i l i b r a t e t o room temperature
b e f o r e sampling. A 10 mL s y r i n g e was used t o withdraw an a l i q u o t
which was d e l i v e r e d t o a 10 mL v o l u m e t r i c f l a s k t o a s s u r e a p r e c i s e
volume. T h i s volume was t r a n s f e r r e d t o a 30 mL screw-top t e s t tube
t o w h i c h 1.0 mL o f hexane was added and t h e tube immediately
capped. I t was i n v e r t e d 5 times and mixed on a v o r t e x - m i x e r f o r
one m i n u t e , i n v e r t e d 5 more times and a l l o w e d t o s t a n d f o r a t l e a s t
5 minutes. The hexane l a y e r was p i p e t t e d i n t o a 1 mL v i a l f o r
automated gas c h r o m a t o g r a p h i c analysis.
D e g r a d a t i o n r a t e c o n s t a n t s were o b t a i n e d by l i n e a r r e g r e s s i o n
l e a s t s q u a r e s a n a l y s i s o f p l o t s o f l o g % EDB r e m a i n i n g v s t i m e .
P s e u d o - f i r s t o r d e r r a t e c o n s t a n t s were used t o g e n e r a t e A r r h e n i u s
p l o t s ( l o g r a t e c o n s t a n t v s 1/T K) t o e s t i m a t e a c t i v a t i o n e n e r g i e s
(E ) and t o make e x t r a p o l a t e d e s t i m a t e s o f r a t e c o n s t a n t s and
h a l f - l i f e v a l u e s a t ambient t e m p e r a t u r e .
At l e a s t 2 samples i n each i n c u b a t i o n t r i a l were f o r t i f i e d
ll
w i t h *C-EDB ( a p p r o x i m a t e l y 500 y C i / g Amersham, A r l i n g t o n H e i g h t s ,
IL) and p e r i o d i c a l l y sampled t o check t h e i n t e g r i t y o f t h e system.
1 1 +
Total C - a c t i v i t y was measured by l i q u i d s c i n t i l l a t i o n c o u n t i n g o f
1.0 mL o f sample added t o 15 mL o f A q u a - S o l 2 l i q u i d s c i n t i l l a t i o n
c o c k t a i l (New E n g l a n d N u c l e a r , B o s t o n , MA). C o u n t i n g was done on a
S e a r l e A n a l y t i c a l 92 l i q u i d s c i n t i l l a t i o n c o u n t e r w i t h a S i l e n t 700
e l e c t r o n i c data t e r m i n a l . Quenching was e v a l u a t e d by comparing
a d d i t i o n s o f t h e f o r t i f i e d w a t e r s o r hexane e x t r a c t s t o a d d i t i o n s
l l + 6
of known amounts o f C - t o l u e n e ( 4 x l 0 dpm/mL, New E n g l a n d N u c l e a r ,
B o s t o n , MA). E f f i c i e n c i e s and p r e c i s i o n o f e x t r a c t i o n o f EDB from
t h e w a t e r s were e v a l u a t e d i n a s i m i l a r f a s h i o n .
Gas C h r o m a t o g r a p h i c A n a l y s i s .
Hexane e x t r a c t s o f sample a l i q u o t s were a n a l y z e d f o r EDB as w e l l as
o t h e r c l o s e l y r e l a t e d s u s p e c t e d m e t a b o l i t e s (bromoethane, bromoace-
t i c a c i d and bromoethanol) on a H e w l e t t - P a c k a r d 5840 A gas chroma-

6 3
t o g r a p h equipped w i t h a N i e l e c t r o n capture detector. A 2 m
g l a s s column packed w i t h 15% p o l y p r o p y l e n e g l y c o l on GasChrom Q
80/100 mesh was used w i t h a 5% methane/95% A r c a r r i e r gas a t a f l o w
of 52 mL/min. Temperatures m a i n t a i n e d d u r i n g a n a l y s i s were 100C
f o r the column, 300C f o r t h e d e t e c t o r , and 225C f o r the i n j e c t o r
port. S t a n d a r d c u r v e s o f d e t e c t o r r e s p o n s e over t h e range o f 20 t o
1500 pg/yL o f EDB were c o n s t r u c t e d and used f o r q u a n t i t a t i o n u s i n g
l i n e a r r e g r e s s i o n l e a s t s q u a r e s a n a l y s i s and were p r e p a r e d d a i l y .
S o i l and Sludge D e g r a d a t i o n E x p e r i m e n t s .
S o i l s were sampled from s i t e s i n J a c k s o n , P o l k and Highlands
c o u n t i e s where water from w e l l s has been c o n t a m i n a t e d w i t h EDB t o
test t h e EDB degrading a b i l i t y of the indigenous m i c r o f l o r a .
Samples from each s i t e were c o l l e c t e d a t depths o f 1 and 3 m w i t h
auger b o r e s . Groundwater was not r e a c h e d i n any o f the s a m p l i n g .
Two s l u d g e s were u s e d t o s t u d y the EDB d e g r a d i n g p o t e n t i a l o f a

b r o a d spectrum o f m i c r o f l o r a . One s l u d g e was from a p r i m a r y s l u d g e
c o n t a c t tank a t t h e U n i v e r s i t y o f F l o r i d a c o n t a i n i n g a r i c h f l o r a
of f a c u l t a t i v e organisms. The second s l u d g e was o b t a i n e d from the
methane d i g e s t e r o f D r . P a u l Smith ( U n i v e r s i t y o f F l o r i d a ) and was
known t o c o n t a i n a s i g n i f i c a n t methanogenic f l o r a .
The b o t t l e - f i l l i n g and i n c u b a t i o n p r o c e d u r e s were adapted from
Bouwer and McCarty (17) and the medium was t h a t o f A l e x a n d e r and
L u r t i g m a n ( 2 4 ) . The s t e r i l i z e d medium (121C, 15 p s i , 20 min) was
b o i l e d and then f l u s h e d w i t h N 2 while cooling. I t then was
f o r t i f i e d w i t h EDB t o a c o n c e n t r a t i o n o f 400 ppb u s i n g an a l c o h o l
solution of the p e s t i c i d e (Aldrich C h e m i c a l , Milwaukee, WI);
11+
C-EDB (Amersham, A r l i n g t o n H e i g h t s , I L ) was added t o t h e medium
t o g i v e 4000-5000 dpm/mL as a t r a c e r . F e S 0 7 H 0 (0.25 g/L) and
i+ 2
N a S * 9 H 0 (0.1 g/L) were added as r e d u c t a n t s .

2 2 The medium was
m a i n t a i n e d under N 2 u n t i l s i p h o n e d i n t o serum b o t t l e s (100 mL)
c o n t a i n i n g e i t h e r 5 g s o i l o r 10 mL o f s l u d g e . The b o t t l e s were
flushed with N 2 d u r i n g f i l l i n g and capped w i t h T e f l o n l i n e d crimp
caps. At each s a m p l i n g , an u n f o r t i f i e d s o i l a l o n g w i t h t h r e e
fortified and three s t e r i l i z e d fortified soil replicates were
analyzed.
The b o t t l e s were i n c u b a t e d a t 25C and a n a l y z e d a t 1, 5, 10
and 30 days t h e n monthly t h e r e a f t e r f o r seven months. T h r e e 20 mL
p o r t i o n s from each b o t t l e were removed f o r C 0 analysis.
2 One
p o r t i o n was t r e a t e d w i t h 2 mLs o f c o n c e n t r a t e d H S 0 i and one w i t h 1
2 +
mL o f a s a t u r a t e d B a C l 2 solution. The t h i r d 20 mL p o r t i o n was

untreated. A 1.0 mL sample from each b o t t l e was added t o 15 mL of
A q u a - s o l 2 and counted by l i q u i d s c i n t i l l a t i o n . The p r e s e n c e o f
l l f l l f
C0 i s i n d i c a t e d by t h e t r e a t e d samples h a v i n g l e s s
2 C-activity
t h a n t h e u n t r e a t e d samples.
Samples were a l s o e x t r a c t e d t h r e e t i m e s (1:1) w i t h hexane and
a p o r t i o n o f each hexane e x t r a c t was a n a l y z e d by GC, as p r e v i o u s l y
described. A 1.0 mL p o r t i o n o f each e x t r a c t and a 1.0 mL p o r t i o n
o f t h e r e s i d u a l water was counted by liquid scintillation as
described before.
I d e n t i f i c a t i o n o f Gaseous P r o d u c t s .
Gases produced d u r i n g s o i l and s l u d g e i n c u b a t i o n s were a n a l y z e d by
i n j e c t i o n s o f headspace o f t h e sample on a F & M S c i e n t i f i c 700 gas
chromatograph equipped w i t h a thermal c o n d u c t i v i t y d e t e c t o r i n
15. WEINTRAUB E T A L . Degradation of 1,2-Dibromoethane 299
s e r i e s w i t h a P a c k a r d 894 gas p r o p o r t i o n a l c o u n t e r . G l a s s columns

(2 m) packed w i t h Chromosorb 101 ( A p p l i e d S c i e n c e , S t a t e C o l l e g e ,
PA) o r Porapak Q (Waters A s s o c . , Framingham, MA) were u s e d f o r
determination of ethylene or C 0 , respectively. 2 C a r r i e r gas was N 2
at 20 mL/min and oven was a t ambient t e m p e r a t u r e ,
pH-Dependence o f D e g r a d a t i o n i n S o l u t i o n s .
3
A s e r i e s o f 5 10 M b u f f e r systems (25) were used t o m a i n t a i n
the EDB f o r t i f i e d w a t e r s a t pH v a l u e s r a n g i n g from 4.0 t o 9.0. The
b u f f e r s i n c l u d e d b o r a x / s u c c i n i c a c i d , phathalate/NaOH, borate/NaOH,
b o r a x / p h o s p h o r i c a c i d , and c a r b o n a t e / b i c a r b o n a t e ( a n a l y t i c a l g r a d e ,
F i s h e r S c i e n t i f i c , F a i r Lawn, N J ) . I n c u b a t i o n s were conducted a t
62C and samplings and a n a l y s e s were performed a s d e s c r i b e d b e f o r e .
A n a l y s i s f o r P u r g e a b l e Brominated D e g r a d a t i o n P r o d u c t s .
Water samples f o r t i f i e d w i t h EDB t o c o n c e n t r a t i o n s o f 1 and 4 ppm
and i n c u b a t e d a t 80C were a n a l y z e d f o r b r o m i n a t e d p r o d u c t s by

b u b b l i n g h e l i u m t h r o u g h 25 mL o f sample f o r 22 m i n u t e s a t ambient
temperature onto Tenax a d s o r b e n t . P u r g e a b l e s were d i r e c t e d i n t o
the GC column o f a F i n n i g a n 4021 q u a d r u p o l e gas chromatograph/ mass
s p e c t r o m e t e r by h e a t i n g t h e a b s o r b e n t t o 120C. A g l a s s column
packed w i t h t h e same m a t e r i a l u s e d f o r EDB a n a l y s i s was used under
similar conditions.
A n a l y s i s o f E t h y l e n e G l y c o l , Formaldehyde and Bromide i o n i n Water.

E t h y l e n e g l y c o l c o n c e n t r a t i o n s i n w a t e r were d e t e r m i n e d by GC
a n a l y s i s o f t h e 2 - n i t r o p h e n y l h y d r a z i n e d e r i v a t i v e o f formaldehyde,
2-nitrophenylhydrazone. To 2 o r 4 mL a l i q u o t s o f t h e water sample,
6
a 20 u l a l i q u o t o f 5 1 " M p e r i o d i c a c i d ( a n a l y t i c a l g r a d e ,
M a l l i n c k r o d t , P a r i s , NY) was added and t h e sample was t h e n a l l o w e d
to s t a n d a t room temperature i n t h e d a r k f o r 20 h o u r s . Excess
p e r i o d i c a c i d was p r e c i p i t a t e d by t h e a d d i t i o n o f 25 uL o f KN0 and 3
a l l o w e d t o s t a n d f o r 1 hour i n an i c e b a t h . S t a n d a r d aqueous
s o l u t i o n s o f e t h y l e n e g l y c o l were a s s a y e d by t h e same p r o c e d u r e
each day o f a n a l y s i s t o c o n s t r u c t a s t a n d a r d c u r v e f o r q u a n t i t a
t i o n . To q u a n t i t a t e formaldehyde i n aqueous s o l u t i o n , e i t h e r formed
by t h e o x i d a t i o n o f e t h y l e n e g l y c o l o r p r e s e n t i n s o l u t i o n a s a
d e g r a d a t i o n p r o d u c t o r s t a n d a r d , 600 uL o f a 2 M aqueous s o l u t i o n
of 2 - n i t r o p h e n y l h y d r a z i n e (ICN P h a r m a c e u t i c a l s , P l a i n v i e w , NY;
r e c r y s t a l i z e d from hexane) was added t o t h e r e a c t i o n m i x t u r e which
was t h e n i n c u b a t e d i n a water b a t h a t 40C f o r 50 m i n u t e s . The
2 - n i t r o p h e n y l h y d r a z o n e was e x t r a c t e d by t h e a d d i t i o n o f 5 mL o f
hexane t o t h e tube w h i c h was then mixed on a v o r t e x - m i x e r f o r 1
minute. The hexane l a y e r was p i p e t t e d t o a 1 mL v i a l f o r automated
GC a n a l y s i s on a 2 m g l a s s column packed w i t h 4% 0V-225 on Chromo
s o r b Q 80/100 mesh; a 5% methane/95% A r c a r r i e r gas a t 30 mL/min, a
column temperature o f 173C, a d e t e c t o r temperature o f 3 0 0 , and an
i n j e c t o r temperature o f 225C were employed.
Bromide i o n i n aqueous s o l u t i o n s was a n a l y z e d by S t a n d a r d
Methods P r o c e d u r e n o . 405 C ( 2 6 ) . I t was o x i d i z e d by c h l o r o a m i n e
to bromine w h i c h b r o m i n a t e s p h e n o l r e d ( b o t h r e a g e n t s from F i s h e r
S c i e n t i f i c , F a i r Lawn, N J ) . The b r o m i n a t e d p r o d u c t was measured by
absorbance o f t h e r e a c t i o n m i x t u r e a t 590 nm on a Beckman DU-8
spectrophotometer. S t a n d a r d aqueous s o l u t i o n s o f bromide were
a s s a y e d t o c o n s t r u c t a s t a n d a r d c u r v e o v e r a range o f 50 t o a t
l e a s t 1000 ppb.
RESULTS AND DISCUSSION
Groundwater D e g r a d a t i o n K i n e t i c S t u d i e s .
A l l k i n e t i c p l o t s c o n s t r u c t e d from t h e d a t a i n d i c a t e d t h a t t h e
disappearance o f EDB from s o l u t i o n a t a l l temperatures (40 t o
70 C) i n the waters t e s t e d f o l l o w e d simple p s e u d o - f i r s t - o r d e r
k i n e t i c s (Figure 2). L i n e a r r e g r e s s i o n by l e a s t squares a n a l y s i s
shows t h a t c o r r e l a t i o n coefficients range from .90 for lower
temperature incubation t r i a l s , to l a r g e r than .99 f o r higher
temperature incubation t r i a l s . K i n e t i c r e s u l t s obtained i n the
b u f f e r e d w a t e r s i n c u b a t e d a t 63C a r e shown i n T a b l e I . The r a t e
c o n s t a n t s o b s e r v e d i n t h e d i f f e r e n t w a t e r s v a r y o n l y s l i g h t l y and
i n d i c a t e t h a t n e i t h e r a c i d or b a s e - c a t a l y z e d h y d r o l y s i s i s favored
w i t h i n the pH range examined (pH 4-9) ( F i g u r e 3 ) . At pH 5 and 8 an
i n c r e a s e i n the r a t e c o n s t a n t s o f about 10% i s o b s e r v e d , but
because t h e s e p o r t i o n s o f t h e p l o t a r e not c o n s i s t e n t w i t h a
pH-dependent t r e n d , i . e . a c o n s t a n t s l o p e o v e r a c o n s i d e r a b l e pH
range, t h e s e d e v i a t i o n s can be a t t r i b u t e d t o s p e c i f i c c o n t r i b u t i o n s
o f the b u f f e r type u s e d . Such a c o n t r i b u t i o n by s p e c i f i c b u f f e r
3
c a t a l y s i s even a t b u f f e r c o n c e n t r a t i o n s o f 5 10 M (as used i n
the p r e s e n t s t u d y ) o r l e s s i s r e a s o n a b l e ( 2 7 ) .
The l a c k o f pH-dependence shown i n t h i s study i s c o n s i s t e n t
w i t h r e s u l t s p r e s e n t e d elsewhere for a l k y l halides (9). This
i m p l i e s t h a t f o r the o b s e r v e d d e g r a d a t i o n r a t e c o n s t a n t , k , is
r H
approximately equal to ^ n e u ^ (
t r a P ? ) w i t h i n t h e examined pH
range.
The mechanism f o r the c h e m i c a l r e a c t i o n i s assumed t o be the
same o v e r t h e e n t i r e temperature range when a s t r a i g h t l i n e i s
o b t a i n e d i n the p l o t o f I n k v s 1/TK f o r the r e a c t i o n o b s e r v e d and
the s l o p e o f the l i n e i s e q u a l t o -E /RT. Such a r e l a t i o n s h i p i s
d e r i v e d from i n t e r g r a t i o n o f the A r r h e n i u s e q u a t i o n t o E q u a t i o n 1.
I n k = -E /RT + constant (1)

a
where k i s t h e r a t e c o n s t a n t a t temperature T (K) and R i s the gas
constant (1.987 c a l / d e g - m o l ) . E x t r a p o l a t i o n from t h e A r r h e n i u s
p l o t a l l o w s t h e c a l c u l a t i o n o f the r a t e c o n s t a n t , k, a t tempera
t u r e s o t h e r than t h o s e t e s t e d . The h a l f - l i f e ( t ) i s c a l c u l a t e d
x
f o r a f i r s t - o r d e r o r p s e u d o - f i r s t - o r d e r r a t e c o n s t a n t by s u b s t i t u
t i o n i n t o E q u a t i o n 2.
= 0.693/k (2)
A t y p i c a l A r r h e n i u s p l o t of data obtained i n t h i s study i s

shown i n F i g u r e 4. E x t r a p o l a t i o n s of r e s u l t s o f A r r h e n i u s p l o t s
f o r the v a r i o u s E D B - f o r t i f i e d w a t e r s t o common groundwater tempera
t u r e s a r e shown i n T a b l e I I . A c t i v a t i o n e n e r g i e s c a l c u l a t e d f o r
t h e h y d r o l y s i s a t 22C range from 19.6 t o 24.2 K c a l / d e g - m o l . The
pH v a l u e s o f the samples d u r i n g t h e d e g r a d a t i o n experiments were i n
most c a s e s about 1 pH u n i t h i g h e r t h a n t h e r e c o r d e d pH a t t h e time
of sampling a t the w e l l s i t e s . T h i s i s presumably due t o l o s s o f
dissolved C0 . 2 However, as the pH-dependence e x p e r i m e n t s have
i n d i c a t e d , t h i s pH s h i f t s h o u l d not have a s i g n i f i c a n t e f f e c t on
the d e g r a d a t i o n r a t e c o n s t a n t s . T h e r e f o r e , i t was i g n o r e d i n t h e
calculations.
The differences in the rates of degradation were evident
Figure 2. EDB h y d r o l y s i s i n groundwaters at various tempera

tures.
Table I. K i n e t i c Data f o r EDB H y d r o l y s i s i n B u f f e r e d S o l u t i o n s (63C, lOOppb)
pH *buffer 1 0 k , \t
3
x (days) 3
**10 kSD ( p o o l e d data)
ObS -"2
Polk Highlands Jackson Deion.
4.0-4.4 a 2.31 2.31 2.34 2.48 2.360.13

301 302 298 280
4.0-4.9 b 2.94 2.61 2.45 2.54 2.630.29

236 266 283 273
4.7-5.3 b 2.84 2.56 3.46 3.10 3.23+0.45

208 225 200 225
5.3-5.6 a 2.41 2.44 3.47 3.10 2.4010.10

288 288 287 295
6.1-6.5 c 2.45 2.98 2.64 2.83 2.7310.23

283 233 263 285
7.6-7.7 d 2.68 2.68 2.52 2.63 2.9510.62

259 259 275 263
7.8-7.9 e 4.39 3.96 3.83 4.17 4.1710.38

158 175 181 166
8.0-8.3 f 3.76 2.81 3.56 3.62 3.4410.44

266 247 195 191
8.6-9.0 g 3.07 2.61 2.41 2.95 2.9510.48

224 267 288 235
3
* 5 10 M b u f f e r s : a = b o r a x / s u c c i n i c a c i d , b=potassium p h a t h a l a t e ,
c = b o r a x / s u c c i n i c a c i d , d=borax/phosphate, e , f = b o r i c a c i d , g=carbonate
** p o o l e d d a t a o f a l l samples, n=8.
l o g k (obs)
-2 r Polk water
H i g h l a n d s water
-2.25
J a c k s o n water
-2.5 D e i o n i z e d water
T -
-2.75
4 5 6 7 8 9
PH
F i g u r e 3. P r o f i l e o f EDB h y d r o l y s i s rate constants vs pH in
b u f f e r e d s o l u t i o n s a t 63C.
( = .05) i n s e v e r a l groundwater samples. F o r example, t h e water

from t h e P o l k county s i t e f o r t i f i e d t o 10 ppb EDB had a t ^ about
40% lower than i n t h e 100 ppb f o r t i f i e d w a t e r , and i n H i f h l a n d s
w a t e r , t h e 10 ppb f o r t i f i c a t i o n had a t ^ about 60% l a r g e r t h a n t h e
100 ppb f o r t i f i c a t i o n . The J a c k s o n w a t l r r e s u l t s showed a d i f f e r
ence between t h e f i l t e r e d and a u t o c l a v e d p r e p a r a t i o n s a c c o u n t i n g
f o r a l a r g e v a r i a t i o n i n t h e 10 ppb samples making comparison w i t h
the 100 ppb samples m e a n i n g l e s s . In c o n t r a s t , the observed degra
d a t i o n r a t e s i n d e i o n i z e d w a t e r a t t h e two c o n c e n t r a t i o n s were
identical. These r e s u l t s suggest t h a t t h e c o n s t i t u e n t s o f ground
water may have an i n f l u e n c e on t h e h y d r o l y s i s o f EDB.
H a l f - l i v e s i n t h e range o f 1.5 t o 2 y e a r s c a n be e x p e c t e d f o r
EDB i n groundwater i n v a r i o u s r e g i o n s o f F l o r i d a ( 2 2 C ) . I n more
n o r t h e r n l o c a t i o n s o f t h e U.S. h a l f - l i v e s o f about 2 t o 5 y e a r s
c o u l d be e x p e c t e d s i n c e t h e i r t y p i c a l groundwater t e m p e r a t u r e i s
l e s s than 15C ( T a b l e I I ) .
H y d r o l y s i s Degradation Product Studies.

l t f
At e l e v a t e d temperatures (60, 72, 80C) t h e d e c r e a s e i n C - a c t i v -
i t y p a r t i t i o n e d i n t h e hexane phase a f t e r e x t r a c t i o n p a r a l l e l e d t h e
EDB d e c l i n e determined by GC as shown i n F i g u r e 5. Exhaustive
e x t r a c t i o n s o f t h e aqueous phase d i d n o t r e s u l t i n d e t e c t i o n o f
o t h e r b r o m i n a t e d compounds. Nor were p u r g e a b l e b r o m i n a t e d compounds
d e t e c t e d i n t h e aqueous phase by GC/MS.
F i g u r e 6 shows a t y p i c a l p r o f i l e t h e c o n c e n t r a t i o n s o f EDB,
1 4
ethylene g l y c o l , bromide i o n and p a r t i t i o n i n g of C-activity
during i n c u b a t i o n s o f water samples at various temperatures
i n i t i a l l y f o r t i f i e d t o 1 t o 4 ppm o f EDB. D u r i n g t h e s e i n c u b a
t i o n s , t h e s e p r o d u c t s accounted f o r 60-100% o f t h e i n i t i a l EDB.
The c o n v e r s i o n o f EDB t o e t h y l e n e g l y c o l and bromide i o n was
e s s e n t i a l l y complete a f t e r about 7 d a y s . However, beyond t h a t
p o i n t o t h e r p r o d u c t s may have been f o r m i n g as i n d i c a t e d by t h e
changing c o n c e n t r a t i o n s o f the observed products. This result
suggests the p o s s i b i l i t y of t h e presence of s m a l l q u a n t i t i e s of
u n i d e n t i f i e d products. The mechanism shown i n F i g u r e 7 i s p r o p o s e d
f o r t h e h y d r o l y s i s o f EDB. Bromoethanol h a s n o t been d e t e c t e d a s a
p r o d u c t i n i n c u b a t e d samples, s u g g e s t i n g t h a t i t i s a s h o r t - l i v e d
species. E t h y l e n e o x i d e has been r e p o r t e d t o have a h a l f - l i f e o f
about 12 days i n n e u t r a l s o l u t i o n s a t 25C ( 9 ) .
The o v e r a l l c o n v e r s i o n o f EDB t o e t h y l e n e g l y c o l i s thermody-
namically favored. The G i b b s f r e e e n e r g i e s a r e -8.58 and -46.76
K c a l / m o l f o r t h e n e u t r a l and b a s e - c a t a l y z e d r e a c t i o n s , r e s p e c t i v e
ly. Thermodynamic data a r e not a v a i l a b l e f o r bromoethanol.
K i n e t i c d a t a f o r h y d r o l y s i s o f t h e i n t e r m e d i a t e s p e c i e s would be
h e l p f u l f o r f u r t h e r e v a l u a t i o n o f t h e mechanism o f EDB h y d r o l y s i s
proposed here.
Prompted by a r e c e n t s t u d y which showed t h a t EDB c o u l d be
o x i d i z e d under anhydrous c o n d i t i o n s t o formaldehyde by t h e a c t i o n
of superoxide i o n ( 2 9 ) , we fortified water solutions with
p a r t - p e r - m i l l i o n c o n c e n t r a t i o n s o f EDB, i n c u b a t e d them a t e l e v a t e d
temperatures, analyzed them and found them t o have low b u t
c o n s i s t e n t l e v e l s o f f o r m a l d e h y d e , b u t o n l y a f t e r a l l t h e EDB had
been h y d r o l y z e d . S t u d i e s conducted w i t h n a t u r a l and d e i o n i z e d
water f o r t i f i e d t o 10 ppm w i t h e t h y l e n e g l y c o l and i n c u b a t e d a t
85C showed t h a t t h e amounts o f formaldehyde d e t e c t e d v a r i e d from
about 350 ppb t o 2 ppm a f t e r 40 days o f i n c u b a t i o n . These f i n d i n g s
T a b l e I I . E x t r a p o l a t e d P s e u d o - F i r s t - O r d e r K i n e t i c s V a l u e s from A r r h e n i u s P l o t s
f o r EDB H y d r o l y s i s i n N a t u r a l and D e i o n i z e d Waters a t E n v i r o n m e n t a l
Temperatures
5 E
EDB pH 10 k \ a
County Water (ppb) (0.05) (hr) (daysSD) (Kcal/deg-mol)
22C
Polk 10 8.20 11.12 259 35 19.7
100 6.65 435 47 20.9
Highlands 10 8.20 3.74 772 94 24.2
100 9.37 308 66 19.2

Jackson 10 8.00 4.38 659 343 23.0
100 7.83 369 69 19.7
D e i o n i z e d Water
(22C) 10 7.60 8.94 323 55 19.6
100 8.94 323 55 19.6
(30C) 25.50 130 16

(15C) 3.57 809 109
( 8C) 1 .35 2136 461
XLEGENDX
' i n i t i a l t o t a l C-14
^ EDB; hexane (GC)

C-14; hexane
Q
A" C-14; aqueous
20 40 60 80
Time (hours)
ll+
Figure 5. Partitioning of C-EDB and p r o d u c t s during incuba-
tion o f aqueous solutions a t 80C.; i n i t i a l 60, 30 ppb/ 18,000,
9,000 dpm/mL.
15. WEINTRAUB E T A L . Degradation of 1,2-Dibromoethane 305
t a k e n t o g e t h e r i n d i c a t e t h a t h y d r o l y s i s o f EDB i s r e q u i r e d as a
f i r s t s t e p f o r formaldehyde p r o d u c t i o n and t h a t EDB i s n o t c o n v e r t -
ed t o formaldehyde by d i r e c t o x i d a t i o n a s was found i n t h e s u p e r -
oxide study. More work, c u r r e n t l y underway i s r e q u i r e d t o d e t e r -
mine t h e f a c t o r s a f f e c t i n g t h e f o r m a t i o n o f formaldehyde ( i . e .
oxygen c o n c e n t r a t i o n , o t h e r o x i d a n t s , competing r e a c t i o n s ) .
S o i l and Sludge D e g r a d a t i o n S t u d i e s .
N e i t h e r s o i l s o r s l u d g e s showed e v i d e n c e o f C 0 p r o d u c t i o n from EDB
2
i n c u b a t i o n s ; t h a t i s , t h e dpm/mL o b s e r v e d i n H S0i+-treated and

2
B a C l - t r e a t e d samples were n e v e r s i g n i f i c a n t l y below t h o s e o f t h e

2
u n t r e a t e d samples. This r e s u l t i s consistent with the negative

r e s u l t s r e p o r t e d by Bouwer and McCarty (18,19) f o r C 0 p r o d u c t i o n .
2
F i g u r e 8 shows t h e d e c r e a s e i n dpm/mL found i n t h e hexane

e x t r a c t o f t h e methanogenic s l u d g e d u r i n g i n c u b a t i o n , i n d i c a t i n g
t h a t EDB i s b e i n g degraded. O n l y a s l i g h t i n c r e a s e i n dpm/mL i n
t h e r e s i d u a l water f o r b o t h n a t u r a l and s t e r i l e s l u d g e s i n d i c a t e s
l i t t l e d i s s o l v e d C 0 o r other water-soluble degradation
2 product(s)
i s b e i n g formed, s u g g e s t i n g t h e f o r m a t i o n o f a v o l a t i l e p r o d u c t o r
products during incubation. I n f a c t , a s i g n i f i c a n t amount o f
gaseous p r o d u c t (2-4 mLs) was p r o d u c e d . T h i s was o b s e r v e d a s an
i n c r e a s i n g head-space i n t h e b o t t l e s . A n a l y s i s by GC/gas p r o p o r -
t i o n a l c o u n t i n g r e v e a l e d t h a t t h e headspace was a m i x t u r e o f N , 2
CH^ and C H ; o n l y t h e C ^
2 1+ 2 was r a d i o a c t i v e . F i g u r e 9 shows t h e GC
peak f o r e t h y l e n e d e t e c t e d by t h e r m a l c o n d u c t i v i t y and i t s c o r r e -
sponding peak d e t e c t e d by gas p r o p o r t i o n a l c o u n t i n g . F i g u r e 10
shows t h e r e s u l t s o f GC a n a l y s e s f o r EDB o f t h e same s l u d g e i n c u b a -
tions.
The r e s u l t s from t h e f a c u l t a t i v e s l u d g e samples were s t r i k i n g -
l y s i m i l a r t o t h e methogenic s l u d g e . I n 60 days a l l t h e EDB was
degraded and l i t t l e r a d i o a c t i v e m a t e r i a l remained i n t h e r e s i d u a l
water a f t e r t h e t r i p l e hexane e x t r a c t i o n . S i m i l a r l y , the sludge
produced t h e same gaseous p r o d u c t s , o f w h i c h o n l y t h e e t h y l e n e was
radioactive.
These r e s u l t s c o n f i r m t h e h y p o t h e s i s o f Bouwer and McCarty
(19) t h a t t h e w a t e r - i n s o l u b l e v o l a t i l e p r o d u c t d e r i v e d from t h e i r
EDB seeded culture incubations i s ethylene. They o b s e r v e d a
s h o r t e r p e r i o d o f time f o r t o t a l d e g r a d a t i o n , (14 days) p r o b a b l y
due t o t h e lower i n i t i a l c o n c e n t r a t i o n s o f EDB i n t h e i r e x p e r i -
ments, and r e p o r t e d no l a g p e r i o d i n t h e i r i n c u b a t i o n . Our r e s u l t s
i n F i g u r e s 8 and 10 i n d i c a t e g r a d u a l d e c l i n e o f EDB p r i o r t o 40
days w i t h a r a p i d d e c l i n e t h e r e a f t e r . I t i s a l s o noted that a
s i g n i f i c a n t l o s s o f EDB i n t h e s t e r i l e samples o c c u r r e d a f t e r 40
d a y s . T h i s i s a l s o c o n s i s t e n t w i t h t h e i r r e s u l t s and c o u l d r e f l e c t
r e a c t i o n o f EDB w i t h s u l f i d e r e d u c t a n t ( 2 8 ) .
The F l o r i d a s o i l s t e s t e d were o n l y weakly c a p a b l e o f d e g r a d i n g
EDB under a n a e r o b i c c o n d i t i o n s . A s o i l p r e p a r a t i o n from t h e 1 m
d e p t h from P o l k county showed a 40% d e c r e a s e o f l a b e l e d and n o n -
l a b e l e d EDB, a f t e r seven months. No C 0 was produced and t h e r e was
2
no more m C - a c t i v i t y i n t h e r e s i d u a l w a t e r a f t e r hexane e x t r a c t i o n s
than f o r the s t e r i l e p r e p a r a t i o n s . This i n d i c a t e s that the degra-
d a t i o n p r o d u c t o r p r o d u c t s a r e v o l a t i l e , such a s e t h y l e n e . A l l
o t h e r s o i l s f a i l e d t o degrade EDB under s i m i l a r c o n d i t i o n s over
equally long incubation periods. T h i s i m p l i e s that e i t h e r appro-
p r i a t e organism(s) a r e not present o r the s o i l s contained i n s u f f i -
c i e n t secondary carbon sources necessary t o m a i n t a i n cometabolism.
4000 XLEGEND*
* ,&1 . 1, 2-Dibromoethane
v
u 3000 Bromide i o n
Ethylene glycol
2000
C-14 i n hexane phase

1000
C-14 l e f t i n water
12 IB
Time (days)
F i g u r e 6. P r o d u c t s o f h y d r o l y s i s o f EDB during i n c u b a t i o n of
aqueous s o l u t i o n s a t 83C.
Br (Br OH / ~ x
y \ Br" / \ * Br"
V 1
B or O H
1 or H 2 Br
2
OH 2
OH
\ /
F i g u r e 7. P r o p o s e d mechanism o f h y d r o l y s i s o f EDB i n aqueous

solutions.
hexane e x t r a c t
residual H 0 2
Natural Sterile
10 20 40 10 20 40 60
Incubation, d a y s Incubation, days
F i g u r e 8. D e g r a d a t i o n o f EDB i n methanogenic s l u d g e monitored

11+
by e x t r a c t i o n o f C-EDB.
A c t i v a t e d Sludge E x t r a c t
(anaerobic)
N C h r o m o s o r b 101 2 0 C
2
N2 C a r r i e r 3 0 m L / m i n
T C D / G a s Prop. C o u n t e r

CL
(
4)
ce

L
o
Ethylene

0 2 4 6 8 10
Time (min)
F i g u r e 9. Detection of llf
C-ethylene produced during incuba
t i o n o f EDB i n s l u d g e s .
T h r e e r e p o r t s , i n c l u d i n g t h i s one, have p r e s e n t e d evidence

i n d i c a t i n g e t h y l e n e i s t h e major o r s o l e p r o d u c t of anaerobic
d e g r a d a t i o n o f EDB (16,19). I n c o n t r a s t , Bouwer and McCarty (18)
found 1,2-dichloroethane (DCE) was degraded under similar
c o n d i t i o n s t o C 0 . Thus, s u b s t i t u t i o n o f B r f o r C I appears t o make
2
the d i f f e r e n c e between c o m e t a b o l i s m (EDB) and t r u e m e t a b o l i s m

(DCE).
D e g r a d a t i o n o f EDB has been o b s e r v e d i n t h i s l a b o r a t o r y i n
sludge p r e p a r a t i o n s under a e r o b i c c o n d i t i o n s . The p r o d u c t o r
products, contrary to the anaerobic i n c u b a t i o n s , a r e not v o l a t i l e ,
but h i g h l y w a t e r - s o l u b l e . The d e t a i l s o f t h i s work w i l l be r e p o r t -
ed e l s e w h e r e .
SUMMARY
EDB was d e t e r m i n e d t o have a c h e m i c a l h a l f - l i f e o f 1.5 t o 2 y e a r s

i n t h e F l o r i d a groundwaters a t 22C. Whether t h e c o n c e n t r a t i o n o f

i n i t i a l EDB p r e s e n t was 10 o r 100 ppb made a s i g n i f i c a n t d i f f e r e n c e
i n r a t e o f d e g r a d a t i o n i n two o f t h e t h r e e w a t e r s t e s t e d , w h i l e i n
d e i o n i z e d w a t e r i t d i d n o t , s u g g e s t i n g t h a t groundwater c o n s t i t u -
e n t s may a f f e c t d e g r a d a t i o n . Such d i f f e r e n c e s due t o s o u r c e o f
the water were l e s s e v i d e n t . H y d r o l y s i s i s t h e major mode o f
d e g r a d a t i o n , g i v i n g e t h y l e n e g l y c o l and bromide i o n , and i s n o t
pH-dependent between pH 4 and 9. A r e a s o n a b l e mechanism i n which
bromoethane and e t h y l e n e oxide are intermediate products was
suggested. F u r t h e r m o r e , e t h y l e n e g l y c o l was o x i d i z e d t o f o r m a l d e -
hyde a f t e r extended i n c u b a t i o n a t e l e v a t e d t e m p e r a t u r e s .
Two d i f f e r e n t s l u d g e m a t e r i a l s r e a d i l y degraded EDB a n a e r o b i c -
ally, yielding ethylene as the o n l y o r g a n i c product, whereas
F l o r i d a s o i l s examined were n e a r l y i n c a p a b l e o f d e g r a d i n g EDB under
t h e s e c o n d i t i o n s o r a r e e x t r e m e l y slow i n d o i n g s o .
ACKNOWLEDGMENTS
We a r e g r a t e f u l t o F l o r i d a Department o f E n v i r o n m e n t a l Regulation
f o r f u n d i n g t h i s and c o n t i n u i n g work ( c o n t r a c t EDB 005) and p r o v i d -
i n g groundwater and s o i l samples.
We a l s o thank Mr. F.A. Bordeaux o f P a u l Smith's l a b o r a t o r y ,
U n i v e r s i t y o f F l o r i d a , f o r h e l p w i t h methanogenic s l u d g e and D r . T.
P h e l p s o f D.C. White's l a b o r a t o r y , F l o r i d a S t a t e U n i v e r s i t y , f o r
h e l p i n p e r f o r m i n g t h e GC/gas p r o p o r t i o n a l c o u n t i n g .
LITERATURE CITED
1. Cohen, S.Z; Carsel, R.F.; et al. Potential for pesticide con-

tamination of ground water resulting from agricultural uses in
"Treatment and Disposal of Pesticide Wastes." Am. Chem. Soc.
Sympos. Ser. #259, Krueger, Seiber (Eds.), Wash., DC (1984).
2. Fishbein, L. Potential Industrial Carcinogens and Mutagens -
Studies in Environmental Science, Elservier, Amsterdam, Vol.
4, p. 241 (1979).
3. Olson, W.A; Habermann, R.T.; et al. J. Natl. Cancer Inst.,
51,1993 (1973).
4. van Bladeren, P.J.: Breimer, D.D.; et al. The role of gluta-

thione conjugation in the mutagenicity of 1,2-dibromoethane.
Biochem. Pharmacol, 29,2975 (1980).
5. Kluwe, W.M.; McNish, R.; et al. Depletion by 1,2-dibromoeth-
ane, 1,2-dibromo- 3-chloropropane, tris (2,3-dibromopropyl)-
phosphate, and hexachloro-1,3,butadiene of reduced non-protein
sulfhydryl groups in target and non-target organs. Biochem.
Pharmacol., 2(8)499 (1981).
6. White, R.D.; et al. Characterization of the hepatic DNA
damage caused by 1,2-dibromoethane using the alkaline elution
technique. Carcinogen, 2(9)839 (1981).
7. Hamaker, J.W.; Kerlinger, H.O. Vapor Pressure of Pesticide in
"Pesticidal Formulations Research Physical and Colloidal
Chemical Aspects;" Wallenburg, J.W., Ed.; Adv. Chem. Ser. 86,
Am. Chem. Soc: Wash., DC, p. 46 (1969).
8. Gunther, F.A.; Westlake, W.E.; et al. Residue Rev., 20,45
(1968).
9. Lyman, W.J. Solubility in Water in "Handbook of Chemical Pro-

perty Estimation Methods, Environmental Behavior of Organic
Compounds;" Lyman, W.J.; Reehl, W.F.; et al, Eds., McGraw-Hill:
New York (1982).
10. Roger, R.D.; McFarlane, J.C. Sorption of carbon tetrachloride,
ethylene dibromide, and trichloroethylene on soil and clay.
Environ. Monitor, and Assess., 1,155 (1981).
11. Heuser, S.G. Residues in wheat and wheat products after fumi-
gation with ethylene dibromide. J. Sci. Fd. Agric, 12,103
(1961).
12. Sinclair, W.B.; Lindgred, D.L.; et al. Recovery of ethylene
dibromide residues from fumigated whole kernel and milled wheat
fractions. J. Econ. Entomol., 55(6)836 (1962).
13. Beckman, H.; Crosby, D.G.; et al. The inorganic bromide con-
tent of foodstuffs due to soil treatment with fumigants. J.
Fd. Sci., 32,138 (1967).
14. John, R. "Air Pollution Assessment of Ethylene Dibromide."
MITRE Tech. Report, MTR7144 (1976).
15. NIOSH. Criteria for a recommended standard: Occupational
exposure to ethylene dibromide. U.S. Dept. HEW, Wash., DC,
DHEW Public #77-221 (1977).
16. Castro, E.E.; Besler, N.O. Biodehalogenation. Reductive
dehalogenation of the biocides ethylene dibromide, 1,2-dibromo-
3-chloropropane, and 2,3-dibromobutane in soil. Environ. Sci.
and Technol., 2(10)779 (1968).
17. Bouwer, E.J.; McCarty, P.L. Transformations of halogenated
organic compounds under denitrification conditions. J. Appl.
and Environ. Micro., 45(4)1295 (1983).
18. Bouwer, E.J.; McCarty, P.L. Transformations of 1- and 2-carbon
halogenated aliphatic organic compounds under methanogenic
conditions. Appl. and Environ. Micro., 45(4)1286 (1983).
19. Bouwer, E.J.; McCarty, P.L. Ethylene dibromide transformations
under methanogenic conditions. Appl. and Environ. Micro., in
press (1985).
20. Nguyen, T.; Ollis, D.F. Complete heterogeneous photocatalyzed
transformation of 1,1- and 1,2-dibromoethane to C0 and HBr.
2
J. Phys. Chem., 88,3386 (1984).
21. Castro, C.E.; Besler, N.O. Photohydrolysis of ethylene

dibromide. J. Agric. Fd. Chem., 33,536 (1985).
22. Atkerson, T. Groundwater Protection Task Force/Groundwater
Epidem. Division, FL HRS (1985), personal communication.
23. Fernald, E.A.; Patton, D.J. (Eds.) "Water Resources Atlas of
Florida." Inst. Sci. and Publ. Affairs, Fla. State University,
Publ., pp 36,58 (1984).
24. Alexander, M.; Lurtigman, B.K. Effect of chemical structure on
microbial degradation of substituted benzenes. J. Agric. and
Fd. Chem., 14,410 (1966).
25. "Documenta Geighy-Scientific Tables," 6th ed.; Diem, ., Ed.
Geigy Pharmaceuticals, p. 314 (1962).
26. "Standard Methods for the Examination of Water and Wastewater",
15th d., APHA-AWWA-WPCF, p.261 (1980).
27. Perdue, E.M.; Wolfe, N.L. Prediction of buffer catalysis in
field and laboratory studies of pollutant hydrolysis reactions.
Environ. Sci. and Tech., 17(11)635 (1983).
28. Calderwood, T.S., Sawyer, D.T. Oxygenation by superoxide ion

of l,2-dibromo-l,2-diphenylethane, 2,3-dibromobutane, ethylene
dibromide (EDB), and 1,2-dibromo-3-chloropropane (DBCP). J.
Am. Chem. Soc, 106,7185 (1984).
29. Schwarzenbach, R.P.; Giger, W.; et al. Groundwater contamina-
tion by volatile halogenated alkanes: abiotic formation of
volatile sulfur compounds under anaerobic conditions. Environ.
Sci. and Tech., 19,322 (1985).
16
Movement of Selected Pesticides and Herbicides
through Columns of Sandy Loam
1 1 1 1
Viorica Lopez-Avila , Pat Hirata , Susan Kraska , Michael Flanagan ,
1 2 3 3
John H . Taylor, Jr. , Stephen C. Hern , Sue Melancon , and Jim Pollard
1
Acurex Corporation, Mountain View, C A 94039
2
U.S. Environmental Protection Agency, Las Vegas, NV 89114
3
University of Nevada, Las Vegas, NV 89114
The mobility of chemicals through soils following landfill disposal

or agricultural application is of concern whenever there is
potential threat to contaminate the groundwater by leaching. This
movement is evaluated by simulation modeling. Several models,
including the Pesticide Root Zone Model (1) and the Seasonal Soil
Compartment Model (2) are available, and are currently being
evaluated by the Environmental Protection Agency-Las Vegas. The
evaluation study consists of conducting a laboratory experiment in
which lysimeter columns containing test chemicals at levels
corresponding to agricultural application rates are irrigated with
water at a constant rate for 30 days. Leachate samples collected
daily from the lysimeter columns and soil cores obtained at the
completion of the experiment are analyzed for the test chemicals.
The observed concentrations are compared with the model predictions
to establish how well the model can simulate the actual situation.
Prior to the initiation of such an experiment (5 lysimeter columns
60 cm ID by 200 cm h e i g h t ) , a s m a l l - s c a l e experiment (3 columns
4.8 cm ID by 50 cm h e i g h t ) was performed t o e s t a b l i s h : breakthrough
volumes o f the t e s t c h e m i c a l s , whether or n o t the s e l e c t i o n o f the
t e s t c h e m i c a l s was a p p r o p r i a t e , and t o determine i f the a n a l y t i c a l
m e t h o d o l o g i e s were adequate. The purpose o f t h i s paper i s t o
summarize the r e s u l t s o f the s m a l l - s c a l e e x p e r i m e n t . The s i x t e s t
c h e m i c a l s s e l e c t e d f o r i n v e s t i g a t i o n were: dicaraba, 2,4-D,
a t r a z i n e , d i a z i n o n , pentachlorphenol, and l i n d a n e . Their
p h y s i c o - c h e m i c a l p r o p e r t i e s are p r e s e n t e d i n Table I . Dicamba and
2,4-D were chosen f o r t h i s s t u d y because o f t h e i r r e l a t i v e l y h i g h
water s o l u b i l i t y . C o n s e q u e n t l y , they were e x p e c t e d t o move q u i c k l y
t h r o u g h the s o i l column and be the f i r s t c h e m i c a l s t o appear i n the
leachate. D e s p i t e the f a c t t h a t 2,4-D was known t o degrade q u i c k l y
i n the s o i l , i t was f e l t t h a t due t o i t s h i g h water s o l u b i l i t y ,
2,4-D would a l s o l e a c h q u i c k l y from the s o i l column and w i l l
p r o b a b l y b r e a k t h r o u g h i m m e d i a t e l y f o l l o w i n g dicamba. The o t h e r
c h e m i c a l s e x p e c t e d t o l e a c h from the s o i l column were a t r a z i n e and
d i a z i n o n and b o t h were p r o b a b l y o f i n t e r m e d i a t e m o b i l i t y .
0097-6156/ 86/ 0315-0311 $06.00/ 0

Table I. Physico-chemical Properties of the T e s t C h e m i c a l s
T f perty P i ca"m5a"" frtrTfne^ DiazinrT PentachlorophenoT" Lindane
4
Vapor p r e s s u r e 3.75 10-3 1.05 10-2 ( ) a 5 3 10*7 (7) 3.4 10-5 (3) i.i x iQ-4 ( )9 (3.3-2.1) " (13)
(mm Hg) T = 1 0 0 C (3) 6 10-7 ()) - 8.0 10-6 (TO) 9.4 10-6 (14) ~
4
1.6 " (15")
Water s o l u b i l i t y 4,500 (3) 725 (7) 70 (7) 40 (8) 14 (11) 7.52 0.04 (16)
(mg/L) 520 (b) 5.75 to 7 . 4 0 T 1 7 - 1 9 )
900 (J)
m
Log o c t a n o l / w a t e r 2.41 (4) 2.74 (4) 2.68 (4) NA 5.01 (12) 3.72 (17) $
parti tion 6 . 3 (IDT 5.43 ( r
c
coefficient

0 (3) 60 (6) 170 (6) NA NA 80-500 (20)b
2!

fNumber3 i n p a r e n t h e s e s a r e r e f e r e n c e s
15
Va l u e g i v e n i s f o r and n o t K o c

NA data not a v a i l a b l e in the literature reviewed by authors 5

c

D
I
16. LOPEZ-AVILA ET AL. Movement of Selected Pesticides and Herbicides 313
P e n t a c h l o r phenol and l i n d a n e were s e l e c t e d p r i m a r i l y because they

were r e p o r t e d t o be the l e a s t m o b i l e c h e m i c a l s ; i n f a c t , based on
t h e i r o c t a n o l / w a t e r p a r t i t i o n c o e f f i c i e n t s , i t was e x p e c t e d t h a t
these c h e m i c a l s would n o t l e a c h a t a l l . These c h e m i c a l s were s p i k e d
i n t o the s o i l a t 16.2 ppm and were l e a c h e d f o r 30 days w i t h
o r g a n i c s - f r e e water a t a r a t e o f 55.8 mL/day. R e s u l t s a r e p r e s e n t e d
as amount l e a c h e d v e r s u s time and c o n c e n t r a t i o n o f c h e m i c a l i n s o i l
at v a r i o u s depths i n s o i l column. F u r t h e r m o r e , mass b a l a n c e s a r e
p r e s e n t e d f o r e a c h c h e m i c a l . Subsequent s e c t i o n s p r e s e n t the
e x p e r i m e n t a l d e t a i l s and the r e s u l t s o f t h i s e x p e r i m e n t .
Experimental
Leaching Experiment. Three p o l y e t h y l e n e columns (4.8 cm ID by 50 cm

h e i g h t ) were employed t o i n v e s t i g a t e the m o b i l i t y o f dicamba, 2,4-D,
a t r a z i n e , d i a z i n o n , pentachlorphenol, and l i n d a n e . Each column was
packed w i t h 1,080g o f f r e s h s o i l t o a depth o f 40 cm (sandy loam

s o i l from S o i l s I n c o r p o r a t e d , P u y a l l u p , Washington: pH 5.9 t o 6.0;
89 p e r c e n t sand; 7 p e r c e n t s i l t ; 4 p e r c e n t c l a y ; c a t i o n exchange
c a p a c i t y 7.5 raeq/lOOg).
Each column was i r r i g a t e d from the bottom w i t h HPLC grade water
(Baker A n a l y z e d Reagent) and a l l o w e d t o d r a i n f o r 1 hour. To remove
r e s i d u a l s a l t , two pore volumes (500 mL) o f HPLC grade water were
s l o w l y d r i p p e d t h r o u g h e a c h column. Next, 100g o f s o i l , s p i k e d w i t h
1.62 mg e a c h o f dicamba, 2,4-D, a t r a z i n e , d i a z i n o n ,
p e n t a c h l o r o p h e n o l , and l i n d a n e , t o s i m u l a t e an a p p l i c a t i o n r a t e o f
8 l b / a c r e , were l o a d e d onto e a c h column.
The contaminated s o i l was packed on t o p o f e a c h s o i l column t o
a depth o f 3.7 cm r e s u l t i n g i n a t o t a l column depth o f 43.7 cm. To
t h i s , 32g o f f r e s h sandy loam s o i l were added t o b r i n g the t o t a l
s o i l column h e i g h t t o 45 cm. The c o n t a m i n a t e d s o i l was p r e p a r e d as
follows: 162-yL a l i q u o t s o f s i x s t o c k s o l u t i o n s o f e a c h c h e m i c a l
( c o n c e n t r a t i o n 10 mg/mL; dicamba, 2,4-D, and p e n t a c h l o r o p h e n o l s t o c k
s o l u t i o n s were i n acetone; the r e s t i n methanol) were c o m p o s i t e d .
Acetone (100 yL) was added t o the composite s o l u t i o n t o b r i n g the
volume t o 1,072 y L . The composite s o l u t i o n was added t o 20 mL HPLC
grade water which was then mixed w i t h 100g o f f r e s h s o i l . The
p u r i t y o f the c h e m i c a l s used f o r t h i s experiment was g r e a t e r than
99 p e r c e n t .
C h e m i c a l s were l e a c h e d from the s o i l column by a p p l y i n g w a t e r ,
twice d a i l y , a t a r a t e o f 55.8 mL per d a y , per column, f o r 30 d a y s .
The i r r i g a t i o n water (27.9 mL per a p p l i c a t i o n ) was a p p l i e d a t 8 a.m.
and 2 p.m., each day, f o r 30 d a y s . L e a c h a t e s from the s m a l l columns
were c a p t u r e d d a i l y and s t o r e d i n the dark a t 4C u n t i l a n a l y z e d
(column I l e a c h a t e s were a n a l y z e d w i t h i n 3 days a f t e r c o l l e c t i o n ;
column I I and I I I l e a c h a t e s were s t o r e d f o r almost 30 days p r i o r t o
extraction). A f t e r the 30-day e x p e r i m e n t , each column was c r o s s
s e c t i o n e d i n t o n i n e d i s c r e t e segments (5 cm i n d e p t h ) . P r i o r t o
segmenting, the s o i l columns were f r o z e n a t -10C f o r 8 hours t o
facilitate sectioning. A l l s o i l samples were kept f r o z e n a t - 1 0 C
u n t i l a n a l y s i s was p e r f o r m e d .
The three s o i l columns were kept c o v e r e d w i t h aluminum f o i l
t h r o u g h o u t the 30-day e x p e r i m e n t . A n a l y s e s were performed by gas
chromatography/mass s p e c t r o m e t r y (GC/MS) f o l l o w i n g the sample

e x t r a c t i o n procedure o u t l i n e d below.
A d s o r p t i o n Study. The a d s o r p t i o n of the t e s t compounds by the sandy

loam s o i l ( p a r t i c l e s i z e l e s s than 35 mesh) was determined by
measuring the d i f f e r e n c e i n the c o n c e n t r a t i o n of an aqueous s o l u t i o n
of e a c h c h e m i c a l , b e f o r e and a f t e r e q u i l i b r a t i o n w i t h s o i l . Four t o
f i v e c o n c e n t r a t i o n s per c h e m i c a l were t e s t e d and t h r e e r e p l i c a t e
measurements were performed at e a c h c o n c e n t r a t i o n . W a t e r - t o - s o i l
r a t i o s of 2:1 to 10:1 were employed i n a l l e x p e r i m e n t s . The time
r e q u i r e d to r e a c h e q u i l i b r i u m was determined s e p a r a t e l y f o r e a c h
c h e m i c a l at one c o n c e n t r a t i o n and a s p e c i f i c w a t e r - t o - s o i l r a t i o .
F o l l o w i n g e q u i l i b r a t i o n w i t h s o i l , the aqueous s o l u t i o n was
s e p a r a t e d by c e n t r i f u g a t i o n at 2,800 rpm and was a n a l y z e d d i r e c t l y
by h i g h - p r e s s u r e l i q u i d chromatography (HPLC). The e x p e r i m e n t a l
c o n d i t i o n s f o r HPLC a n a l y s i s are g i v e n i n Reference 21. Attempts to
a n a l y z e l i n d a n e i n the aqueous phase by HPLC w i t h u l t r a v i o l e t

d e t e c t i o n , w i t h o u t p r e c o n c e n t r a t i o n , were u n s u c c e s s f u l . Lindane was
a n a l y z e d by gas chromatography w i t h e l e c t r o n c a p t u r e d e t e c t i o n
f o l l o w i n g p r e c o n c e n t r a t i o n on C^g-reverse phase r e s i n and e l u t i o n
w i t h t e t r a h y d r o f u r a n . Other d e t a i l s can be found i n Reference 21.
S o i l D e g r a d a t i o n Study. One hundred and f o r t y - f o u r amber j a r s

(500 mL) were l o a d e d w i t h 50-g f r e s h sandy loam s o i l and d i v i d e d
i n t o two g r o u p s . Seventy-two of them were a d j u s t e d a t 14 p e r c e n t
m o i s t u r e (group I ) . The o t h e r 72 were a d j u s t e d at 22 p e r c e n t
m o i s t u r e (group I I ) . The 72 samples i n group I were f u r t h e r d i v i d e d
as f o l l o w s : 36 o f them were s p i k e d w i t h dicamba, 2,4-D, and
p e n t a c h l o r o p h e n o l a t 1 yg/g; the o t h e r 36 s p i k e d w i t h l i n d a n e ,
a t r a z i n e , and d i a z i n o n at 1 yg/g. S p i k i n g was performed a f t e r the
s o i l was a d j u s t e d at 14 p e r c e n t or 22 p e r c e n t m o i s t u r e . The s p i k e
was added i n a c o n c e n t r a t e d s o l u t i o n to the s o i l (100 yL of a
0.5 rag/raL s t o c k s o l u t i o n ) and was mixed t h o r o u g h l y w i t h the s o i l .
A l l samples from group I I were t r e a t e d s i m i l a r l y .
The s p i k e d samples were i n c u b a t e d i n an oven at 85F, i n d a r k ,
and i n open system; c o t t o n p l u g s were used to prevent dust from
e n t e r i n g the f l a s k s . The experiment was s e t up f o r 90 days. The
sampling times were 0.04; 0.67; 1.67; 4; 10 or 12; 20; 32; 61 and 93
days from the i n i t i a t i o n o f the e x p e r i m e n t . Three r e p l i c a t e s were
a n a l y z e d at e a c h time i n t e r v a l f o r the t e s t compounds. Soil
m o i s t u r e was m a i n t a i n e d at 14 p e r c e n t and 22 p e r c e n t by a d d i t i o n o f
o r g a n i c s - f r e e water and was v e r i f i e d twice a week d u r i n g the
experiment. Other d e t a i l s can be found i n Reference 21.
Analytical Methodologies
Dicamba and 2,4-D A n a l y s i s . A F i n n i g a n 1020 quadrupole mass

s p e c t r o m e t e r c o u p l e d to a P e r k i n - E l m e r Sigma 1 gas chromatograph and
an Incos 2300 d a t a system was used f o r a l l measurements r e p o r t e d
here. C a l i b r a t i o n s t a n d a r d s and sample e x t r a c t s were i n j e c t e d
manually. Compound s e p a r a t i o n s were performed on a 6 - f t g l a s s
column packed w i t h U l t r a b o n d 20M, temperature programmed from 150C
(1 min) t o 240C at 15C/min; c a r r i e r gas He; f l o w r a t e 45 raL/min;
i n j e c t o r temperature 220C.; t r a n s f e r l i n e temperature 250C. The
mass spectrometer o p e r a t i n g c o n d i t i o n s i n c l u d e d : e l e c t r o n e n e r g y
70 eV; and s e l e c t e d i o n m o n i t o r i n g mode f o r i o n s at m/z 188, 203,

206, 400, and 403 i n a t o t a l scan time of 0.65 s e c . Other d e t a i l s
of the gas chromatographic/mass s p e c t r o m e t r i c a n a l y s e s can be found
elsewhere ( 2 1 ) .
A t r a z i n e , D i a z i n o n , Pentachlorphenol, and Lindane Analy_sis_ ^

F i n n i g a n 4021 quadrupole mass spectrometer coupled to a
F i n n i g a n 9610 gas chromatograph and an Incos 2300 d a t a system was
used f o r a l l measurements r e p o r t e d h e r e . C a l i b r a t i o n s t a n d a r d s and
sample e x t r a c t s were i n j e c t e d a u t o m a t i c a l l y by a V a r i a n a u t o s a m p l e r .
Compound s e p a r a t i o n s were performed on a f u s e d s i l i c a c a p i l l a r y
column 30ra 0.25 ram ID DB-5 (J&W S c i e n t i f i c , 0.25-ym f i l m
t h i c k n e s s ) ; s p l i t l e s s i n j e c t i o n at 50C f o l l o w e d by temperature
programming to 300C at 15C/min; i n j e c t o r temperature 260C.;
t r a n s f e r l i n e temperature 280C.; c a r r i e r gas He at 10 p s i p r e s s u r e .
The mass spectrometer o p e r a t i n g c o n d i t i o n s were i o n source
temperature 300C.; e l e c t r o n e n e r g y 70 eV; s e l e c t e d i o n m o n i t o r i n g

mode f o r i o n s at m/z 188, 200, 205, 181, 224, 304, 314, 266, and 272
i n a t o t a l scan time of 0.69 s e c . Other d e t a i l s of the gas
chromatographic/mass s p e c t r o m e t r i c a n a l y s e s can be found elsewhere
(21-22).
Reagents and Standard Compounds. A n a l y t i c a l r e f e r e n c e s t a n d a r d s of

dicamba, 2,4-D, a t r a z i n e , d i a z i n o n , pentachlorphenol, and l i n d a n e
were o b t a i n e d from the U.S. EPA P e s t i c i d e s and I n d u s t r i a l C h e m i c a l s
R e p o s i t o r y (MD-8), R e s e a r c h T r i a n g l e P a r k , NC 27711. Stock
s o l u t i o n s were prepared i n p e s t i c i d e grade methanol or acetone
(Baker r e s i - a n a l y z e d ) and s t o r e d at -10C.
S t a b l e - l a b e l e d i s o t o p e s dicamba-d3, 2,4-D-d3, a t r a z i n e - d 5 ,
d i a z i n o n - d j Q , and l i n d a n e - d ^ were s y n t h e s i z e d by P a t h f i n d e r
Laboratories, St. Louis, M i s s o u r i . Pentachlorophenol-^c^ was
o b t a i n e d from MSD-isotopes, D i v i s i o n of Merck F r o s t Canada I n c . ,
M o n t r e a l , Canada. The d e u t e r a t e d compounds and the ^ C - l a b e l e d
pentachlorphenol were s p i k e d i n t o e v e r y sample at known
c o n c e n t r a t i o n and were used to q u a n t i t a t e the n a t u r a l l y abundant
compounds by s t a b l e - i s o t o p e d i l u t i o n p r o c e d u r e s (23-24).
Leachate E x t r a c t i o n . Known volumes of l e a c h a t e samples ("-50 mL)

were s p i k e d w i t h the s t a b l e - l a b e l e d i s o t o p e s at 80 ug/L and were
e x t r a c t e d at t h e i r o r i g i n a l pH (6 to 6.5) by v i g o r o u s l y shaking f o r
2 min, i n a 250-mL s e p a r a t o r y f u n n e l w i t h 50 mL methylene c h l o r i d e .
E x t r a c t i o n was performed three c o n s e c u t i v e t i m e s , e a c h time u s i n g
f r e s h 50-mL a l i q u o t s of methylene c h l o r i d e . The e x t r a c t s were
combined, moisture was removed by p a s s i n g the e x t r a c t through a
column of anhydrous sodium s u l f a t e , and the e x t r a c t was then
c o n c e n t r a t e d to 4 to 6 mL i n a Kuderna-Danish e v a p o r a t o r . Further
c o n c e n t r a t i o n to 1 mL was performed u s i n g n i t r o g e n blowdown
evaporation. F o l l o w i n g e x t r a c t i o n at pH 6 to 6.5, the aqueous phase
was a c i d i f i e d at pH 1 and was e x t r a c t e d three c o n s e c u t i v e times w i t h
50-mL a l i q u o t s of methylene c h l o r i d e . The a c i d i c e x t r a c t s were
combined and were c o n c e n t r a t e d to 10 mL u s i n g a Kuderna-Danish
evaporator. P r i o r to a n a l y s i s , the a c i d i c e x t r a c t was d e r i v a t i z e d
w i t h p e n t a f l u o r o b e n z y l bromide a c c o r d i n g to procedures d e s c r i b e d i n
Reference 19.
S o i l E x t r a c t l o g . S o i l samples were thawed at room temperature f o r

2 hours and were e x t r a c t e d as f o l l o w s : 50-g a l i q u o t s of the f r e s h
sandy loam s o i l were s l u r r i e d w i t h 10 mL of o r g a n i c s - f r e e water and
s p i k e d w i t h known amounts of s t a b l e - l a b e l e d i s o t o p e s . The s p i k e was
added i n 100 t o 400-yL methanol a l i q u o t s to the wet s o l i and was
a l l o w e d to e q u i l i b r a t e w i t h the s o i l f o r 1 hour. Two separate
a l i q u o t s were e x t r a c t e d f o r e a c h sample. One a l i q u o t was e x t r a c t e d
at n e u t r a l pH to s e p a r a t e a t r a z i n e , l i n d a n e , and d i a z i n o n . The
o t h e r a l i q u o t was e x t r a c t e d at a c i d i c pH to s e p a r a t e dicamba, 2,4-D,
and pentachlorophenol.
The a l i q u o t d e s i g n a t e d f o r e x t r a c t i o n at n e u t r a l pH was
e x t r a c t e d t h r e e t i m e s , w i t h f r e s h 100-mL acetone/hexane ( 5 0 / 5 0 ) . An
u l t r a s o n i c c e l l d i s r u p t o r , i n p u l s e d mode at 50 p e r c e n t duty c y c l e ,
was employed to enhance the c o n t a c t between the e x t r a c t i o n s o l v e n t
and s o i l . F o l l o w i n g e a c h e x t r a c t i o n , the s o i l was a l l o w e d to
s e t t l e , the s o l v e n t d e c a n t e d , and the combined s u p e r n a t a n t s from the
n e u t r a l pH e x t r a c t i o n were d r i e d t h r o u g h a column of anhydrous

sodium s u l f a t e (5-cm bed h e i g h t ; 3-cm d i a m e t e r ) . Concentration of
the e x t r a c t was performed u s i n g a Kuderna-Danish e v a p o r a t o r . Final
volume was a d j u s t e d t o 1 mL u s i n g n i t r o g e n blowdown e v a p o r a t i o n .
The e x t r a c t i o n at a c i d i c pH was performed as f o l l o w s :
50-g a l i q u o t s of the s o i l sample were s l u r r i e d w i t h 10 mL o f
o r g a n i c s - f r e e water and s p i k e d w i t h the s t a b l e - l a b e l e d i s o t o p e s .
F o l l o w i n g e q u i l i b r a t i o n , the s o i l s l u r r y was a d j u s t e d to pH <1 w i t h
a p p r o x i m a t e l y 10 mL of H2SO4 ( 1 + 1 ) and was e x t r a c t e d three times
w i t h 100 mL of acetone/hexane (50/50) u s i n g an u l t r a s o n i c c e l l
disruptor. The e x t r a c t was c o n c e n t r a t e d u s i n g a Kuderna-Danish
e v a p o r a t o r and was s p l i t as f o l l o w s : 1 mL was taken f o r
p e n t a c h l o r o p h e n o l a n a l y s i s and 3 mL were taken f o r a n a l y s i s of
dicamba and 2,4-D. The e x t r a c t c o n t a i n i n g dicamba and 2,4-D was
d e r i v a t i z e d w i t h p e n t a f l u o r o b e n z y l bromide at 60C a c c o r d i n g to
p r o c e d u r e s g i v e n i n Reference 19.
Re s u I t s and Piseussion
L e a c h i n g E x p e r i m e n t . The observed d i s t r i b u t i o n s of a t r a z i n e ,
d i a z i n o n , p e n t a c h l o r o p h e n o l , and l i n d a n e i n s o i l columns, t h a t
r e s u l t e d from i r r i g a t i o n w i t h water f o r 30 d a y s , are p r e s e n t e d i n
F i g u r e s 1 through 6. The amounts l e a c h e d from e a c h s o i l column
d a i l y , f o r 30 d a y s , are p r e s e n t e d i n F i g u r e s 7 t h r o u g h 10. Dicamba
and 2,4-D were not d e t e c t e d i n any o f the s o i l samples or t h e i r
c o n c e n t r a t i o n s i n s o i l were o n l y s l i g h t l y above the method d e t e c t i o n
l i m i t ; t h e r e f o r e , no d i s t r i b u t i o n s p r o f i l e s f o r these c h e m i c a l s i n
s o i l are g i v e n . D i a z i n o n and p e n t a c h l o r o p h e n o l were not d e t e c t e d i n
any of the l e a c h a t e s ; c o n s e q u e n t l y , the l e a c h a t e p r o f i l e s f o r these
two c h e m i c a l s are not p r e s e n t e d .
Table I I i s a summary of the d a t a g e n e r a t e d f o r the s i x
chemicals. The v a r i o u s parameters i n Table I I are d e f i n e d below:
Zone p o s i t i o n (Zp) i s the s o i l column s e c t i o n c o n t a i n i n g the
h i g h e s t c o n c e n t r a t i o n o f the t e s t c h e m i c a l
Zone d i s p e r s i o n (Z^) i s the number of column s e c t i o n s
c o n t a i n i n g the c h e m i c a l d i v i d e d by the c o n c e n t r a t i o n o f the
core c o n t a i n i n g the h i g h e s t c o n c e n t r a t i o n
Depth (d) i s the d i s t a n c e , i n cm, measured from the top o f the
column at which the c h e m i c a l r e a c h e d the maximum c o n c e n t r a t i o n
Concentration (ng/g wet s o i l )
Top 100 200 300 400
I I
Bottom
Atrazine
Diazinon
F i g u r e 1. D i s t r i b u t i o n o f a t r a z i n e and d i a z i n o n i n s o i l
f o l l o w i n g t h e 30-day t e s t (column I ) .
Concentration (ng/g wet soil)
200 300 400

o Atrazine
Diazinon
F i g u r e 2. D i s t r i b u t i o n of a t r a z i n e and d i a z i n o n i n s o i l
f o l l o w i n g the 30-day t e s t (column I I ) .
Concentration (ng/g wet s o i l )
400
oAtrazine
Diazinon
F i g u r e 3. D i s t r i b u t i o n o f a t r a z i n e and d i a z i n o n i n s o i l
f o l l o w i n g t h e 30-day t e s t (column I I I ) .
Top 100 200 300 400 500 600
I
*
I
Bottom
_ _ _ _ _
Lindane
F i g u r e 4. D i s t r i b u t i o n o f l i n d a n e and p e n t a c h l o r o p h e n o l i n s o i l
f o l l o w i n g t h e 30-day t e s t (column I)
100 200 300 400 500 600
--PCP
Lindane
F i g u r e 5. D i s t r i b u t i o n o f l i n d a n e and p e n t a c h l o r o p h e n o l i n s o i l
f o l l o w i n g the 30-day t e s t (column I I ) .
300 400 500 600 700

"

TJ
m
PCP C/3
Lindane H
n
5m
en
F i g u r e 6 D i s t r i b u t i o n o f l i n d a n e and p e n t a c h l o r o p h e n o l i n s o i l

f o l l o w i n g the 30-day t e s t (column I I I ) .

C

D
LOPEZ-AVILA ET AL. Movement of Selected Pesticides and Herbicides
700
Time (days)
F i g u r e 7. Amount o f dicamba (/ig) l e a c h e d from columns I , I I ,

d u r i n g t h e 30-day t e s t .
120
Time (days)
F i g u r e 8. Amount o f 2,4-D (jig) l e a c h e d from columns I , I I , I I I

d u r i n g t h e 30-day t e s t .
60
Time (days)
F i g u r e 9. Amount o f a t r a z i n e 0*g) l e a c h e d from columns I , I I ,

I I I d u r i n g the 30-day t e s t .
Time (days)
F i g u r e 10. Amount o f l i n d a n e (//g) l e a c h e d from columns I , I I ,

I I I d u r i n g the 30-day t e s t .
16. LOPEZ-AVILA ET A L . Movement of Selected Pesticides and Herbicides 325
K O i s the o r g a n i c carbon n o r m a l i z e d a d s o r p t i o n c o e f f i c i e n t o f
C
the t e s t c h e m i c a l . The K Q v a l u e s p r e s e n t e d i n Table I I were

C
determined i n our l a b o r a t o r y by measuring the d i f f e r e n c e i n the

c o n c e n t r a t i o n o f an aqueous s o l u t i o n o f the c h e m i c a l b e f o r e and
a f t e r e q u i l i b r a t i o n w i t h s o i l , f o r a d e f i n e d time i n t e r v a l .
Table I I . C o r r e l a t i o n Between the Movement of Test Chemicals

Through Sandy Loam and K O C
Zone Depth Zone

Position d Dispersion d-Z b
c
Compound (Zp) (cm) (Z ) d
d Koc
Dicamba a a a a 93
2,4-D a a a a 108
Atrazine 1 40-45 0.23;0.24;0.25 10.2 380

Diazinon 1 20-30 0.37;0.33;0.40 9.2 1,700
Pentachlorophenol 1 15-20 0.117;0.119;0.119 2.1 2,500
Lindane 4-5 25-45 0.756;0.526;0.744 23.6 2,700
a
C h e m i c a l l e a c h e d c o m p l e t e l y from the s o i l column (see Table I I I f o r
mass b a l a n c e )
Z j i s a movement c o n s t a n t . I t i s used t o d e s c r i b e how f a s t the
c h e m i c a l moved through the s o i l column.
c
0 r g a n i c carbon c o n t e n t o f the sandy loam s o i l used i n t h i s s t u d y i s
1,290 185 mg/kg
Table I I I i s a summary o f mass b a l a n c e s performed f o r e a c h

c h e m i c a l and d e g r a d a t i o n h a l f - l i v e s a t 85F, i n open system, and
u s i n g sandy loam s o i l o f 14 p e r c e n t and 22 p e r c e n t m o i s t u r e .
Table III. Mass Balance and D e g r a d a t i o n Half-lives f o r the

T e s t Chemicals
H a l f - l i f e (^/ )for
2
D c
Mass B a l a n c e * > Degradation i n S o i l
Compound ( P e r c e n t Recovered) (Days)
Dicamba 62--86 73- 77
2,4-D 39--47 d
Atrazine 48--53 73- 78
Diazinon 9.2--13 17- 22
Pentachlorophenol 18--25 24- 38
Lindane 9.5--13 21
a
V a l u e s g i v e n r e p r e s e n t range v a l u e s f o r the t h r e e columns, and t h e y
r e f e r t o the t o t a l amount o f c h e m i c a l t h a t was r e c o v e r e d from
l e a c h a t e s and s o i l c o r e s .
b_oss through v o l a t i l i z a t i o n from the s o i l column was i n s i g n i f i c a n t
f o r d i a z i n o n , p e n t a c h l o r o p h e n o l , and l i n d a n e .
C t
l / 2 was determined a t 85F, i n open system, and a t 14 p e r c e n t and
22 p e r c e n t m o i s t u r e .
s a s
^ti/2 * f u n c t i o n o f c o n c e n t r a t i o n ( t ^ / 2 * 73 hours a t 1 yg/g and
213 hours a t 10 y g / g ) .
The f o l l o w i n g c o n c l u s i o n s can be drawn from the d a t a p r e s e n t e d

in F i g u r e s 1 t h r o u g h 10 and T a b l e s I I and III
Dicamba was the f i r s t c h e m i c a l t h a t appeared i n the l e a c h a t e .
I t was d e t e c t e d i n the le achate s c o l l e c t e d a t day 4 from e a c h
of the t h r e e columns and r e a c h e d maximum c o n c e n t r a t i o n a t day 6
or 7 o f the experiment ( F i g u r e 7 ) . The amounts r e c o v e r e d i n
l e a c h a t e s account f o r 86 p e r c e n t , 62 p e r c e n t , and 62 p e r c e n t
from the amounts s p i k e d i n columns I , I I , and I I I ,
respectively. Lower r e c o v e r i e s f o r columns I I and I I I might be
due t o the f a c t t h a t l e a c h a t e s from columns I I and I I I were
s t o r e d f o r almost 30 days p r i o r t o e x t r a c t i o n , d u r i n g which
time compound d e g r a d a t i o n might have o c c u r r e d . Dicamba was n o t
d e t e c t e d i n any o f the s o i l samples or the l e v e l s found were
c l o s e t o the method d e t e c t i o n l i m i t (1 t o 2 n g / g ) .
2,4-D was the second c h e m i c a l t o l e a c h from the s o i l columns.
The d a t a shown i n F i g u r e 8 i n d i c a t e t h a t 2,4-D was p r e s e n t i n
the l e a c h a t e s c o l l e c t e d a t day 9 o f the e x p e r i m e n t , i t s

c o n c e n t r a t i o n r e a c h e d a maximum a t day 10, 11, or 12 o f the
e x p e r i m e n t , and c o n t i n u e d t o l e a c h from the s o i l columns u n t i l
day 30 o f the e x p e r i m e n t . The amounts o f 2,4-D r e c o v e r e d i n
l e a c h a t e s account f o r 39 p e r c e n t and 47 p e r c e n t from the
amounts s p i k e d i n columns I and I I , r e s p e c t i v e l y . 2,4-D was
d e t e c t e d i n the s o i l samples a t c o n c e n t r a t i o n s o f 10 t o 20 ng/g
w h i c h account f o r l e s s than 0.5 p e r c e n t o f the amount r e c o v e r e d
in leachate.
A t r a z i n e was the t h i r d c h e m i c a l t o l e a c h from the s o i l columns
(d^Z^ v a l u e i s 10.2). The d a t a shown i n F i g u r e 9 i n d i c a t e t h a t
a t r a z i n e was d e t e c t e d i n l e a c h a t e s c o l l e c t e d a t day 9 o f the
e x p e r i m e n t ; c o n c e n t r a t i o n r e a c h e d a maximum a t days 17, 19,
and 15, o f the experiment f o r columns I , I I , and I I I ,
r e s p e c t i v e l y , and c o n t i n u e d t o l e a c h u n t i l day 30 o f the
e x p e r i m e n t . The t o t a l amounts o f a t r a z i n e r e c o v e r e d i n
l e a c h a t e s account f o r 75 p e r c e n t , 59 p e r c e n t , and 74 p e r c e n t
from the t o t a l amounts o f a t r a z i n e r e c o v e r e d from columns I ,
I I , and I I I , r e s p e c t i v e l y . A t r a z i n e was found i n s o i l a t
l e v e l s r a n g i n g from 28 t o 406 ng/g. The s o i l p r o f i l e s g i v e n i n
F i g u r e s 1 through 3 show t h a t a t r a z i n e moved t h r o u g h the s o i l
column and r e a c h e d a maximum a t a depth o f 40 t o 45 cm. The
t o t a l amounts r e c o v e r e d from e a c h o f the t h r e e columns
r e p r e s e n t 53 p e r c e n t , 51 p e r c e n t and 48 p e r c e n t o f the amount
spiked.
D i a z i n o n was not d e t e c t e d i n any o f the l e a c h a t e s . The s o i l
p r o f i l e s ( F i g u r e s 1 through 3) i n d i c a t e t h a t d i a z i n o n moved
t h r o u g h the column, s i n c e the h i g h e s t c o n c e n t r a t i o n was found
i n the s o i l c o r e s a t 25 t o 30 cm i n columns I and I I , and a t
20 t o 25 cm i n column I I I (<| v a l u e i s 9.2). The amounts
r e c o v e r e d from s o i l account o n l y f o r 10 p e r c e n t , 13 p e r c e n t ,
and 9.2 p e r c e n t . These r e c o v e r i e s are not unexpected i f one
t a k e s i n t o c o n s i d e r a t i o n the f a c t t h a t the h a l f - l i f e f o r
d e g r a d a t i o n o f d i a z i n o n i n s o i l a t 22 p e r c e n t m o i s t u r e was
a p p r o x i m a t e l y 17 d a y s .
P e n t a c h l o r phenol was not d e t e c t e d i n any o f the l e a c h a t e s .
The s o i l p r o f i l e s ( F i g u r e s 4 t h r o u g h 6) i n d i c a t e t h a t
p e n t a c h l o r o p h e n o l moved through the s o i l column, and r e a c h e d
16. LOPEZ-AVILA ET A L . Movement of Selected Pesticides and Herbicides 327
h i g h e s t c o n c e n t r a t i o n a t depths o f 15 t o 20 cm ( d ' Z j v a l u e i s
2.1). The amounts r e c o v e r e d from s o i l account f o r 18 p e r c e n t ,
23 p e r c e n t , and 25 p e r c e n t f o r columns I , I I , and I I I ,
respectively. L i k e w i s e i n the case o f d i a z i n o n , t h e r e seems t o
be a c o r r e l a t i o n between the d e g r a d a t i o n h a l f - l i f e i n s o i l and
the amount r e c o v e r e d a t the end o f the 30-day e x p e r i m e n t .
Lindane was the f o u r t h c h e m i c a l t o l e a c h from the s o i l columns.
The d a t a shown i n F i g u r e 10 i n d i c a t e s t h a t l i n d a n e was d e t e c t e d
i n the l e a c h a t e s c o l l e c t e d from the three columns a t day 18,
15, and 16, r e s p e c t i v e l y ; c o n c e n t r a t i o n r e a c h e d a maximum a t
day 23, 22, and 22 o f the experiment f o r columns I , I I ,
and I I I , r e s p e c t i v e l y ; and c o n t i n u e d t o l e a c h from the s o i l
column u n t i l the day 30 o f the e x p e r i m e n t . The amounts
r e c o v e r e d i n l e a c h a t e account f o r 22 p e r c e n t , 18 p e r c e n t , and
27 p e r c e n t , r e s p e c t i v e l y . Lindane was found i n s o i l a t l e v e l s
r a n g i n g from 39 t o 171 ng/g ( F i g u r e s 4 through 6 ) . I t i s
i n t e r e s t i n g t o note t h a t , i n the case o f l i n d a n e , the Zp i s 4

to 5. The f a c t t h a t l i n d a n e was d e t e c t e d i n the l e a c h a t e
i n d i c a t e s t h a t indeed l i n d a n e moved through the s o i l column
(d'Zd v a l u e i s 23.6) and t h i s i s a l s o c o n f i r m e d by the f a c t
t h a t a l l s o i l c o r e s showed d e t e c t a b l e l e v e l s o f l i n d a n e . The
mechanism by which l e a c h i n g o f l i n d a n e took p l a c e remains y e t
to be e x p l a i n e d . The t o t a l amounts r e c o v e r e d from e a c h o f the
t h r e e columns r e p r e s e n t 9.5 p e r c e n t , 13 p e r c e n t and
10 p e r c e n t .
I n summary, i t can be c o n c l u d e d t h a t the observed d i s t r i b u t i o n s
of the t e s t c h e m i c a l s i n the three s o i l columns t h a t r e s u l t e d from
i r r i g a t i o n w i t h w a t e r , a t c o n s t a n t r a t e , f o r 30 days are i n
e x c e l l e n t agreement. F u r t h e r m o r e , the amounts l e a c h e d from the s o i l
columns and the order i n which the c h e m i c a l s were l e a c h e d are a l s o
i n good agreement. There seems t o be a good c o r r e l a t i o n between the
K Q v a l u e and the movement c o n s t a n t (d'Z^) f o r three o f the
C
c h e m i c a l s ( a t r a z i n e , d i a z i n o n , pentachlorphenol) which s u g g e s t s
t h a t the movement through the s o i l column can be p r e d i c t e d from
adsorption data. S u r p r i s i n g l y , t h i s i s n o t the case f o r l i n d a n e . A
l a r g e - s c a l e experiment i s now underway and the r e s u l t s o f t h i s s t u d y
may h e l p t o c l a r i f y the movement o f l i n d a n e through s o i l s .
Literature Cited
1. Carsel, R. F.; Smith, C. N.; Mulkey, L.A.; Dean J. D.; and P.

Jowise "Users Manual for the Pesticide Root Zone Model (PRZM),"
EPA-600/3-84-109, 1984.
2. Bonazountas, M.; I. Wagner; and B. Goodwin "Evaluation of
Seasonal Soil/Ground Water Pollutant Pathways," Arthur D.
Little, Inc., Final Report, prepared for U.S. EPA, Monitoring
and Data Support Division, EPA Contract No. 68-01-5949/9.
3. Worthing, C. R. "The Pesticide Manual A World Compendium,"
6th Ed., British Crop Protection Council, 1979.
4. Dao, T. H.; T. L. Lavy; J. Dragun Residue Rev. 1983, 87, 91.
5. Hee, S. S. Q.; Sutherland, R. G. "The Phenoxyalkanoic
Herbicides, Volume I, Chemistry, Analysis, and Environmental
Pollution," CRC Press, Inc., Boca Raton, Florida, 1981.
6 "Test Protocols for Environmental Fate and Movement of
Toxicants," Proceedings of a Symposium Association of Official
Analytical Chemists, 94th Annual Meeting, October 21-22, 1980,

Washington D.C., p. 106.
7. Bailey, G. W.; White, J. L. Residue Rev. 1970, 32, 29.
8. Gunther, Residue Rev. 1971, 36, 147.
9. Bevenue, .; Beckman, H. Residue Rev. 1967, 19, 83-134.
10. Leo, .; Hansch,C.;Elkins, D. Chem. Rev. 1971, 7, 52-616.
11. Verschueren, K. Handbook of Environmental Data on Organic
Compounds. Van Nostrand/Reinhold, New York. 1977, p 659.
12. Drahonovsky, J.; Vachek, Z. Col. Czech. Chem. Commun. 1971,
36(10), 3431-3440.
13. Demozay, D.; Marechal, G. "Physical and Chemical Properties in
Lindane: Monograph of an Insecticide," E. Ulmann 1972,
pp. 15-21. K. Schiller, Freiburg im Breisgau.
14. Benchmark, 1975. Draft of Preliminary Summaries of Literature
Surveys of Benchmark Pesticides, George Washington University
Medical Center, October, 30, 1975.
15. Masterton, W. L.; Lee, T. P. Environ. Sci. & Technol. 1973,
6(10), 919-921.
16. Kurihara, N.; Uchida, M.; Fujita, T.; Nakajima, M. Pestic.
Biochem. Physiol. 1973, 2(4), 383-390.
17. Biggar, W. J.; Riggs, R. L. Hilgardia 1974, 42(10), 383-391.
18. Bhavagary, H. M.; Jayaram M. Bull, Grain Technol. 1974, 12(2),
95-99.
19. Lee, H. B.; Chau, A. S. Y. Assoc. Off. Anal. Chem. 1983, 66,
1023-1028.
20. Wolfe, N. L.; Zepp, R. G.; Baughman, G. R.; Fincher, R. C.;
Gordon, J. A. "Chemical and Photochemical Transformation of
Selected Pesticides in Aquatic Environment," EPA 600/3-76-067.
21. Lopez-Avila, V.; Hirata, P.; Kraska, S.; Flanagan, M.; and
Taylor, J. ., Jr. "Analysis of Water and Soil Samples from
Lysimeter Columns," Acurex Final Report prepared for EPA-Las
Vegas, Environmental Assessment Division, EPA Contract
No. 68-03-3100, 1984.
22. Lopez-Avila, V.; Hirata, P.; Kraska, S.; Flanagan, M.; Taylor,
Jr., J. H.; Hern, S. C.; manuscript accepted for publication to
Anal. Chem., 1985.
23. Colby, . N.; Rosecrance, A. E.; Colby, M. E. Anal. Chem. 1981,
53, 1907-1911.
24. "Method 1625 Revision Semivolatile Organic Compounds by
Isotope Dilution GC/MS"; Environmental Protection Agency,
Federal Register 1984, 49, 184-198.
17
Principles of Modeling Pesticide Movement
in the Unsaturated Zone
R. J. Wagenet
Department of Agronomy, Cornell University, Ithaca, NY 14853
The basic principles of modeling the physical,

chemical and biological processes that determine
pesticide fate in unsaturated soil are reviewed. The

mathematical approaches taken to integrate diffusion,
convection, sorption, degradation and volatilization
are presented. Deterministic and stochastic models
formulated to describe these processes in a
soil-water pesticide system are contrasted and
evaluated. The use of pesticide models for research
or management purposes dictates the degree of
resolution with thich these processes are modeled.
The ability of each type of modeling approach to
consider pesticide fate in spatially variable field
systems is discussed.
The movement o f water and c h e m i c a l s t h r o u g h t h e u n s a t u r a t e d zone
has been s t u d i e d f o r a p p r o x i m a t e l y t h e l a s t one hundred t h i r t y
years. S i n c e t h e e a r l y 1950s, t h e s e s t u d i e s have i n t e n s i f i e d and
utilized i n c r e a s i n g l e v e l s o f m a t h e m a t i c a l s o p h i s t i c a t i o n and,
r e c e n t l y , computer t e c h n o l o g y , as t o o l s t o i n t e g r a t e and summarize
the p h y s i c a l , c h e m i c a l and b i o l o g i c a l p r o c e s s e s t h a t d e t e r m i n e t h e
dynamics o f water and s o l u t e s i n t h e system. Early efforts
f o c u s e d on i n o r g a n i c c h e m i c a l s , such as c h e m i c a l f e r t i l i z e r s o r
s a l t s found i n i r r i g a t i o n water o r as n a t u r a l c o n s t i t u e n t s o f t h e
soil profile. Not o n l y were t h e s e c h e m i c a l s o f immediate i n t e r e s t
t o a g r i c u l t u r a l i s t s d u r i n g t h e 1950s and 1960s, i t was a l s o t r u e
t h a t t h e u s e o f o r g a n i c c h e m i c a l s was n o t v e r y w i d e s p r e a d u n t i l
relatively recently. The r e s u l t o f t h e r e s e a r c h a c t i v i t y on
i n o r g a n i c s a l t s was t h e a c c u m u l a t i o n o f a s u b s t a n t i a l body o f
experimental information and theoretical conceptualizations
concerning the physics o f water movement i n homogeneous soil
p r o f i l e s and t h e r e s u l t i n g d i s p l a c e m e n t and c h e m i c a l r e a c t i o n s o f
such solutes as c h l o r i d e , nitrate, s u l f a t e and t h e common
accompanying c a t i o n s . Most o f t h i s i n f o r m a t i o n has been d e v e l o p e d
under c a r e f u l l y c o n t r o l l e d l a b o r a t o r y soil column conditions.
Confirmation that these field scale physical and chemical
0097-6156/86/0315-0330$06.00/0
17. WAGENET Principles of Modeling Pesticide Movement 331
p r o c e s s e s o p e r a t e i n t h e same manner has been attempted d u r i n g t h e

l a s t t e n y e a r s , w i t h mixed r e s u l t s .
These results have served as t h e b e g i n n i n g point f o r
d e s c r i p t i o n o f p e s t i c i d e movement t h r o u g h t h e u n s a t u r a t e d zone.
Y e t , as we i n v e s t i g a t e t h e f i e l d regime more c l o s e l y and a c t u a l l y
measure t h e d i s p l a c e m e n t o f b o t h i n o r g a n i c and o r g a n i c solutes
under f i e l d conditions, two p o i n t s a r e becoming increasingly
clear. F i r s t , t h e r e a r e many c a s e s where c u r r e n t s t a t e - o f - t h e - a r t
m o d e l i n g approaches do n o t p r o v i d e a c c u r a t e d e s c r i p t i o n o f t h e
s p a t i a l and t e m p o r a l d i s t r i b u t i o n o f p e s t i c i d e s o r more common
i n o r g a n i c s a l t s w i t h i n the u n s a t u r a t e d zone. The presumably b a s i c
p r i n c i p l e s we have i d e n t i f i e d i n l a b o r a t o r y s t u d i e s a p p a r e n t l y do
not always o p e r a t e s i m i l a r l y under f i e l d conditions. Second,
b a s e d upon t h e s e o b s e r v a t i o n s , i t i s worthy t o c o n s i d e r t h e
reformulation o f t h e b a s i c a p p r o a c h t a k e n t o p r e d i c t water and
s o l u t e movement under f i e l d c o n d i t i o n s . Strictly mechanistic,
d e t e r m i n i s t i c models, a l t h o u g h c u r r e n t l y t h e b e s t t o o l we have,
a r e p r o b a b l y n o t t h e type o f t o o l we s h o u l d be c o n s i d e r i n g a s we
l o o k twenty y e a r s ahead i n t h e development o f p e s t i c i d e models.
The p r i n c i p l e s o f modeling p e s t i c i d e f a t e i n unsaturated
f i e l d regimes a r e c u r r e n t l y b e i n g re-examined i n t h e l i g h t o f such
c o n c e r n s , and new mdoels a r e under development t h a t o f f e r t h e
promise o f more a c c u r a t e p r e d i c t i o n s under f i e l d c o n d i t i o n s . Y e t ,
we must make d e c i s i o n s today r e g a r d i n g p e s t i c i d e r e g i s t r a t i o n , u s e
and management, and the b e s t t o o l s a t o u r d i s p o s a l must be used i n
the p r o c e s s . I t i s t h e r e f o r e i m p o r t a n t t h a t we a p p r e c i a t e t h e
b a s i c p r i n c i p l e s c u r r e n t l y used i n m o d e l i n g p e s t i c i d e s , u n d e r s t a n d
the structure and organization of contemporary modeling
a p p r o a c h e s , and r e c o g n i z e t h e l i m i t a t i o n s o f t h e s e approaches t h a t
a r e b e i n g i n c r e a s i n g l y demonstrated as we l e a r n more o f t h e f i e l d
regime. These models must be used i n the s h o r t r u n , b u t i n a w i s e
and c a u t i o u s manner c o n s i s t e n t w i t h t h e i r l i m i t s . Examination of
t h e s e l i m i t s i n terms o f c u r r e n t l y r e c o g n i z e d b a s i c p r i n c i p l e s
will i l l u s t r a t e why f u t u r e models w i l l probably bear little
resemblance t o contemporary a p p r o a c h e s .
M o d e l i n g Approaches
T h e r e a r e d i f f e r e n t t y p e s o f models i n t e n d e d t o s e r v e d i f f e r e n t
purposes. B o t h t h e models and t h e p u r p o s e s a r e o f t e n c o n f u s e d .
Although a l l t h e models attempt to include description of
important b a s i c processes, t h e degree o f r e s o l u t i o n used t o
r e p r e s e n t each p r o c e s s d e t e r m i n e s t h e purpose f o r which t h e model
can be used. U n d e r s t a n d i n g t h e s e d i f f e r e n t t y p e s o f models i s a n
important first step i n evaluating t h e u s e f u l n e s s o f models
d e v e l o p e d from b a s i c p r i n c i p l e s .
There a r e a t l e a s t two major c r i t e r i a t h a t c a n be used t o
c l a s s i f y models ( 1 ) . One c r i t e r i o n i s t h e manner i n which b a s i c
p r o c e s s e s a r e c o n s i d e r e d , i . e . , whether they a r e assumed t o be
deterministic or stochastic. A l l p e s t i c i d e models c u r r e n t l y i n
the s c i e n t i f i c l i t e r a t u r e o r i n u s e a r e d e t e r m i n i s t i c . That i s ,
they presume t h a t t h e s o i l - w a t e r - p e s t i c i d e system o p e r a t e s such
that the occurrence of a given s e t o f events leads to a
uniquely-definable outcome. Such models c a n o n l y s i m u l a t e t h e
system's r e s p o n s e t o a s i n g l e s e t o f assumed c o n d i t i o n s , and
whether t h e s e p r e d i c t i o n s a r e a c c u r a t e depends upon the n a t u r e and

e x t e n t of the v a r i a b i l i t y of p h y s i c a l , c h e m i c a l and biological
processes w i t h i n the system. The uncertainties inherent i n
e s t i m a t i n g the r a t e o r magnitude of p r o c e s s e s i n the f i e l d i s
i g n o r e d i n t h e s e f o r m u l a t i o n s . The a l t e r n a t i v e i s the s t o c h a s t i c
approach which c o n s i d e r s the u n c e r t a i n t y o f the system. The
system processes, and the outcome of those processes, are
c h a r a c t e r i z e d i n s t a t i s t i c a l terms, such as the mean, v a r i a n c e o r
o t h e r s t a t i s t i c a l moments. P r e d i c t i o n s a r e not made w i t h r e s p e c t
t o a p a r t i c u l a r c o o r d i n a t e p o s i t i o n i n the s o i l , but i n terms of
a r e a s o r volumes. T h e r e a r e no p e s u i c i d e models o f t h i s type
c u r r e n t l y b e i n g used, a l t h o u g h t h i s c o u l d w e l l change i n the
f u t u r e , as d i s c u s s e d below.
A second way of c l a s s i f y i n g models i s based upon the i n t e n d e d
use. Three types can be distinguished: research,
management/educational, and s c r e e n i n g models. Examples o f each
e x i s t as p e s t i c i d e models, and a l l a r e d e t e r m i n i s t i c i n form.

R e s e a r c h models (2-5) a r e d e v e l o p e d as t o o l s t o a i d i n the t e s t i n g
of hypotheses and the exposure of areas of incomplete
understanding. These models represent basic processes in
fundamental and mechanistic terms, and, represent our most
complete u n d e r s t a n d i n g of b a s i c p r i n c i p l e s . These a r e u s u a l l y
complex models t h a t demand a l a r g e amount o f input charac-
t e r i z a t i o n d a t a , a r e based upon n u m e r i c a l d i f f e r e n c i n g methods,
and are g e n e r a l l y not used by anyone o t h e r than the model
developer. Management o r e d u c a t i o n a l models a r e substantially
s i m p l i f i e d c o n c e p t u a l i z a t i o n s of the n a t u r a l system, i n t e n d e d t o
provide qualitative guidance concerning pesticide fate as a
f u n c t i o n o f major s o i l and c h e m i c a l p r o p e r t i e s , and management
practices. These models (6-8) a r e l e s s m e c h a n i s t i c than r e s e a r c h
models, a r e f l e x i b l e i n the t y p e s o f s i t u a t i o n s they can c o n s i d e r ,
a r e not i n t e n d e d t o p r o v i d e q u a n t i t a t i v e p r e d i c t i o n s o f p e s t i c i d e
c o n c e n t r a t i o n s o r f l u x e s i n the u n s a t u r a t e d zone, and a r e i n t e n d e d
o n l y t o e v a l u a t e the r e l a t i v e , approximate b e h a v i o r o r c h e m i c a l s
w i t h o u t demanding a l a r g e amount of i n p u t c h a r a c t e r i z a t i o n d a t a .
S c r e e n i n g models, such as d e v e l o p e d by J u r y e t a l . ( 9 ) , a r e
developed f o r a t h i r d purpose: the q u a n t i t a t i v e comparison of
pesticide behavior under a v e r y limited, yet carefully and
c o m p r e h e n s i v e l y d e s c r i b e d , s e t of c o n d i t i o n s . Such models r e t a i n
a d e s c r i p t i o n of b a s i c mechanisms as a f o u n d a t i o n , but a r e n o t
i n t e n d e d t o be used under f i e l d conditions. They a r e exact
a n a l y t i c a l s o l u t i o n s f o r a s i n g l e w e l l - d e f i n e d c a s e , and because
of the assumptions needed t o make the mathematics t r a c t a b l e , a r e
not u s e f u l i n p r e d i c t i n g s i t e - s p e c i f i c behavior. Their strength
l i e s i n r e l a t i v e comparisons o f p e s t i c i d e s .
B a s i c P r o c e s s e s A f f e c t i n g P e s t i c i d e F a t e i n the U n s a t u r a t e d Zone
A l l contemporary m o d e l i n g approaches t o p r e d i c t i n g p e s t i c i d e f a t e
i n the u n s a t u r a t e d zone a r e s i m p l y the l o g i c a l r e p r e s e n t a t i o n of
our understanding of the interacting physical, chemical and
biological processes. This understanding has evolved from
l a b o r a t o r y s t u d i e s of t h e b a s i c p h y s i c s and c h e m i s t r y of s o l u t e
transport, combined with information on pesticide-soil
i n t e r a c t i o n , d e g r a d a t i o n and v o l a t i l i z a t i o n . The r e s u l t of such
dependence on laboratory studies is that a conceptual

o n e - d i m e n s i o n a l s o i l column o f homogeneous p r o p e r t i e s i s used t o
f o r m u l a t e t h e s e models. L e s s c o m p l i c a t e d management o r s c r e e n i n g
models have g e n e r a l l y e v o l v e d from t h e s e a p p r o a c h e s . A quick
review o f the b a s i c processes included i n t h e s e models will
p r o v i d e t h e framework f o r e v a l u a t i n g o u r a p p r e c i a t i o n o f b a s i c
principles.
Transport. The mechanisms r e s p o n s i b l e f o r transport are
considered t o be b o t h p h y s i c a l ( c o n v e c t i o n o r mass f l o w ) and
chemical (diffusion). When considered simultaneously, these
p r o c e s s e s have been summarized i n t h e c o n v e c t i v e - d i s p e r s i v e , o r
m i s c i b l e displacement, equation. For a non-interacting solute
(such as c h l o r i d e ) under s t e a d y s t a t e water f l o w c o n d i t i o n s i n a
homogeneous s o i l , t h i s e q u a t i o n can be w r i t t e n as ( 1 0 ) ;
St 3z 3z 2
where c s o l u t e c o n c e n t r a t i o n (m/L ) , D - a p p a r e n t d i f f u s i o n
coefficient (L / ) , i n c o r p o r a t i n g b o t h c h e m i c a l d i f f u s i o n and
hydrodynamic d i s p e r s i o n , = p o r e water v e l o c i t y ( L / T ) , d e f i n e d as
the r a t i o o f t h e water f l u x t o t h e volume water c o n t e n t , and and
t a r e d e p t h (L) and time ( ) , r e s p e c t i v e l y . The lower case m
r e p r e s e n t s mass o f s o l u t e . When a p e s t i c i d e i s t o be d e s c r i b e d ,
we must consider chemical-soil i n t e r a c t i o n , d e g r a d a t i o n and
volatilization. The f i r s t two p r o c e s s e s a r e o f t e n i n c l u d e d i n
Equation 1 as:
2
Se 3s 3 c 3c , / 0v
+ = - - (2)
3t 3t 3z 3z
where s = adsorbed c o n c e n t r a t i o n (m/M), i = d e g r a d a t i o n (chemical
o r b i o l o g i c a l ) and t h e o t h e r terms have been d e f i n e d . The upper
case M d e n o t e s mass o f s o i l . I f p l a n t uptake i s present, i t can
be i n c l u d e d a s a second term analagous t o . The v o l a t i l i z a t i o n
process c a n be included i n several ways. Plant uptake,
v o l a t i l i z a t i o n and f u n c t i o n a l r e l a t i o n s h i p s used f o r s and i a r e
o u t l i n e d below.
The a n a l y t i c a l s o l u t i o n t o E q u a t i o n 2 f o r a range o f boundary
c o n d i t i o n s i s a model o f p e s t i c i d e f a t e t h a t has been used under a
v a r i e t y o f l a b o r a t o r y s i t u a t i o n s t o study the b a s i c p r i n c i p l e s of
s o i l - w a t e r - p e s t i c i d e i n t e r a c t i o n . I t i s i n f a c t l i m i t e d t o such
l a b o r a t o r y c a s e s , as s t e a d y s t a t e water f l o w i s an assumption used
i n d e r i v i n g the equation. As a m o d e l i n g approach i t i s u s e f u l i n
those r e s e a r c h studies i n which c a r e f u l c o n t r o l o f water and
s o l u t e f l u x e s can be u s e d t o s t u d y d e g r a d a t i o n and a d s o r p t i o n .
F o r example, Zhong e t a l . (11) p r e s e n t a s t u d y o f a l d i c a r b i n
which t h e a d s o r p t i o n and d e g r a d a t i o n o f a l d i c a r b , a l d i c a r b s u l f o n e
and aldicarb-sulfoxide were simultaneously determined from
l a b o r a t o r y s o i l column e f f l u e n t d a t a . The s o l u t i o n t o a s e t o f
e q u a t i o n s o f t h e form o f E q u a t i o n 2 was u s e d . A number o f s i m i l a r
s t u d i e s f o r o t h e r c h e m i c a l s c o u l d be c i t e d t h a t have provided
u s e f u l b a s i c i n f o r m a t i o n on p e s t i c i d e b e h a v i o r i n s o i l (4,12,13).
Yet, these equations are not u s e f u l i n the f i e l d unless
r e - f o r m u l a t e d t o d e s c r i b e t r a n s i e n t water and s o l u t e f l u x e s r a t h e r
than s t e a d y ones. E a r l y models o f p e s t i c i d e f a t e based upon
E q u a t i o n 2 (14) were c o n s t r a i n e d by such a s s u m p t i o n s , b u t were
used t o d e s c r i b e f i e l d c a s e s because no o t h e r more a p p r o p r i a t e

t o o l s were a v a i l a b l e .
The transient field regime r e q u i r e s t h a t E q u a t i o n 2 be
d e r i v e d t o r e f l e c t the depth and time dependence of water and
solute. E q u a t i o n 2 then becomes ( 1 0 ) .
- +
1
- i[<e.<>H-<.c]-..t> (3)
3 3
where 6 = 6 ( z , t ) ^ v o l u m e t r i c s o i l - w a t e r c o n t e n t (L /L ) , = s o i l
b u l k d e n s i t y (M/L ) , q = water f l u x (L/T) and D i s now dependent
on and q. P e s t i c i d e d e g r a d a t i o n i s a l s o dependent on and t ,
as i t w i l l v a r y a c c o r d i n g t o the e n v i r o n m e n t a l f a c t o r s t h a t v a r y
w i t h depth and time. Equation 3, when s o l v e d by numerical
methods, forms the c o r e o f models used t o d e s c r i b e p e s t i c i d e f a t e
i n t h e u n s a t u r a t e d zone. I t r e q u i r e s knowledge o f the water
content and water flux changes w i t h depth and time. This
information i s most a c c u r a t e l y p r o v i d e d by calculating water

movement w i t h the n u m e r i c a l solution o f a second non-linear
d i f f e r e n t i a l e q u a t i o n o f t h e form
If - a i ^ O -<-*> >
(4
where K( ) h y d r a u l i c c o n d u c t i v i t y ( L / T ) , dependent upon water

c o n t e n t , U ( z , t ) = p l a n t uptake of water ( 1 / T ) , = h y d r a u l i c head
(L), f o r u n s a t u r a t e d s o i l s d e f i n e d as = h+z, where h i s the
s o i l - w a t e r m a t r i c p o t e n t i a l ( L ) , and the o t h e r terms have been
defined. Coupled s o l u t i o n s o f E q u a t i o n s 3 and 4 have been used t o
d e s c r i b e water and i n o r g a n i c s a l t movement i n a v a r i e t y o f c a s e s
(15-17) and have r e c e n t l y been extended t o p e s t i c i d e s ( 5 , 8 ) . A
key p o i n t t o r e c o g n i z e i n such models i s t h a t any u n c e r t a i n t y i n
the --h r e l a t i o n s h i p , or i n the v a l u e of U, w i l l be m a n i f e s t e d
i n an u n c e r t a i n t y i n c a l c u l a t e d water c o n t e n t s o r water f l u x e s
( c a l c u l a t e d as the water c o n t e n t change over time w i t h i n a d e p t h
interval). These u n c e r t a i n v a l u e s of and q used i n E q u a t i o n 3
to predict pesticide fate w i l l impose an u n c e r t a i n t y i n t h e
p r e d i c t i o n of p e s t i c i d e c o n c e n t r a t i o n s w i t h depth and time. That
i s , the answers o b t a i n e d u s i n g E q u a t i o n s 3 and 4 a r e o n l y as good
as the i n f o r m a t i o n p r o v i d e d on --h, and the r e l a t i o n s h i p between
D, and q.
Mediating Processes
Sorption. The i n t e r a c t i o n o f a p e s t i c i d e w i t h the s o i l s o l i d s o r

o r g a n i c m a t t e r , termed s o r p t i o n , r e t a r d s the p e s t i c i d e movement
through the unsaturated zone. This interaction is being
i n c r e a s i n g l y a s s o c i a t e d w i t h the s o i l o r g a n i c m a t t e r ( 1 8 ) , w i t h
the e x t e n t of the i n t e r a c t i o n dependent upon the type of o r g a n i c
m a t e r i a l s and the m o l e c u l a r c h a r a c t e r i s t i c s of the p e s t i c i d e ( 1 9 ) .
Linear and F r e u n d l i c h isotherms have been used to d e s c r i b e
s o r p t i o n , where
(5)
and
N
s = K_c ; N<1 (6)
w i t h s and c d e f i n e d i n E q u a t i o n 2, and Kp and the appropriate

distribution coefficients. The v a l u e s o f N, an e m p i r i c a l
c o n s t a n t , and and K_ depend upon s o i l and c h e m i c a l p r o p e r t i e s ,
and a r e u s u a l l y o b t a i n e d from l a b o r a t o r y b a t c h - t y p e equilibrium
s t u d i e s , a l t h o u g h a r e c e n t paper (11) has o b t a i n e d them from s o i l
column f l o w e x p e r i m e n t s . Reviews o f such methods and t h e d a t a
o b t a i n e d from them a r e a v a i l a b l e (20,21).
E q u a t i o n s 5 and 6 a r e o f t e n used i n E q u a t i o n s 2 and 3 f o r _ .
Knowledge o f L or and t h e r e b y p r o v i d e t h e a b i l i t y ( i n a
m o d e l i n g c o n t e x t ) t o r e t a r d p e s t i c i d e movement through t h e s o i l i n
a manner c o n s i s t e n t w i t h t h e s o r p t i o n c h a r a c t e r i s t i c s o f t h e
p a r t i c u l a r s o i l and c h e m i c a l o f c o n c e r n . O f t e n t h e v a l u e s o f K_^,
K_ o r a r e unknown, which has l e d t o e s t i m a t i o n methods based
upon e a s i l y a v a i l a b l e i n f o r m a t i o n .
The f i r s t s t e p i n t h e e s t i m a t i o n p r o c e s s i s t h e d e f i n i t i o n o f
a n o r m a l i z e d s o r p t i o n c o e f f i c i e n t , KQ> d e f i n e d as
/ f ( 7 )
K
0C - ( K
D r
V
where f = d e c i m a l f r a c t i o n o f o r g a n i c carbon i n t h e s o i l on a
weight b a s i s . T h i s n o r m a l i z a t i o n has been found t o produce
v a l u e s t h a t a r e e s s e n t i a l l y independent o f s o i l t y p e . V a l u e s or
can be e s t i m a t e d i f o n l y t h e m e l t i n g p o i n t and aqueous
s o l u b i l i t y o f t h e p e s t i c i d e a r e known from ( 2 2 ) :
log _ - -0.921 l o g
- 0.00953 (MP-25) - 0.405
(8a)
ut so J.
C / M W X
- [( sol > " " ' i
S O
55.56 (8b)
where = p e s t i c i d e aqueous s o l u b i l i t y ( g / m l ) , MW = p e s t i c i d e
m o l e c u l a r w e i g h t (g/mole), and MP = p e s t i c i d e m e l t i n g p o i n t ( C ) ,
w h i c h i s s e t e q u a l t o 25C f o r p e s t i c i d e s t h a t a r e l i q u i d s a t
temperatures l e s s than o r e q u a l t o 25C. E q u a t i o n s 8a and 8b a l l o w
the e s t i m a t i o n o f or i f t h e s o i l o r g a n i c carbon c o n t e n t i s
known, as l o n g as o r g a n i c c a r b o n c o n t e n t i s n e i t h e r v e r y h i g h n o r
low ( 2 3 ) .
A d d i t i o n a l e f f o r t s t o measure K^ o r K_ as w e l l as more
a c c u r a t e methods t o e s t i m a t e them a r e needed. A l m o s t a l l p e s t i c i d e
models, whether r e s e a r c h , management o r s c r e e n i n g u s e one o f t h e s e
three parameters to represent pesticide-soil/organic matter
interaction. A l t h o u g h more c o m p l i c a t e d e x p r e s s i o n s o f s o r p t i o n
phenomena may b e t t e r r e p r e s e n t fundamental r e l a t i o n s h i p s , such
r e s o l u t i o n i s n o t needed i n most m o d e l i n g approaches, given the
l e v e l o f r e s o l u t i o n w i t h which o t h e r p r o c e s s e s a r e c o n s i d e r e d
(water f l o w , p l a n t uptalce, d e g r a d a t i o n ) and t h e s e n s i t i v i t y o f t h e
s o i l - w a t e r system t o c l a s s i c a l s o r p t i o n phenomena. I n f a c t , f u t u r e
m o d e l i n g approaches may r e f o r m u l a t e t h e s o r p t i o n p r o c e s s t o a l a r g e
degree, c o n s i d e r i n g part of the chemical t o be s o r b e d to a
s t a t i o n a r y s o i l / o r g a n i c phase, and p a r t o f t h e c h e m i c a l sorbed t o a
s o l u b l e , m o b i l e o r g a n i c f r a c t i o n t h a t i s c a p a b l e o f moving through
o n l y a f r a c t i o n of t h e t o t a l pore s p a c e . Such r e f o r m u l a t i o n i s
c u r r e n t l y b e i n g s u g g e s t e d as t h e r e s u l t o f f i e l d o b s e r v a t i o n s o f
p e s t i c i d e movement.
Degradation. Pesticide loss to both m i c r o b i o l o g i c a l and
chemical transformational processes is collectively termed
degradation. In the root zone, degradation proceeds by
m i c r o b i o l o g i c a l p r o c e s s e s t h a t a r e f a s t e r than t h e c h e m n i c a l ones.
However, t h e r e i s l i t t l e b i o l o g i c a l a c t i v i t y below t h e r o o t zone,
and d e g r a d a t i o n i s t h e r e f o r e a c c o m p l i s h e d a t a much slower r a t e i n
the deeper u n s a t u r a t e d zone, as w e l l as i n groundwater.
A number o f e x p e r i m e n t a l s t u d i e s have e s t a b l i s h e d t h a t b o t h
m i c r o b i a l and c h e m i c a l d e g r a d a t i o n can be a p p r o x i m a t e l y d e s c r i b e d
by f i r s t - o r d e r k i n e t i c s ( 2 4 ) . Most p e s t i c i d e models employ such an
approach. As with linear sorption, this relatively naive
r e p r e s e n t a t i o n o f a f u n d a m e n t a l l y more c o m p l i c a t e d p r o c e s s i s a
s i m p l i f y i n g assumption t o make m a t h e m a t i c a l s o l u t i o n s p o s s i b l e and
data requirements reasonable. I m p l i c i t i n t h e assumption i s the

b e l i e f t h a t t h e a c c u r a c y o f s i m u l a t i o n o f p e s t i c i d e f a t e i s more
dependent upon o t h e r f a c t o r s than a v e r y p r e c i s e r e p r e s e n t a t i o n o f
the degradation process. These factors include spatial and
temporal v a r i a b i l i t y o f t h e d e g r a d a t i o n p r o c e s s i t s e l f as a f f e c t e d
by water, temperature, s u b s t r a t e , and pH, and v a r i a b i l i t y i n t h e
t r a n s p o r t o f p e s t i c i d e through t h e s o i l p r o f i l e . There i s l i t t l e
i n f o r m a t i o n t o s u b s t a n t i a t e t h i s assumption, a l t h o u g h some f i e l d
experiments on water and s o l u t e movement ( d i s c u s s e d below) i n d i c a t e
i t t o be r e a s o n a b l e a t t h i s p o i n t i n model development.
F i r s t o r d e r k i n e t i c s o f d e g r a d a t i o n a r e d e f i n e d by
= = kc ( 9 )
* It ""
where and c a r e d e f i n e d i n E q u a t i o n 2 and k = f i r s t - o r d e r r a t e
c o e f f i c i e n t ( 1 / T ) . E q u a t i o n 9 can be i n t e g r a t e d from c ( 0 ) = c t o
c ( t ) and r e a r r a n g e d i n terms o f t t o g i v e t h e h a l f - l i f e , t as
the time r e q u i r e d f o r c t o e q u a l c /2. Rao and D a v i d s o n (2D) have
c o m p i l e d t h e v a l u e s o f b o t h k and f o r a number o f p e s t i c i d e s .
Values measured i n both the f i e l d and l a b o r a t o r y e x h i b i t e d
coefficients of variation generally less than 100%. This
represents a relatively narrow range c o n s i d e r i n g the d i v e r s e
c o n d i t i o n s i n which they were d e t e r m i n e d . A d d i t i o n a l l y , i t was
found t h a t l a b o r a t o r y measured v a l u e s o f k were g e n e r a l l y s m a l l e r
than those measured under f i e l d c o n d i t i o n s . T h i s consequence o f
the m u l t i p l e d e g r a d a t i o n pathways o p e r a t i n g i n t h e f i e l d i n d i c a t e s
that t h e use o f l a b o r a t o r y - d e r i v e d v a l u e s i n models tends t o
o v e r - e s t i m a t e p e s t i c i d e p e r s i s t e n c e under f i e l d c o n d i t i o n s .
The p r e s e n t a p p r o a c h by t h e modeler i s t o e s t i m a t e k from
l a b o r a t o r y s t u d i e s , assuming t h a t t h e s e s t u d i e s approximate t h e
degradation process under field conditions. Recognizing the
probability that degradation rates are both spatially and
t e m p o r a l l y v a r i a b l e , d e t e r m i n i s t i c r e s e a r c h and management models
s h o u l d b o t h be executed w i t h a range o f k v a l u e s t o r e p r e s e n t t h e
i n f l u e n c e upon p e s t i c i d e f a t e o f t h e f i e l d v a r i a t i o n o f d e g r a d a t i o n
processes. Y e t , s e n s i t i v i t y a n a l y s i s o f models o r comparison o f
such p r e d i c t i o n s with field data on this basis i s almost
non-existent. Development o f f u n c t i o n a l r e l a t i o n s h i p s between k
and t h e e n v i r o n m e n t a l v a r i a b l e s c i t e d above would be v e r y u s e f u l ,
and would p r o v i d e a feedback mechanism whereby p r e d i c t e d water

c o n t e n t s o r temperatures c o u l d be used t o e s t i m a t e a p p r o p r i a t e k
values. A d d i t i o n a l l y , while some p r o g r e s s has been made i n
estimating sorption c o e f f i c i e n t s using physical-chemical properties
of t h e p e s t i c i d e s , s i m i l a r developments i n r e l a t i n g m i c r o b i a l o r
chemical degradation rates to chemical structure are not w e l l
d e v e l o p e d , and would be q u i t e u s e f u l . I n summary, f i r s t - o r d e r
k i n e t i c s i s used because i t i s an a p p r o p r i a t e r e p r e s e n t a t i o n o f
d e g r a d a t i o n i n t h e c o n t e x t o f model s t r u c t u r e and a l s o because n o t
enough i s known o f d e g r a d a t i o n under f i e l d c o n d i t i o n s t o u t i l i z e
more c o m p l i c a t e d k i n e t i c s .
Volatilization. The v o l a t i l i z a t i o n flux of p e s t i c i d e i s
u s u a l l y d e t e r m i n e d by f i r s t c o n s i d e r i n g i t s aqueous s o l u b i l i t y and
sorption. E x c e s s p e s t i c i d e beyond t h a t w h i c h w i l l d i s s o l v e i n s o i l
water and be sorbed by t h e s o i l i s considered available f o r
d i f f u s i o n a c r o s s t h e s o i l s u r f a c e and i n t o t h e atmosphere. Most
models t h a t c o n s i d e r v o l a t i l i z a t i o n t h e r e f o r e r e q u i r e a s i n p u t t h e
p e s t i c i d e aqueous s o l u b i l i t y and t h e s a t u r a t e d v a p o r d e n s i t y . One
method o f p a r t i t i o n i n g between t h e l i q u i d and vapor phases i s ( 9 ) .
c g = KJJC (10)
3
where c = gas c o n c e n t r a t i o n o f p e s t i c i d e (m/L ) , = Henry's
constant? and c h a s been d e f i n e d above. The v a l u e of is
c a l c u l a t e d from
h C
- g* / c
sol ( 1 1
>
where c = s a t u r a t e d v a p o r d e n s i t y and c
g Q ^ i s defined i n Equation
8b. Th^se v a l u e s a r e u s u a l l y i n c l u d e d as Manufacturer's d a t a , and
a r e assumed c o n s t a n t w i t h temperature and changes i n s o i l s o l u t i o n
composition.
Once v a l u e s o f c ( z , t ) a r e e s t i m a t e d , t h e v o l a t i l i z a t i o n f l u x
i s c a l c u l a t e d from a d i f f u s i o n e q u a t i o n t h a t c o n s i d e r s t h e g r a d i e n t
in c and a p a r t i a l l y w a t e r - f i l l e d soil porosity. Such flux
c a l c u l a t i o n s a r e d i f f i c u l t due t o t h e near i n f i n i t e g r a d i e n t i n gas
c o n c e n t r a t i o n from s o i l t o atmosphere. Often the v o l a t i l i z a t i o n
f l u x i s c a l c u l a t e d u s i n g E q u a t i o n s 10-11 and c o n s i d e r i n g o n l y t h e
v e r y s h a l l o w e s t upper l a y e r o f t h e p r o f i l e . V o l a t i l i z a t i o n models
a r e n o t i n c l u d e d i n most p e s t i c i d e management models, and i n o n l y a
few p e s t i c i d e r e s e a r c h models.
Plant uptake. P e s t i c i d e uptake by p l a n t s h a s n o t been
c o n s i d e r e d i n most m o d e l i n g e f f o r t s . T h i s i s p r i m a r i l y due t o an
almost total lack of quantitative experimental information
a v a i l a b l e t o t h e modeler, and t h e p r e s u m p t i o n t h a t t h e a b s o l u t e
mass o f p e s t i c i d e absorbed by t h e p l a n t i s s m a l l compared t o t h e
mass r e m a i n i n g i n t h e system. Due t o these considerations,
modelers have a p p a r e n t l y assumed t h a t any i n a c c u r a c y i n s i m u l a t i o n
of p e s t i c i d e f a t e t h a t r e s u l t s from n o t c o n s i d e r i n g p l a n t uptake i s
w i t h i n t h e " n o i s e " o f i n a c c u r a c i e s produced by o t h e r assumptions
about t h e p h y s i c a l , c h e m i c a l , and b i o l o g i c a l p r o c e s s e s o p e r a t i n g i n
the system. While this assumption i s unproven f o r p e s t i c i d e
a b s o r p t i o n , i t c l e a r l y cannot be a c c e p t e d f o r water a b s o r p t i o n by
the p l a n t ( t h e U ( z , t ) term i n E q u a t i o n 4 ) . P l a n t e x t r a c t i o n o f
water g r e a t l y i n f l u e n c e s water flux, which affects pesticide
displacement. The v a l i d i t y of almost a l l assumptions r e l a t e d t o

p l a n t e x t r a c t i o n of water and p e s t i c i d e a r e r e l a t i v e l y unproven and
will c e r t a i n l y need t o be i n v e s t i g a t e d b e f o r e more e f f o r t is
expended incorporating further detail into pesticide models
r e l a t i v e to d e g r a d a t i o n , s o r p t i o n o r v o l a t i l i z a t i o n .
V a l i d i t y of C u r r e n t M o d e l i n g Approaches
A l l the above i n f o r m a t i o n on the p r i n c i p l e s of p e s t i c i d e m o d e l i n g

have a common o r i g i n . Whether we c o n s i d e r the b a s i c water f l o w
( E q u a t i o n 4) and s o l u t e t r a n s p o r t ( E q u a t i o n s 2-3) e q u a t i o n s o r the
approaches t a k e n t o d e s c r i b e s o r p t i o n , d e g r a d a t i o n , v o l a t i l i z a t i o n
and plant uptake, they a l l derive primarily from laboratory
experience. Any c r e d i b i l i t y of the supposed " b a s i c p r i n c i p l e s "
r e l a t e d to d e s c r i b i n g p e s t i c i d e f a t e t h a t has e v o l v e d from t h e s e
s t u d i e s remains almost c o m p l e t e l y u n s u b s t a n t i a t e d i n the f i e l d . As
more f i e l d d a t a a r e c o l l e c t e d , t h e r e i s i n f a c t more doubt c a s t

upon the use under f i e l d c o n d i t i o n s of the c l a s s i c a l e q u a t i o n s and
formulations of b a s i c p r o c e s s e s . The n e t r e s u l t i s t h a t a l t h o u g h
we u n d e r s t a n d how t o model w e l l - d e f i n e d s o i l columns, we u n d e r s t a n d
very little regarding the magnitude, i n t e n s i t y , v a r i a t i o n and
interaction of the processes under field conditions. A few
examples w i l l i l l u s t r a t e the p o i n t , and a l t h o u g h t h e s e examples do
not s p e c i f i c a l l y t r e a t p e s t i c i d e s (because p e s t i c i d e s a r e not much
studied i n the field), they a r e e n t i r e l y appropriate for the
g e n e r a l case of s o l u t e movement, of w h i c h p e s t i c i d e s c o n s t i t u t e a
subset.
Much of the p r e s e n t c o n c e r n about the c r e d i b i l i t y o f model
p r e d i c t i o n s f o c u s e s upon i s s u e s r e l a t e d t o s p a t i a l v a r i a b i l i t y of
water and s o l u t e movement. The f i r s t l a r g e - s c a l e experiment (25)
t h a t measured on a f i e l d b a s i s the --h r e l a t i o n s h i p used i n
E q u a t i o n 4 and the v a l u e s of b o t h D and ( E q u a t i o n 2) demonstrated
quite clearly that a l l t h e s e v a l u e s were s p a t i a l l y variable.
Subsequent s t u d i e s by a number of i n d i v i d u a l s have c o n f i r m e d o v e r a
wide range of s o i l t y p e s t h a t a s i n g l e f i e l d i s c h a r a c t e r i z e d by
v a l u e s of K, D and t h a t each v a r y by o r d e r s of magnitude f o r a
g i v e n water c o n t e n t . Such p h y s i c a l r e a l i t i e s , presumably due to
m i c r o - s c a l e v a r i a t i o n i n the geometry of the porous media, i n f e r
t h a t we a r e b e i n g e x t r e m e l y n a i v e i n c o n s t r u c t i n g deterministic
models of the type f o r m u l a t e d from E q u a t i o n 2-4. Whether the model
i s i n t e n d e d f o r r e s e a r c h o r management p u r p o s e s , the c r e d i b i l i t y of
its predictions are cast i n t o doubt by the r e a l i z a t i o n that
whatever u n i q u e set of conditions are used in a particular
execution of the model, these conditions and the resulting
p r e d i c t i o n s r e p r e s e n t o n l y one p o s s i b l e s c e n a r i o of many t h a t c o u l d
be o c c u r r i n g s i m u l t a n e o u s l y i n the f i e l d . The assumption t h a t the
model i s d e s c r i b i n g the f i e l d case i s t h e r e f o r e u n r e a l i s t i c . The
usefulness of the model t o p r e d i c t p e s t i c i d e c o n c e n t r a t i o n on a
very l i m i t e d or a very l a r g e - s c a l e b a s i s i s questionable.
The formulation of a p e s t i c i d e model upon the basis of
E q u a t i o n 2-4 has a l s o been c a s t i n t o doubt by f i e l d s t u d i e s t h a t
demonstrate t h a t many f i e l d s o i l s do not meet the underlying
assumptions used i n d e v e l o p i n g t h o s e e q u a t i o n s . The assumption
that a s i n g l e pore s i z e d i s t r i b u t i o n p r e v a i l s i n a f i e l d soil,
t h r o u g h w h i c h water and s o l u t e s move u n i f o r m l y o v e r the e n t i r e
c r o s s - s e c t i o n a l a r e a , i s n o t o f t e n met. Many s o i l s c o n t a i n c r a c k s ,
wormholes, p r e f e r r e d pathways o r r e l a t i v e l y immobile porosity
r e s u l t i n g from s p e c i f i c s o i l f o r m i n g o r a g g r e g a t i o n p r o c e s s e s .
These s o i l s a r e n o t c h a r a c t e r i z e d by water f l o w t h r o u g h t h e e n t i r e
s o i l p o r e space, b u t t r a n s m i t l a r g e q u a n t i t i e s o f water d u r i n g wet
p e r i o d s t h r o u g h a r e l a t i v e l y few l a r g e p o r e s . This " a r t i f i c i a l " or
non-matrix transport of water and solute, often termed
" s h o r t - c i r c u i t i n g " , c a n r e s u l t i n s u b s t a n t i a l p e s t i c i d e movement t o
deep s o i l depths i n v e r y s h o r t time p e r i o d s . Such d i s p l a c e m e n t i s
not d e s c r i b e d by t h e models c o n s t r u c t e d from E q u a t i o n s 2-4, and
a g a i n t h e p r e d i c t i o n s o f such models w i l l be q u i t e m i s l e a d i n g i n
such c a s e s .
S e v e r a l s t u d i e s c u r r e n t l y i n p r o g r e s s c a s t f u r t h e r doubt upon
the e x i s t i n g d e t e r m i n i s t i c r e s e a r c h and management models. These
studies a r e demonstrating that s o r p t i o n c o e f f i c i e n t s a r e s p a t i a l l y
variable, and t h a t even strongly sorbed pesticides c a n be
s i m u l t a n e o u s l y found a t t h e s o i l s u r f a c e and a t deeper depths i n

the s o i l p r o f i l e . T h i s i n d i c a t e s t h a t some p e s t i c i d e may be s o r b e d
t o a m o b i l e , s o l u b l e o r g a n i c f r a c t i o n and d i s p l a c e d i n t h e same
manner a s a n o n - i n t e r a c t i n g solute. The b a l a n c e o f t h e p e s t i c i d e
i s s o r b e d and r e t a i n e d n e a r t h e s o i l s u r f a c e as would be p r e d i c t e d
w i t h E q u a t i o n s 5-6. O t h e r s t u d i e s a r e d e m o n s t r a t i n g t h a t i n some
sites the non-uniformity of pesticide application greatly
i n f l u e n c e s the r e s u l t i n g v a r i a b i l i t y of p e s t i c i d e d i s t r i b u t i o n i n
the s o i l p r o f i l e . None o f t h e s e p r o c e s s e s i s i n c l u d e d i n the
" b a s i c p r i n c i p l e s " d i s c u s s e d above, y e t may p l a y an i m p o r t a n t r o l e
in determining the accuracy and r e l i a b i l i t y o f any m o d e l i n g
predictions.
F u t u r e Use and Development o f P e s t i c i d e Models
The above i s s u e s r a i s e s e r i o u s q u e s t i o n s about t h e manner i n w h i c h

c u r r e n t p e s t i c i d e models s h o u l d be used, t h e r e l i a b i l i t y o f t h e i r
predictions, and t h e d i r e c t i o n of future pesticide modeling
efforts.
Our current understanding of the basic principles that
d e t e r m i n e p e s t i c i d e f a t e i n t h e f i e l d i s i n c o m p l e t e , y e t we must
make d e c i s i o n s now c o n s i d e r i n g p e s t i c i d e r e g u l a t i o n and management.
C u r r e n t p e s t i c i d e models used by r e g u l a t o r s and academics r e p r e s e n t
the b e s t t o o l s we have t o e s t i m a t e p e s t i c i d e f a t e as a f u n c t i o n o f
soil, climate and management factors. Y e t , we have every
i n d i c a t i o n t h a t t h e i r p r e d i c t i o n s a r e n o t u n i v e r s a l l y r e l i a b l e , and
almost no p r o o f o f t h e i r c r e d i b i l i t y i n t h e f i e l d . The q u e s t i o n i s
whether we c a n f e e l c o n f o r t a b l e about t h e p r e d i c t i o n s produced by
t h e s e models, o r whether we s h o u l d a b s t a i n from t h e i r u s e as
predictive tools u n t i l their c r e d i b i l i t y i s better established. A
h e a l t h y and c o n t i n u i n g i n t e l l e c t u a l argument i s i n p r o g r e s s on t h i s
i s s u e , and w i l l p r o b a b l y p e r s i s t f o r some t i m e . During this
d e b a t e , t h e u s e o f e x i s t i n g models f o r r e g u l a t o r y and management
p u r p o s e s w i l l c o n t i n u e , and w i l l r e s u l t i n some good d e c i s i o n s , and
p r o b a b l y some m i s t a k e s .
Several points are c l e a r . F i r s t , no p e s t i c i d e model e x i s t s
t h a t has been p r o v e n t o e s t i m a t e c o n s i s t e n t l y and a c c u r a t e l y t h e
s p a t i a l and temporal d i s t r i b u t i o n o f p e s t i c i d e c o n c e n t r a t i o n s i n
the u n s a t u r a t e d zone. This i s true regardless of the r e s o l u t i o n
used t o r e p r e s e n t b a s i c p r i n c i p l e s i n t h e model, and whether t h e

model f a l l s i n t o t h e r e s e a r c h o r management c a t e g o r y . Second, i t
f o l l o w s t h a t c u r r e n t models s h o u l d be used o n l y t o compare t h e
r e l a t i v e , not absolute, behavior of p e s t i c i d e s i n f i e l d soils.
T h i r d , t h e f i r s t two p o i n t s i n d i c a t e t h a t our a p p r o a c h t o m o d e l i n g
p e s t i c i d e f a t e i n u n s a t u r a t e d f i e l d s o i l s must change i f we a r e t o
d e v e l o p a new g e n e r a t i o n o f p e s t i c i d e models t h a t do n o t s u f f e r
from t h e l i m i t a t i o n s o f t h e c u r r e n t models.
It appears that a stochastic, rather than deterministic,
a p p r o a c h s h o u l d be c o n s i d e r e d when m o d e l i n g water and c h e m i c a l
movement i n t h e u n s a t u r a t e d zone. T h i s w i l l r e p r e s e n t no s m a l l
change i n our c o n c e p t u a l i z a t i o n of b a s i c p r i n c i p l e s of p e s t i c i d e
m o d e l i n g . The r e s u l t i n g models w i l l almost c e r t a i n l y n o t r e p r e s e n t
b a s i c p r o c e s s e s i n fundamental m e c h a n i s t i c terms, b u t w i l l i n s t e a d
represent the s o i l - w a t e r - p e s t i c i d e system i n s t a t i s t i c a l terms.
Predictions o f such models s h o u l d be p r o b a b i l i s t i c , and s h o u l d
include the confidence l i m i t s of the p r e d i c t i o n . Given the

h e t e r o g e n e o u s , v a r i a b l e n a t u r e o f s o i l systems, t h i s a p p r o a c h may
o f f e r t h e b e s t o p p o r t u n i t y t o p r e d i c t p e s t i c i d e f a t e i n terms
commensurate w i t h o u r a b i l i t y t o q u a n t i f y s o i l p r o c e s s e s . Several
such models t h a t can s e r v e as b e g i n n i n g p o i n t s have been r e c e n t l y
reported (26,27), and development work i s c o n t i n u i n g . U n t i l such
time t h a t t h e i r r e l i a b i l i t y i s e s t a b l i s h e d , we s h o u l d be q u i t e
c a u t i o u s i n o u r u s e and i n t e r p r e t a t i o n o f contemporary p e s t i c i d e
models.
Literature Cited
1. Addiscott, T.M.; Wagenet, R.J. J. Soil Sci. 1985,

36, 411-424.
2. Leistra, M. Plant Soil 1978, 49,569-580.
3. Leistra, M. Soil Sci. 1979, 128,303-311.
4. Lindstrom, F.T.; Boersma, L.; Gardiner, H. Soil Sci. 1968,
105,107-113.
5. Hutson, J.L.; Wagenet, R.J. "LEACHM: A model for simulating
the leaching and chemistry of solutes in the plant root zone";
New York State Agric. Exp. Stn.; Ithaca, N.Y., 1985, (in
press).
6. Rao, P.S.C.; Davidson, J.M.; Hammond, L.C. In "Residual
Management by Land Disposal"; U.S. Environ. Prot. Ag.
EPA-600/9-76-015, 1976; pp 235-242.
7. Steenhuis, T.; Pacenka, S.; Hughes, H.; Gross, M. "Math-
ematical model summary", Dep. of Agric. Engineering, Cornell
Univ., Ithaca, NY, 1983; 12pp.
8. Carsel, R.F.; Smith, D.N.; Lorber, M.N. "Users manual for the
Pesticide Root Zone Model (PRZM), Release 1"; U.S. Environ.
Prot. Ag. EPA-600/3-84-109, 1984; 216 pp.
9. Jury, W.A.; Spencer, W.F.; Farmer, W.J. J. Env. Quality.
1983, 12,558-564.
10. Wagenet, R.J. In "Chemical Mobility and Reactivity in Soil
Systems"; Nelson, D.W.; Elrick, D.E.; Tanji, K.K., Eds.; Spec.
Publ. No. 11, Am. Soc. Agronomy, Madison, WI., 1983; pp.
123-140.
11. Zhong, W.-Z.; Wagenet, R.J.; Lemley, A.T. In chapter 4 of
this book.
12. vanGenuchten, M.Th.; Davidson, J.M.; Wierenga, P.J. Soil Sci.

Soc. Amer. Proc. 1974, 38,29-35.
13. Selim, H.M.; Davidson, J.M.; Rao, P.S.C. Soil Sci. Soc. Amer.
J. 1977, 41,3-10.
14. Enfield, C.G.; Carsel, R.F. In "Test Protocols for
Environmental Fate and Movement of Toxicants"; Assoc. Official
Anal. Chem.: Washington, D.C. 1981; pp. 233-250.
15. Childs, S.W.; Hanks, R.J. Soil Sci. Soc. Amer. Proc. 1975,
39,617-622.
16. Davidson, J.M.; Graetz, D.A.; Rao, P.S.C.; Selim, H.M.
"Simulation of Nitrogen Movement, Transformation and Plant
Uptake in the Plant Root Zone", U.S. Environ. Prot. Ag.
EPA-600/3-78-029, 1978; 106 pp.
17. Tillotson, W.R.; Wagenet, R.J. Soil Sci. 1982, 133, 133-143.
18. Karickhoff, S.W. In "Proc. of the Symposium on Processes
Involving Contaminants and Sediments"; Baker, R.A., Ed.; Ann
Arbor Sci. Publ. Co., Ann Arbor, MI, Vol. 2, 1980; pp.
193-205.
19. Helling, C.S.; Dragun, J. In "Test Protocols for
Environmental Fate and Movement of Toxicants"; Assoc. Official
Anal. Chem.: Washington, D.C., 1981; pp. 43-88.
20. Rao, P.S.C.; Davidson, J.M. In "Environmental Impact of
Nonpoint Source Pollution"; Overcash, M.R.; Davidson, J.M.,
Eds.; Ann Arbor Sci. Publ. Co., Ann Arbor, MI, 1980; pp.
23-67.
21. Green, R.E.; Davidson, J.M.; Biggar, J.W. In "Agrochemicals
in Soils"; Banin, .; Kafkaffi, U., Eds.; Pergammon Press, New
York, 1980; pp. 73-82.
22. Karickhoff, S.W. Chemosphere 1981, 10,833-846.
23. Hamaker, J.W.; Thompson, J.M. In "Organic Chemicals in the
Environment"; Goring, C.A.I.; Hamaker, J.W., Eds., Marcel
Dekker, New York, 1972; pp. 49-143.
24. Goring, C.A.I.; Laskowski, D.A.; Hamaker, J.W.; Meikle, R.W.
In "Environmental Dynamics of Pesticides"; Hague, R.; Freed,
V.H., Eds,; Plenum Press, New York, 1975; pp. 135-172.
25. Nielsen, D.R.; Biggar, J.W.; Erh, K.T. Hilgardia 1973, 42,
215-259.
26. Jury, W.A. Water Resour. Res. 1982, 18, 363-368.
27. Dagan, G.; Bresler, E. Soil Sci. Soc. Amer. J. 1979, 43,
461-467.
18
A Method for the Assessment of Ground Water
Contamination Potential
Using a Pesticide Root Zone Model (PRZM) for the Unsaturated Zone
M. N. Lorber and Carolyn K. Offutt
Office of Pesticide Programs (TS-769C), U . S . Environmental Protection Agency,

The PRZM model was used to evaluate the potential

of aldicarb to leach through soil and contaminate
ground water in three use sites: tobacco grown on a
sandy loam soil in North Carolina and potatoes grown
on a sandy loam and a loamy sand in Wisconsin.
Calibration with the use of field data on these
sites allowed field values of aldicarb decay rate
and partition coefficient to be estimated. Long
term simulations then permitted evaluation of the
effect of soil type, date of application, and irri-
gation on the leaching potential of aldicarb in
these use sites. Results showed little to no poten-
tial for leaching on the sandy loam soils, but
significant potential on the loamy sand, with between
1 and 19% of applied to leach below 2 meters, and
six-month plume solution concentrations as high as
103 ppb at two meters. Applying later in the season
reduced leaching by about one-half, and irrigation
increased leaching 3-5 times.
The findings i n 1979 of 1,2-dibromochloropropane i n ground water

in five states and aldicarb in ground water in Long Island, New
York, began an intense effort on the part of the Office of
Pesticide Programs in the U.S. Environmental Protection Agency
(EPA) to evaluate the potential for pesticides used i n agriculture
to leach through soils and cause contamination of ground water
( 1). A critical component of this effort i s the use of mathemati-
cal models, which can predict the fate and transport of pesticides.
An early model used was called PESTANS, the Pesticide Analytical
Solution model ( 2 ) , which employed a steady state solution to the
analytical equation describing solute transport in a homogenous
s o i l . However, the transient aspect of the wetting and drying
cycle i n the root zone, and the inhomogenous character of soil
necessitated a model which would consider variations in weather
patterns and allow for temporal and vertical reassignment of model
parameters. The Pesticide Root Zone Model (3.,) was developed at

18. LORBER A N D OFFUTT Assessment of Ground Water Contamination Potential 343
the US EPA Environmental Research Laboratory in Athens, Georgia, to

meet this need.
The ability to predict the transport of pesticides leaching
ttirough soil allows for an evaluation exercise known as an
"exposure assessment". Strictly defined, an exposure assessment
would result in an estimation of the concentrations of pesticide in
drinking water. However, PRZM and related models such as PESTANS
only predict the mass flux and the concentration in the "vadose",
or unsaturated zone, which includes the root zone, and some defined
distance below the root zone. Although the science and mathematics
of predicting transport in the saturated zone exist, and aldicarb
transport in the saturated zone has been modeled (5,6) > there are
s t i l l several practical difficulties in modeling this process.
Quantifying the dispersion process and estimating the rate of
pesticide decay in the saturated zone are the two main problems in
parameter estimation. As well, there are no adequate field data
bases available to test a model which i s capable of predicting the

movement of pesticide from the point of application to and through
an aquifer.
Although also a complex phenomena, movement of water and solute
in the unsaturated zone has been studied more extensively. Several
field site data bases, including the three used to calibrate PRZM
in this paper (7-9) , are becoming available to use in conjunction
with unsaturated models. Quantification of pesticide movement in
the unsaturated zone can be accomplished effectively with an ade-
quate number of soil cores taken at regular intervals following
pesticide application ( 1 0 ) . In contrast, wells penetrating the
aquifer either above or below the pesticide plume, or well samples
taken before or after the plume has passed the well will result in
false negative findings.
A major advantage to models such as PRZM or PESTANS i s that
they are transportable: they can simulate a variety of situations
with simple changes in weather input and parameters. More Impor-
tantly, however, is the fact that in most situations, 90$ or more
of applied pesticide would have runoff, volatilized, been taken
up by the plant, or otherwise decayed before any of i t leaches
below the root zone. It makes sense, therefore, to develop the
capability to predict the fate of pesticides in the root zone, and
hence determine the potential for pesticides to contaminate ground
water.
The purpose of this paper is to present an assessment exercise
of a leaching pesticide using the PRZM model. The assessment
begins with a calibration of PRZM for the pesticide aldicarb applied
to tobacco in North Carolina and potatoes in Wisconsin. Following
these calibrations, long term simulations are performed using
these same calibration scenarios. Examination of key PRZM output
indicates the "potential" for aldicarb to contaminate ground water
in the scenarios modeled.
Description of PRZM
As the name of the model implies, PRZM models the unsaturated zone,
which includes the root zone and a user-specified depth below the
root zone within the "vadose" zone. The simulation uses a daily
344 E V A L U A T I O N O F P E S T I C I D E S IN G R O U N D W A T E R
time step, and mass balances of water and pesticide are maintained
in "zones" of finite depth, usually 5 cm. Model parameters can
vary as a function of both space and time. Complete details of
model theory, including equations, sensitivity analysis, and other
applications are presented elsewhere (3.>i0.
The water balance algorithm i s based on the Soil Conservation
Service Curve Number approach ( 1 1 ) , which estimates daily runoff
as a function of the antecedent moisture condition (wetness of the
s o i l profile prior to a storm) and a curve number determined from
f i e l d conditions (soil type, crop type, etc). Simply put, rainfall
f
is partitioned into runoff and infiltration - that which doesn t
run off, infiltrates. Following a storm, the soil drains by
gravity to field capacity in one day. A "slow drainage" option
allows the accumulation of water above field capacity, which then
drains over the next several days. Between storms, water is ex-
tracted from the root zone via vapotranspiration, which can be
determined from daily pan evaporation, i f i t is available, or from

an empirical equation based on average daily a i r temperature. The
parameters for the soil water model include: runoff curve numbers,
s o i l field capacity and wilting point, soil bulk density, crop
planting, maturity, and harvest dates, root depth, and crop surface
area coverage.
Mass balance equations of pesticide fate and transport are
developed for the surface and subsurface zones i n PRZM. In the
surface zone, avenues of loss include soluble loss in runoff,
percolation to the next zone, sorbed loss in erosion, and decay i n
both phases. In the subsurface zones, losses include plant uptake
and percolation i n the soluble phase, and decay in both phases. A
backward difference, implicit numerical scheme i s used to solve
the partial differential solute transport equations, with a time
step of one day and a spatial increment specified by the user.
The important assumptions for the pesticide model are: instan-
taneous, linear, reversible adsorption described by an adsorption
partition coefficient, K^, and first-order decay described by an
overall decay rate, k. Parameters for the pesticide model include:
universal soil loss equation parameters ( i f erosion loss i s to be
modeled), pesticide application information (rate, date, and
method of application), K^, k, and a dispersion coefficient.
Calibration of PRZM
The appropriate means to "test" a model i s dependent on the biases

of the model tester and the purposes of his exercise. Words such
as calibration, validation, and verification have been used to
describe a model testing procedure. For this study, PRZM was
calibrated to three f i e l d sites to determine appropriate parameters
for longer term simulations. These long term simulations employed
the same parameters as the calibration simulations, and their
purpose was to examine trends i n pesticide leaching as expressed
by PRZM output.
PRZM was calibrated to field data on the pesticide aldicarb
applied to two potato sites i n Wisconsin and one tobacco site i n
North Carolina ( 7 - 9 ) . Field data required for the calibration
exercise include: soil physical parameters, crop cultural
information, aldicarb rate and date of application, depth of in-

corporation, on-site weather data including daily rainfall and
average a i r temperature (or pan evaporation i f available), and
field observations of pesticide leaching over time. Specifically,
these observations were soil cores taken at several dates following
application and measured for total aldicarb residues. Aldicarb
degrades rapidly in soil to aldicarb sulfoxide and aldicarb sulfone.
In this paper, aldicarb refers to the sum of parent aldicarb and
dgradtes sulfoxide and sulfone. The physical parameters for
the three sites are given in Table I.
The purpose of the calibration exercise was to determine
appropriate parameters which would result in a best-fit match be-
tween model simulations and the soil core field observations. The
f i r s t step in the procedure was to assign values to field-measured,
physically-based, parameters which include a l l parameters for the
water balance and crop development portions of the model. The
second step was to calibrate chemically and biologically based

parameters which are not easily measured i n the field. These i n -
clude the adsorption partition coefficient, K^, and the first-order
rate of decay, k, of aldicarb. Using reasonable ranges of and
k as defined by the literature, a trial-and-error method was used
until model predictions matched field observations.
In Table II are the values of the aldicarb parameters which
were calculated from field data. The calculated was determined
assuming a K for aldicarb of 36 (1), a ratio of organic matter to
oc
organic carbon of 1.7, and field data for soil organic matter for the
different soil layers. The decay rate was assumed uniform within
the soil profile. The range of "observed" decay rates was deter-
mined from the field observations made on different dates. They
were calculated by estimating mass of aldicarb remaining on the
observation date (based on soil concentrations and soil bulk density),
and then applying the first-order equation of pesticide decay. In
estimating the decay rate from field observations, the important
assumption is made that the residues measured represent the fate of
a l l aldicarb applied, i.e., that no aldicarb was lost in runoff,
leached below the depth of sampling, or was taken up by the crop.
Table III summarizes the several calibration scenarios, which
are now described.
Site 1 - North Carolina tobacco. This site i s located in Hertford

County, North Carolina. The soil is classified as a sandy loam,
with 0.85% organic matter in the top 0 . 3 m of s o i l . The mechanical
analysis for the top 3 meters i s as follows: 55-69% sand, 18-38%
s i l t , and 7-16% clay. Aldicarb was incorporated to a depth of 10
cm at a rate of 3.36 kg/ha at tobacco transplanting on May 1 3 ,
1983. Pre treatment samples taken prior to aldicarb application
insured that the soil was free of aldicarb residues. Daily rainfall
and pan evaporation for this site were obtained from a nearby
weather station. Soil cores were obtained by bucket auger to a
depth of 3 meters, separated into increments of 0 - 0 . 3 m, 0 . 3 - 0 . 6 m,
0 . 6 - 1 . 2 m, 1 . 2 - 1 . 8 m, 1 . 8 - 2 . 4 m, and 2 . 4 - 3 . 0 m. The plot was
divided into four subplots, and four samples were taken per subplot
and composited at each date of observation, resulting i n a total of
four samples per date per core depth. These four samples were
Table I. Summary of PRZM soil and crop parameters for calibration

and exposure assessment exercises for North Carolina
and Wisconsin (parameters developed from data i n 7-9).
Parameter North Carolina Wisconsin Wisconsin

Description Cameron Hancock
- Soil
Classification sandy loam sandy loam loamy sand
- Runoff Curve row crops row crops row crops
Number straight row straight row straight row
Assumptions good condition good condition good condition

ff ,f !t
"B" soil group B soil group "A soil group
residue after residue after residue after
harvest harvest harvest
- Water Holding
Capaci ties, cnP/cnP
field capacity
0-30 cm 0.18 0.38 0.11
30-300 cm 0.24 0.20 0.08
wilting point
0-30 cm 0.06 0.20 0.05
30-300 cm 0.10 0.08 0.03
i n i t i a l soil water
0-30 cm 0.16 0.20 0.10
30-300 cm 0.24 0.20 0.08
- Bulk Density, gm/crrP
0-30 cm 1.47 1.46 1.48
30-60 cm 1.34 1.54 1.54
60-300 cm 1.56 1.54 1.54
- Zone Depths, cm
core 300 300 300
root 45 30 30
evaporation 20 15 15
storage 5 5 5
- Erosion not considered not considered not considered
- Crop Grown tobacco potatoes potatoes
- Year 1983 1982 1982 1983
- Crop Development
emergence May 20 June 4 May 28 June 21
maturity Aug 1 July 15 July 15 Aug 1
harvest Nov 1 Nov 1 Nov 1 Nov 1
- Rain interception, 0.20 0.15 0.15
cm
Table II. Summary of PRZM calibration parameters for aldicarb use

in North Carolina and Wisconsin (calculated values for
K(3 and k from f i e l d site data are given i n parentheses
besides calibrated values).
Parameter North Carolina Wisconsin Wisconsin

Description Cameron Hancock
Adsorption Partition
Coefficient, K^, ml/gm
0 - 15 cm 0.50 (0.18) 1.00 (0.22) 1.00 (0.16)

15 - 30 cm 0.15 (0.18) 0.50 (0.22) 0.50 (0.16)
30 - 60 cm 0.01 (0.04) 0.05 (0.04) 0.05 (0.01)
60 - 300 cm 0.01 (0.01) 0.01 (0.01) 0.01 (0.01)
First-Order Decay
1
Rate, k, day"
planting, 0-300 cm 0.016 0.010 0.010
(0.018-0.026) (0.011) (0.013-0.019)
emergence, 0-300 cm 0.015 0.015
(0.016) (0.014-0.049)
Equivalent h a l f - l i f e ,
days
43 69 69
planting, 0-300 cm (27-39) (63) (36-53)
46 46
emergence, 0-300 cm (43) (14-49)
Date of Application May 15 May 19
1982 planting June 4 May 28
emergence
1983 planting May 13 May 10
emergence June 21
Rate of Application, kg/ha

1982 & 1983
planting 3.36 .36 3.36
emergence 2.24 .24 2.24
Depth of
Incorporation, cm 10 10 10

Library
1155 16th St., N.W.
Table III. Summary of PRZM calibration runs.
Run # Location Crop Soil Date/Rate Irr*
1 North Carolina tobacco sandy loam 5/13/83; 3.36
2 Cameron, Ws. potato sandy loam 5/15/82; 3.36 M
3 Cameron, Ws. potato sandy loam 6/4/82; 2.24 M
4 Hancock, Ws. potato loamy sand 5/19/82; 3.36 M
6 Hancock, Ws. potato loamy sand 5/19/82; 3.36 H

7 Hancock, Ws. potato loamy sand 5/28/82; 2.24 H
* Irrigation regimes practiced: = no irrigation; M = medium

irrigation schedule; H = high irrigation schedule
averaged to represent "observed" results. Observations were taken

on June 6 , July 1 4 , Sep. 1 5 , and Nov. 3 0 , and these are represented
by the dashed lines shown in Figure 1. Further details on this
f i e l d site are given i n Jones et a l . ( 7 ) . The simulated results
are shown by the solid line curves in Figure 1. The observations
are matched against predictions for the Nov. 30 date in tabular form
in Figure 1. Table IV summarizes the simulated water balance, and
Table V s u m m a r i 2 e s the aldicarb fate and transport for this North
Carolina calibration site.
Site 2 - Cameron, Wisconsin potatoes. This field site is located

on a commercial potato farm in northwestern Wisconsin i n Cameron.
The soil i s an Onamia sandy loam, with 1.03% organic matter in the
top 0 . 3 m of s o i l . The mechanical analysis for the top three
meters of soil i s as follows: 83-99% sand, 0-13% s i l t , and 1-8%
clay. The experimental field was divided i n half, with one-half
receiving 3.36 kg/ha aldicarb incorporated at potato planting on
May 1 5 , 1982, and the other half receiving 2.24 kg/ha at emergence
on May 2 8 . Soil cores were taken prior to application to insure
that the profile was free of aldicarb. The procedure i n North
Carolina for post-treatment sampling including subplots, composites,
and soil coring was also followed in Wisconsin. In addition, 11.7
cm of irrigation was applied between May 15 and Dec. 8 to meet the
evapotranspirative demands of the crop when rainfall was insuffi
cient. This irrigation was directly input as part of the rainfall
record and as such, was treated as rainfall by PRZM. Daily totals

of rainfall were recorded on-site ( 8 ) . Evapotranspiration was
estimated on-site using Penman* s equation between June and September
( 8 ) , and was directly input to PRZM. Otherwise, daily average a i r
temperature was used to estimate evapotranspirative demand. Model
predictions are compared with observations on June 8 and Dec. 8 .
Samples were also taken on July 13 and Sep 2 2 , but only the f i r s t
and last were chosen for illustration in this study. Additional
details on this field site are given in Wynan et a l ( 8 ) . Figure 2
shows the planting and emergence simulations vs. observations,
including tabular summaries for the Dec. 8 date. Table IV summarizes
the water balance for the Cameron calibration, and Table V summarizes
aldicarb fate and transport.
Site 3 - Hancock, Wisconsin potatoes. Aldicarb was applied i n 1982

and 1983 at the University of Wisconsin Experimental Farm at Hancock
in central Wisconsin. The soil at this site is a Plainfield loamy

sand. The organic matter i n the top 0 . 3 m i n this soil i s 0.77%.
The mechanical analysis for the three meter core depth sampled
was: 89-97% sand, 0-6% s i l t , and 1-9% clay. Like the Cameron
site, there was a planting (May 1 9 , 3.36 kg/ha) and an emergence
(June 4 , 2.24 kg/ha) application of aldicarb in 1982, and two
similar applications i n 1983 (May 10, 3.36 kg/ha; and June 2 1 , 2.4
kg/ha). There were two irrigation regimes practiced i n 1982, and
one in 1983. One irrigation scheme was similar to the irrigation
in Cameron in that i t sought to meet evapotranspirative demand.
This was called the "medium schedule". The second irrigation
scheme, which was only practiced in 1982, was termed the "heavy
schedule" i n that 60% more water than estimated to meet the evapo-
transpirative demand was applied with identical timing as the
medium schedule. In summary, there were a total of six separate
scenarios at Hancock: four in 1982 which included permutations of
application date (and rate) and irrigation strategy, and two i n
1983 having different application dates. Daily rainfall was ob-
tained on-site for 1982 and 1983. Actual vapotranspiration was
estimated on-site for 1982 with Penman's equation and directly
input to PRZM, while pan evaporation was available for 1983. The
methodology for soil coring was similar to the Cameron and North
Carolina sites. Additional details on the Hancock site can be
found in Wynan et al ( 8 , 9 ) . Figures 3-5 summarize the Hancock
calibration results, and Tables IV and V summarize the water
balance and aldicarb fate and transport for the Hancock scenarios.
Discussion of Calibration Results
Table IV summarizes the water balance results of a l l the calibration

scenarios. A trend that can be seen from this data is that vapo-
transpiration demand i n Wisconsin is consistantly around 43 cm for
the summer months between May and September, regardless of irriga-
tion added or soil type. Recharge was higher for the loamy sand
soil in Hancock, 35 cm, than for the sandy loam i n Cameron, 26 cm.
Recharge increased to 53 cm when 19 cm of extra irrigation water
was added to the sand s o i l , indicating that this extra irrigation
was not needed by the crop. Evapotranspiration i n North Carolina
R U N #1
Concentration, ppb
Depth, cm
3.36 kg/ha Aldicarb Applied

May 13,1983
JUNE 6 J U L Y 14
100 200 300 500 200 300 400 500

I _1_ I
I -JL_ _1_ -J
Depth Obs Pred

cm ppb
0-30 7 5
30-60 4 16
60-120 4 4
120-180 ND 0
180-300 ND 0
S E P T E M B E R 15 N O V E M B E R 30
Figure 1. Calibration results of PRZM, scenario 1 (see

Table 3): concentration-depth profiles for predicted
(smooth curves) vs. observed (dashed lines) aldicarb
applied to tobacco i n North Carolina (observed data
from 7).
RUN #2
Concentration, ppb
300 100
I
Depth, cm Depth Obs Pred

cm ppb
0-30 47 45
30-60 10 19
60-120 12 10
120-180 ND 2
May 15,1982
180-240 ND 0
240-300 ND 0
JUNE 8 DECEMBER 8
RUN #3
100 200 100 300

I L_ I
Depth Obs Pred

cm ppb
0-30 13 13
30-60 ND 6
60-120 2 3
June 4 , 1 9 8 2 120-180 ND 1
180-240 ND 0
240-300 ND 0
JUNE 8 DECEMBER 8
Figure 2. Calibration results of PRZM, scenarios 2 & 3

(see Table 3): concentration-depth profiles for predicted
applied to potatoes i n Cameron, Wisconsin (observed
data from 8).
was higher than in Wisconsin, at 50 cm for the period of testing

between May and November. Recharge was only a small fraction of
rainfall during this period, equalling 14 cm.
Table IV. Summary of water balance results for calibration

scenarios ( a l l quantities in cm/yr).
Description Calibration Run #

1 2^3 4,5
Dates May-Nov May-Nov May-Sep May-Sep May-Sep

1983 1982 1982 1982 1983
Precipitation 71.4 86.4 44.7 43.4 59.3

Irrigation 0.0 11.7 31.7 50.8 24.4
Runoff 6.9 2.9 0.9 1.0 3.6
Evapotrans-
piration 50.4 44.6 41.4 41.9 44.4
Recharge 14.0 25.6 35.1 52.5 37.0
Snow Storage 0.0 24.8 0.0 0.0 0.0
Change in
Soil Storage +0.1 +0.2 -1.0 -1.2 -1.3
The calibrated half-life for aldicarb i s longer than the half-

l i f e which was calculated based on field data (Table II). This
occurs because runoff loss of aldicarb as well as leaching below
the depth of sampling are not accounted for in field-calculated
half-lives, which are calculated based only on aldicarb remaining
at each sampling date. An additional possible avenue of loss i s
plant uptake of aldicarb. However, the total amount of uptake was
not estimated in the f i e l d , nor was i t simulated in PRZM. As such,
i t can be considered that plant uptake loss was "lumped" in the
calibrated (and calculated) half-lives.
Table V summarizes the fate and transport of aldicarb in the
calibration scenarios. In North Carolina, the simulations predict
that 4.2% of applied aldicarb was lost via runoff and none leached
below the depth of sampling. The runoff result cannot be verified
since field data of runoff were not taken. However, since the
s o i l was a loam s o i l , some water runoff would be expected, and a
fraction of the soluble aldicarb present in top zone on the date
of runoff would also run off. As a result, the calibrated half-
l i f e , 43 days, is higher than the range calculated, 27-39 days.
In the Cameron, Wisconsin simulations, aldicarb did not leach
below the depth of sampling for the planting or emergence appli-
Table V. Summary of fate and transport results for aldicarb

calibration scenarios ( a l l results expressed i n
percent of applied).
Calibration Run #
Description 1 2 3 4 5 6 7 8 9
Applied 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
Decay 91.9 73.5 92.9 73.8 83.9 67.9 78.5 75.9 77.7
Runoff 4.2 2.1 1.3 0.3 0.4 0.2 0.3 0.0 0.0
Leached Below
3 meters 0.0 0.0 0.0 1.5 1.3 15.2 10.9 2.1 1.3
Remained in
profile 3.9 24.4 5.8 24.4 14.4 16.7 10.3 22.0 21.0
cation. However, a small percentage of applied was found to

runoff for both application dates, 2.1 and 1.3%. As a result, the
calibrated half-life, 69 and 46 days for planting and emergence
applications, respectively, were only slightly higher than the
calculated half-lives, 65 and 43 days.
In Hancock, where there was a loamy sand s o i l , leaching below
the depth of sampling was simulated with a l l scenarios, particu-
l a r l y the scenarios of high irrigations. Approximately 15 and 11%
of applied aldicarb leached below 3 meters i n these high irrigation
scenarios (runs # 6 & 7). The field-calculated half-life for
these intense irrigation scenarios is i n the neighborhood of 35
days; the calibrated half-life was 69 days. As noted earlier, the
extra irrigation did not add to the consumptive use of water.
Therefore, the field calculated half-life was misleading for these
scenarios of intense irrigation. Between 1.3 and 2.1% of applied
aldicarb was simulated to leach below 3 meters for the scenarios
of medium irrigation, again resulting in higher calibrated half-
lives than were calculated.
One other important observation that i s evident from both
field observations and simulations i s that the half-life decreases
with later application dates. This occurs because the aldicarb is
applied during warmer weather and i s hence subject to a healthier
environment for microbes, which can degrade i t more quickly. As
seen i n Table V, the amount of leaching i n Hancock decreased from
planting applications, 1.5, 15.2, and 2.1% of applied (runs 4,6,8),
to emergence applications, 1.3, 10.9, and 1.3 (runs 5,7,9). A
more appropriate simulation approach might be to make the rate of
decay a function of a i r or soil temperature, or to simulate a
step-wise change in rate of decay as a function of time. Nonethe-
less, this more rapid rate of decay for later applications results
in less leaching for later applications.
In order to force the simulated profiles to match the observed
RUN #4
500 600 750 300 400 500

I I I
L
2*7
Depth Obs Pred
cm ppb
0-30 37 63
30-60 14 28
60-120 20 19
Q
120-180 12 17
May 19,1982
180-240 12 12
240-300 3 7
JUNE 9 S E P T E M B E R 20
RUN # 5
300 400 500
1
I I I
Depth Obs Pred

cm ppb
0-30 28 28
30-60 8 12
60-120 5 8
120-180 7 7
May 28,1982
180-240 2 5
240-300 ND 3
Figure 3 . Calibration results of PRZM, scenarios 4 & 5

(see Table 3 ) : concentration-depth profiles for predicted
applied to potatoes i n Hancock, Wisconsin (observed data
from 8 ) .
RUN # 6
Concentration, ppb
300 400 500 600 1300 200 400 500

I \ L_ I I
Depth Obs Pred

cm ppb
0-30 16 18
30-60 ND 11
3.36 kg/ha Aldicarb Applied 60-120 2 9

May 19,1982
120-180 17 13
180-240 4 15
240-300 5 15
RUN #7
100 300 400

I I I
IT
Depth Obs Pred
cm ppb
0-30 ND
30-60 2
2.24 kg/ha Aldicarb Applied 60-120 ND

May 28, 1982
120-180 ND
180-240 ND
240-300 ND
Figure 4 . Calibration results of PRZM, scenarios 6 & 7

( see Table 3 ) : concentration-depth profiles for predicted
applied to potatoes i n Hancock, Wisconsin (observed data
from 8 ) .
RUN #8
Concentration, ppb
300 400 500

1 I
Depth Obs Pred

cm ppb
0-30 45 53
30-60 6 24
60-120 3 16

120-180 2 15
May 10,1983 180-240 ND 12
240-300 ND 7
J U N E 23 S E P T E M B E R 21
R U N #9
300 400 500

J I I
Depth Obs Pred

cm ppb
0-30 74 50
30-60 37 17
60-120 11 10
2.24 kg/ha Aldicarb Applied 120-180 5 8

June 21,1983 180-240 3 5
240-300 ND 3
J U N E 23 S E P T E M B E R 21
Figure 5. C a l i b r a t i o n r e s u l t s o f PRZM, s c e n a r i o s 8 & 9

(see Table 3 ) : concentration-depth p r o f i l e s f o r p r e d i c t e d
(smooth c u r v e s ) v s . o b s e r v e d (dashed l i n e s ) a l d i c a r b
a p p l i e d t o p o t a t o e s i n Hancock, W i s c o n s i n ( o b s e r v e d d a t a
from 9 ) .
profiles, a higher adsorption partition coefficient, K^, was re-

quired for the top zone than would be calculated based on aldicarb
K ocand soil organic matter. In North Carolina, the required
for the top 15 cm was 0.50, and in Wisconsin, was 1.00 for the top
15 cm and 0.50 for the 15-30 cm layer. These are the highest
assumed for aldicarb as compared to other published modeling efforts
on aldicarb, which range in from 0.0-0.3 (3,5*12,13) The reasons
for this discrepancy are not known. Several possibilities exist
which include:
1) PRZM may be overestimating the amount of water to
percolate from the top zones to lower zones. This would occur
i f the water holding capacities measured in the field and
assigned in PRZM are too low, resulting in less vapotranspiration
and more percolation. This could also occur with inacurrate
estimations of runoff - i f more runoff occurs than i s being
simulated, then percolation will be overestimated.
2) It may be connected to the granular formulation of aldicarb.

The outer protective layer dissolves upon contact with moisture,
releasing the active ingredient, aldicarb. Furthermore, granules
are incorporated, leading to the possibility of pockets of high
granular concentration. If this is the case, a wetting event
might not dissolve the protective coating of a l l the granules,
leaving some partially dissolved granules. However, i n several
aldicarb test plots, high chloride concentrations (where chloride
was applied as a tracer) also remain near the surface. This would
seem to indicate that the granular formulation is not the cause of
high surface aldicarb concentrations (14).
3) I t is possible that evaporation demand at the soil surface
results i n water translocating upward from shallow depths, <15 cm,
keeping aldicarb near the soil surface. Since PRZM does not simu-
late the upward movement of water, the high assigned for aldi-
carb near the surface is an a r t i f i c i a l way to maintain high surface
concentrations.
4) The assumption made i n PRZM and similar models i s that
equilibrium between sorbed and soluble phases occurs instantly.
However, i t has been shown that while adsorption occurs rapidly,
there is a time delay associated with desorption. Incoming rain-
f a l l typically infiltrates a dry soil surface rapidly, not allowing
the time necessary for equilibrium to be reestablished. This
tendency for rapid infiltration has been called "macropore" flow,
which can be visualized as the flow of water through preferential
flow paths, created by inhomogeneous soil structure, wormholes,
and so on. When this occurs, not a l l the pesticide "sees" the
water flowing by during the i n i t i a l period i n a storm. Only a
portion of actual infiltration carries soluble pesticide available
through the equilibrium adsorption/desorption process. Therefore,
a higher K<j may be required to limit the transport of pesticides
residues below the soil surface. Another problem which may occur
as a result of macropore flow (one not associated with the necessity
for a high K 3 ) i s that soluble pesticide picked up by macropore
flow can be rapidly transported deep into the profile, resulting i n a
skewed distribution of pesticide concentration. This has also been
seen i n the field.
The dilemma of requiring a higher to keep a pesticide near
the surface in leaching simulations also occurred with simulations

of DBCP i n Hawaii (15). In that case, K<js of 4 and 17 were required
to match the observed pattern of DBCP remaining near the surface
over time. The reported of DBCP i s in the neighborhood of 0.13-
2.10 (1).
Below 30 cm, the calibrated and calculated Kj for aldicarb are
similar. At that depth, phenomena such as undissolved granules,
upwardly moving evaporation water, and macropore flow are much less
likely to occur. Therefore, the calibration of aldicarb i s more
straightforward and a function of soil organic matter.
As stated earlier, the means by which to test a model are
dependent on the biases of the model tester and the purposes of
his exercise. The purpose of the calibration in this study i s to
set up the exposure assessment simulations, which will determine
the potential for aldicarb to contaminate the ground water i n the
scenarios modeled. As will be seen shortly, this potential i s
represented by model results at a point deep in the unsaturated

zone. As such, i t becomes imperative to accurately portray aldi-
carb fate in the unsaturated zone. Since these field studies
showed that high concentrations of aldicarb were maintained near
the soil surface, parameters were adjusted to portray that behavior.
If anything, this exercise has uncovered a discrepancy between
model theory and reality, and a future direction i n PRZM develop-
ment and/or field testing might be to test the theories proposed.
Nonetheless, the calibration i n this study i s valid since the
purpose i s to duplicate reality, given the limitations of the
model.
Figures 1-5 show the final calibrated results. Despite some
differences, i t can be seen that the important considerations of
mass balance and trends in concentration-depth profiles are well
met in the calibration exercise.
Leaching Assessment of Aldicarb
The purpose of the leaching assessment was to determine trends i n

the potential for aldicarb to leach to ground water in the scenarios
modeled. The "potential" to contaminate ground water in the context
of this exercise i s indicated by predictions of "significant"
concentrations (and/or mass) of aldicarb to leach to a "low depth"
in the unsaturated zone. These predicted concentrations will
not, i n most cases, be equivalent to concentrations in the ground
water, since the aldicarb will continue to decay as i t traverses
vertically to the water table and then horizontally to a well
where i t could be extracted. However, the rate of decay will be
slower once the aldicarb leaves the biologically active root zone.
Its major mode of decay i n the saturated zone i s hydroloysis, and
the aldicarb hydrolysis half-life i s estimated to be 10-650 weeks
(1), depending on conditions. Therefore, the predicted concentra-
tions at two meters in these long-term simulations represent an
upper bound on what might be expected in the ground water.
A measure of "significance" for aldicarb i s given by the
"Health Advisory Level" (HAL) for aldicarb. "Health Advisories"
suggest concentrations of a contaminant in drinking water at which
adverse health effects would not be anticipated, with a margin of
18. LORBER A N DOFFUTT Assessment of Ground Water Contamination Potential 359
safety, for 1-day, 10-day and longer-term exposure periods (from a

few months to 1-2 years)." (16). The HAL for aldicarb i s 10 ppb
(17). Wisconsin adopted this level of 10 ppb in legislation con-
cerning aldicarb (18), while New York state opted for a more
stringent level of 7 ppb (19).
The appropriate "low depth" i n the unsaturated zone i s not as
well defined, and i s arbitrarily chosen in this exercise to be two
meters. PRZM was calibrated to a depth of two meters i n North
Carolina and three meters i n Wisconsin. Two meters i s f e l t to be
a generally valid depth for PRZM assessments considering such
factors as the unlikelihood of water table intrusion above that
level, and sufficient depth such that conclusions of "potential" to
contaminate ground water are meaningful. As well, the assumption
is made that the soil column drains from saturation to field capacity
in one day in PRZM. This assumption loses i t s validity as the
depth of the soil column increases, i.e., the velocity of water
increases as the depth of flow increases. For example, i t i s

reasonable to assume that drainage below two meters will occur in
one day, but less reasonable to assume that drainage will be
complete below ten meters in one day. (note: a slow drainage
option i s available in PRZM, which would allow for column drainage
in several days, but i t was not used in the simulations of this
paper).
The scenarios chosen for the assessment were essentially
identical to the calibration exercise. A l l the parameters, includ-
ing s o i l , crop, and most Importantly, aldicarb and k, were un-
changed in the leaching assessment. The rate of aldicarb appli-
cation was set at 2.24 kg/ha for a l l planting dates so that concen-
tration comparisons between scenarios were meaningful. Five years
of weather record were generated using a statistical model of
weather generation developed by Richardson (20). The weather
record for the North Carolina scenario was statistically similar
to that of Raleigh, and the weather for Wisconsin was statistically
similar to Madison. Pan evaporation data were not statistically
generated, so vapotranspiration was estimated as a function of
daily average temperatures. Aldicarb was applied at planting to a
North Carolina tobacco crop on a sandy loam, at planting to a
Wisconsin potato crop on a sandy loam, and at planting and emergence
to a Wisconsin potato crop on a loamy sand. Irrigation was also
evaluated for its effect on leaching on the loamy sand, leading to
four scenarios on the loamy sand (planting and emergence applications;
irrigation and no irrigation). The irrigation scenario was designed
from the aldicarb f i e l d trials used for calibration. In these
trials, approximately 25 cm/yr of irrigation was added for the
"medium" schedule, with daily rates ranging from 0.5 to 2.5 cm.
For the assessment, an average of 24 cm/yr of irrigation was applied
during June, July, August, and September, at daily rates of 2.5 cm
only when rain had not fallen for at least four days. A summary of
the leaching assessment scenarios are given on Table VI.
Discussion of Leaching Assessment Results
A summary of the water balance results i s given i n Table VII. The

statistically generated annual average rainfall, 108 cm/yr, for
Table VI. Summary of aldicarb exposure assessment PRZM simulations.
Run # Location Crop Soil Date/Rate Irr*
1 Raleigh, tobacco sandy loam May 1; 2.24

N. Carolina
2 Madison, potato sandy loam May 15; 2.24

Ws.
3 Madison, potato loamy sand May 15; 2.24

Ws.
4 Madison, potato loamy sand June 10; 2.24

Ws.
5 Madison, potato loamy sand May 15; 2.24 M

Ws.
6 Madison, potato loamy sand June 10; 2.24 M

Ws.
* Irrigation schedule: = no irrigation; M = medium irrigation;

24 cm/yr average
Raleigh, North Carolina, was similar to the historical average for

Raleigh, 117 cm/yr (21). An equal amount of water recharged as
did evapotranspire, 52 cm/yr (48% of precipitation). These water
balance results differ from the calibration water balance, which
showed only 14 cm/yr recharge (20% of precipitation) for a simu
lation between the months of May and November. The major reason
for this i s that 42 cm/yr of precipitation typically falls between
December and April (21) and most of this would percolate rather
than evapo transpire i n the cool winter months in North Carolina.
Another possible reason has to do with the use of pan evaporation i n
the estimation of vapotranspiration. For a l l calibration scenarios,
pan evaporation or actual on-site vapotranspiration was supplied
and used to estimate vapotranspiration, while an empirical formula
used a i r temperature to estimate vapotranspiration for the leaching
assessment exercises. I t has been speculated that this empirical
formula will underestimate vapotranspiration. Testing with PRZM
showed this to be true; however, only for hot summer months typical
of the Southeast (22).
The generated rainfall i n Wisconsin, 80 cm/yr, was similar to
the historical average for Madison, Wisconsin, 76 cm/yr (21).
Recharge equalled 35% (28 cm/yr) of incoming precipitation for the
sandy loam, while vapotranspiration equalled 58% (46 cm/yr) of
precipitation. On the other hand, recharge comprised a larger
proportion of incoming rainfall in the loamy sand s o i l . In the
5-year simulations, recharge and vapotranspiration were 56% (45
cm/yr) and 43% (34 cm/yr) of incoming water, respectively. The 24

cm of annual irrigation on the loamy sand increased consumptive use
of water by the potato crop by 6 cm and recharge by 17 cm. This
may have been an overestlmation of recharge because the 2.5 cm/day
irrigation amount may have been too high and caused recharge i t s e l f .
S t i l l , irrigation will have a tendency to increase recharge i n
general, not so much on the day of irrigation, but two or three
days later, when a rainfall does not encounter a dry soil profile,
but rather recharges through a wet profile.
Table VII. Summary of water balance for leaching assessment

simulations (all units in cm/yr average).
Leaching Assessment Run #

Description 1 2 3,4 5,6
Precipitation 108.0 80.0 80.0 80.0
Irrigation 0.0 0.0 0.0 24.0
Runoff 2.0 6.0 1.0 2.0
Evapotrans-
piration 54.0 46.0 34.0 40.0
Recharge 52.0 28.0 45.0 62.0
Table VIII summarizes aldicarb fate and transport results for

the 5-year leaching assessments, including the percent of applied
aldicarb predicted to leach below 2 meters and soluble concentra-
tions at 2 meters. These soluble concentrations are described
as "plume" and "average". The plume concentration has been arbi-
trarily defined as an average of a continuous six-month period of
high aldicarb concentration at the 2-meter depth, which occurs
before the next application of aldicarb. This recognizes that
aldicarb does, in fact, move with a plume and the plume will pass
the 2-meter mark for approximately a 6 month period. For a May
application, the plume usually reached the 2-meter mark by June.
The "average" concentration i s simply the 12-month average soluble
concentration, taking into account non-plume months of low or
absent concentrations of aldicarb.
As shown i n Table VIII, there was essentially no potential for
aldicarb to leach in the sandy loam soil modeled i n Wisconsin, and
very l i t t l e potential to leach in the North Carolina sandy loam.
The small amount of aldicarb which leached i n North Carolina, 0.5%
of applied, can be attributed to high water recharge, 52 cm/yr
vs. 29 cm/yr in Wisconsin. One can conclude from this exercise
that aldicarb will most likely not pose a leaching threat i n North
Carolina and Wisconsin soils similar to the sandy loam soils model-
ed i n this study.
On the other hand, aldicarb shows the potential to leach on

a l l scenarios of the loamy sand in Wisconsin. Between 1.4 to
18.9% of applied leached below 2 meters, the plume concentration
ranged from 11 to 103 ppb, and the average concentration ranged
from 8 to 64 ppb.
Table VIII. Leaching assessment results for aldicarb including:

percent of applied to leach below two meters, average
annual soil water concentrations at two meters,
and plume concentrations at two meters*.
Leaching Assessment Run #

Description 1 2 3 4 5 6
Percent of
applied to
leach below
two meters 0.5 0.0003 5.4 1.4 18.9 8.6
Plume soil
water concen-
trations at
two meters,
ppb. 3.0 <0.1 40 11 103 53
Average soil
water concen-
trations at
two meters,
ppb. 2.0 <0.1 31 8 64 33
plume concentration = average concentration for consecutive

six-month period following application
average concentration = average annual concentration
Irrigation significantly increased aldicarb leaching, by as

much as 3-5 times. There are two reasons for this. One i s
related to the increase in recharge water discussed earlier.
Intuitively, an increase i n the quantity of water recharge will
result i n an increase i n aldicarb recharge. Secondly, the i r r i -
gation event i t s e l f , while not necessarily a leaching event, will
s t i l l cause aldicarb to move lower within the unsaturated zone as
incoming irrigation water f i l l s the profile.
The date of application also affected leaching, with later
applications at emergence resulting in a reduction i n leaching.
This i s due primarily to more rapid decay rate at the later appli-
cation date. I t i s also possible that one or more storms occurred
between the earlier and the later application date, resulting i n
more leaching for the earlier date. In any case, i t i s clear from
this exercise that applying aldicarb at the date of potato emergence

will reduce leaching of aldicarb by approximately one-half as
compared to planting applications.
Summary and Conclusions
The PRZM model was calibrated to aldicarb used on three use sites
comprising a total of nine distinct scenarios, which are summarized
in Table III. One use site was tobacco on a sandy loam soil in
North Carolina, one on potato on a sandy loam soil i n Wisconsin,
and one on a loamy sand soil in Wisconsin. Tables I and II show
the parameters and assumptions used in the PRZM simulations and
Figures 1-5 show the results of the calibration expressed as con-
centration-depth profiles comparing predicted and observed concen-
trations of aldicarb. Tables IV and V summarize the water balance
and fate and transport results for these calibration scenarios,

respectively. As can be seen in Figures 1-5, the PRZM model accu-
rately portrayed the field behavior of aldicarb for the important
considerations of mass balance and trends in concentration depth
profiles.
The calibrated rates of decay in the unsaturated zone were
equivalent to half-lives of 6 weeks i n North Carolina, 10 weeks
for planting applications in Wisconsin, and 6.5 weeks for emergence
applications in Wisconsin. These calibrated half-lives are slightly
longer than the half-lives that are calculated from soil core data
alone. The half-life calculated from soil core data alone can be
unrealistically short i f other avenues of transport, including
runoff and leaching below the depth of sampling, are not accounted
for. Modeling offers the opportunity to estimate these quantities.
Therefore, the "lumped" calibrated half-life is a more accurate
estimate of a l l other avenues of pesticide dissipation, including
plant uptake, volatilization, and degradation processes of photo-
lysis, hydrolysis, and microbial decay.
The calibrated adsorption partition coefficient was 0.50 i n
the top 15-cm zone for North Carolina, and 1.00 i n the top 15-cm
zone in Wisconsin. These are higher than would be calculated based
upon the ko of aldicarb and the soil organic matter of these f i e l d
C
sites, and higher than has been used in published aldicarb modeling
exercises. However, the observed data of these and other aldicarb
f i e l d studies indicate that aldicarb, i n fact, does stay near the
surface more than would be surmised based on a calculated parti-
tion coefficient. The reasons for this are unclear, but four
possible explanations were offered: 1) Top soil water percolation
is overestimated due either to an underestimation of water holding
capacity of the soil or an underestimation of surface runoff.
2) The granular formulation of aldicarb requires a wetting
event to dissolve the protective outer cover, releasing the active
ingredient. Since aldicarb i s incorporated, the potential exists
for localized pockets of granules to exist, and wetting events may
not completely dissolve a l l the outer layers of the aldicarb
granules immediately. 3) Atmospheric evaporation demand may result
in upward movement of soil water near the soil surface, bringing
with i t leached aldicarb back to the surface. 4) The assumption of
instantaneous equillibriura between sorbed and soluble phases i s

inaccurate: desorption i s slower than adsorption. "Macropore"
flow has been defined as rapid and deep infiltration of rainfall
at the onset of a storm as the rain follows preferential flowpaths
in the s o i l . Hence, not a l l the aldicarb in the surface zones
will "see" the water as i t flows by, and desorb according to the
equilibrium assumption. I t i s d i f f i c u l t to determine which, i f
any, of these possibilities explain the maintainance of high aldi-
carb concentrations near the soil surface. Nonetheless, the high
assigned partition coefficient is the way i n which the model a r t i -
f i c i a l l y duplicates this behavior.
Long term simulations were performed using identical scenarios
as the calibration scenarios. The purpose was to assess trends
in aldicarb leaching by examining key PRZM outputs of aldicarb
mass and concentration at 2 meters below the soil surface. The
results indicate that there was l i t t l e to no potential for aldicarb
to leach i n the sandy loam soils modeled i n North Carolina and

Wisconsin.
On the other hand, a significant potential was indicated for
leaching of aldicarb i n the loamy sand modeled i n Wisconsin. The
percent of application to leach below 2 meters ranged from 1.4-
18.9. The plume concentration (defined as an average concentra-
t i o n for a continuous 6-month period of high aldicarb concentra-
tion) ranged from 11-103 ppb, and the average annual solution
concentration of aldicarb at two meters ranged from 8-64 ppb.
With a Health Advisory Level of 10 ppb for aldicarb, clearly the
potential for ground water contamination exists for this and
similar soil types.
Irrigation increased the amount of recharge water, i f not
adding to recharge on the day of irrigation, than at the next
rainfall, when the rain encountered a wet rather than a dry profile.
Irrigation also tended to move aldicarb lower in the profile.
As a result, 3-5 times as much aldicarb leached below two meters
with irrigation. Applications at potato emergence decreased the
amount to leach by about one-half as compared to earlier applications
at planting. The reasons for this are two-fold: avoidance of some
spring rain for later applications, and a more rapid rate of decay
for later applications.
The appropriate direction to take at this point to complete
the leaching assessment for aldicarb would be to determine the
extent of the loamy sand soils in Wisconsin (and elsewhere), and
define the hydrogeology of these areas in detail. Based on infor-
mation such as depth to ground water, rate of ground water movement,
pH of ground water, and other factors affecting transport and
persistence in ground water, one can draw further conclusions as
to the potential of aldicarb to contaminate the ground water i n
these areas.
Literature Cited
1. Cohen, S.Z.; Creeger, S.M.; Carsel, R.F.; Enfield, C.G. In
"Treatment and Disposal of Pesticide Wastes"; Krueger, R.F.;
Seiber, J.N., Eds.; ACS SYMPOSIUM SERIES No. 259, American
Chemical Society: Washington, D.C., 1984; pp. 297-325.
2. Enfield, C.G.; Carsel, R.P.; Cohen, S.Z.; Phan, T.; Walters,
D.M. Ground Water 1982, 20(6), 711-22.
18. LORBER AND OFFUTT Assessment of Ground Water Contamination Potent
3. Carsel, R.F.; Mulkey, L.A.; Lorber, M.N.; Baskin, L.B.

Ecological Modeling 1985 (in press).
4. Carsel, R.P.; Smith, C.N.; Mulkey, L.A.; Dean, J.D.; Jowise, P.
"Users Manual for the Pesticide Root Zone Model (PRZM). Release
I." EPA Research Report EPA-600/3-84-109, 1984.
5. Intera Environmental Consultants, Inc. "Mathematical Simulation
of Aldicarb Behavior on Long Island: Unsaturated Flow and
Ground-Water Transport"; 1980.
6. Anderson, M.P. "Field Validation of Groundwater Models",
189th American Chemical Society National Meeting, PEST 57,
Florida, 1985.
7. Jones, R.L.; Hansen, J.L.; Romine, R.R.; Marquardt, T.E.
"Movement of Aldicarb and Aldoxycarb Residues in Soil".
To be submitted for publication, 1985.
8. Wynan, J..; Jensen, J.S.; Curwen, D.; Jones, R.L.; Mar
quardt, T.E. Env. Tox. and Chem. 1985, 4, 641-651.
9. Wynan, J..; Medina, J.; Curwen, D.; Hansen, J.S.; Jones,

R.L. "Movement of Aldicarb and Aldoxycarb Residues in
Soil". To be submitted for publication, 1985.
10. Cohen, S.Z.; Eiden, C.; Lorber, M.N. "Ground-Water Monitoring
of Pesticides in the USA", 189th American Chemical Society
National Meeting, PEST 34, Florida, 1985.
11. "SCS National Engineering Handbook," U.S. Department of
Agriculture, Soil Conservation Service, 1971.
12. Jones, R.L.; Back, R.C. Env. Tox. and Chem. 1984, 3, 9-20.
13. Jones, R.L.; "Movement and Degradation of Aldicarb Residues
in Soil and Ground Water" presented at the Society of Envi
ronmental Toxicology and Chemistry Conference on Multidisci-
plinary Approaches to Environmental Problems, Crystal City,
Va, 1983.
14. Jones, R.L., personal communication.
15. Green, R.E.; Liu, C.C.K.; Tamraker, N. "Modeling Pesticide
Movement in the Unsaturated Zone in Hawaii Soils Under Agri
cultural Use", 189th American Chemical Society National
Meeting, PEST 54, Florida, 1985.
16. "Health Advisory Program. Part 7," Office of Drinking
Water, U.S. EPA.
17. Cotruvo, J..; Director, Criteria and Standards Division,
Office of Drinking Water, U.S. EPA, letter to Hank Weiss,
Dept. of Health and Social Service, Madison, Wisconsin,
dated May 30, 1980.
18. "Proposed Rules Relating to Special Restrictions on the
Use in Wisconsin of Pesticides Containing Aldicarb,"
State of Wisconsin, Department of Agriculture, Trade and
and Consumer Protection, proposed S. Ag. 29.17, Wis. Adm.
Code, submitted October 1982.
19. Mahfouz, H.Z.; Moran, D.; Harris, D. American Journal
of Public Health 1982, 72, 1391-95.
20. Richardson, C.W. Water Resources Research 1981, 17, 182-90.
21. "Climates of the States," National Oceanic and Atmospheric
Administration, 1978.
22. Carsel, R.F., personal communication.
19
Modeling Pesticide Movement in the Unsaturated Zone
of Hawaiian Soils under Agricultural Use
1 2 2
R. E. Green , C. C. K. L i u , and N. Tamrakar
1
Department of Agronomy and Soil Science, University of Hawaii, Honolulu, H I 96822
2
Department of Civil Engineering, University of Hawaii, Honolulu, H I 96822
Two instances of pesticide leaching to groundwater have

been examined by modeling approaches which incorporated

appropriate pesticide inputs to the soil, measured
pesticide sorption coefficients and water balance
calculations based on actual rainfall and estimated
evapotranspiration and runoff. First, an analytical
model was used to examine movement of DBCP which was
accidentally spilled near a deep well on Oahu. The
model features the convective-dispersive solute
transport equation with an upper boundary condition
which approximates volatile losses over time from a soil
layer near the surface. The second study examined DBCP
movement under pineapple culture. The analysis combined
a two-dimensional analytical model, to compute the time
varying distribution and dissipation of DBCP in the plow
layer, and a one-dimensional numerical model to simulate
both water and DBCP movement in a layered profile below
the surface layer. Both modeling efforts were only
moderately successful in predicting pesticide
concentration profiles, as evidenced by a comparison of
computed and measured DBCP concentrations with depth,
but the results were useful in assessing the impact of
key processes and in identifying data requirements for
future modeling efforts. Model calculations and
laboratory experiments both showed that sorption
coefficients for long-term DBCP residues were much
larger than was indicated by conventional batch
equilibration measurements. Thus, successful prediction
of the leaching and volatilization of DBCP residues
requires a better understanding of sorption mechanisms.
The d e t e c t i o n o f DBCP and o t h e r t o x i c o r g a n i c s i n H a w a i i w e l l w a t e r s
has l e d t o m o d e l i n g s t u d i e s w i t h t h e o b j e c t i v e o f a n a l y z i n g t h e
i n t e r a c t i o n o f c h e m i c a l s and s o i l s i n r e l a t i o n t o t h e i r p r o p e r t i e s
and t h e dynamic p r o c e s s e s i n v o l v e d i n p e s t i c i d e movement t o
groundwater. I t was a n t i c i p a t e d t h a t t h e s e s t u d i e s would ( a ) e x p l a i n
0097-6156/ 86/ 0315-0366S06.00/ 0

19. GREEN ET AL. Pesticide Movement in the Unsaturated Zone of Hawaiian Soils 367
why DBCP moved t o groundwater when i t was n o t p r e v i o u s l y c o n s i d e r e d a

l i k e l y contaminant, (b) a s s i s t i n the assessment o f t h e impact o f
p r e s e n t DBCP r e s i d e s on f u t u r e water c o n t a m i n a t i o n , and ( c ) p r o v i d e a
f o u n d a t i o n f o r m o d e l i n g c h e m i c a l movement t o groundwater i n t h e
c o n t e x t of H a w a i i ' s unique h y d r o g e o l o g y and a g r i c u l t u r a l c h e m i c a l
practices. T h i s paper summarizes and i n t e g r a t e s the r e s u l t s o f
m o d e l i n g s t u d i e s and f i e l d m o n i t o r i n g and l a b o r a t o r y measurements
which have or w i l l be r e p o r t e d i n d e t a i l e l s e w h e r e ( 1 - 3 ) . It i s
hoped t h a t the a p p a r e n t i n a d e q u a c i e s o f t h e models used i n t h e s e
s t u d i e s w i l l encourage the development of improved m a t h e m a t i c a l
d e s c r i p t i o n s of a c t u a l processes i n the f i e l d . Only t h e n can dynamic
m o d e l i n g o f p e s t i c i d e b e h a v i o r i n s o i l s become a u s e f u l p a r t o f r i s k
assessment p r o c e d u r e s w h i c h w i l l a s s i s t i n r e g u l a t i n g p e s t i c i d e use
i n H a w a i i i n the c o n t e x t o f groundwater q u a l i t y r e q u i r e m e n t s .
Background
Until r e c e n t y e a r s c o n c e r n s about c o n t a m i n a t i o n o f water by

p e s t i c i d e s i n H a w a i i f o c u s e d p r i m a r i l y on s u r f a c e w a t e r s ( 4 , 5 . ) .
Assessments of p o t e n t i a l c o n t a m i n a t i o n o f groundwater were l i m i t e d t o
c h e m i c a l s used i n sugarcane c u l t u r e . W h i l e n i t r a t e s from f e r t i l i z e r s
were known t o r e a c h groundwater i n i r r i g a t e d sugarcane a r e a s , t h e
l i k e l i h o o d o f h e r b i c i d e s r e a c h i n g b a s a l w a t e r s was c o n s i d e r e d remote
(6.). I n r e t r o s p e c t , the f a i l u r e o f r e s e a r c h e r s t o examine the
l e a c h a b i l i t y of v o l a t i l e n e m a t i c i d e s used i n p i n e a p p l e c u l t u r e was
s h o r t - s i g h t e d , but n e m a t i c i d e r e s i d u e s i n s o i l s were c o n s i d e r e d
i n s i g n i f i c a n t i n r e l a t i o n t o the amounts a p p l i e d .
The d e t e c t i o n o f w i d e s p r e a d DBCP c o n t a m i n a t i o n o f w e l l s i n
C a l i f o r n i a i n 1979 l e d t o t h e m o n i t o r i n g o f H a w a i i w e l l s f o r t o x i c
o r g a n i c s i n 1980. C o n t a m i n a t i o n o f b a s a l w a t e r s by DBCP and EDB was
f i r s t d e t e c t e d i n a w e l l s u p p l y i n g p o t a b l e water near K u n i a v i l l a g e
on Oahu; s u b s e q u e n t l y DBCP was d e t e c t e d i n s e v e r a l w e l l s on Oahu and
i n one w e l l on Maui i s l a n d . A program o f s o i l b o r i n g was i n i t i a t e d
i n 1980, f i r s t i n the v i c i n i t y of t h e K u n i a w e l l (1,7.) > and l a t e r i n
1983, i n seven p i n e a p p l e f i e l d s on Oahu (8) and t h r e e p i n e a p p l e
f i e l d s on Maui (2.). The a v a i l a b i l i t y of measured DBCP c o n c e n t r a t i o n
p r o f i l e s a t the K u n i a s p i l l s i t e and on p i n e a p p l e f i e l d s on Maui
encouraged the m o d e l i n g e f f o r t s which a r e summarized i n t h i s p a p e r .
Modeling Strategy
The sequence of models used i n these s t u d i e s c o n s t i t u t e d a

p r o g r e s s i o n from a s i m p l e a n a l y t i c a l model of the c o n v e c t i o n -
d i s p e r s i o n type w i t h f i x e d parameters, a s s o c i a t e d w i t h the a s s u m p t i o n
of a s e m i - i n f i n i t e homogenous p r o f i l e , t o a c o n v e c t i o n - d i s p e r s i o n
n u m e r i c a l model, which i n c o r p o r a t e d dynamic water and s o l u t e movement
through a m u l t i l a y e r e d p r o f i l e . I n b r i e f , the sequence was as
follows: (a) o n e - d i m e n s i o n a l a n a l y t i c a l model w i t h an upper boundary
c o n d i t i o n that allowed f i r s t - o r d e r decrease i n c o n c e n t r a t i o n over
time ( K u n i a s i t e ) ; (b) t w o - d i m e n s i o n a l n u m e r i c a l model t o c a l c u l a t e
the approximate s h o r t - t e r m v e r t i c a l c o n c e n t r a t i o n p r o f i l e i n the plow
l a y e r f o r s h a n k - i n j e c t e d DBCP; the r e s u l t s were used t o s p e c i f y
i n i t i a l c o n d i t i o n s i n a subsequent o n e - d i m e n s t i o n a l n u m e r i c a l model
(Maui f i e l d s i t e s ) ; ( c ) s i m p l e o n e - d i m e n s i o n a l a n a l y t i c a l model w i t h
an upper boundary c o n d i t i o n w h i c h p r o v i d e s f o r DBCP vapor l o s s t o the
atmosphere o v e r t i m e ; t h i s model was used t o e s t i m a t e an a p p r o p r i a t e

value of f o r t h e plow l a y e r o f t h e Maui f i e l d s by c a l i b r a t i o n o f
the model w i t h measured f i e l d d a t a ; (d) a dual-model a p p r o a c h i n
w h i c h t h e a n a l y t i c a l model i n ( c ) above was used t o c a l c u l a t e t h e
c o n c e n t r a t i o n - t i m e r e l a t i o n s h i p a t t h e bottom o f t h e zone o f DBCP
a p p l i c a t i o n ; t h i s output was used i n d e f i n i n g t h e upper boundary
c o n d i t i o n f o r t h e o n e - d i m e n s i o n a l a n a l y t i c a l model o f ( a ) above,
a l l o w i n g t h e use o f d i f f e r e n t v a l u e s i n t h e zone o f a p p l i c a t i o n
and below t h e plow l a y e r ; ( e ) o n e - d i m e n s i o n a l n u m e r i c a l model
i n c o r p o r a t i n g both w a t e r and s o l u t e movement t h r o u g h m u l t i p l e l a y e r s ,
with adjusted with depth.
A l l o f t h e models used i n these s t u d i e s a r e based upon t h e
c o n v e c t i o n - d i s p e r s i o n e q u a t i o n f o r s o l u t e t r a n s p o r t t h r o u g h porous
media and thus a r e c o n s t r a i n e d by the i n h e r e n t l i m i t a t i o n s o f t h i s
mathematical r e p r e s e n t a t i o n of a c t u a l processes. These l i m i t a t i o n s ,
a n a l y z e d i n some d e t a i l i n a number o f r e c e n t papers (91011,12,13)
a r e r e a l f o r many f i e l d c o n d i t i o n s . On t h e o t h e r hand, a l t e r n a t i v e
approaches ( e . g . s t o c h a s t i c t r a n s f e r m o d e l s ) a r e s t i l l i n a n e a r l y
state o f development f o r solute transport applications.
C o n s e q u e n t l y , we have i n i t i a t e d our m o d e l i n g e f f o r t s w i t h t h e
t r a d i t i o n a l transport equations. H o p e f u l l y , improved approaches w i l l
be d e v e l o p e d i n t h e n e a r f u t u r e .
Each o f t h e models i d e n t i f i e d i n t h e above sequence i s d e s c r i b e d
b r i e f l y below w i t h o n l y t h e most important f e a t u r e s b e i n g n o t e d .
D e t a i l e d d e s c r i p t i o n s a r e given i n the referenced papers.
One-Dimensional A n a l y t i c a l Model W i t h l s t - O r d e r Loss A t Upper

Boundary. The unique i n i t i a l and boundary c o n d i t i o n s a s s o c i a t e d w i t h
the K u n i a p e s t i c i d e s p i l l (i,7.) r e q u i r e d t h a t t h e s u r f a c e l a y e r ,
c o n t a i n i n g the concentrated p e s t i c i d e , l o s e DBCP r a p i d l y by
volatilization. Thus an upper boundary was e s t a b l i s h e d such t h a t
C ( z , t ) = C e yt
0 = 0, t>0 (1)
where C i s t h e s o l u t e c o n c e n t r a t i o n i n s o l u t i o n [ML~3], C i s t h e 0
c o n c e n t r a t i o n when downward movement s t a r t s , and t a r e t h e space

and time v a r i a b l e s , r e s p e c t i v e l y , and i s an e m p i r i c a l source decay
coefficient [T~l]. L o s s o f DBCP was assumed t o occur by
v o l a t i l i z a t i o n only. The c o n v e c t i o n - d i s p e r s i o n t r a n s p o r t e q u a t i o n
was used t o d e s c r i b e DBCP movement i n t h e s o i l s o l u t i o n , v i z .
(p K d + ) ( 3 C/ 3 t ) = ( 32C/ 8z2) - q 3C/3 - k'C (2)
i n w h i c h i s t h e s o i l b u l k d e n s i t y , K^ i s t h e s o r p t i o n d i s t r i b u t i o n
coefficient, i s the s o i l water content, D i s the
d i f f u s i o n - d i s p e r s i o n c o e f f i c i e n t , q i s t h e Darcy water f l u x , and k'
i s t h e f i r s t - o r d e r r a t e c o e f f i c i e n t , w i t h k'C kCf, where
k' = k ( PKrf + ) and kQr denotes t h e f i r s t - o r d e r decay of t h e t o t a l
concentration of p e s t i c i d e r e s i d u a l i n the s o i l , i . e .
kC-j; = k ( K D + e)C. I n o r d e r t o use t h e simple a n a l y t i c a l model,
c o n s t a n t v a l u e s o f , D and q a r e u s e d . The adequacy of t h i s
s i m p l i f y i n g a p p r o a c h depends m a i n l y on t h e assumed v a l u e o f q w h i c h
i n d i c a t e s an a v e r a g e w a t e r f l u x o v e r a l o n g p e r i o d .
The system e q u a t i o n a l o n g w i t h boundary and i n i t i a l c o n d i t i o n s
were s o l v e d a n a l y t i c a l l y u s i n g a L a p l a c e i n t e g r a l t r a n s f o r m ( ; a
computer program by C l e a r y (14) was m o d i f i e d f o r use i n t h i s s t u d y .
19. GREEN ETAL. Pesticide Movement in the Unsaturated Zone of Hawaiian Soils 369
Two-Dimensional N u m e r i c a l Model. A p p l i c a t i o n o f DBCP by shank

i n j e c t i o n i n a p i n e a p p l e bed (Maui f i e l d s ) p r o v i d e s a l i n e source o f
p e s t i c i d e a t a depth o f about 30 cm w h i c h cannot be modeled i n a
o n e - d i m e n s i o n a l mode w i t h o u t f i r s t e v a l u a t i n g t h e impact o f i n i t i a l
concentration d i s t r i b u t i o n . The geometry of t h e system i s i n d i c a t e d
by t h e c r o s s - s e c t i o n a l diagram o f two p i n e a p p l e beds i n F i g u r e 1.
The s e c t i o n o f F i g u r e 1 d e l i n e a t e d by AA-BB r e p r e s e n t s a t y p i c a l
section. The o b j e c t i v e was t o model t h e movement o f DBCP from an
assumed s o u r c e zone (8 cm wide 10 cm deep s e c t i o n c e n t e r e d a t 30 cm
depth) t o determine t h e approximate time r e q u i r e d t o j u s t i f y the
assumption o f a u n i f o r m l a t e r a l d i s t r i b u t i o n o f DBCP i n t h e plow
l a y e r f o r subsequent o n e - d i m e n s i o n a l m o d e l i n g . An a p p r o p r i a t e model
and n u m e r i c a l s o l u t i o n f o r t h i s case was g i v e n by Hemwell (15) and
the d e t a i l s o f t h e p r e s e n t a p p l i c a t i o n a r e p r e s e n t e d e l s e w h e r e (3.).
In b r i e f , t h e two-dimensional e q u a t i o n s o l v e d i s
3 C/ 3 t - D ' ( 3 2c/ 3 x2 + a 2c/ 3 2 ) - kC z (3)
i n which D' - D / ( K + + aKH) and a i s t h e a i r - f i l l e d p o r o s i t y , K H

d
i s Henry's Law c o n s t a n t [ l 3 s o l u t i o n / L 3 g a s ] and t h e o t h e r v a r i a b l e s

a r e as d e f i n e d p r e v i o u s l y . The boundary c o n d i t i o n a t t h e s o i l
s u r f a c e (z=0) i s d e f i n e d by
-D'( 3 C/ 3 z) = -(Dîr/Rd) c (4)
in which i s the v a p o r - a i r d i f f u s i o n coefficient, d i s the

t h i c k n e s s o f t h e s t a g n a n t a i r l a y e r , and R = ( K D + + a K R ) / K H .
The i n i t i a l c o n c e n t r a t i o n o f p e s t i c i d e i n t h e zone o f a p p l i c a t i o n was
c a l c u l a t e d from t h e amount a p p l i e d ( w i t h assumed 10% a p p l i c a t i o n
l o s s ) , g i v i n g 3 . 5 4 105 ppb f o r Maui P i n e a p p l e Company F i e l d 234 and
2.96 105 ppb f o r F i e l d 2 1 0 .
One-Dimensional A n a l y t i c a l Model W i t h D i f f u s i v e Vapor L o s s A t Upper

Boundary. T h i s model was d e v e l o p e d by J u r y e t a l . (16.) t o p r o v i d e a
c o m p u t a t i o n a l method f o r c l a s s i f y i n g o r g a n i c c h e m i c a l s f o r t h e i r
r e l a t i v e s u s c e p t i b i l i t y t o d i f f e r e n t l o s s pathways ( v o l a t i l i z a t i o n ,
l e a c h i n g and d e g r a d a t i o n ) . Although the b a s i c equation i s
e s s e n t i a l l y the same as E q u a t i o n 2, i n c o n t r a s t t o E q u a t i o n 2 i t
i n c l u d e s t r a n s p o r t i n both t h e vapor and l i q u i d p h a s e s . An e f f e c t i v e
d i f f u s i o n c o e f f i c i e n t , D E , i d e f i n e d such t h a t i t i n c l u d e s b o t h t h e
s
vapor component, K ^ D G , and l i q u i d component, D L , i n t h e f o l l o w i n g

manner :
D
E - (KHDG + DL)/RL
where R L = K D + + a K H . The i n i t i a l l y a p p l i e d c h e m i c a l was

assumed (based on 2-D c a l c u l a t i o n s ) t o be u n i f o r m l y d i s t r i b u t e d i n
the t o p l a y e r o f s o i l o f depth L, g i v i n g an i n i t i a l c o n d i t i o n o f
C ( z , 0 ) - C f o r 0 < < L and C ( z , 0 ) = 0 f o r > L .
Q
A l t h o u g h t h i s s i m p l e a n a l y t i c a l model c o u l d n o t be e x p e c t e d t o
d e s c r i b e DBCP movement t h r o u g h a s o i l p r o f i l e w h i c h v a r i e d s e v e r a l
f o l d i n o r g a n i c carbon c o n t e n t (and hence i n K<i) o v e r a v e r t i c a l
d i s t a n c e o f even a few meters, i t was c o n s i d e r e d adequate t o compute
A A
GROUND SURFACE
30 cm
8 cm
0 010 cm 0 0
A A
54 cm 66 cm
F i g u r e 1. C r o s s - S e c t i o n a l Diagram o f S h a n k - I n j e c t e d DBCP i n Two

P i n e a p p l e Beds.
19. GREEN E T AL. Pesticide Movement in the Unsaturated Zone of Hawaiian Soils 371
c h e m i c a l movement i n t h e t i l l e d s u r f a c e l a y e r , as was done w i t h the

two-dimensional model. The model was used i n a c a l i b r a t i o n mode t o
determine an apparent v a l u e f o r the s u r f a c e l a y e r . Using the
estimate of K d o b t a i n e d by c a l i b r a t i o n o f the model w i t h measured
c o n c e n t r a t i o n a t a depth of 30 cm, the model was used t o c a l c u l a t e
the t o t a l c o n c e n t r a t i o n o f DBCP a t = 36 cm over t i m e . The r e s u l t s
of these c a l c u l a t i o n s were l a t e r used i n the dual-model a p p r o a c h
d e s c r i b e d below.
Dual A n a l y t i c a l Model Approach. T h i s s i m u l a t i o n i n v o l v e d the

s e q u e n t i a l use o f two o n e - d i m e n s i o n a l a n a l y t i c a l models f o r the
purpose of incorporatiang different parameters and boundary
c o n d i t i o n s f o r the upper and lower s o i l zones. F i r s t t h e model of
J u r y e t a l . (16) was a p p l i e d t o t h e s u r f a c e l a y e r as d e s c r i b e d above.
The computed c o n c e n t r a t i o n s o f DBCP a t 36 cm o v e r time were t h e n
f i t t e d t o a f i r s t o r d e r e q u a t i o n so t h a t E q u a t i o n 1 c o u l d be used as
input f o r the model of L i u e t a l . ( 1_), which was a p p l i e d t o t h e lower

layer.
One-Dimensional N u m e r i c a l Model. The e q u a t i o n s a r e i n f i n i t e

d i f f e r e n c e form and a r e based on the model d e s c r i b e d by S e l i m and
Iskandar ( 1 7 ) . The w a t e r f l o w e q u a t i o n was s o l v e d i n terms o f s o i l
water p r e s s u r e head, h, r a t h e r than water c o n t e n t , , g i v i n g
Cap(h) 3 h/ a t = 3 /3 (K3 h/3 ) + 3 /3 (5)
i n which i s the h y d r a u l i c c o n d u c t i v i t y ( a f u n c t i o n o f h) and

Cap(h) = d0/dh i s t h e water c a p a c i t y term. The s o l u t i o n , s t a b i l i t y
c o n d i t i o n s and o t h e r d e t a i l s a r e g i v e n e l s e w h e r e (3.). The n u m e r i c a l
s o l u t i o n t o the water movement model was t e s t e d a g a i n s t the
e x p e r i m e n t a l d a t a of W a r r i c k e t a l . ( 1 8 ) .
The accompanying s o l u t e t r a n s p o r t e q u a t i o n i s the finite
d i f f e r e n c e e q u i v a l e n t of E q u a t i o n 2. The upper boundary c o n d i t i o n i s
r e p r e s e n t e d by a f l u x e q u a t i o n ,
- D 3C/3 + vC = - ( D a i r / d ) K c H (6).
G
The model was f o r m u l a t e d w i t h t h r e e or f o u r l a y e r s i n an attempt t o

r e p r e s e n t changes i n w i t h depth. D e t a i l s of the s o l u t i o n and a
l i s t i n g o f s u b r o u t i n e s a r e g i v e n by Tamrakar (3.).
Chemical and H y d r a u l i c Inputs
Kunia. To determine i n i t i a l c o n d i t i o n s f o r the K u n i a s p i l l i t was

n e c e s s a r y t o e s t i m a t e the a r e a o f the s p i l l and c a l c u l a t e the
approximate depth of p e s t i c i d e p e n e t r a t i o n . A s i m p l e mass b a l a n c e
a n a l y s i s i n d i c a t e d t h a t the s o i l s o l u t i o n was s a t u r a t e d w i t h DBCP t o
a depth of 5 cm soon a f t e r the s p i l l . We e s t i m a t e d v o l a t i l i z a t i o n
l o s s o f DBCP i n a t h r e e - d a y p e r i o d p r i o r t o the f i r s t r a i n f a l l w i t h a
f i r s t - o r d e r decay c o e f f i c i e n t of 1.26 d a y ~ l ( 1 9 ) . The c a l c u l a t e d
i n i t i a l s o l u t i o n c o n c e n t r a t i o n i n the s o i l s o l u t i o n a t t h e f i r s t
r a i n f a l l was 3480 ppb. C l e a r l y , t h i s q u a n t i t y c o u l d be i n e r r o r , so
t h a t subsequent c a l c u l a t e d c o n c e n t r a t i o n s a r e s u s p e c t .
An average water f l u x f o r the K u n i a s i t e f o r the 3-year p e r i o d
a f t e r the s p i l l was c a l c u l a t e d from a s i m p l e w a t e r b a l a n c e , u s i n g
l o c a l e s t i m a t e s o f r u n o f f and e v a p o r a t i o n , d u r i n g and b e t w e e n e a c h
r a i n f a l l e v e n t t o g e t i n f i l t r a t i o n ( 1_). This h i g h l y aggregated s o i l
was c o n s i d e r e d t o h a v e a n a v e r a g e e f f e c t i v e w a t e r c o n t e n t o f 0.15
cm3/cm3 c o n t r i b u t i n g t o s o l u t e t r a n s p o r t .
Maui. DBCP was a p p l i e d by s h a n k i n j e c t i o n a s i l l u s t r a t e d i n F i g u r e 1

a t 75.6 k g / h a i n F i e l d 234 a n d 46.9 k g / h a i n F i e l d 2 1 0 . When a 1 0 %
a p p l i c a t i o n l o s s was a s s u m e d , t h e i n i t i a l c o n c e n t r a t i o n i n t h e s m a l l
r e c t a n g u l a r z o n e o f a p p l i c a t i o n s h o w n i n F i g u r e 1 was 3.54 105 ppb
f o r F i e l d 234 a n d 2.96 105 ppb f o r F i e l d 2 1 0 . The t w o - d i m e n s i o n a l
m o d e l was c a l i b r a t e d w i t h f i e l d d a t a f o r F i e l d 234 ( t w o w e e k s
p o s t - a p p l i c a t i o n ) a n d t h e n u s e d t o c a l c u l a t e t h e a v e r a g e DBCP
c o n c e n t r a t i o n i n the plow l a y e r f o r subsequent s p e c i f i c a t i o n o f
i n i t i a l c o n d i t i o n s f o r the one-dimensional models.
The w a t e r r e c h a r g e f o r t h e M a u i f i e l d s was c a l c u l a t e d w i t h a
simple h y d r o l o g i e balance f o r each f i e l d u s i n g r a i n f a l l data from
nearby rain gauges. Both fields were n o n - i r r i g a t e d . A

r a i n f a l l - r u n o f f r e l a t i o n s h i p was d e v e l o p e d f o r e a c h f i e l d u s i n g t h e
USDA-Soil C o n s e r v a t i o n S e r v i c e " c u r v e number" a p p r o a c h . The v a l i d i t y
o f t h i s a p p r o a c h f o r H a w a i i c o n d i t i o n s was d e m o n s t r a t e d by C o o l e y and
Lane ( 2 0 ) . P o t e n t i a l vapotranspiration f r o m p i n e a p p l e f i e l d s was
a s s u m e d t o be o n e - t h i r d o f p a n e v a p o r a t i o n t h r o u g h o u t t h e s t u d y
p e r i o d , b a s e d o n r e s u l t s o f E k e r n (21) > b u t a c t u a l ET was a d j u s t e d
f o r t h e w a t e r i n p u t f o r e a c h month (3_).
Water b a l a n c e c a l c u l a t i o n s f o r each month r e s u l t e d i n c u m u l a t i v e
i n f i l t r a t i o n a m o u n t s o f 29.4 cm f o r F i e l d 234 ( 6 - m o n t h p e r i o d ) a n d
541 cm f o r F i e l d 210 ( 3 . 5 y e a r s ) . For the a n a l y t i c a l models, average
w a t e r f l u x e s were c a l c u l a t e d from t h e c u m u l a t i v e i n f i l t r a t i o n and
elapsed time. For the one-dimensional n u m e r i c a l model the r a i n f a l l
f o r e a c h r a i n y d a y was a s s u m e d t o be d i s t r i b u t e d u n i f o r m l y t h r o u g h o u t
the day. The s t a b i l i t y c o n d i t i o n f o r t h e w a t e r f l o w s u b m o d e l
r e q u i r e s t h a t t h e t i m e i n c r e m e n t be s m a l l d u r i n g t h e p e r i o d o f
i n f i l t r a t i o n , r e s u l t i n g i n l a r g e computation times f o r each r a i n f a l l
event. To r e d u c e c o m p u t a t i o n c o s t s f o r t h e 3.5 y e a r s i m u l a t i o n o f
F i e l d 210 t h e r a i n f a l l f o r e a c h m o n t h was l u m p e d a s a s i n g l e r a i n f a l l
e v e n t , o c c u r i n g f o r a p e r i o d o f one o r two d a y s , d e p e n d i n g o n t h e
t o t a l r a i n f a l l i n the month. A sensitivity analysis indicated this
a p p r o x i m a t i o n was j u s t i f i e d ( 3 . ) . A n o t h e r f e a t u r e o f t h e p r o g r a m
w h i c h r e d u c e s c o m p u t a t i o n a l t i m e i s a l i m i t a t i o n o n when downward
m o v e m e n t o f DBCP c a n o c c u r : only during the period of i n f i l t r a t i o n
and s i g n i f i c a n t r e d i s t r i b u t i o n . At other times the p e s t i c i d e i s
a s s u m e d t o r e m a i n i m m o b i l e , e x c e p t i n t h e t o p l a y e r i n w h i c h DBCP
v o l a t i l i z a t i o n occurs.
Parameter Estimation
A m a j o r l i m i t a t i o n o f s o l u t e t r a n s p o r t s i m u l a t i o n ( e v e n when t h e
model r e p r e s e n t s f i e l d p r o c e s s e s w e l l ) i s the d i f f i c u l t y of o b t a i n i n g
good e s t i m a t e s o f key p a r a m e t e r s . Some a s p e c t s o f t h i s p r o b l e m w i l l
be considered i n the D i s c u s s i o n s e c t i o n l a t e r . Fundamental
p a r a m e t e r s i d e n t i f i e d i n E q u a t i o n s 1, 3, 4, a n d 6 w h i c h r e q u i r e
specification are: K
d > D, k, D g i r
% and . Most o t h e r p a r a m e t e r s
are d e r i v e d from t h e s e , w i t h the e x c e p t i o n of the parameters r e q u i r e d
t o d e f i n e h y d r a u l i c c o n d u c t i v i t y and w a t e r c o n t e n t as f u n c t i o n s o f
s o i l w a t e r p r e s s u r e head, f o r the water flow e q u a t i o n i n the
19. GREEN E TAL. Pesticide Movement in the Unsaturated Zone of Hawaiian Soils 373
n u m e r i c a l model. The e s t i m a t i o n o f t h e fundamental parameters w i l l

be d i s c u s s e d b r i e f l y ; d e t a i l s a r e g i v e n i n r e f e r e n c e s (I) and 0 3 ) .
Sorption D i s t r i b u t i o n C o e f f i c i e n t . Measurements o f DBCP a d s o r p t i o n

on s o i l s from t h e K u n i a s i t e a t s o l u t i o n c o n c e n t r a t i o n s r a n g i n g from
about 0.25 g/ml t o 290 g /ml i n d i c a t e d t h a t a l i n e a r i s o t h e r m
d e s c r i b e d s o r p t i o n r e a s o n a b l y w e l l ; when s o r p t i o n d a t a were f i t t e d
N
w i t h t h e F r e u n d l i c h e q u a t i o n , S = K f C , t h e v a l u e s o f on s o i l s
e
from t h r e e depths were 0.92, 0.76 and 0.95 U). Subsequently,

s o r p t i o n was determined a t o n l y one i n i t i a l c o n c e n t r a t i o n , 0.35
g / m l , and the e q u a t i o n S = K^C was assumed t o a p p l y . S o r p t i o n was
measured by the b a t c h - s u s p e n s i o n method (22) f o r most samples ; f o r
deep s a p r o l i t e samples h a v i n g v e r y low s o r p t i o n a f l o w - e q u i l i b r a t i o n
t e c h n i q u e (22) p r o v i d e d improved s e n s i t i v i t y and p r e c i s i o n .
In addition t o the c o n v e n t i o n a l sorption distribution
c o e f f i c i e n t s w h i c h were based on the a d d i t i o n of a s o l u t i o n o f known
DBCP c o n c e n t r a t i o n t o s o i l , d e s o r p t i o n c o e f f i c i e n t s were measured by

d e s o r b i n g DBCP r e s i d u e s i n t o water w i t h a 3-hour e q u i l i b r a t i o n p e r i o d
(2.). When d i s t r i b u t i o n c o e f f i c i e n t s determined by these two methods
were found t o be v e r y d i f f e r e n t , e s t i m a t e s o f K were a l s o o b t a i n e d
d
by c a l i b r a t i n g the o n e - d i m e n s i o n a l a n a l y t i c a l model t o f i e l d d a t a .
The v a r i o u s e s t i m a t e s o f K a r e compared i n t h e R e s u l t s s e c t i o n .
d
Solute D i f f u s i o n - D i s p e r s i o n C o e f f i c i e n t . I n these s t u d i e s D was

assumed t o be c o n s t a n t and n o t a f u n c t i o n o f f l o w v e l o c i t y . F o r low
f l o w v e l o c i t i e s t h i s assumption seems r e a s o n a b l y v a l i d ( 2 3 ) . F o r t h e
n a t u r a l r a i n f a l l c o n d i t o n s o f these s t u d i e s the f l o w v e l o c i t i e s were
g e n e r a l l y q u i t e low. I n l i e u o f a c t u a l measured D v a l u e s on t h e two
Maui s o i l s , an e s t i m a t e o f D o b t a i n e d on a somewhat s i m i l a r s o i l on
Oahu by Khan (24) was used i n t h i s s t u d y . An average v a l u e o f D =
0.6 cm^/hr was measured i n t h e f i e l d w i t h a steady water f l u x o f 10
cm/day.
F i r s t - O r d e r D e g r a d a t i o n Rate C o e f f i c i e n t . DBCP i s h i g h l y r e s i s t a n t
t o biodgradation and i s a l s o s t a b l e a g a i n s t h y d r o l y s i s . We have no
measurements o f DBCP d e g r a d a t i o n i n H a w a i i s o i l s , but W i l l i a m s e t a l .
(2) p r e s e n t e v i d e n c e t h a t DBCP i s debrominated i n t h e r o o t zone o f
pineapple. Assuming 15 p e r c e n t DBCP b e i n g debrominated w i t h i n two
weeks, t h e decay r a t e was c a l c u l a t e d t o be 4.8 10 h r ~ ^ C 3 ) , which
i s s i m i l a r t o t h e v a l u e 4.2 10"^ hr""* o b t a i n e d f o r DBCP i n s o i l by
C a s t r o and B e l s e r ( 2 5 ) . D e g r a d a t i o n l o s s e s o f DBCP a r e p r o b a b l y
s u f f i c i e n t l y s m a l l r e l a t i v e t o v o l a t i l i z a t i o n l o s s e s t o be c o n s i d e r e d
i n s i g n i f i c a n t i n the present modeling context.
2
Vapor and L i q u i d D i f f u s i o n C o e f f i c i e n t s . The v a l u e s o f 247.1 cm /hr
i r z
for D g and 6.184 10"^ m /day f o r D p t e r were c a l c u l a t e d by
methods u t i l i z i n g c h e m i c a l p r o p e r t i e s ( 3 ) . Other approximations
s u g g e s t e d by J u r y et a l . were used t o o b t a i n t h e e f f e c t i v e d i f f u s i o n
c o e f f i c i e n t , Dgj t h e vapor phase d i f f u s i o n c o e f f i c i e n t , D , and t h e
G
l i q u i d phase d i f f u s i o n c o e f f i c i e n t , Dj,, f o r s o i l s . Using the

equation D E F = D K + 1^ f o r t h e Maui s o i l s w i t h 59% p o r o s i t y and 30%
G H
2
water, a v a l u e o f D - 0.195 cm /hr was o b t a i n e d (3.).
E F The
c a l c u l a t e d vapor phase d i f f u s i o n c o e f f i c i e n t , D , f o r these same
G
z
c o n d i t o n s was 11.5 cm /hr. E x p e r i m e n t a l measurements on a s i m i l a r
H a w a i i s o i l by P r i n g l e e t a l . (26) gave a DBCP l i q u i d - v a p o r d i f f u s i o n
c o e f f i c i e n t of 9.5 cm2/hr by the method o f J u r y e t a l . (27)

s u g g e s t i n g t h a t the e s t i m a t i o n methods used to obtain diffusion
c o e f f i c i e n t s are reasonably v a l i d .
Henry's Law C o n s t a n t . The c a l c u l a t i o n o f K ' from vapor p r e s s u r e , P,

H
and s o l u b i l i t y , S, a t a g i v e n temperature, as s u g g e s t e d by Mackay and

W o l k o f f ( 2 8 ) . r e s u l t e d i n K ' = 0.3558 atm - L/mole a t 20C.
H For use
as a p a r t i t i o n c o e f f i c i e n t % i s best d e f i n e d as a r a t i o of
c o n c e n t r a t i o n i n the vapor phase t o c o n c e n t r a t i o n i n t h e l i q u i d
phase, K H = Cy/CL. The v a l u e o b t a i n e d f o r DBCP was K H 0.0148 (2)
w i t h d i m e n s i o n s o f [L3 l i q u i d / L 3 v a p o r ] .
Other Parameters D e f i n i n g S o i l P r o p e r t i e s . I n l i e u o f measured d a t a

on the Maui s o i l s , the h y d r a u l i c p r o p e r t i e s and b u l k d e n s i t y f o r the
Wahiawa s o i l on Oahu were used i n n u m e r i c a l s i m u l a t i o n s (3_).
E x p e r i m e n t a l r e s u l t s (29) f o r the s o i l depths o f 20, 60 and 90 cm
were used i n s i m u l a t i o n s o f a t h r e e l a y e r system w i t h a t i l l e d l a y e r

of 45 cm depth, a s u b s o i l l a y e r 45 t o 90 cm, and a s u b s t r a t u m l a y e r
a t depths e x c e e d i n g 90 cm. Bulk d e n s i t y v a l u e s corresponding t o
t h e s e t h r e e l a y e r s were 1.25, 1.25 and 1.4 g/cm3.
DBCP R e s i d u e s i n F i e l d Soils
Kunia. Background i n f o r m a t i o n on t h e K u n i a s i t e and c o r e sampling

were r e p o r t e d by Mink (7.). The s p i l l a r e a has an e l e v a t i o n o f 260 m.
The s o i l i s i n t h e K u n i a s e r i e s , of t h e U s t o x i c Humitropept subgroup;
k a o l i n c l a y s dominate the m i n e r a l f r a c t i o n . A three-meter s o i l
p r o f i l e i s u n d e r l a i n by weathered b a s a l t ( s a p r o l i t e ) t o a depth of 46
meters and unweathered b a s a l t c o n t i n u e s t o t h e b a s a l water t a b l e . At
each s a m p l i n g l o c a t i o n , s i x t e e n c o r e s 45 cm l o n g were t a k e n from each
c o r i n g h o l e t o a t o t a l depth o f about 16 meters (52 f e e t ) .
Maui. Data from two o f t h r e e Maui P i n e a p p l e Company f i e l d s which

were sampled f o r DBCP movement were s e l e c t e d f o r the m o d e l i n g s t u d y .
Both f i e l d s a r e l o c a t e d on E a s t Maui a t e l e v a t i o n s below 185 m, and
the s o i l s , Pauwela c l a y f o r F i e l d 210 and Hamakuapoko c l a y f o r F i e l d
234, a r e members o f t h e taxonomic group Tropohumults. These s o i l s
a r e h i g h l y weathered, w i t h l o w - a c t i v i t y k a o l i n and o x i d e m i n e r a l s .
F i e l d 210 had r e c e i v e d o n l y one a p p l i c a t i o n o f DBCP 3.5 y e a r s p r i o r
t o t h e deep b o r i n g s which were o b t a i n e d a t two l o c a t i o n s i n t h e
field. F i e l d 234 had r e c e i v e d s i x p r e - p l a n t a p p l i c a t i o n s o f DBCP
s i n c e 1958, the l a s t b e i n g s i x months p r i o r t o s o i l b o r i n g s t a k e n a t
f i v e l o c a t i o n s i n the f i e l d . In a d d i t i o n t o the s o i l borings (taken
t o a maximum depth o f 19 m) samples were a l s o t a k e n by hand two weeks
a f t e r a p p l i c a t i o n from a 2-meter deep t r e n c h w h i c h had been dug w i t h
a backhoe. Other d e t a i l s o f sampling and sample p r e p a r a t i o n a r e
g i v e n by W i l l i a m s e t a l (2.).
A n a l y s i s o f DBCP i n s o i l samples was by c o - d i s t i l l a t i o n w i t h
benzene and a n a l y s i s o f the benzene by e l e c t r o n - c a p t u r e gas
chromatography.
Results
W h i l e we have used v a r i o u s models, both a n a l y t i c a l and n u m e r i c a l , i n

t h i s p r e l i m i n a r y m o d e l i n g e f f o r t , the p r i n c i p a l f o c u s o f t h e a n a l y s i s
of r e s u l t s h e r e i s on t h e way i n w h i c h t h e o n e - d i m e n s i o n a l models
r e f l e c t t h e impact o f s o r p t i o n changes w i t h depth i n t h e s o i l
profile. Thus we o b s e r v e d t h e performance o f t h e models u s i n g
measured K d v a l u e s from v a r i o u s s o i l depths, and a l s o used t h e
a n a l y t i c a l model o f J u r y e t a l . (.16) t o d e r i v e Kd v a l u e s f o r the
s u r f a c e l a y e r by c a l i b r a t i o n o f t h e model w i t h measured f i e l d
concentrations.
DBCP S o r p t i o n on S o i l and S a p r o l i t e . F o r t h e K u n i a s i t e , s o r p t i o n K^
v a l u e s were measured o n samples from s e v e r a l depths i n B o r e h o l e s 2
and 3 as w e l l as from t h r e e s h a l l o w depths near t h e w e l l . The
b o r e h o l e s o r p t i o n d a t a , o b t a i n e d by f l o w e q u i l i b r a t i o n , a r e g i v e n i n
Table I. B a t c h e q u i l i b r a t i o n gave r e s u l t s which were about 20%
h i g h e r f o r samples w i t h t h e h i g h e s t s o r p t i o n , but t h e b a t c h method
had i n a d e q u a t e p r e c i s i o n when s o r p t i o n was low, as f o r samples 2-1,
2-3 and 3-2. The p r e c i s i o n o f t h e f l o w - e q u i l i b r a t i o n method f o r DBCP
i s l i m i t e d o n l y by t h e GC a n a l y s i s . Zero v a l u e s i n T a b l e I i n d i c a t e
s o r p t i o n Kd < 0.01 ml/gm. Of t h e s e v e r a l b o r e h o l e samples, o n l y
sample 3-1 showed s u b s t a n t i a l s o r p t i o n o f DBCP. I n both b o r e h o l e s
t h e r e was l i t t l e s o r p t i o n below 1 meter. The d i m i n i s h e d s o r p t i o n o f
DBCP w i t h i n c r e a s i n g depth appears t o be r e l a t e d p r i n c i p a l l y t o a
decrease i n o r g a n i c c a r b o n w i t h depth.
Table I. DBCP S o r p t i o n by F l o w - E q u i l i b r a t i o n on S o i l from Two

Boreholes a t the Kunia Site, Oahu, Hawaii
Borehole Depth Organic Carbon

Sample (meter) (%) (ml/gm)
2-1 0.5 2.3 0.01

2-3 2.3 0.6 0.02
2-7 5.9 0.3 0
3-1 0.5 4.1 1.94

3-2 1.4 1.3 0.06
3-3 2.3 0.8 0
3-5 4.1 0.4 0
3-7 5.9 0.2 0
3-9 7.8 0.2 0
S o r p t i o n K^ v a l u e s f o r Maui F i e l d 234 a r e g i v e n i n T a b l e I I .
These d a t a a r e s e l e c t e d from s o r p t i o n v a l u e s measured by W i l l i a m s e t
a l (2.) t o show the l a r g e d i f f e r e n c e i n K v a l u e s o b t a i n e d by the
d
c o n v e n t i o n a l b a t c h e q u i l i b r a t i o n method and by d e s o r p t i o n o f r e s i d u a l
DBCP i n f i e l d samples. Desorption K values are c l e a r l y several
d
times l a r g e r than those o b t a i n e d by b a t c h e q u i l i b r a t i o n . Although i t

might be e x p e c t e d t h a t d e s o r p t i o n e q u i l i b r a t i o n times much l o n g e r
t h a t those used i n these t e s t s (3 h o u r s ) might have r e s u l t e d i n
s m a l l e r d i f f e r e n c e s , r e c e n t measurements u s i n g 24-hour s o r p t i o n and
desorption equilibrations also indicated a several-fold difference i n
K d between s o r p t i o n o f DBCP from r e c e n t l y added DBCP s o l u t i o n and
d e s o r p t i o n o f DBCP added t o d r y s o i l a few weeks e a r l i e r ( 3 0 ) .
Table II. Comparison o f DBCP K d V a l u e s from C o n v e n t i o n a l Batch

E q u i l i b r a t i o n and D e s o r p t i o n o f F i e l d R e s i d u e s
(Maui P i n e a p p l e Co. F i e l d 234)
S o i l Core Depth d K
(ml/gm)
No. (m) Sorption Desorption
0.3 0.60 18.0

1.2 0 3.4
3.0 0 3.8
0.3 0.46 24.3
The l a r g e e f f e c t i v e d e s o r p t i o n K f o r DBCP suggests t h a t DBCP

d
r e s i d u e s i n the s u r f a c e s o i l a r e much l e s s m o b i l e than i s i n d i c a t e d

by the c o n v e n t i o n a l s o r p t i o n measurement.
One-Dimensional S i m u l a t i o n o f DBCP Movement a t K u n i a . DBCP

d i s t r i b u t i o n t h r e e y e a r s a f t e r the p e s t i c i d e s p i l l was s i m u l a t e d by
the o n e - d i m e n s i o n a l a n a l y t i c a l model w i t h e x p o n e n t i a l decay source
term a t the s u r f a c e (1.); p r e d i c t e d c o n c e n t r a t i o n s a r e shown i n F i g u r e
2. Measured c o n c e n t r a t i o n s from B o r e h o l e s 2, 3 and 5 a r e a l s o shown
i n F i g u r e 2 f o r comparison w i t h s i m u l a t e d r e s u l t s . The three
measured DBCP c o n c e n t r a t i o n p r o f i l e s a r e q u i t e v a r i a b l e , both i n
shape and i n magnitude of c o n c e n t r a t i o n s . The r e a s o n f o r the
v a r i a t i o n i n measured p r o f i l e s i s not known, but may be due t o
d i f f e r e n c e s i n the amount of DBCP which e n t e r e d the s o i l a t each
l o c a t i o n and v a r i a t i o n i n s o i l p r o p e r t i e s between b o r e h o l e s i t e s .
T h e r e appears t o be a c o r r e l a t i o n between the s o r p t i o n v a l u e s i n
T a b l e 1 f o r B o r e h o l e s 2 and 3 and t h e r e t e n t i o n o f DBCP near the
s u r f a c e a t these two l o c a t i o n s , i e . h i g h s o r p t i o n i n the s u r f a c e s o i l
at s i t e 3 r e s u l t e d i n h i g h r e t e n t i o n o f DBCP, i n c o n t r a s t t o s i t e 2.
The s i m u l a t e d c o n c e n t r a t i o n p r o f i l e i n F i g u r e 2 was obtained
u s i n g a weighted s o r p t i o n c o e f f i c i e n t ( K = 0.15)
d f o r the 0 t o 7
meter zone of B o r e h o l e 3. Use of a w e i g h t e d v a l u e i s an u n d e s i r a b l e
s i m p l i f i c a t i o n , e s p e c i a l l y when the s o r p t i o n c o e f f i c i e n t changes so
r a p i d l y w i t h depth ( T a b l e I ) . However, we were c o n s t r a i n e d by the
a n a l y t i c a l model t o use a s i n g l e s o r p t i o n c o e f f i c i e n t f o r the e n t i r e
profile. The s i m u l a t e d DBCP c o n c e n t r a t i o n p r o f i l e has the shape of
B o r e h o l e 5 d a t a and t h e c o n c e n t r a t i o n range of B o r e h o l e 3 d a t a .
S i m u l a t e d DBCP Movement i n Plow L a y e r Two D i m e n s i o n a l N u m e r i c a l

Model. Of the s e v e r a l i n p u t parameters r e q u i r e d f o r E q u a t i o n s 3 and
4 (Hemwell model) the most d i f f i c u l t t o s p e c i f y w i t h c o n f i d e n c e a r e
Kd and D. Our o b j e c t i v e i n u s i n g the 2-D model was t o c a l c u l a t e
i n i t i a l DBCP c o n c e n t r a t i o n i n the upper l a y e r i n o r d e r t o s p e c i f y
i n i t i a l c o n d i t i o n s f o r the o n e - d i m e n s i o n a l models used t o p r e d i c t
deep p e n e t r a t i o n o f DBCP. For t h i s r e a s o n the 2-D model was
c a l i b r a t e d w i t h f i e l d d a t a by a d j u s t i n g K and D w i t h i n r e a s o n a b l e
d
limits. Combinations o f parameters used and t h e r e s u l t s a r e shown i n

T a b l e I I I . The use o f K^ = 4.10 was based on a c a l i b r a t i o n o f the
J u r y e t a l . a n a l y t i c a l model w i t h f i e l d s u r f a c e l a y e r d a t a s i x months
a f t e r a p p l i c a t i o n as d e s c r i b e d e a r l i e r . T h i s v a l u e i s o b v i o u s l y too
h i g h f o r r e c e n t l y a p p l i e d DBCP a t the e x t r e m e l y h i g h c o n c e n t r a t i o n
e x i s t i n g soon a f t e r a p p l i c a t i o n . The c o m b i n a t i o n o f = 0.1 ml/gm
and D = 1.05 cm2/hr gave r e s u l t s w h i c h matched the f i e l d measured
average c o n c e n t r a t i o n a t 30 cm two weeks a f t e r a p p l i c a t i o n . The
c o n c e n t r a t i o n p r o f i l e f o r F i e l d 234, based on the a v e r a g e computed
c o n c e n t r a t i o n a t each depth, i s shown i n F i g u r e 3. Tamrakar e t a l .
(3.) show a l s o the p l o t f o r an uncovered s u r f a c e .
Table III. Comparison of 2-D Model and F i e l d Data, Maui Pineapple

F i e l d 234, Two Weeks a f t e r A p p l i c a t i o n
Average DBCP Cone, i n

DBCP L o s s i n 2 Weeks S o i l a t 30 cm.
Kd D Simulated Measured Simulated Measured
(ml/gm) (cm2/hr) (%) (%) (ppb) (ppb)
4.10 0.20 0 75 32200 3408

0.10 0.20 20 75 12940 3408
0.10 1.05 76 75 3580 3408
D u a l A n a l y t i c a l 1-D Model. A comparison o f c a l c u l a t e d and measured

DBCP c o n c e n t r a t i o n p r o f i l e s f o r F i e l d 210 i s shown i n F i g u r e 4. The
Kd parameter f o r the s u r f a c e 36 cm used i n t h i s s i m u l a t i o n was the
c a l i b r a t i o n v a l u e o b t a i n e d w i t h the J u r y e t a l . model f o r F i e l d 234
s u r f a c e s o i l , K^ = 4,1. The two f i e l d s were thought t o be
s u f f i c i e n t l y s i m i l a r t o use the same v a l u e ; measured K v a l u e s were
d
about 0.6 ml/gm f o r s u r f a c e s o i l i n both f i e l d s (2.). For s o i l below

36 cm, K d = 0.56 ml/gm was used, even though t h i s v a l u e was i n i t i a l l y
thought t o be more a p p r o p r i a t e f o r the s u r f a c e l a y e r than f o r deeper
layers (Table I I ) . The comparison between p r e d i c t e d and measured
data i n F i g u r e 4 does not encourage the use of a n a l y t i c a l models t o
p r e d i c t r e s i d u a l DBCP c o n c e n t r a t i o n s i n the s o i l p r o f i l e , even w i t h
accomodation f o r parameter changes between the upper and lower
layers. The model p r e d i c t s l e a c h i n g o f DBCP from the t o p l a y e r i n a
broad zone, w i t h a peak a t about 400 cm; no such peak i s e v i d e n t i n
the measured r e s u l t s . The l i m i t a t i o n s of the a n a l y t i c a l model
encouraged development of the n u m e r i c a l model w h i c h would a l l o w more
d e t a i l e d s p e c i f i c a t i o n of s o i l p r o p e r t i e s w i t h depth.
N u m e r i c a l 1-D Model R e s u l t s . S i m u l a t i o n o f DBCP movement was

a c c o m p l i s h e d w i t h the DBCP a p p l i c a t i o n and h y d r o l o g i e i n p u t s f o r both
Maui f i e l d s . The measured DBCP d i s t r i b u t i o n s shown i n the f o l l o w i n g
f i g u r e s r e p r e s e n t average v a l u e s f o r f i v e s e t s o f core samples i n
F i e l d 234 and two s e t s i n F i e l d 210. A l t h o u g h the c o n c e n t r a t i o n s
between s i t e s w i t h i n a g i v e n f i e l d v a r i e d up t o s e v e r a l f o l d ,
e s p e c i a l l y a t the s h a l l o w e s t depths (0.3 and 1.2 m), the shape of the
c o n c e n t r a i o n p r o f i l e was c o n s i s t e n t between sampling s i t e s .
I n i t i a l c o n c e n t r a t i o n s i n the top 36 cm were o b t a i n e d from the
2-D simulations discussed e a r l i e r . The absence of s i g n i f i c a n t
r a i n f a l l d u r i n g the two weeks a f t e r DBCP a p p l i c a t i o n a l l o w e d t h i s
approach. One-dimensional n u m e r i c a l s i m u l a t i o n s i n d i c a t e d l i t t l e
d i f f e r e n c e i n computed p r o f i l e s whether i n i t i a l d i s t r i b u t i o n o f DBCP
DBCP IN SOIL (ppb)

0.1 1 10 100
H< 1 1 -
CALCULATED
X BOREHOLE 5
BOREHOLE 3
BOREHOLE 2
F i g u r e 2. S i m u l a t e d ( C u r v e ) and Measured (Data P o i n t s ) DBCP

C o n c e n t r a t i o n s i n S o i l a t t h e K u n i a , Oahu S i t e .
CONCENTRATION (ppb)
0 1000 2000 3000 4000
DEPTH (cm) 20
F i g u r e 3. S i m u l a t e d Average L a t e r a l DBCP C o n c e n t r a t i o n s (Dry

S o i l B a s i s ) i n Maui P i n e a p p l e F i e l d 234 Two Weeks A f t e r
A p p l i c a t i o n ; S u r f a c e 43% Covered; 2-D N u m e r i c a l Model.
CONCENTRATION (ppb)
0.01 0.1 1
0i
100
200
300
DEPTH (cm)
400
500
600
F i g u r e 4. S i m u l a t e d (Dual-Model Approach) and Measured DBCP

C o n c e n t r a t i o n s (Dry S o i l B a s i s ) 3.5 y e a r s a f t e r A p p l i c a t i o n ,
Maui P i n e a p p l e F i e l d 210. Average d e v i a t i o n i s i n d i c a t e d f o r
mean o f two b o r e h o l e s .
was as shown i n F i g u r e 3 or u n i f o r m l y d i s t r i b u t e d i n the top 36 cm

(3.) For F i e l d 234, DBCP r e s i d u e s e x i s t e d i n the p r o f i l e p r i o r t o
the DBCP a p p l i c a t i o n c o n s i d e r e d i n the simulation. The
p r e - a p p l i c a t i o n c o n c e n t r a t i o n s a t depths o f 0.3, 1, 1.5 and 2.1
meters were 22, 6, 13, and 11 ppb. There were no r e s i d u e s i n F i e l d
210 p r i o r t o the a p p l i c a t i o n c o n s i d e r e d i n t h e s i m u l a t i o n .
I n i t i a l l y , n u m e r i c a l s i m u l a t i o n s were done f o r both f i e l d s w i t h
t h r e e s o i l l a y e r s h a v i n g depth i n t e r v a l s o f 0 t o 45 cm, 45 t o 90 cm,
and g r e a t e r than 90 cm. Input parameters i n c l u d e d Kd v a l u e s o f 4.1,
4.1 and 0.12 ml/gm and k (decay r a t e ) v a l u e s o f 1.6 10~4,
1.4 10~4 and 6 10~5 d a y ~ l f o r the t h r e e l a y e r s , r e s p e c t i v e l y .
Other parameter v a l u e s were d e f i n e d e a r l i e r i n the p a p e r .
S i m u l a t e d r e s u l t s f o r F i e l d 234 a r e shown i n F i g u r e 5. The
s i m u l a t e d c o n c e n t r a t i o n s t o a depth of about 100 cm a r e r e a s o n a b l y
c l o s e t o measured v a l u e s , p a r t l y as a r e s u l t of u s i n g a Kd v a l u e i n
the upper p r o f i l e w h i c h had been o b t a i n e d by c a l i b r a t i o n of the 1-D
a n a l y t i c a l model w i t h F i e l d 234 d a t a . The secondary s i m u l a t e d peak

a t 200 cm i s a p p a r e n t l y due t o the p r e - a p p l i c a t i o n DBCP r e s i d u e ,
which was not a c t u a l l y as m o b i l e as the s i m u l a t i o n s u g g e s t s .
Use of the same s o r p t i o n c o e f f i c i e n t s f o r F i e l d 210 as were used
i n the F i e l d 234 s i m u l a t i o n r e s u l t e d i n c o n c e n t r a t i o n s i n t h e s u r f a c e
l a y e r which were about an o r d e r of magnitude too low and
c o n c e n t r a t i o n s a t g r e a t e r depths which were an o r d e r too h i g h . Thus
i t was not p o s s i b l e t o use the Kd o b t a i n e d from F i e l d 234 f o r F i e l d
210. S u b s e q u e n t l y , the 1-D a n a l y t i c a l model was used t o determine by
c a l i b r a t i o n an a p p r o p r i a t e Kd v a l u e f o r F i e l d 210; the r e s u l t was
=
Kd 17.0. Thus f o r the n u m e r i c a l s i m u l a t i o n , Kd = 17 was used f o r 0
t o 90 cm and Kd = 0.12 was a s s i g n e d f o r depths g r e a t e r than 90 cm.
The r e s u l t of s i m u l a t i o n w i t h these v a l u e s i s shown i n F i g u r e 6. The
e f f e c t of the abrupt change i n Kd a t 90 cm i s e v i d e n t i n the
simulated r e s u l t . An a d d i t i o n a l s i m u l a t i o n was done u s i n g f o u r
l a y e r s w i t h Kd v a l u e s o f 17, 12 and 1.8 f o r the f i r s t t h r e e l a y e r s
(each 45 cm t h i c k ) and 0.12 f o r the u n d e r l y i n g l a y e r . The r e s u l t i n g
s i m u l a t e d c o n c e n t r a t i o n p r o f i l e , shown i n F i g u r e 7, i n d i c a t e s a
c o n s i d e r a b l e improvement i n t h e performance of the model when the
s o r p t i o n v a r i a t i o n w i t h depth i s a d e q u a t e d l y r e p r e s e n t e d by the
model. I t i s o f i n t e r e s t t o note t h a t the measured Kd v a l u e s f o r
F i e l d 210 were 0.64, 0.11 and 0.074 ml/gm f o r 0.3, 1.2 and 2.1
meters, r e s p e c t i v e l y (2.) Thus the Kd v a l u e s r e q u i r e d t o g i v e a
r e a s o n a b l e s i m u l a t i o n a r e much l a r g e r t h a n those measured by the
conventional batch e q u i l i b r a t i o n .
D i s c u s s i o n and Conclusions
The m o d e l i n g e x e r c i s e s r e p o r t e d h e r e cannot be c o n s i d e r e d r i g o r o u s
t e s t s o f the s u i t a b i l i t y of the models examined f o r two p r i n c i p a l
reasons: (a) key i n p u t parameters were not a d e q u a t e l y q u a n t i f i e d ,
and (b) measured DBCP c o n c e n t r a t i o n p r o f i l e s v a r i e d c o n s i d e r a b l y
within a given f i e l d . On the otherhand, some g e n e r a l o b s e r v a t i o n s as
t o the a p p a r e n t s u i t a b i l i t y of the v a r i o u s models a r e j u s t i f i e d .
The s i m p l e a n a l y t i c a l model i s i n a d e q u a t e p r i n c i p a l l y because i t
cannot accomodate changes i n s o i l p r o p e r t i e s w i t h d e p t h . Measured
s o r p t i o n c o e f f i c i e n t s d e c r e a s e d s t r i k i n g l y w i t h depth a t b o t h the
K u n i a and Maui s i t e s . The attempt t o i n c o r p o r a t e some change i n
s o r p t i o n w i t h depth by u s i n g the d u a l a n a l y t i c a l model d i d n o t r e s u l t
E V A L U A T I O N O F P E S T I C I D E S IN G R O U N D W A T E R
CONCENTRATION (ppb)
0.01 0.1 1 10 100 1000
0i 1 1 1 1 1
DEPTH (cm)
3501
F i g u r e 5. N u m e r i c a l S i m u l a t i o n (Three S o i l L a y e r s ) o f DBCP
P r o f i l e S i x Months a f t e r A p p l i c a t i o n , Maui P i n e a p p l e F i e l d 234.

Average d e v i a t i o n i s i n d i c a t e d f o r mean o f f i v e b o r e h o l e s .
CONCENTRATION (ppb)
0.01 0.1 1 10
04 , , 1
F i g u r e 6. N u m e r i c a l S i m u l a t i o n (Three S o i l L a y e r s ) o f DBCP
P r o f i l e 3.5 Y e a r s a f t e r A p p l i c a t i o n , Maui P i n e a p p l e F i e l d 210.
Average d e v i a t i o n i s i n d i c a t e d f o r mean o f two b o r e h o l e s .
CONCENTRATION (ppb)
0.01 0.1 1 10
F i g u r e 7. N u m e r i c a l S i m u l a t i o n (Four S o i l L a y e r s ) o f DBCP
P r o f i l e 3.5 Y e a r s a f t e r A p p l i c a t i o n , Maui P i n e a p p l e F i e l d 210.
i n a s a t i s f a c t o r y p r e d i c t i o n of f i e l d behavior. The n u m e r i c a l model,

on t h e o t h e r hand, p r o v i d e s f o r changes i n s o i l p r o p e r t i e s w i t h depth
and a l s o i n c o r p o r a t e s a more r e a l i s t i c d e s c r i p t i o n o f w a t e r f l o w .
C o n s i d e r i n g t h e i n c r e a s e d a v a i l a b i l i t y of h i g h speed computers and
the low c o s t o f computation r e l a t i v e t o o t h e r a s p e c t s o f groundwater
c o n t a m i n a t i o n a n a l y s e s , we c o n c l u d e t h a t n u m e r i c a l m o d e l i n g i s by f a r
the most a p p r o p r i a t e .
How U s e f u l I s a Measured S o r p t i o n C o e f f i c i e n t ? The n u m e r i c a l model

p r o v i d e d r e a s o n a b l y good p r e d i c t i o n s o f f i e l d DBCP l e a c h i n g b e h a v i o r
o n l y when t h e Kd v a l u e s used i n t h e t o p l a y e r were o b t a i n e d by
calibration. S o r p t i o n c o e f f i c i e n t s measured by c o n v e n t i o n a l b a t c h
e q u i l i b r a t i o n were much t o o low t o d e s c r i b e t h e l e a c h i n g o f r e s i d u a l
DBCP over a p e r i o d o f months o r y e a r s . I t i s s i g n i f i c a n t t h a t t h e Kd
v a l u e o b t a i n e d f o r F i e l d 234 by c a l i b r a t i o n o f t h e a n a l y t i c a l model
(Kd = 4.1) was g r e a t e r than t h e s o r p t i o n c o e f f i c i e n t measured by
b a t c h e q u i l i b r a t i o n (Kd = 0.6), but l e s s than t h e v a l u e o b t a i n e d by

d e s o r p t i o n o f r e s i d u a l DBCP i n f i e l d samples (Kd = 2 2 ) . Similar
r e s u l t s were o b t a i n e d f o r Maui P i n e a p p l e Company F i e l d 210, w i t h
b a t c h e q u i l i b r a t i o n g i v i n g K^ = 0.64 and model c a l i b r a t i o n g i v i n g
Kd = 17. These r e s u l t s have i m p l i c a t i o n s f o r a) a n a l y s i s o f
mechanisms o f p e s t i c i d e t r a n s p o r t i n s o i l s and b) t h e p r o c e d u r e s used
t o measure s o r p t i o n c o e f f i c i e n t s f o r m o d e l i n g p u r p o s e s .
F i r s t , some assumptions i n h e r e n t i n t h e use o f t h e c o n v e c t i o n -
d i s p e r s i o n e q u a t i o n a r e s u s p e c t f o r most f i e l d s o i l s . I t i s now
abundantly c l e a r t h a t an average water f l o w v e l o c i t y does n o t
g e n e r a l l y represent adequately the c o n t r i b u t i o n of convection t o
solute transport. P r e f e r e n t i a l flow through the l a r g e s t pore
sequences c o n t r i b u t e s t o a l a r g e apparent d i s p e r s i o n , w i t h s m a l l
q u a n t i t i e s o f s o l u t e b e i n g c a r r i e d l a r g e d i s t a n c e s and a major
p o r t i o n o f the s o l u t e i n s m a l l m i c r o p o r e s b e i n g r e t a i n e d n e a r t h e
s o i l s u r f a c e because o f " f l o w b y - p a s s i n g " . A number o f e x p e r i m e n t a l
and m o d e l i n g s t u d i e s have demonstrated t h i s phenomenon ( e . g . 31_> 32_,
33, 34, 35., 36., 37.) > one o f these s t u d i e s (34) was conducted o n a
H a w a i i O x i s o l w i t h s t r u c t u r a l p r o p e r t i e s s i m i l a r t o those o f t h e Maui
s o i l s o f our s t u d y . Recent a n a l y t i c a l r e v i e w s (.9, 10., !!* 12) bave
examined t h e c o n s i d e r a b l e body of e v i d e n c e and suggest that
p r e d i c t i o n of s o l u t e t r a n s p o r t i n f i e l d s o i l s w i l l r e q u i r e modeling
approaches w h i c h i n c o r p o r a t e some d e s c r i p t i o n o f t h e wide range o f
pore v e l o c i t i e s , whether by s t o c h a s t i c o r d e t e r m i n i s t i c means.
Another common s i m p l i f y i n g assumption i s that of sorption
e q u i l i b r i u m , which i s i n h e r e n t i n t h e use o f Kd i n E q u a t i o n 2.
D u r i n g a r a i n f a l l o r i r r i g a t i o n event, and s u b s e q u e n t l y d u r i n g water
r e d i s t r i b u t i o n , t h e dynamics o f water movement has a g r e a t impact on
the r a t e o f s o l u t e d i f f u s i o n out o f a g g r e g a t e m i c r o p o r e s and
c o n s e q u e n t l y on t h e e x t e n t o f s o r p t i o n e q u i l i b r i u m both i n m i c r o p o r e s
and macropores. Thus p r e f e r e n t i a l w a t e r f l o w , s o l u t e d i f f u s i o n and
s o r p t i o n k i n e t i c s a r e l i n k e d processes which a r e e s s e n t i a l l y ignored
when we use t h e c o n v e n t i o n a l c o n v e c t i o n - d i s p e r s i o n e q u a t i o n .
P r o g r e s s has been made i n m o d e l i n g t h i s complex system (36) but
a p p l i c a t i o n t o f i e l d s i t u a t i o n s i s l i m i t e d by t h e d i f f i c u l t y of
s p e c i f y i n g key parameters.
The r e s u l t s o f our s t u d i e s suggest t h a t e q u i l i b r i u m s o r p t i o n
c o e f f i c i e n t s measured by c o n v e n t i o n a l b a t c h e q u i l i b r a t i o n may be
u s e f u l f o r m o d e l i n g t h e s h o r t - t e r m movement o f p e s t i c i d e s but w i l l
not a d e q u a t e l y represent s o r p t i o n of residues. Considering the

p o s s i b l e i n t e r a c t i o n o f p r e f e r e n t i a l w a t e r f l o w t h r o u g h l a r g e pores
and e o r p t i o n - d e s o r p t i o n dynamics, one might expect t h a t t h e
apparently i n f l a t e d v a l u e s o b t a i n e d by model c a l i b r a t i o n were t h e
r e s u l t of p e s t i c i d e i n micropores being by-passed i n the l e a c h i n g
process. But i n f a c t , v a l u e s measured by d e s o r p t i o n o f DBCP
r e s i d u e s were a l s o much l a r g e r than v a l u e s measured by t h e
conventional s o r p t i o n procedure, i n d i c a t i n g that the model-derived
v a l u e s were a t r u e r e p r e s e n t a t i o n o f a c t u a l s o r p t i o n b e h a v i o r i n t h e
field. We c o n c l u d e t h a t i t may be a p p r o p r i a t e t o i n c o r p o r a t e a
s o r p t i o n - d e s o r p t i o n h y s t e r e s i s submodel i n t h e n u m e r i c a l model o f
pesticide transport. The s o r p t i o n - d e s o r p t i o n r e l a t i o n s h i p i s l i k e l y
t o be time dependent i n most cases and thus may be d i f f i c u l t t o
s p e c i f y a p r i o r i f o r a g i v e n system.
Acknowledgment
The work d e s c r i b e d i n t h i s paper was funded i n p a r t by the U.S.

Environmental P r o t e c t i o n Agency through the P e s t i c i d e H a z a r d
Assessment Program, P a c i f i c B i o m e d i c a l R e s e a r c h C e n t e r , U n i v e r s i t y of
Hawaii. The c o n t e n t s do n o t n e c e s s a r i l y r e f l e c t t h e v i e w s o f t h e
Agency and no o f f i c i a l endorsement s h o u l d be i n f e r r e d .
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Water Resour. Res. Center, 1982.
30. Buxton, D.S.; Green R.E. 1985 unpublished data.
31. Biggar, J.W.; Nielsen, D.R. Soil Sci. Soc. Amer. Proc. 1962,
26, 125-128.
32. Green, R.E.; Rao, P.S.C.; Corey, J.C. Proc. Joint Symp. Fund.
Transport Phenomena in Porous Media, Guelph, Ont. 1972, 2,
732-752.
33. Kissel, D.E.; Ritchie, J.T.; Barnett, E. J . Environ. Qual.
1974, 3, 401-404.
34. Rao, P.S.C.; Green, R.E.; Balasubramanian, V; Kanehiro, Y. J .
Environ. Qual. 1974, 3, 197-202.
35. Quisenberry, V.L.; Phillips, R.E. Soil Sci. Soc. Am. J . 1978,
43, 675-679.
36. van Genuchten, M.Th.; Wierenga, P.J. Soil Sci. Soc. Am. J .
1976, 40, 473-480.
37. Amoozegar-Fard, .; Nielsen, D.R.; Warrick, A.W. Soil Sci. Soc.
Am. J . 1982, 46, 3-9.

20
Evaluation of Pesticide Transport Screening Models
under Field Conditions
William A. Jury, Hesham Elabd, L. Denise Clendening, and Margaret Resketo
Department of Soil and Environmental Sciences, University of California, Riverside,

C A 92521
Two field experiments investigating the mobility of

pesticides leached by sprinkler irrigation are

discussed. The first experiment applied a pulse of
chloride and napropamide, a moderately adsorbed her-
bicide, to a 0.6 ha field which was subsequently
leached with 25 cm water low in chloride over a two-
-week period. Soil core samples were taken at 36 loca-
tions to 300 cm and were analyzed in 10 cm increments
for chloride and pesticide. Distribution coefficient K D
measurements were made at each sampling location by

batch equilibrium and column flow through methods.
K values obtained by either method had coefficients
D
or variation of approximately 30% between replicates.

Correlation between measurements by the two methods
was not significant, even though their field average
values and variances were similar. Approximately 80%
of the pesticide recovered in the cores was found
within 20 cm of the soil surface, which was consistent
with the predicted behavior based on the measured K D
values. However the remaining 20% of the pesticide

was located randomly between 20 and 180 cm, suggesting
that this portion of the applied chemical moved
without adsorbing.
A second experiment was conducted on 14 plots on
the same site. The soil surface on these plots was
sprayed with a mixture containing four chemicals:
bromide, bromacil, napropamide and prometryn, which
were leached during two weeks of sprinkler irrigation.
Field-wide leaching behavior was similar to that of
the earlier experiment, with the strongly adsorbed
chemicals napropamide and prometryn showing split con-
centration peaks in each core with most of the chemi-
cal located near the soil surface, and the remainder
randomly located between the surface and depths
approaching those reached by the mobile chemical
(bromide). It was concluded that existing chemical
0097-6156/86/0315-0384$06.00/0
20. JURY ET AL. Evaluation of Pesticide Transport Screening Models 385
t r a n s p o r t models a f t e r c a l i b r a t i o n w i t h l a b o r a t o r y
v a l u e s are capable of d e s c r i b i n g the l o c a t i o n of
the adsorbed p o r t i o n of the c h e m i c a l but are u n a b l e to
p r e d i c t the l o c a t i o n of the p o r t i o n which bypasses the
adsorption s i t e s . The p r e d i c t e d r e l a t i v e m o b i l i t y of
the f o u r c h e m i c a l s was c o n s i s t e n t w i t h f i e l d o b s e r
v a t i o n s , suggesting that environmental screening t e s t s
may s t i l l be u s e f u l i n c l a s s i f y i n g p e s t i c i d e s .
Widespread o c c u r r e n c e of p e s t i c i d e c h e m i c a l s i n groundwater and s u r

f a c e water s u p p l i e s has prompted an i n c r e a s e d r e s e a r c h e f f o r t to
d e v e l o p improved methods f o r e s t i m a t i n g p e s t i c i d e m o b i l i t y .
A l t h o u g h the most comprehensive method f o r e s t i m a t i n g m o b i l i t y i s to
conduct t r a n s p o r t experiments under n a t u r a l c o n d i t i o n s , t h i s p r o c e
dure i s c l e a r l y not f e a s i b l e to c a r r y out on the l a r g e number of
e x i s t i n g c h e m i c a l s and new c h e m i c a l s i n t r o d u c e d each y e a r . For t h i s

r e a s o n , p e s t i c i d e t r a n s p o r t or e n v i r o n m e n t a l s c r e e n i n g models have
been d e v e l o p e d to a i d i n p e s t i c i d e m o b i l i t y c l a s s i f i c a t i o n .
P e s t i c i d e s i m u l a t i o n models are not new. Considerable success
has been a c h i e v e d over the l a s t 15 y e a r s i n s i m u l a t i n g o u t f l o w con
c e n t r a t i o n s from l a b o r a t o r y columns u s i n g a c o n v e c t i o n - d i s p e r s i o n
c h e m i c a l t r a n s p o r t model c o u p l e d w i t h a r e p r e s e n t a t i o n of p e s t i c i d e
a d s o r p t i o n onto m i n e r a l or o r g a n i c s o l i d phases ( 1 - 6 ) . The most
comprehensive a d s o r p t i o n models i n c l u d e a n o n - l i n e a r a d s o r p t i o n
i s o t h e r m and r a t e - l i m i t e d d i f f u s i v e t r a n s p o r t from s o l u t i o n to
a d s o r b e d phases (4,6^. However, these models c o n t a i n many unknown
p a r a m e t e r s and a r e d i f f i c u l t to c a l i b r a t e u s i n g f i e l d d a t a . Most
p r o p o s a l s f o r m o b i l i t y c l a s s i f i c a t i o n , t h e r e f o r e , are based on
s i m p l e l i n e a r a d s o r p t i o n i s o t h e r m s c o n t a i n i n g a s i n g l e parameter,
the d i s t r i b u t i o n c o e f f i c i e n t fcmS/g'), to r e p r e s e n t the a d s o r p t i o n
a f f i n i t y of the c h e m i c a l ,K). because the parameter is soil
s p e c i f i c , i t has a l s o been s i m p l i f i e d by d e f i n i n g an o r g a n i c carbon
coefficient which i s e q u a l to the d i s t r i b u t i o n c o e f f i c i e n t \^
d i v i d e d by the o r g a n i c carbon f r a c t i o n f . The f o r m u l a t i o n has
OC O
been shown to reduce the c o e f f i c i e n t of v a r i a t i o n or a g i v e n chemi-
c a l ' s a d s o r p t i o n a f f i n i t y between d i f f e r e n t s o i l s compared to
K n (7,8).
These m o b i l i t y i n d i c e s or e q u i v a l e n t r e p r e s e n t a t i o n s such as
t h i n - l a y e r chromatography r e t e n t i o n time (9) p l a y a s i g n i f i c a n t r o i e
i n e n v i r o n m e n t a l s c r e e n i n g c l a s s i f i c a t i o n s of r e l a t i v e m o b i l i t y
(10). E n v i r o n m e n t a l s c r e e n i n g o f f e r s one means whereby l a r g e num-
b e r s of c h e m i c a l s mav be grouped i n t o a s m a l l number of c a t e g o r i e s
d i s p l a y i n g s i m i l a r e n v i r o n m e n t a l b e h a v i o r to reduce the e x p e r i m e n t a l
r e q u i r e m e n t s (10^.
A l t h o u g h the l a b o r a t o r y e x p e r i m e n t a l e v i d e n c e i s c o n s i d e r a b l e ,
t h e r e have been to date no comprehensive f i e l d - s c a l e s t u d i e s of
p e s t i c i d e movement under n a t u r a l c o n d i t i o n s . In f a c t , u n t i l 10
y e a r s ago t h e r e were v i r t u a l l y no s t u d i e s of water or m o b i l e chemi-
c a l t r a n s p o r t i n the n a t u r a l f i e l d environment.
I n f o r m a t i o n o b t a i n e d from f i e l d - s c a l e experiments conducted
d u r i n g the l a s t decade on m o b i l e w a t e r - t r a c e r c h e m i c a l s i s not
encouraging. E x t e n s i v e v e r t i c a l and l a t e r a l v a r i a b i l i t y of water
and c h e m i c a l t r a n s p o r t and r e t e n t i o n parameters has c r e a t e d d i f -
f i c u l t i e s i n t e s t i n g l a b o r a t o r y s c a l e models ( U ) . Furthermore, a
386 EVALUATION O F P E S T I C I D E S IN G R O U N D WATER
growing body of e v i d e n c e s u g g e s t s t h a t the consensus l a b o r a t o r y

s c a l e model f o r s o l u t e movement, the c o n v e c t i o n - d i s p e r s i o n e q u a t i o n ,
may not c o r r e c t l y d e s c r i b e f i e l d - s c a l e m o b i l e c h e m i c a l movement near
the s o i l s u r f a c e (12-14).
The l i m i t e d s u c c e s s t h a t l a b o r a t o r y - s c a l e models have had i n
s i m u l a t i n g m o b i l e c h e m i c a l movement experiments on the f i e l d s c a l e
l e d us to s e t two p r i o r i t i e s f o r our f i r s t f i e l d experiments w i t h
organic pesticides. R a t h e r than s e e k i n g to c a l i b r a t e and v a l i d a t e
an a c t u a l s i m u l a t i o n model, we f o c u s e d on two more r e s t r i c t e d o b j e c
tives. The f i r s t experiment was d e s i g n e d to c h a r a c t e r i z e the
v a r i a b i l i t y of the d i s t r i b u t i o n c o e f f i c i e n t of a s i n g l e p e s t i c i d e
o v e r a l a r g e f i e l d and a l s o to compare i t s v a l u e s measured by two
d i f f e r e n t methods, b a t c h e q u i l i b r i u m and f l o w through methods. A
two-week l e a c h i n g experiment f o l l o w e d by a f i e l d - w i d e sampling p r o
v i d e d the f i r s t comprehensive i n f o r m a t i o n about the e x t e n t o f
l a t e r a l and v e r t i c a l v a r i a b i l t y of p e s t i c i d e movement i n t o the s o i l .
The second experiment f o c u s e d on a t e s t of the p r e d i c t i v e c a p a b i l i t y

of K q c or v a l u e s f o r d e t e r m i n i n g the r e l a t i v e b e h a v i o r of a group
o f p e s t i c i d e s s u b j e c t e d to l e a c h i n g i n f i e l d p l o t s . These e x p e r i
ments a r e p r e s e n t e d below.
M a t e r i a l s and Methods
Napropamide f i e l d s t u d y . Koth experiments were conducted on the

i n n e r 0.64 h e c t a r e of a loamy sand fmixed, t h e r m i c , t y p i c xeropsam-
ments) l o c a t e d i n *!tiwanda, C a l i f o r n i a . Tn the f i r s t experiment a
c o n c e n t r a t e d p u l s e of water c o n t a i n i n g 15 meq/1 KC1 was added j u s t
a f t e r 50 ppm of napropamide, a c o m m e r i c a l l y a v a i l a b l e h e r b i c i d e , was
s p r a y e d over the e n t i r e f i e l d . The c h e m i c a l s were l e a c h e d i n t o the
s o i l d u r i n g two weeks of d a i l y s p r i n k l e r i r r i g a t i o n u n t i l 25 cm net
a p p l i e d water had e n t e r e d the s o i l . At t h i s time a h y d r a u l i c sam
p l i n g t r u c k was brought onto the f i e l d and 36 s o i l c o r e s were taken
on a 6 6 g r i d to a depth of 300 cm. These c o r e s were s u b d i v i d e d
i n t o 10 cm i n c r e m e n t s and a n a l y z e d f o r napropamide and c h l o r i d e .
T h i r t y - s i x u n d i s t u r b e d s o i l columns were taken on a 6 6
s a m p l i n g g r i d immediately a d j a c e n t to the f i e l d c o r e l o c a t i o n s , and
were brought t o the l a b o r a t o r y . The columns were l e a c h e d a t 2 cm/d
u n t i l steady s t a t e was reached, a t which time a p u l s e of KC1 and
napropamide was added to the i n l e t end. a f f l u e n t breakthrough curves
f o r each c h e m i c a l were f i t t e d to the c o n v e c t i o n - d i s p e r s i o n e q u a t i o n
by the method of moments ( 1 1 ) . The e f f e c t i v e r e t a r d a t i o n f a c t o r R,
w h i c h may be c a l c u l a t e d from the r a t i o of the c h l o r i d e and
v
napropamide n a p v e l o c i t y parameters o b t a i n e d by f i t t i n g the
c o n v e c t i o n - d i s p e r s i o n e q u a t i o n , i s e q u a l to
= V / V 1 +
* cl nap - ' <"
where p. i s dry b u l k d e n s i t y (g/cm ) and 0 i s v o l u m e t r i c water con

3
t e n t (2_). E q u a t i o n 1 was used to c a l c u l a t e K^.

Kach h o l e l e f t i n the f i e l d where the 36 u n d i s t u r b e d columns
were taken was sampled and the s o i l was brought t o the l a b o r a t o r y
f o r a b a t c h e q u i l i b r i u m d e t e r m i n a t i o n of X^, e s t i m a t e d as the l i n e a r
s l o p e of the p l o t of adsorbed v e r s u s d i s s o l v e d napropamide con
c e n t r a t i o n a t e q u i l i b r i u m . F u r t h e r d e t a i l s of the experiments a r e
g i v e n i n FAabd ( 1 5 ) .
20. JURY E T A L . Evaluation of Pesticide Transport Screening Models 387
P l o t experiments. The second experiment on t h e same f i e l d used 14

2m 2m p l o t s randomly l o c a t e d a c r o s s the f i e l d . On each o f t h e s e
p l o t s , a c o n c e n t r a t e d s p r a y c o n t a i n i n g p o t a s s i u m bromide, b r o m a c i l ,
napropamide and prometryn were added, ^ a l f o f the p l o t s
e q u i l i b r a t e d f o r 72 hours a f t e r the s p r a y a p p l i c a t i o n w h i l e c o v e r e d
to p r e v e n t e v a p o r a t i o n and exposure t o s u n l i g h t . A f t e r the 72-hour
p e r i o d , t h e r e m a i n i n g p l o t s were sprayed and t h e e n t i r e f i e l d was
l e a c h e d d a i l y by s p r i n k l e r i r r i g a t i o n . The p l o t s were c o v e r e d a f t e r
each i r r i g a t i o n was completed, f l i g h t o f the p l o t s were sampled
a f t e r 10 cm o f a p p l i e d water had been added t o the f i e l d and the
r e m a i n i n g s i x p l o t s were sampled a f t e r 18 cm o f a p p l i e d water had
been added. A s i n g l e c o r e p r o f i l e was taken t o 300 m from t h e C
c e n t e r o f the p l o t and was a n a l y z e d f o r the c o n c e n t r a t i o n o f each

c h e m i c a l i n 10 cm i n c r e m e n t s , f u r t h e r d e t a i l s o f t h i s experiment
are given i n Clendening ( 1 6 ) .
Results
S o i l and c h e m i c a l p r o p e r t i e s . T a b l e I g i v e s v a r i o u s s o i l a d s o r p t i o n
p r o p e r t i e s of the f o u r c h e m i c a l s used i n t h e two e x p e r i m e n t s . The
o r g a n i c carbon p a r t i t i o n c o e f f i c i e n t s were o h t a i n e d from a l i t e r a
t u r e s u r v e y , except f o r t h e v a l u e s f o r napropamide, which were
c a l c u l a t e d from t h e v a l u e s measured by b a t c h e q u i l i b r i u m and
measured o r g a n i c carbon f r a c t i o n v a l u e s a t each l o c a t i o n . Also
g i v e n i n T a b l e T. a r e the b u l k d e n s i t y , water c o n t e n t and o r g a n i c
c a r b o n f r a c t i o n measurements f o r the f i e l d and t h e i r v a r i a b i l i t y
among t h e 36 r e p l i c a t e s ( 1 5 ) . The r e t a r d a t i o n f a c t o r v a l u e s R g i v e n
i n t h e t a b l e a r e c a l c u l a t e d from A q u a t i o n 1. The R v a l u e d e f i n e s
t h e p r e d i c t e d r e t a r d a t i o n o f a l i n e a r l y adsorbed p e s t i c i d e r e a c h i n g
equilibrium. T t may be viewed as an i n d e x o f p e s t i c i d e m o b i l i t y
r e l a t i v e t o a f r e e - w a t e r t r a c e r such as bromide o r c h l o r i d e ( 1 0 ) .
Thus, when a bromide p u l s e moves 10 cm, t h e p r e d i c t e d movement o f an
adsorbed c h e m i c a l i n the same s o l u t i o n i s 10/R cm. I n t h e absence
of d i r e c t f i e l d o b s e r v a t i o n s , the i n f o r m a t i o n i n Table I r e p r e s e n t s
t h e consensus l a b o r a t o r y p r e d i c t i o n o f r e l a t i v e m o b i l i t y f o r the
c h e m i c a l s i n our s t u d y .
S p a t i a l v a r i a b i l i t y o f a d s o r p t i o n . T a b l e IT shows t h e mean, s t a n
d a r d d e v i a t i o n , and c o e f f i c i e n t o f v a r i a t i o n o f v a r i o u s p e s t i c i d e
a d s o r p t i o n parameters measured i n the study o f F.labd (15>, i n c l u d i n g
c o r r e l a t i o n c o e f f i c i e n t s between d i f f e r e n t p r o p e r t i e s measured a t
t h e same l o c a t i o n . Two s i g n i f i c a n t f e a t u r e s a r e e v i d e n t . First,
a l t h o u g h the b a t c h e q u i l i b r i u m and s o i l column f l o w through methods
for determining gave a p p r o x i m a t e l y t h e same f i e l d average over
3
t h e 36 r e p l i c a t e s , (2.01 and 1.91 cm /gm r e s p e c t i v e l y ) , the c o r r e l a
t i o n between i n d i v i d u a l measurements a t t h e same l o c a t i o n was n e g l i
gible. Second, d i v i s i o n o f by o r g a n i c carbon f r a c t i o n d i d n o t
r e d u c e t h e c o e f f i c i e n t of v a r i a b i l i t y f o r e i t h e r the b a t c h o r f l o w
t h r o u g h method measurements, s u g g e s t i n g t h a t on our sandy s o i l both
m i n e r a l and o r g a n i c a d s o r p t i o n s i t e s were s i g n i f i c a n t . For either
a d s o r p t i o n i n d e x , t h e f i e l d wide c o e f f i c i e n t o f v a r i a b i l i t y i s l a r g e
( 3 0 7 ) , but t h e f i e l d average v a l u e c o u l d s t i l l be e s t i m a t e d r e l a
t i v e l y a c c u r a t e l y from a few samples.
T a b l e T. V a r i o u s A d s o r p t i o n Parameters f o r the C h e m i c a l s Hsed

i n the F i e l d Experiments
*
+
Number of s o i l s R Reference
oc T)
or replicates Number
3 1 3 1
(cm ^" ) fcrn ^ )
bromide 0 0 1
Bromacil 41 + 30% 7 soils 0.25 2.2 Q7)

34 25% 6 soils 0.20 2.0 (8)
72 109% 2 soils 0.43 3.1 (8)
Napropamide 335 30% 36 r e p l i c a t e s 2.01 10.6 (15)
Prometryn 810 1 4.86 24.1 (19)

518 17% 102 2.40 12.4 (7)
614 99% 38 3.68 18.5
f = ,006 31% (15)

oc
p b = 1.38 6% (15)
= 0.29 5% (15)

= f
T) oc oc
+R = 1 + p K^/G h
20. JURY E TA L . Evaluation of Pesticide Transport Screening Models 389
T a b l e I I . Means, Standard D e v i a t i o n s , C o e f f i c i e n t s o f V a r i a t i o n and

C r o s s C o r r e l a t i o n s (N=36> Between V a r i o u s A d s o r p t i o n Parameters
Standard Coefficient
Parameter Mean Deviation of V a r i a t i o n
batch 2.01 (ml/g) 0.63 31
column 1.91 Cml/g) 0.49 26

K q c batch 357.7 (ml/g) 142.6 39
K
oc c o l u m n
33R.9 (ml/g) 84.6 25
f 0-?0 cm .0058 .0013 23

oc
3
1.38 (g/cm ) .08 6
.29 .01 4
batch column - .21
* n batch f 0-10 .18

oc
K n batch f 0-20 - .06

oc
batch - .28
column f 0-10 .38

oc
column f 0-20 .57

oc
column - .28
Napropamide f i e l d e x p e r i m e n t . F i g u r e 1 p r e s e n t s napropamide c o n
c e n t r a t i o n s as a f u n c t i o n of depth measured i n 18 of the f i e l d c o r e s
which were taken a t the end of the two-week l e a c h i n g p e r i o d . A
s i g n i f i c a n t amount of deep p e n e t r a t i o n i s p r e s e n t i n a l l c o r e s ,
s u g g e s t i n g t h a t a p o r t i o n of the a p p l i e d c h e m i c a l a t each l o c a t i o n
i s moving downward w i t h o u t a d s o r h i n g to s o l i d s u r f a c e s . Each of the
r e p l i c a t e s o i l c o r e c o n c e n t r a t i o n s at a g i v e n depth were averaged to
produce a f i e l d - m e a n c o n c e n t r a t i o n - d e p t h d i s t r i h u t i o n f o r hoth
napropamide and f o r c h l o r i d e , which was added i n a p u l s e a t the same
time as napropamide ( F i g u r e 2). T h i s average curve shows most of
the napropamide c o n c e n t r a t e d i n the top 20 cm w i t h the remainder
d i s p e r s e d hetween 20 and 180 cm. ^he c h l o r i d e , which a c t s as a
water t r a c e r , i s found to depths as g r e a t as 300 cm.
A l s o shown i n F i g u r e 2 i s the p r e d i c t e d napropamide d i s t r i h u
t i o n , c a l c u l a t e d by assuming t h a t i t f o l l o w s the same water f l o w
pathways as c h l o r i d e , hut i s r e t a r d e d hv a c o n s t a n t f a c t o r R = 10.6
( T a b l e 1>. T h i s curve i s c o n s t r u c t e d by p l o t t i n g R C1(Z) v e r s u s

Z/R where C1(Z) i s the c h l o r i d e c o n c e n t r a t i o n at depth 7 i n the
figure. S i n c e both the c h l o r i d e and napropamide c u r v e s are n o r
m a l i z e d to have u n i t a r e a under the c o n c e n t r a t i o n - d e p t h c u r v e , the
p r e d i c t e d c u r v e p l o t t e d i n t h i s manner has the same s c a l e .
P l o t experiments. F i g u r e s 3 and 4 show f i e l d average p r o f i l e s f o r

h r o m a c i l , bromide, prometryn and napropamide f o r each of the two
r e p l i c a t e d p l o t experiments, ^ e s e p r o f i l e s are s c a l e d so as to
g i v e u n i t a r e a u n d e r n e a t h the c u r v e s f o r each c h e m i c a l . The p r o
f i l e s of both s t r o n g l y adsorbed p e s t i c i d e s , napropamide and p r o
metryn, show s u b s t a n t i a l r e t e n t i o n i n the s u r f a c e l a y e r s , and deep
p e n e t r a t i o n of a p o r t i o n of the a p p l i e d c h e m i c a l , which i s c o n
s i s t e n t w i t h the b e h a v i o r of napropamide i n the e a r l i e r e x p e r i m e n t .
S i m i l a r l y , t h e s e d i s p e r s e d p r o f i l e s o c c u r r e d i n a l l r e p l i c a t e s of
the p l o t s t u d i e s . F u r t h e r m o r e , no s i g n i f i c a n t d i f f e r e n c e s were
o b s e r v e d between the p l o t s which e q u i l i b r a t e d f o r 72 hours and those
w h i c h were l e a c h e d immediately a f t e r a p p l i c a t i o n .
discussion
S p a t i a l v a r i a b i l i t y of a d s o r p t i o n . The f i e l d average c o n c e n t r a t i o n
c u r v e s f o r napropamide and c h l o r i d e ( F i g u r e 4) c l e a r l y i l l u s t r a t e the
i n f l u e n c e of both water f l o w v a r i a b i l i t y and a d s o r p t i o n v a r i a b i l i t y
on the c h e m i c a l d i s p l a c e m e n t p r o c e s s . The c h l o r i d e curve may be
r e g a r d e d as a r e p r e s e n t a t i o n o f the s p a t i a l v a r i a b i l i t y of water
f l o w a c r o s s the f i e l d , r e s u l t i n g i n a l a r g e d i s p e r s i o n of the p u l s e
which was i n i t i a l l y added w i t h a s m a l l q u a n t i t y of i r r i g a t i o n w a t e r .
However, the napropamide d i s t r i b u t i o n cannot be e x p l a i n e d s o l e l y on
the b a s i s of water f l o w v a r i a b i l i t y . The f i e l d - w i d e napropamide
c u r v e i s c h a r a c t e r i z e d by s i g n i f i c a n t detainment w i t h i n the top 20
cm and a broad d i s p l a c e m e n t between 20 and 180 cm. S i n c e the maxi
mum depth reached by the c h l o r i d e was 300 cm , then the maximum
d e p t h which would be reached by napropamide i f i t were c o m p l e t e l y
a d s o r b e d i s 300/10.6 * 28 cm, assuming a c o n s t a n t p a r t i t i o n c o e f

ficient R 10.6. A l t h o u g h the v a l u e s measured by the two
methods were v a r i a b l e , the observed 30% c o e f f i c i e n t of v a r i a t i o n
even when superimposed on the v a r i a b l e water f l o w c o u l d not e x p l a i n
the e x t r e m e l y deep p e n e t r a t i o n of p a r t of the c h e m i c a l . One i s l e f t
JURY E T A L . Evaluation of Pesticide Transport Screening Models 391
e
- 1. 1
1 > I
12 1 2 1 2 1 2 1 2 1
SOIL DEPTH (m)
F i g u r e 1 Napropamide c o n c e n t r a t i o n v e r s u s s o i l d e p t h found i n
18 o f t h e s o i l c o r e s i n the experiment o f F l a b d ( 1 5 ) ,
100 200 300
SOIL DEPTH (cm)

F i g u r e 2. F i e l d average p e s t i c i d e c u r v e ( r e c t a n g l e s ) t o g e t h e r
w i t h f i e l d average c h l o r i d e c u r v e (dashed l i n e ) and p r e d i c t e d
p e s t i c i d e c u r v e ( d o t t e d l i n e ) assuming constant =2,01
(ml/g) measured i n l a b o r a t o r y and v a r i a b l e water f l o w .
1=10 cm
BROMIDE
BROMRCIL
NAPROPAMIDE
PROMETRYN
50
SOIL D E P T H (cm)
F i g u r e 3. Average c h e m i c a l c o n c e n t r a t i o n s f o r a l l r e p l i c a t e s o f
f i e l d p l o t experiment sampled a f t e r 10 cm a p p l i e d w a t e r .
w i t h the c o n c l u s i o n t h a t the p o r t i o n s of napropamide which reached

depths s i g n i f i c a n t l y g r e a t e r than 30 cm were not a d s o r b e d .
The l a c k of c o r r e l a t i o n between the f l o w through method and the
b a t c h e q u i l i b r i u m method of d e t e r m i n i n g K_ i s q u i t e s u r p r i s i n g , p a r
t i c u l a r l y s i n c e the means and v a r i a n c e s o n t a i n e d w i t h the two
methods were s i m i l a r . S i n c e a t a g i v e n s i t e t h e s e experiments were
performed on i m m e d i a t e l y a d j a c e n t samples, one would not expect
s i g n i f i c a n t v a r i a t i o n s i n o r g a n i c carbon or m i n e r a l a d s o r p t i o n s i t e
distribution. F u r t h e r m o r e , s i n c e the methods gave the same average
v a l u e s , d i f f e r e n c e s between methods cannot be a t t r i b u t e d to r a t e -
l i m i t e d a d s o r p t i o n by l o s s of a d s o r p t i o n s i t e s caused by s o i l s t r u c
t u r e i n the s o i l column method. C l e a r l y , f u r t h e r r e s e a r c h i s needed
on the r e l a t i o n s h i p between f l o w through experiments and b a t c h
e x p e r i m e n t s f o r measuring c h e m i c a l a d s o r p t i o n c o e f f i c i e n t s .
p
l o t experiments. The two f i e l d p l o t s t u d i e s summarized i n F i g u r e s
3 and 4 o f f e r e v i d e n c e t h a t the deep p e n e t r a t i o n of napropamide

o b s e r v e d i n the e a r l i e r experiment ( F i g u r e 1> was not an a r t i f a c t .
Roth napropamide and prometryn c o n c e n t r a t i o n p r o f i l e s showed the
same p a r t i a l p e n e t r a t i o n observed e a r l i e r w i t h most of the a p p l i e d
c h e m i c a l p u l s e l o c a t e d near the s u r f a c e and the remainder found
s p o r a d i c a l l y d i s t r i b u t e d at g r e a t e r d e p t h s . The v a r i a b i l i t y of the
bromide l e a c h i n g i s s i m i l a r to t h a t of the c h l o r i d e p r o f i l e observed
i n the e a r l i e r experiment, s u g g e s t i n g t h a t the water f l o w regime was
s i m i l a r i n both e x p e r i m e n t s . The b r o m a c i l p r o f i l e , a l t h o u g h main
t a i n i n g a c o n t i n u o u s s t r u c t u r e , was somewhat r e t a r d e d w i t h r e s p e c t
to the bromide p r o f i l e .
A major g o a l of the second experiment was to determine the
e x t e n t t o which l a b o r a t o r y c h a r a c t e r i z a t i o n s of r e l a t i v e m o b i l i t y
were u s e f u l i n d e s c r i b i n g r e l a t i v e f i e l d b e h a v i o r . The consensus
l a b o r a t o r y i n f o r m a t i o n i n T a b l e p r e d i c t s t h a t the r e l a t i v e o r d e r
of p e n e t r a t i o n of the f o u r c h e m i c a l s s h o u l d be bromide: b r o m a c i l :
napropamide: p r o m e t r y n : . F i g u r e s 5 and 6 p r e s e n t graphs of the
c u m u l a t i v e p r o b a b i l i t y of b e i n g found above depth as a f u n c t i o n of
f o r each of the f o u r c h e m i c a l s i n the two e x p e r i m e n t s , o b t a i n e d by
i n t e g r a t i n g the c o n c e n t r a t i o n p r o f i l e s i n F i g u r e s 3 and 4 w i t h depth.
These c u r v e s s u b s t a n t i a t e the l a b o r a t o r y p r e d i c t i o n s f o r the r e l a
t i v e movement of the c h e m i c a l s i n the 10 cm sampling i n f i g u r e %
showing t h a t a t any g i v e n depth the r e l a t i v e r e t a r d a t i o n of the che
m i c a l s was i n the p r o p e r o r d e r . The 18 cm sampling i n F i g u r e 6
showed a g r e a t e r r e t a r d a t i o n of napropamide than prometryn i n the
top 20 cm, a l t h o u g h t h i s was r e v e r s e d below t h a t depth. However, as
shown i n T a b l e the l i t e r a t u r e v a l u e s of K q c f o r prometryn a r e
quite variable. I n f a c t , one of the s t u d i e s r e p o r t e d i n (7) had a
v a l u e o f 310 which i s s m a l l e r than the napropamide v a l u e
measured f o r our f i e l d . Tt i s p o s s i b l e t h a t t h e s e c h e m i c a l s s h o u l d
be c l a s s i f i e d as s i m i l a r i n m o b i l i t y based on t h e i r e x p e r i m e n t a l
evidence.
C o n c l u d i n g Remarks
The f i e l d experiments r e p o r t above o f f e r a p e s s i m i s t i c f o r e c a s t f o r

t h e f u t u r e of p e s t i c i d e s i m u l a t i o n models. Adsorbed c h e m i c a l s i n
a l l r e p l i c a t e s of two experiments on our f i e l d showed s i g n i f i c a n t
bypass which i s e v i d e n c e t h a t a d s o r p t i o n i s not r e t a r d i n g a f r a c t i o n
JURY ETAL. Evaluation of Pesticide Transport Screening Models 393
BROMIDE

01
\~
BROMACIL
Lu
U

NflPROPRMIDE

PROMETRYN
Ld
0 50 100 150 2 0 0 2 5 0
SOIL DEPTH (cm)
f i g u r e 4. Average c h e m i c a l c o n c e n t r a t i o n s f o r a l l r e p l i c a t e s o f
f i e l d p l o t experiment sampled a f t e r 18 cm a p p l i e d water.
/ / 1=10 cm
0 50 100 150 200

SOIL DEPTH (cm)
F i g u r e 5. C u m u l a t i v e p r o b a b i l i t y curve f o r p l o t averages calcu
l a t e d from F i g u r e 3.
SOIL DEPTH (cm)
F i g u r e 6 C u m u l a t i v e p r o b a b i l i t y curve f o r p l o t averages calcu

l a t e d from F i g u r e 4.
o f t h e c h e m i c a l added t o t h e s o i l s u r f a c e . T h i s phenomenon was p r e

s e n t even when t h e p l o t s e q u i l i b r a t e d f o r 72 hours p r i o r t o
leaching. No e x i s t i n g o r proposed p e s t i c i d e t r a n s p o r t model i s
c a p a b l e o f d e s c r i b i n g t h i s deep p e n e t r a t i o n .
However, t h e l i m i t e d t e s t o f t h e s c r e e n i n g model m o b i l i t y p r e
d i c t i o n i s more e n c o u r a g i n g . G i v e n t h a t a c e r t a i n amount o f
v a r i a b i l i t y w i l l o c c u r under f i e l d c o n d i t i o n s , t h e l a b o r a t o r y
V
Q Cvalues d i d present a p i c t u r e of the r e l a t i v e order of leaching
or t h e f o u r c h e m i c a l s i n t h e two p l o t e x p e r i m e n t s . Tf t h i s r e s u l t
i s o b t a i n e d when t h e f i e l d experiment i s r e p e a t e d on l a r g e numbers
o f c h e m i c a l s i n d i f f e r e n t s o i l s , i t may e v e n t u a l i t y a l l o w f u t u r e
comprehensive f i e l d r e s e a r c h s t u d i e s t o f o c u s on r e p r e s e n t a t i v e s o f
d i f f e r e n t m o b i l i t y c a t e g o r i e s r a t h e r than r e q u i r i n g p r o h i b i t i v e num
b e r s o f e x p e r i m e n t s t o be conducted on each c h e m c i a l .
The r e s e a r c h a l s o p o i n t s o u t a number o f a r e a s f o r f u t u r e
study. The l a c k o f c o r r e l a t i o n between t h e two methods o f measuring
i s s u r p r i s i n g and s h o u l d be i n v e s t i g a t e d f o r o t h e r c h e m i c a l s ,
e p a r t i a l deep l e a c h i n g o f b o t h prometryn and napropamide on our
f i e l d s i t e may i n d i c a t e t h a t an o v e r l o o k e d mechanism o f adsorbed
c h e m i c a l t r a n s p o r t i s o p e r a t i n g , which c o u l d i n v o l v e e i t h e r a m o b i l e
o r g a n i c complex o r c o n c e i v e a b l y attachment t o f i n e c o l l o i d a l
suspended p a r t i c l e s . These h y p o t h e s e s s h o u l d be i n v e s t i g a t e d n o t
o n l y on d i f f e r e n t f i e l d s i t e s b u t a l s o under c o n t r o l l e d l a b o r a t o r y
conditions. Our r e s e a r c h group a t R i v e r s i d e i s p l a n n i n g such
experiments i n the f u t u r e .
Acknowledgment
The a u t h o r s would l i k e t o thank t h e S o u t h e r n C a l i f o r n i a E d i s o n

Company and the U S - I s r a e l BAPD Fund f o r f i n a n c i a l a s s i s t a n c e i n t h i s
project.
Literature Cited
1. Davidson, J. M.; Chang, R. K. Soil Sci. Soc. Amer. Proc.
1972, 36, 251-261.
2. van Genuchten, M. Th.; Davidson, J. M.; Wierenga, P. J. Soil
Sci. Soc. Amer. Proc. 1974, 38, 29-34.
3. van Genuchten, M. Th.; Wierenga, P. J. Soil Sci. Soc. Amer. J.
1977, 41, 278-285.
1976, 40, 473-480.
1977, 41, 272-8.
6. Lindstrom, F. T.; Haque, P.; Freed, V. H.; Boersma, L. Env.
Sci. Tech. 1967, 1, 561-5.
7. Hamaker, J. W.; Thompson, T. M. In "Organic Chemicals in the
Soil Environment"; Goring, I.; Hamaker, J. S., Eds.; Marcel
Dekker, New York, 1972.
8. Rao, P. S. C.; Davidson, J. M. In "Environmental Impact of
Nonpoint Source Pollution"; Overcash, M. R., Ed.; Ann Arbor
Science, Michigan, 1980.
9. Helling, C. S. Soil Sci. Soc. Amer. Proc. 1971, 35, 737-743.
10. Jury, W. .; Spencer, W. F.; Parmer, W. J. J . Env. Qual.
1983, 12, 558-564.
20. JURY ET AL. Evaluation of Pesticide Transport Screening Models
395
11. Jury, W. .; Sposito, G. Soil Sci. Soc. Amer. J. 1985.

Nov.-Dec., (In pressa).
12. Dagan, G.; Bresler, E. Soil. Sci. Soc. Amer. J. 1979, 43,
461-6.
13. Jury, W. .; Stolzy, L. H.; Shouse, Peter. Water Resources
Res. 1982, 18, 369-374.
14. Jury, W. .; Elabd, H. Proc. of NWWA/USEPA Conference on
Characterization and Monitoring of the Vadose Zone. 1983.
15. Elabd, H. Ph.D.Thesis,university of California, Riverside,
1984.
16. Clendening, L. Denise. Master's Thesis, University of
California, Riverside, 1985.
17. Corwin, D. Ph.D. Thesis, University of California, Riverside,
1985.
18. Gerstl, Z.; Saltzmann, S.; Kliger, L . ; Yaron, B. Irrig. Sci.
1981, 2, 155-166.
19. Kenaga, E. E. Etox. and Env. Safety. 1980, 4, 26-38.
RECEIVED January 21, 1986

21
Field Validation of Ground Water Models
Mary P. Anderson
Department of Geology and Geophysics, University of Wisconsin-Madison, Madison,

WI 53706
Rigorous field validation or calibration of a

groundwater model is often impossible because of
uncertainties in input parameters. Nevertheless, an
attempt should always be made to demonstrate that a

model is capable of predicting concentrations measured
in the field. The biggest uncertainty in model input
often lies in quantifying the source function. The
amount and concentration of contaminants entering the
groundwater system depend not only on the amount
infiltrating the land surface but also on uptake and
chemical reactions occurring in the unsaturated zone.
Ideally, a groundwater model should be linked to a
model of the unsaturated zone. Other uncertainties
typically arise owing to a lack of information on the
degradation characteristics of the contaminant in the
subsurface and the heterogeneous nature of the porous
material that constitutes the aquifer. Heterogeneities
influence the configuration of the velocity field and
may be critical to proper quantification of contaminant
movement but there is no consensus among researchers
on the proper way to simulate dispersion of con-
taminants in groundwater. Moreover, modelers must
confront the fact that most groundwater models are
designed to simulate two-dimensional flow fields when
in reality many groundwater contamination problems are
three-dimensional. Whereas, groundwater flow problems
generally can be simplified to two dimensions, it
appears doubtful that three-dimensional contaminant
plumes can be adequately represented by two-dimensional
models. The expense of collecting sufficient three-
-dimensional field data to validate a three-dimensional
model will be prohibitive for most studies. These
points are demonstrated through discussion of a case
example involving the application of a two-dimensional
contaminant transport model to simulate the movement
of aldicarb in groundwater in Wisconsin.
0097-6156/ 86/ 0315-0396S06.00/ 0

21. ANDERSON Field Validation of Ground Water Models 397
P r e d i c t i n g the f u t u r e i s n o t an easy t a s k . Based on e n g i n e e r i n g

and g e o l o g i c judgement, i t i s c e r t a i n l y p o s s i b l e to make p r e d i c -
t i o n s a b o u t the n a t u r e and e x t e n t o f the m i g r a t i o n o f c h e m i c a l s i n
groundwater. However, i t i s o f t e n p r e f e r a b l e to use a m a t h e m a t i c a l
model i n o r d e r to remove some o f the s u b j e c t i v i t y i n h e r e n t i n
making p r e d i c t i o n s . A m a t h e m a t i c a l model c o n s i s t s o f a s e t o f
e q u a t i o n s t h a t have been demonstrated to mimic the e f f e c t s o f
v a r i o u s p h y s i c a l p r o c e s s e s o p e r a t i v e i n the r e a l w o r l d . However,
the d e r i v a t i o n and s o l u t i o n o f the e q u a t i o n s always r e q u i r e a
number o f assumptions t h a t s i m p l i f y the way i n which p r o c e s s e s
o c c u r i n the r e a l w o r l d . F o r t h i s r e a s o n , models a r e n e v e r
c o m p l e t e l y a c c u r a t e and c a n n o t be e x p e c t e d to p r e d i c t the f u t u r e
with certainty. The degree o f c o n f i d e n c e t h a t c a n be p l a c e d i n
m o d e l i n g p r e d i c t i o n s depends on: 1. how w e l l the r e a l w o r l d
s i t u a t i o n conforms to the assumptions imposed by the model;
2. the c e r t a i n t y w i t h which v a r i o u s i n p u t parameters a r e known
from f i e l d d a t a .
F o r the purposes o f t h i s paper, groundwater models c a n be
c l a s s i f i e d i n t o two g e n e r a l c l a s s e s : flow models and c o n t a m i n a n t
t r a n s p o r t models. Among groundwater h y d r o l o g i s t e , a t t e n t i o n i s
c u r r e n t l y f o c u s e d on c o n t a m i n a n t t r a n s p o r t models. However, the
c o n f i g u r a t i o n o f the groundwater flow f i e l d i s n e c e s s a r y i n p u t to
these models and thus i t i s e s s e n t i a l to have i n f o r m a t i o n on the
head d i s t r i b u t i o n . A groundwater flow model i s o f t e n used as an
a i d i n c o n c e p t u a l i z i n g t h e f l o w f i e l d and d e f i n i n g the head
distribution. The v e l o c i t y d i s t r i b u t i o n , which i s used d i r e c t l y
i n a contaminant t r a n s p o r t model, i s c a l c u l a t e d from the head
distribution.
C a l i b r a t i o n o f models r e f e r s to the p r o c e s s by which the
v a l u e s o f c e r t a i n parameters a r e a d j u s t e d by t r a i l and e r r o r u n t i l
the model y i e l d s r e s u l t s which approximate a s e t o f f i e l d d a t a .
When c a l i b r a t i n g a groundwater flow model, the o b j e c t i v e i s to
match the o b s e r v e d head d i s t r i b u t i o n . When c a l i b r a t i n g a con-
taminant t r a n s p o r t model, a t t e m p t s a r e made to r e p r o d u c e the
measured c o n c e n t r a t i o n d i s t r i b u t i o n o f a g i v e n c h e m i c a l c o n s t i t u e n t .
The p r o c e s s o f c a l i b r a t i o n has a l s o been c a l l e d h i s t o r y matching
(1). L o o s e l y s p e a k i n g , f i e l d v a l i d a t i o n o f models i s synonymous
with c a l i b r a t i o n . S t r i c t l y s p e a k i n g , f i e l d v a l i d a t i o n r e f e r s to
a model p r e d i c t i o n made s e v e r a l y e a r s i n t o the f u t u r e , which i s
l a t e r v e r i f i e d i n the f i e l d . Under t h i s s t r i c t d e f i n i t i o n , no
groundwater contaminant t r a n s p o r t model has been f i e l d v a l i d a t e d
to d a t e .
I n t h i s paper, p r o c e d u r e s f o r c a l i b r a t i n g flow models and
c o n t a m i n a n t t r a n s p o r t models a r e o u t l i n e d and some o f the d i f -
f i c u l t i e s f r e q u e n t l y encountered during c a l i b r a t i o n a r e discussed.
An example o f a c o n t a m i n a n t t r a n s p o r t model a p p l i e d to a problem
i n v o l v i n g a l d i c a r b m i g r a t i o n i n groundwater i n W i s c o n s i n i s a l s o
presented.
Dimensionality
R e a l w o r l d problems a r e t h r e e - d i m e n s i o n a l i n n a t u r e b u t t h r e e -
d i m e n s i o n a l models a r e seldom used i n p r a c t i c e because i t i s r a r e
to have adequate t h r e e - d i m e n s i o n a l f i e l d d a t a . Moreover, t h r e e -

d i m e n s i o n a l models a r e cumbersome to use. T h e r e f o r e , a key c o n c e r n
i n s e l e c t i n g a m a t h e m a t i c a l model i s whether the problem a t hand
c a n be s i m p l i f i e d to one o r two d i m e n s i o n s .
Most flow problems c a n be r e a d i l y s i m p l i f i e d t o two-dimensions
and most o f the s t a n d a r d methods f o r t r e a t i n g groundwater s u p p l y
problems a r e b u i l t around two-dimensional a n a l y s e s . I t i s less
easy to j u s t i f y the use o f two-dimensional a n a l y s e s f o r contaminant
t r a n s p o r t problems. However, because t h r e e - d i m e n s i o n a l contaminant
t r a n s p o r t models a r e p a r t i c u l a r l y unwieldy, most r e a d i l y a v a i l a b l e
t r a n s p o r t models and most r e p o r t e d a p p l i c a t i o n s a r e two-dimensional
i n nature.
Flow Models
The two-dimensional g o v e r n i n g e q u a t i o n used i n most s i m u l a t i o n s o f

groundwater flow i s :
< > +
4 (
7 >
" S
f t " W
(1)
where h i s head; T and T a r e components o f the t r a n s m i s e i v i t y

x y
t e n s o r ; S i s s t o r a g e c o e f f i c i e n t and W i s the r e c h a r g e r a t e .
The c a l i b r a t i o n p r o c e s s f o r flow models i d e a l l y c o n s i s t s o f two
s t e p s a s t e a d y s t a t e c a l i b r a t i o n phase and a t r a n s i e n t c a l i b r a t i o n
phase, sometimes c a l l e d model v e r i f i c a t i o n ( 2 ) . D u r i n g the s t e a d y
s t a t e c a l i b r a t i o n phase, the t r a n s m i s e i v i t y d i s t r i b u t i o n and the
r e c h a r g e r a t e a r e a d j u s t e d w i t h i n a p r e - d e t e r m i n e d r e a s o n a b l e range
u n t i l the s t e a d y s t a t e heads o b s e r v e d i n the f i e l d a r e matched.
Boundary c o n d i t i o n s may a l s o be a d j u s t e d . I d e a l l y , the parameters
determined d u r i n g the s t e a d y s t a t e c a l i b r a t i o n phase a r e v e r i f i e d
d u r i n g a t r a n s i e n t c a l i b r a t i o n phase. D u r i n g t r a n s i e n t c a l i b r a t i o n ,
the s t o r a g e c o e f f i c i e n t i s a d j u s t e d and minor adjustments may a l s o
be made i n the t r a n s m i s s I v i t y d i s t r i b u t i o n . However, t r a n s i e n t d a t a
s e t s such as drawdown d a t a from w e l l pumping, o r a r e c o r d o f the
d e c l i n e o f water l e v e l s d u r i n g a drought, a r e seldom a v a i l a b l e and
i t i s common to s k i p the v e r i f i c a t i o n phase. A good d i s c u s s i o n o f
the s t e p s i n v o l v e d I n c a l i b r a t i o n o f a flow model c a n be found i n
(3).
T r a n s m i s s i v i t y and s t o r a g e c o e f f i c i e n t a r e s t a n d a r d a q u i f e r
parameters t h a t c a n be e s t i m a t e d from g e o l o g i c d a t a . Recharge r a t e
i s one o f the most d i f f i c u l t parameters to e s t i m a t e w i t h c o n f i d e n c e
and i t i s s t a n d a r d p r a c t i c e to l e t r e c h a r g e e q u a l a f r a c t i o n o f the
average annual p r e c i p i t a t i o n . The r a t i o o f r e c h a r g e to p r e c i p i t a
t i o n w i l l v a r y w i t h the g e o g r a p h i c l o c a t i o n o f the study s i t e .
Groundwater r e c h a r g e i n W i s c o n e i n i e r o u g h l y e e t i m a t e d to be one-
t h i r d o f p r e c i p i t a t i o n , o r a b o u t 10 i n / y r (254 mm/yr). However,
i t i e l i k e l y t h a t a c t u a l a v e r a g e a n n u a l r e c h a r g e varie w i t h i n the
e t a t e from c l o e e to z e r o i n p a r t e o f e a e t e r n Wieconein, where t h e r e
a r e n e a r l y i m p e r v i o u s s o i l s , to perhaps as much as 15 i n / y r
(381 mm/yr) i n the c e n t r a l and n o r t h e r n p o r t i o n s o f the s t a t e ,
where t h e r e a r e sandy g l a c i a l deposit's a t the s u r f a c e .
I d e a l l y the e n t i r e s u b s u r f a c e s h o u l d be t r e a t e d i n a s i n g l e
model. The g o v e r n i n g e q u a t i o n f o r groundwater flow c a n be g e n e r a l
i z e d to i n c l u d e the u n s a t u r a t e d zone and a model based on t h i s
g o v e r n i n g e q u a t i o n a l l o w s the r e c h a r g e p r o c e s s to be s i m u l a t e d
d i r e c t l y w i t h i n the model ( 4 - 6 ) . However, these types o f models
a r e unwieldy and u s u a l l y a r e a v o i d e d f o r p r a c t i c a l a p p l i c a t i o n s .
O t h e r i n v e s t i g a t o r s (7) a d v o c a t e d the use o f l i n k e d models i n which
a o n e - d i m e n s i o n a l u n s a t u r a t e d column model i s used to c a l c u l a t e
amounts o f r e c h a r g e a r r i v i n g a t the water t a b l e . T h i s a p p r o a c h has
r e c e n t l y been a p p l i e d to a problem i n v o l v i n g p e s t i c i d e movement i n
the s u b s u r f a c e ( 8 ) .
The o u t p u t o f a flow model c o n s i s t s o f the head d i s t r i b u t i o n
i n time and space. D a r c y ' s Law i s used to c o n v e r t the head
d i s t r i b u t i o n to a v e l o c i t y d i s t r i b u t i o n s u i t a b l e f o r Input to a
c o n t a m i n a n t t r a n s p o r t model. I n a two-dimensional a p p l i c a t i o n ,
D a r c y ' s Law i s used to compute two s e t s o f v e l o c i t y components:
K
~ x 9_h
9
*
(2)
K
" y 3h
3y
where v and v a r e the components o f the average l i n e a r v e l o c i t y ;

x y
K and Ky a r e components o f the h y d r a u l i c c o n d u c t i v i t y t e n s o r and

x
i s effective porosity. H y d r a u l i c c o n d u c t i v i t y i s r e l a t e d to
t r a n s m i s s i v i t y as f o l l o w s :
T x - K b x
(3)
Ty = Kyb
where b i s the s a t u r a t e d t h i c k n e s s o f the a q u i f e r . The e f f e c t i v e

p o r o s i t y i s a measure o f the i n t e r c o n n e c t e d v o i d space and g e n e r a l l y
ranges between 0.15 and 0.35. F o r sandy m a t e r i a l s , e f f e c t i v e
p o r o s i t y can be taken e q u a l to s p e c i f i c y i e l d . A compilation of
r e p r e s e n t a t i v e v a l u e s f o r groundwater flow parameters f o r use i n
m o d e l i n g c a n be found i n ( 9 ) .
Contaminant T r a n s p o r t Models
The t w o - d i m e n s i o n a l g o v e r n i n g e q u a t i o n used i n most contaminant

transport applications i s :
3 /~ 9c , _
T&>\\ ax" 12 3cv
+
3y> +, 3
97<l>21
3c , ^
a7 + 22
3c
37) - 3 /^ c v* )
x
- ^(cVy) = R _ + XcR - _ (4)

D
l l =
L c o s 6 2
+ s i n 8 ; D 2 2 = &L s i n 6 +
2 2
cos e;2
D 1 2 = D i =
2 (OL-0 ) T s i n Q c o s e
where c i s c o n c e n t r a t i o n and c' i s the s o u r c e c o n c e n t r a t i o n ;

i s the l o n g i t u d i n a l d i s p e r s i o n c o e f f i c i e n t and Dr i s the t r a n s v e r s e
d i s p e r s i o n c o e f f i c i e n t ; i s the a n g l e o f r o t a t i o n between the l o c a l
and g l o b a l c o o r d i n a t e systems and R i s the r e t a r d a t i o n f a c t o r . When
s u f f i c i e n t f i e l d data a r e a v a i l a b l e , c a l i b r a t i o n c o n s i s t s of
a t t e m p t s to r e p r o d u c e the c o n f i g u r a t i o n o f an o b s e r v e d plume o f
c o n t a m i n a t e d water. Unknown parameters s u b j e c t to adjustment d u r i n g
c a l i b r a t i o n i n c l u d e the d i s p e r s i o n parameters known as l o n g i t u d i n a l
and t r a n s v e r s e d i s p e r s i v i t y ( 1 0 ) . D i s p e r s i v i t i e s a r e r e l a t e d to the
d i s p e r s i o n c o e f f i c i e n t s as f o l l o w s :
* I I
D
L = L + D*
D T = a J J
T + D* (5)
= / v x + v y
where a^ and a? a r e the d i s p e r s i v i t i e s and D* i s the c o e f f i c i e n t o f

molecular d i f f u s i o n . R e p r e s e n t a t i v e v a l u e s f o r parameters used i n
c o n t a m i n a n t t r a n s p o r t models c a n be found i n ( 9 ) .
A key c o n s i d e r a t i o n d u r i n g model c a l i b r a t i o n i s the dimen
s i o n a l i t y o f the problem. I f a two-dimensional model i s used to
s i m u l a t e a t h r e e - d i m e n s i o n a l plume, some d i s c r e t i o n must be used i n
s e l e c t i n g c o n c e n t r a t i o n d a t a a g a i n s t which to c a l i b r a t e the model.
For example, i n a t w o - d i m e n s i o n a l a r e a l modeling a p p l i c a t i o n i t i s
g e n e r a l l y assumed t h a t the contaminant i s u n i f o r m l y d i s t r i b u t e d
t h r o u g h o u t the e n t i r e s a t u r a t e d t h i c k n e s s o f the a q u i f e r . I f the
plume i s s t r a t i f i e d o r does n o t p e n e t r a t e the f u l l t h i c k n e s s o f the
a q u i f e r , c o n c e n t r a t i o n d a t a o b t a i n e d from v e r t i c a l l y n e s t e d w e l l s
s h o u l d be a v e r a g e d b e f o r e comparing f i e l d d a t a to model r e s u l t s .
A n o t h e r s t r a t a g e m may be n e c e s s a r y i f t h e r e a r e n o t enough f i e l d
d a t a to c a l c u l a t e r e l i a b l e v e r t i c a l l y averaged c o n c e n t r a t i o n s .
Examples o f model c a l i b r a t i o n a r e c i t e d i n (11) and (12) and
an example o f an a t t e m p t to f i e l d v a l i d a t e a model i s d i s c u s s e d i n
(13). An example o f a t w o - d i m e n s i o n a l model a p p l i c a t i o n f o r a case
i n which the f i e l d d a t a were i n s u f f i c e n t f o r c a l c u l a t i n g r e l i a b l e
v e r t i c a l a v e r a g e s and were a l s o i n s u f f i c i e n t f o r d e f i n i n g the a r e a l
e x t e n t o f the plume, i s p r e s e n t e d below.
Case Study
Introduction. A problem i n v o l v i n g the movement o f a l d i c a r b i n

groundwater i n the c e n t r a l sand p l a i n a r e a o f W i s c o n s i n ( F i g u r e 1)
w i l l be p r e s e n t e d to i l l u s t r a t e the d i f f i c u l t i e s i n v o l v e d i n model
calibration. A l d i c a r b i s a s y s t e m i c p e s t i c i d e manufactured by U n i o n
C a r b i d e under the t r a d e name Temik. I n W i s c o n s i n , Temik i s a p p l i e d
i n p o t a t o f u r r o w s d u r i n g p l a n t i n g to c o n t r o l a v a r i e t y o f i n s e c t s ,
m i t e s and nematodes. The f i e l d study which s u p p l i e d the f i e l d d a t a
ANDERSON Field Validation of Ground Water Models 401
or
Figure 1. L o c a t i o n map o f the C e n t r a l Sand P l a i n i n Wisconsin.

f o r t h i s s i m u l a t i o n was p a r t o f an i n v e s t i g a t i o n of a l d i c a r b
c o n t a m i n a t i o n o f groundwater beneath s e v e r a l a g r i c u l t u r a l f i e l d s
i n W i s c o n s i n (14-17). The f i e l d d a t a r e p o r t e d i n t h i s paper were
taken from these s o u r c e s .
The computer code used i n t h i s problem s o l v e s the a d v e c t i o n -
d i s p e r s i o n e q u a t i o n i n two dimensions u s i n g a random walk t e c h n i q u e
(18). The code a l s o c o n t a i n s a two-dimensional flow model com-
ponent t h a t i n t e r f a c e s w i t h the random walk model. The g r i d shown
i n F i g u r e 2 was adapted from p r e l i m i n a r y m o d e l i n g s i m u l a t i o n s (16)
and was used f o r a l l the s i m u l a t i o n s r e p o r t e d h e r e . A l d i c a r b was
a p p l i e d i n 1979 and 1980, to the p o r t i o n o f the f i e l d shaded i n
F i g u r e 2, a t a r a t e of 3 l b s / a c r e of a c t i v e i n g r e d i e n t o f Temik.
A l d i c a r b was a p p l i e d to the e n t i r e shaded a r e a i n 1979, but to o n l y
the w e s t e r n h a l f o f the shaded a r e a i n 1980. A l d i c a r b was detected
i n f o u r o b s e r v a t i o n w e l l s e t s , C2, C7, C4 and C9, l o c a t e d b e n e a t h
and downgradient o f the a l d i c a r b - t r e a t e d p o r t i o n o f the f i e l d . The
l o c a t i o n s o f the w e l l s e t s a r e shown i n F i g u r e 2. A well set (or

w e l l n e s t ) c o n s i s t s of two o r more p i e z o m e t e r s f i n i s h e d a t d i f f e r e n t
depths below the water t a b l e . E a c h p i e z o m e t e r was c o n s t r u c t e d w i t h
a 3 f o o t (0.91 m) w e l l s c r e e n . A bundle p i e z o m e t e r s i m i l a r to the
type d e s c r i b e d i n (19) was l o c a t e d n e a r the c o n v e n t i o n a l n e s t e d
p i e z o m e t e r s a t s i t e 4. The bundle p i e z o m e t e r ( o r m u l t i l e v e l
s a m p l e r ) c o n s i s t e d o f 9 s a m p l i n g p o r t s , each open to a p p r o x i m a t e l y
6 i n c h e s o f the a q u i f e r . The d i s t a n c e between sampling p o r t s was
a b o u t 1.5 f e e t (0.46 m).
Flow M o d e l i n g . The flow component of the random walk model was used
to produce the head d i s t r i b u t i o n shown i n F i g u r e 3a. The h y d r a u l i c
c o n d u c t i v i t y o f the a q u i f e r was s e t e q u a l to 200 f t / d a y (61 m/day).
The s a t u r a t e d t h i c k n e s s o f the a q u i f e r i s e q u a l to the e l e v a t i o n o f
the water t a b l e above the impermeable bedrock; the water t a b l e
e l e v a t i o n i s a d j u s t e d a u t o m a t i c a l l y d u r i n g the i t e r a t i o n p r o c e s s
used to s o l v e the flow e q u a t i o n .
Boundary c o n d i t i o n s used i n the s i m u l a t i o n c o n s i s t e d o f
s p e c i f i e d heads a l o n g the e a s t e r n and w e s t e r n s i d e s o f the modeled
a r e a and no flow c o n d i t i o n s a l o n g the n o r t h e r n and s o u t h e r n edges.
Under these boundary c o n d i t i o n s water Is s u p p l i e d to the a q u i f e r as
a r e s u l t o f an Imposed head g r a d i e n t . Hence, i t was n o t n e c e s s a r y
to s u p p l y water to the a q u i f e r v i a r e c h a r g e and the r e c h a r g e r a t e
was s e t e q u a l to z e r o f o r the purposes of c r e a t i n g the flow f i e l d
shown i n F i g u r e 3a. However, s e t t i n g r e c h a r g e e q u a l to z e r o i n the
flow model causes an I n c o n s i s t e n c y between the flow component and
the random walk component o f the model. When s o l v i n g the random
walk component, i t i s n e c e s s a r y to s p e c i f y a l o a d i n g r a t e , d e f i n e d
to be the v o l u m e t r i c r e c h a r g e r a t e to the water t a b l e times the
c o n c e n t r a t i o n of the l e a c h a t e . During c a l i b r a t i o n e f f o r t s
d e s c r i b e d below, the l o a d i n g r a t e was e s t i m a t e d to be 0.0548 l b / a c r e
(6.14 kg/km^) o f a l d i c a r b . I d e a l l y , one s h o u l d s p e c i f y a non z e r o
r e c h a r g e r a t e d u r i n g those time p e r i o d s when l e a c h i n g i s assumed to
o c c u r and s o l v e f o r the t r a n s i e n t head d i s t r i b u t i o n d u r i n g and a f t e r
leaching episodes. S e n s i t i v i t y t e s t i n g o f the flow model assuming
a r e c h a r g e r a t e of 10 i n / y r (254 mm/yr) d u r i n g l e a c h i n g e p i s o d e s ,
demonstrated t h a t t r a n s i e n t head d i s t r i b u t i o n s a r e not a p p r e c i a b l y
ANDERSON Field Validation of Ground Water Models 403
290 FT.
. 2 3 4 5 10 H 20 30
H 290 FT
L
29
1/2 MILE
F i g u r e 2. G r i d used i n the m o d e l i n g s i m u l a t i o n . Locations of
w e l l s used i n the model c a l i b r a t i o n a r e a l s o shown. The shaded
a r e a d e s i g n a t e s the p o r t i o n o f the f i e l d t r e a t e d w i t h a l d i c a r b
i n 1979-80.
O IRRIGATION WELL 0.25

OBSERVATION WELL
<) MULTILEVEL SAMPLER
F i g u r e 3. (a) S i m u l a t e d water t a b l e c o n t o u r s . Datum

i s 1000 f t above sea l e v e l . Magnitudes o f s i m u l a t e d w a t e r
l e v e l s a r e the same as those measured i n May 1981.
(b) Water t a b l e c o n t o u r s based on heads measured i n the f i e l d
d u r i n g August 1981 ( a d a p t e d from 15). Datum i s sea l e v e l .
d i f f e r e n t from the steady s t a t e d i s t r i b u t i o n shown i n F i g u r e 3a.

Assuming a steady s t a t e flow f i e l d g r e a t l y s i m p l i f i e s model c a l c u l a -
tions. Hence, the s t e a d y s t a t e head d i s t r i b u t i o n shown i n F i g u r e 3a
was assumed f o r the purposes o f c a l c u l a t i n g v e l o c i t i e s which were
h e l d c o n s t a n t f o r the d u r a t i o n of the s i m u l a t i o n .
The heads a l o n g the e a s t e r n and w e s t e r n s i d e s o f the modeled
a r e a were a d j u s t e d d u r i n g c a l i b r a t i o n u n t i l the steady s t a t e flow
f i e l d shown i n F i g u r e 3a was o b t a i n e d . T h i s head d i s t r i b u t i o n
resembles the flow f i e l d s r e p o r t e d i n (15-16). The magnitudes o f
the heads i n t h i s f i e l d change s e a s o n a l l y but the c o n f i g u r a t i o n o f
the w a t e r t a b l e i s r e l a t i v e l y s t a b l e and the head drop a c r o s s the
f i e l d i s r e l a t i v e l y c o n s t a n t (10 f t o r 3 m). The flow p a t t e r n
measured i n the f i e l d i n A u g u s t 1981, i s shown i n F i g u r e 3b. The
p a t t e r n of flow and the t o t a l head drop a c r o s s the f i e l d Is r o u g h l y
the same as the s i m u l a t e d flow f i e l d i n F i g u r e 3a a l t h o u g h the a b s o -
l u t e magnitudes o f the heads a r e d i f f e r e n t . The magnitudes o f heads
shown i n F i g u r e 3a a r e the same as the heads measured i n May 1981

(15-16).
The steady s t a t e head d i s t r i b u t i o n shown i n F i g u r e 3a was used
to c a l c u l a t e the v e l o c i t y d i s t r i b u t i o n , u s i n g a h y d r a u l i c conduc-
t i v i t y o f 200 f t / d a y (61 m/day) and an e f f e c t i v e p o r o s i t y o f 0.30.
V e l o c i t i e s ranged from 0.8 to 1.2 f t / d a y (0.24 - 0.37 m/day) b u t
were around 1.1 f t / d a y (0.34 m/day) beneath most o f the f i e l d .
Groundwater f l o w s i n a w e s t e r l y or n o r t h w e s t e r l y d i r e c t i o n , as can
be i n f e r r e d from the groundwater p o t e n t i a l s shown i n F i g u r e 3.
Contaminant T r a n s p o r t M o d e l i n g . A major d i f f i c u l t y i n the

c a l i b r a t i o n o f any t w o - d i m e n s i o n a l c o n t a m i n a n t t r a n s p o r t model Is
r e l a t i n g the t w o - d i m e n s i o n a l s i m u l a t e d plume to the r e a l t h r e e -
d i m e n s i o n a l plume. A model based on E q u a t i o n 4 can s i m u l a t e two
d i m e n s i o n s In c r o s s s e c t i o n o r a r e a l view. An a r e a l view was
s e l e c t e d f o r the problem c o n s i d e r e d here. Use o f a t w o - d i m e n s i o n a l
a r e a l view model i m p l i e s t h a t the c o n t a m i n a n t i s u n i f o r m l y spread
o u t through the e n t i r e s a t u r a t e d t h i c k n e s s o f the a q u i f e r . However,
i n the f i e l d the a l d i c a r b plume i s o n l y around 10 f e e t ( 3 m ) thick
w h i l e the a q u i f e r i s around 70 f e e t (21 m) t h i c k . Moreover, the
c o n c e n t r a t i o n data were c o l l e c t e d from w e l l s h a v i n g 3 f t (0.91 m)
w e l l s c r e e n s and hence a r e r e p r e s e n t a t i v e o f o n l y a s m a l l f r a c t i o n
o f the t o t a l a q u i f e r t h i c k n e s s . I t was d e c i d e d to c a l i b r a t e the
model to c o n c e n t r a t i o n s r e p r e s e n t a t i v e o f the c e n t e r o f the plume
vertically. T h a t i s , the model was c a l i b r a t e d to maximum measured
c o n c e n t r a t i o n s i n each w e l l n e s t . As a r e s u l t , the l o a d i n g r a t e to
the model i s i n f l a t e d o v e r p r o b a b l e f i e l d v a l u e s . The model assumes
the l o a d to the model i s d i s t r i b u t e d o v e r the f u l l a q u i f e r t h i c k n e s s ,
when i n the f i e l d the zone o f maximum c o n c e n t r a t i o n i s p r o b a b l y no
more than 3 f e e t t h i c k . T h e r e f o r e , the p r o b a b l e l o a d i n g r a t e i n the
f i e l d i s r o u g h l y 3/70 o r 4% o f t h a t used to c a l i b r a t e the model.
The c a l i b r a t i o n p r o c e d u r e c o n s i s t e d o f attempts to r e p r o d u c e
the t r a n s i e n t response a t each o f the f o u r w e l l s e t s , to the p u l s e
o f a l d i c a r b moving through the a q u i f e r . The unknown parameters
s u b j e c t to c a l i b r a t i o n i n c l u d e the r e t a r d a t i o n f a c t o r , d i s p e r s i o n
p a r a m e t e r s , l o a d i n g r a t e and h a l f l i f e i n s h o r t , a l l the parameters
i n E q u a t i o n 4. Of these p a r a m e t e r s , the r e t a r d a t i o n f a c t o r i s known
w i t h the most c e r t a i n t y .
Retardation Factor. Reported d i s t r i b u t i o n c o e f f i c i e n t s f o r

a l d i c a r b range from 0.16 - 0.073 ml/gm ( 2 0 ) , or a r e e f f e c t i v e l y
e q u a l to z e r o , s u g g e s t i n g t h a t a l d i c a r b moves a t the same speed as
the groundwater. I n o r d e r to e l i m i n a t e the d i s t r i b u t i o n c o e f f i c i e n t
as a v a r i a b l e s u b j e c t to s e n s i t i v i t y a n a l y s i s , i t was s e t e q u a l to
zero f o r a l l simulations. A d i s t r i b u t i o n c o e f f i c i e n t of zero i s
e q u a l to a r e t a r d a t i o n f a c t o r o f one.
D i s p e r s i o n Parameters. The d i s p e r s i o n parameters ( l o n g i t u d i n a l

and t r a n s v e r s e d i s p e r s i v i t y ) a r e unknown b u t s e n s i t i v i t y a n a l y s e s
proved t h a t a t the s c a l e o f t h i s model, r e s u l t s were i n s e n s i t i v e
to v a r i a t i o n s i n these parameters. The l o n g i t u d i n a l d i s p e r s i v i t y
was v a r i e d from z e r o to 70 f t (21 m) and the t r a n s v e r s e d i s p e r s i v i t y
was v a r i e d from z e r o to 7 f t (2.1 m), w i t h no a p p r e c i a b l e e f f e c t on
the s i m u l a t i o n r e s u l t s . D i s p e r s i v i t y v a l u e s o f 70 f t and 7 f t were
s e l e c t e d f o r the r e m a i n i n g s i m u l a t i o n s .
L o a d i n g R a t e . T r i a l and e r r o r s i m u l a t i o n s assuming no d e g r a d a t i o n
2
s u g g e s t e d t h a t a l o a d i n g r a t e o f 0.0548 l b / a c r e (6.14 kg/km ) d u r i n g
200 day l e a c h i n g e p i s o d e s i n 1979 and 1980 p r o v i d e d a r e a s o n a b l e f i t
to the e a r l y c o n c e n t r a t i o n d a t a i n w e l l s C2 and C7 ( F i g u r e 4 ) . The
a c t u a l l o a d i n g r a t e i n the f i e l d i s e s t i m a t e d to be 4% o f the simu-
2
l a t e d v a l u e o r 0.0022 l b / a c r e (0.246 kg/km ), which i s l e s s t h a t
0.1% o f the a p p l i c a t i o n r a t e a t the s u r f a c e . W e l l s s e t s C2 and C7
a r e l o c a t e d d i r e c t l y beneath the t r e a t e d p o r t i o n o f the f i e l d where
the e f f e c t s o f d e g r a d a t i o n can be e x p e c t e d to be m i n i m a l a t e a r l y
times. T h e r e f o r e , d u r i n g the e a r l y phases o f the c a l i b r a t i o n ,
emphasis was p l a c e d on f i t t i n g the model to the e a r l y d a t a a t w e l l
s i t e s C2 and C7. F i g u r e 4 shows the r e s u l t s o f one o f these e a r l y
s i m u l a t i o n s i n which i t was assumed t h a t a l d i c a r b does n o t degrade
below the w a t e r t a b l e . A c t u a l measured c o n c e n t r a t i o n s a t each w e l l
s i t e a r e a l s o shown f o r comparison. I t i s a p p a r e n t t h a t con-
c e n t r a t i o n s a r e too h i g h a t l a t e r times a t w e l l s i t e s C2 and C7 and
a l s o too h i g h a t the downgradient w e l l s i t e s C4 and C9, suggesting
t h a t d e g r a d a t i o n does o c c u r below the water t a b l e .
Half L i f e . U n i o n C a r b i d e s c i e n t i s t s have suggested t h a t the h a l f

l i f e o f a l d i c a r b i n groundwater i n W i s c o n s i n i s around 900 days
(21). F i g u r e 5 shows the r e s u l t s o f s i m u l a t i o n s i n w h i c h h a l f l i f e
was s e t e q u a l to e i t h e r 900 days or 1800 days. F i e l d c o n c e n t r a t i o n s
a r e a l s o shown. B o t h s i m u l a t i o n s p r o v i d e r e a s o n a b l e f i t s to the
observed c o n c e n t r a t i o n s . The e x c e p t i o n to t h i s i s a t w e l l s i t e C9,
where a l a r g e sudden i n c r e a s e i n a l d i c a r b was d e t e c t e d i n the f i e l d
b u t n o t r e p r o d u c e d by the model when the h a l f l i f e was s e t e q u a l to
900 days. W i t h h a l f l i f e e q u a l to 1800 days, the model p r e d i c t s a
c o n c e n t r a t i o n peak c l o s e r to t h a t o b s e r v e d i n w e l l 9C, a l t h o u g h the
s i m u l a t e d peak i s o f f s e t . The t i m i n g o f the i n i t i a l a r r i v a l o f
a l d i c a r b i s a l s o s l i g h t l y o f f s e t i n b o t h runs o f the model,
s u g g e s t i n g t h a t the s i m u l a t e d v e l o c i t y f i e l d i s n o t a c c u r a t e
between the t r e a t e d f i e l d and w e l l s i t e C9.

ON
WELL C2
WELL C9
100. fr
80.
x w e l l C2B
60. ^ + w e l l C2BH
40.
20.
40. " 80~0~ ~ 1200. 1600. 400. 800 2od. ^ " l b o . 2000.
DAYS AFTER LOADING DAYS AFTER LOADING
WELL C4 WELL C7
140. r
x bundle p i e z o m e t e r c
+ c o n v e n t i o n a l piezome w e l l C7B
120. r
+ w e l l C7BH
100. j-
"
m
C/3
H
20. r

b. 400. 800. 120'(T. 1600.
5
m
DAYS AFTER LOAD ING DAYS AFTER LOADING C/

73

C
F i g u r e 4. Comparison o f p r e d i c t e d v s . o b s e r v e d concentrations 2!
assuming no d e g r a d a t i o n o f a l d i c a r b .
i
m
F i g u r e 5. Comparison o f p r e d i c t e d vs. o b s e r v e d c o n c e n t r a t i o n s
assuming t h a t h a l f l i f e o f a l d i c a r b e q u a l s e i t h e r 900 o r
1800 days.
D i s c u s s i o n of R e s u l t s . A l t h o u g h t h e r e a r e d i s c r e p a n c i e s between
f i e l d o b s e r v a t i o n s and model p r e d i c t i o n s f o r both c h o i c e s o f h a l f
l i f e shown i n F i g u r e 5, the model does p r o v i d e a r e a s o n a b l e f i t
to the f i e l d d a t a . The d i s c r e p a n c i e s which stand o u t a r e the l o n g
t a i l s on the s i m u l a t e d b r e a k t h r o u g h c u r v e s f o r w e l l C4 and the
o f f s e t o f the sharp peak measured i n the f i e l d i n w e l l C9 a t 1400
days. I n a d d i t i o n , the model u n d e r e s t i m a t e s the c o n c e n t r a t i o n s a t
e a r l y times a t w e l l s i t e C2.
T h e r e a r e many f a c t o r s which u n d o u b t e d l y c o n t r i b u t e to these
discrepancies. Among them a r e :
1. A steady s t a t e flow f i e l d was assumed when the heads do change
i n r e s p o n s e to f l u c t u a t i o n s i n r e c h a r g e r a t e . Hence, the head
d i s t r i b u t i o n used i n the model i s an approximate one.
2. The v e l o c i t y f i e l d i s n o t e x a c t l y r e p r o d u c e d . The model assumes
c o n s t a n t h y d r a u l i c c o n d u c t i v i t y and e f f e c t i v e p o r o s i t y and uses
an a p p r o x i m a t e head d i s t r i b u t i o n to compute the v e l o c i t y f i e l d .
3. A t w o - d i m e n s i o n a l model was used to r e p r e s e n t a t h r e e - d i m e n s i o n a l

plume.
4. C o n c e n t r a t i o n s c a l c u l a t e d by the model a r e a v e r a g e s f o r the
290 f t by 290 f t c e l l s shown i n F i g u r e 2. The f i e l d measured
c o n c e n t r a t i o n s are e s s e n t i a l l y p o i n t values.
5. A c o n s t a n t l e a c h i n g r a t e and a 200 day l e a c h i n g p e r i o d were
assumed. The l e a c h i n g r a t e p r o b a b l y v a r i e s both s p a c i a l l y and
temporally. The random walk model used i n t h i s example i n t r o -
duced the c o n t a m i n a n t randomly i n space by means o f an a l g o r i t h m
t h a t i n v o l v e s a random number g e n e r a t o r . Consequently, d i f f e r e n t
runs of the model g i v e somewhat d i f f e r e n t r e s u l t s . The c u r v e s
shown i n F i g u r e s 4-6 a r e r e p r e s e n t a t i v e o f the g e n e r a l n a t u r e o f
the s o l u t i o n s . O t h e r runs o f the model u s i n g the same parameters
gave s i m i l a r b u t s l i g h t l y d i f f e r e n t r e s u l t s .
6. D e g r a d a t i o n r a t e and r e t a r d a t i o n f a c t o r may v a r y s p a c i a l l y w i t h i n
the f i e l d .
A n o t h e r key q u e s t i o n i s r e l a t e d to the uniqueness o f the
calibration. S p e c i f i c a l l y , i s i t p o s s i b l e that another s e t of para-
meters might a l s o y i e l d a good f i t to the f i e l d data? F o r example,
i t has been suggested t h a t the h a l f l i f e o f a l d i c a r b i n groundwater
i n W i s c o n s i n c o u l d be as low as 475 days ( 2 2 ) . F i g u r e 6 shows the
r e s u l t s of a s i m u l a t i o n i n w h i c h the l o a d i n g r a t e was doubled to
2
0.1096 l b / a c r e (12.28 kg/km ) and the h a l f l i f e was reduced to
450 days. T h i s s i m u l a t i o n a l s o p r o v i d e s a good f i t to the d a t a f o r
w e l l s i t e C4 b u t the f i t i s l e s s s a t i s f a c t o r y f o r the o t h e r t h r e e
well sites.
A q u e s t i o n t h a t i s f r e q u e n t l y posed i s : "How many w e l l s a r e
n e c e s s a r y to e n s u r e t h a t enough f i e l d d a t a can be c o l l e c t e d to
c a l i b r a t e a groundwater model?" G i v e n i n f o r m a t i o n from one w e l l ,
" c a l i b r a t i o n " i s r e l a t i v e l y easy. T h a t i s , i t i s easy to f i n d a
s e t o f parameters f o r which the model r e s u l t s w i l l be i n agreement
w i t h the data s e t from one w e l l . No one, o f c o u r s e , would p u t much
f a i t h i n this s o r t of c a l i b r a t i o n . The c a l i b r a t i o n task becomes
more and more d i f f i c u l t as i n f o r m a t i o n from o t h e r w e l l s a r e added to
the d a t a base. As b e f o r e , the model can be r e a d i l y c a l i b r a t e d to
one w e l l , b u t then o t h e r w e l l s go o u t o f c a l i b r a t i o n . As more and
more w e l l s a r e added to the data base, the c a l i b r a t i o n o b j e c t i v e i s
F i g u r e 6. Comparison o f p r e d i c t e d v s . o b s e r v e d c o n c e n t r a t i o n s
assuming a h a l f l i f e o f 450 days and a l o a d i n g r a t e d o u b l e t h a t
used i n F i g u r e s 4 and 5.
410 EVALUATION O F P E S T I C I D E S IN G R O U N D W A T E R
to f i n d a r e a l i s t i c s e t o f parameters t h a t w i l l a l l o w most o f the

w e l l s to be a p p r o x i m a t e l y i n c a l i b r a t i o n .
I n the p r e s e n t example, a v a l u e o f h a l f l i f e between 900 and
1800 days and a s i m u l a t e d l o a d i n g r a t e o f 0.0548 l b / a c r e (6.14
2
kg/km ), w h i c h c o r r e s p o n d s to an e s t i m a t e d f i e l d l o a d i n g r a t e o f
2
0.0022 l b / a c r e (0.246 kg/km ), g i v e a r e l a t i v e l y good o v e r a l l f i t
to the a v a i l a b l e f i e l d d a t a . Hence, one I s tempted t o c o n c l u d e
t h a t a t t h i s s i t e the h a l f l i f e i s between 900 and 1800 days and
t h a t l e s s than 0.1% o f the a l d i c a r b a p p l i e d t o t h e l a n d s u r f a c e I n
1979-80 r e a c h e d the w a t e r t a b l e . However, i n c i t i n g these c o n c l u
s i o n s one must b e a r i n mind t h a t e v e r y model i s a n a p p r o x i m a t i o n o f
r e a l i t y and t h a t t h i s c a l i b r a t i o n i s based on d a t a from f o u r w e l l
sites. Whether o r n o t f o u r w e l l s i t e s a r e enough to a c h i e v e a good
c a l i b r a t i o n i s a s u b j e c t i v e judgement.
A f t e r a model c a l i b r a t i o n i s a c c e p t e d as v a l i d , the n e x t s t e p
g e n e r a l l y i s to u s e the model f o r p r e d i c t i v e p u r p o s e s . I n the
p r e s e n t a p p l i c a t i o n , one m i g h t want t o p r e d i c t the a r e a l e x t e n t

o f the peak c o n c e n t r a t i o n s w i t h i n the plume. F i g u r e 7 shows the
s p a c i a l c o n c e n t r a t i o n d i s t r i b u t i o n s a t t h r e e d i f f e r e n t times a s
computed by the model w i t h h a l f l i f e e q u a l to 900 days.
CONCENTRATIONS AT 400 DAYS
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 5 0 9 0 9 5 \ 4 9 0 0 0
0 00 0 0 0 0 0 0 0 0128 j&jgj^lb 4^ 3b(fjlJ)| 0 0
0 0 0 0 0 0 0 0 0 0 5 14(5^30 63\^_22 40 4 0
0 0 0 0 0 0 0 0 0 0 5 14 37 32^8 58 55)40 44VQ 0 0
0 0 0 0 0 0 0 0 0 0 9 V L i i ^ j 0 2 27)63r45 44 31 13) 0 0
0 0 0 0 0 0 0 0 0 0 0 7 ^ ^ ) 5 ^ 6 ) 3 6 40 26 A 0 0
0 0 0 0 0 0 0 0 0 5 9 28(55/18 5 22 27 49 35 ( 9 4 0
0 0 0 0 0 0 0 0 0 0 9 14 12 41@\i45 4 9 ^ ) 2 2 I?) 0 0
0 0 0 0 0 0 0 0 0 0 5 37 27 45 K 36 35 26 IV 0 0
0 0I 0 0 0 0 0 0 0 0 5 fa ^ 14 4 ?6 1ft 4Q 1 / " I 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
(a)
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 3 0 6 3 0 Q Q 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 59 V\ 17 19 23 15^5 0 0 0 0 0
0 0I 0 0 0 0 3 Q 0 22 44 33 49J&4 Bo)1J> 15151 2 5 I0 0
0 0 0 0 0 0 5 0 l l 8 29(60 5 2 Q 38 25 27 10 7 0 0 0 0
0 0 0 0 0 0 3 8(j5 21 l 7 \ 6 82\35 20 15 15 2 2 0 0 0
0 0 0 0 0 0 5 5^1)33 47 4?\77j32 37 13 1jJ 0 0 0 0 0
0 0 0 0 0 0 3 3 3 20 45 49 40 42 36 12 2 2 0 0 0
0 0 0 0 3 0 3 0 18 23 49 46 39 35 20 18 2 0 0 0 0
0 0 0 0 0 0 0 3 21 4<2 54V]2 27 32 5 0 0 0 0
0 0 0 0 0 0 0 3 8 18 44 3 9 1 4 9 22 18 5 0 2 0 0 0
0 0I 0 0 0 0 3 0 *25 21 25 32 18 23 Iff 5 0 0 0| 0 0
0 0 0 0 0 0 0 0 0 0 0 3 0 0 " 2 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Figure 7(a,b). P r e d i c t e d a r e a l d i s t r i b u t i o n o f t h e plume u s i n g a

h a l f l i f e o f 900 days. The numbers r e p r e s e n t a l d i c a r b
c o n c e n t r a t i o n s i n ppb; c o n t o u r l i n e s f o r 10 and 50 ppb a r e shown.
0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 4 3 5 6 3 1 0 1 0 0 0 0 0 0 0 0
0 0 0 0 1 1 8/17 19 14 13 1 5 ^ 9 3 4 1 0 1 0 0 0 0
1 0 0 0 6 6^5 25 20 28 18 24 14] 1 3 0 1
0 0 0
0 0 2 4 3,)15 19 22 27 26 17 21 13 M 3 3 0 0 0 0 0
0 1 1 o< ^ 2 1 11 23 27 37 14 9 1 0 1 0 0 0 0 0
0 0 1 3 3 <42 13 19 32 35 12 11 4 4 3 0 0 0 0 0 0
0 3 0 1 0 7)11 21 19 21 30 20 / 4 7 4 1 0 0 0 0 0 0
0 0 3 0 3 9/23 25 28 24 10 11 0 3 3 0 0 0 0 0 0
0 0 1 6 1 AO 12 19 42 16 15 16 1 7 1 0 0 0 0 0 0 0
0 0 1 1 3 J 2 18 22 22 18 13/ D 3l 1 0 0 0 0 0 0 0
0 0 2 0 0 1 0 7 7\15XS ft 5 1 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 1 1 0 0 0 1 2 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
(c)
F i g u r e 7 ( c ) . P r e d i c t e d a r e a l d i s t r i b u t i o n o f t h e plume u s i n g a
h a l f l i f e o f 900 d a y s . The numbers r e p r e s e n t a l d i c a r b
c o n c e n t r a t i o n s i n ppb; c o n t o u r l i n e s f o r 10 and 50 ppb a r e shown.
The a l d i c a r b - t r e a t e d p o r t i o n o f t h e f i e l d i s shown h e r e .
Acknowledgments
R i c h Manser and Frank Jones c o l l e c t e d the f i e l d d a t a used i n t h i s

modeling e x e r c i s e . R i c h Manser a l s o t e s t e d the m o d e l i n g p r o c e d u r e
d u r i n g p r e l i m i n a r y computer r u n s . A l d i c a r b a n a l y s e s were performed
by l a b o r a t o r i e s a t the U n i v . o f Wise.-Stevens P o i n t and the U n i v .
o f Wise.-Madison. Q u a l i t y c o n t r o l checks on s p i k e d samples were
performed by U n i o n C a r b i d e . Funds f o r the computer s i m u l a t i o n were
p r o v i d e d by a g r a n t from the ARCO F o u n d a t i o n .
Literature Cited
1. Mercer, J.W.; Faust, C. "Ground-Water Modeling"; National
Water Well Assoc.: Worthington, Ohio, 1981, p. 60.
2. Wang, H.F.; Anderson, M.P. "Introduction to Groundwater
Modeling: Finite Difference and Finite Element Methods";
W.H. Freeman and Co.: San Francisco, 1982; p. 237.
3. Karanjac, J.; Altunkaynak,M.; Ovul, G. Ground Water 1977,
15(5), 348-57.
4. Freeze, R.A. Water Resour. Res. 1971, 7(2), 347-66.
5. Frind, E.O.; Verge, M.J. Water Resour. Res. 1978, 14(5),
844-56.
6. Winter, T.C. Water Resour. Res. 1983, 19(5), 1203-18.
7. Pikul, M.F.; Street, R.L.; Remson, I. Water Resour. Res.
1974, 10(2), 295-302.
8. Jones, R.: "Movement and Degradation of Aldicarb Residues in

Soil and Groundwater"; presented at the Envir. Toxicology and
Chemistry Conf. on Multidisciplinary Approaches to Envir.
Problems, Crystal City, VA, 1983.
9. Mercer, J.W.: Thomas, S.D., Ross, B. "Parameters and Variables
Appearing in Repository Siting Models"; NUREG/CR-3066, Nuclear
Regulatory Commission: Washington, D.C., 1982, p. 244.
10. Anderson, M.P. In "Groundwater Contamination";
Bredehoeft, J.D., Ed.; National Academy Press: Washington,
D.C., 1984, pp. 37-45.
11. Anderson, M.P. CRC Critical Reviews in Environmental Control
1979, 9(2), 97-156.
12. "Groundwater Contamination from Hazardous Wastes," Princeton

Water Resources Program, Prentice-Hall: New Jersey, 1984,
p. 163.
13. Lewis, B.D; Goldstein, F.J. "Evaluation of a Predictive Ground
Water Solute Transport Model at the Idaho National Engineering
Laboratory, Idaho"; U.S. Geol. Surv. Water Resour. Investig.
82-25, U.S. Geol. Survey: Washington, D.C., 1982, p. 71.
14. Rothschild, E.R.; Manser, R.J.; Anderson, M.P. Ground Water
1982, 20(4), 437-45.
15. Chesters, G., Anderson, M.P., Shaw, B.H., Harkin, J.M.,
M. Meyer, E. Rothschild, Manser, R.J. "Aldicarb in
Groundwater"; Wisc. Water Resources Center: Madison, Wisc.,
1982, 38 pp.
16. Manser, R.J. M.S. Thesis, Univ. of Wisc.-Madison, 1983.
17. Jones, F. Prospectus for Ph.D. Research, Univ. of Wisc.-
Madison, 1984.
18. Prickett, T.A.; Naymik, T.G.; Lonnquist C.G. "A Random-Walk
Solute Transport Model for Selected Groundwater Quality
Evaluations" Bull. 65 111. State Water Survey: Champaign,
111., 1981, p. 103.
19. Pickens, J.F.; Cherry, J..; Grisak, G.E.; Merritt, W.F.;
Risto, B.A. Ground Water 1978, 16(5), 322-27.
20. Enfield, C.G., Carsel, R.F., Cohen, S.Z., Phan .,
Walters, D.M. Ground Water 1982, 20(6), 711-22.
21. Hansen, J.L.; Spiegel, M.H. Envir. Toxicology and Chemistry
1983, 2, 147-153.
22. Harkin, J.M.; Jones, F.A.; Falhulla, R; Dzantor, E.K.;
O'Neill, E . J . ; Kroll, D.G.; Chesters, G. "Pesticides in
Groundwater beneath the Central Sand Plain of Wisconsin";
WIS WRC 84-01, Wise. Water Resour. Center, Madison, Wise.,
1984, p. 46.
RECEIVED November 4, 1985
22
Reproductive and Developmental Toxicity
Risk Assessment
Jerry M. Smith
Rohm and HaasCo.,Independence Mall West, Philadelphia, P A 19105
Risk assessment of reproductive and developmental

toxicity requires 1) hazard identification, 2)
dose-effect, dose-response evaluation, 3) exposure

assessment, and 4) risk characterization.
Reproductive hazards may involve either male or
female, and range from decreased libido to failure
of the mother to properly nurse the infant.
Developmental hazards affect the conceptus and
range from death to the formation of viable but
societally dependent offspring. Subchronic,
chronic, multigeneration and teratogenic studies
provide the majority of data used for hazard
identification and dose-effect, dose-response
evaluation. Genetic, pharmacokinetic, metabolism,
and specially designed investigative studies
provide data on the mode of action, target site,
delivered dose, primary versus secondary effects,
etc. required for characterization of risk. With
good characterization of reproductive and
developmental risk and exposure assessments, sound
risk assessments can be made.
Due to vast improvements in food supply and nutrition,
r e p r o d u c t i v e s u c c e s s has improved markedly i n many areas o f t h e
world. T h i s has been a c c o m p l i s h e d l a r g e l y t h r o u g h advances i n
agricultural p r a c t i c e s and t h e use o f p e s t i c i d e s . However, t h e
thalidomide and Minamata tragedies, t h e more r e c e n t dibromo-
c h l oropropane (DBCP) event, and t h e h y s t e r i a of Love Canal
demonstrate t h e p o t e n t i a l , r e a l o r p e r c e i v e d , o f a r e p r o d u c t i v e o r
developmental c a l a m i t y t h a t might o c c u r w i t h t h e c o n t a m i n a t i o n o f
ground water by a p o t e n t r e p r o d u c t i v e o r developmental pesticide
toxicant. Therefore, t h e developed world must be a l e r t to
potential r e p r o d u c t i v e and developmental hazards and a s s o c i a t e d
r i s k t h a t may accompany t h e use o f p e s t i c i d e s .
While the potential f o r a reproductive or developmental
c a l a m i t y t h r o u g h c o n t a m i n a t i o n o f underground o r s u r f a c e water i s
real, it need not happen and w i l l not happen with prudent
p e s t i c i d e use and s u r v e i l l a n c e . We have t h e t o o l s , t h e awareness,
0097-6156/ 86/ 0315-0414S06.00/ 0

22. SMITH Reproductive and Developmental Toxicity Risk Assessment 415
and the responsibility to assure that it does not happen.

Essential f o r c o n t i n u e d a p p r o p r i a t e use o f p e s t i c i d e s i s good
sound s c i e n t i f i c r i s k assessment i n c l u d i n g an assessment o f r i s k
a s s o c i a t e d w i t h c o n t a m i n a t i o n o f ground w a t e r .
Assessment o f r e p r o d u c t i v e and development r i s k s associated
w i t h t h e use o f p e s t i c i d e s , whether f o r m i x e r - l o a d e r o r consumer,
f o l l o w s t h e same g e n e r a l g u i d e l i n e s used f o r any t o x i c i t y risk
assessment. The National Research C o u n c i l (NRC) (1) has r e c e n t l y
p u b l i s h e d a monograph on r i s k assessment and management and t h e i r
procedure i s recommended f o r r e p r o d u c t i v e and developmental risk
assessment w i t h some s l i g h t a d d i t i o n s and m o d i f i c a t i o n s .
The NRC document calls for hazard identification, dose-
response assessment, exposure assessment, and risk
characterization. In an e f f o r t t o p l a c e d e s c r i p t i v e e x p e r i m e n t a l
t o x i c i t y r e s u l t s i n a c l e a r e r p e r s p e c t i v e and p l a c e more emphasis
on evaluation, this outline deviates slightly from t h e NRC
document and c a l l s f o r hazard e v a l u a t i o n , hazard e x t r a p o l a t i o n ,

exposure assessment and r i s k c h a r a c t e r i z a t i o n . In a d d i t i o n , a few
comments on r i s k a c c e p t a b i l i t y a r e g i v e n . Exposure assessments
have been a d e q u a t e l y d i s c u s s e d elsewhere i n t h i s symposium and
will be discussed here only as they relate to hazard
identification, evaluation, extrapolation and risk
characterization.
L a b o r a t o r y s t u d i e s p r o v i d e d a t a f o r assessment o f r e p r o d u c t i v e
and developmental toxicity, and laboratory and environmental
s t u d i e s p r o v i d e d a t a f o r assessment o f p o t e n t i a l e x p o s u r e . These
d a t a have demonstrated t h a t f o r some p e s t i c i d e s and p e s t i c i d e
c a n d i d a t e s , a p o t e n t i a l may e x i s t f o r e x p o s u r e , and r e p r o d u c t i v e
or developmental toxicity. This paper does not present an
assessment o f t h e p o t e n t i a l r i s k f o r t h e s e p e s t i c i d e s but examines
the e s s e n t i a l s t e p s and c r u c i a l elements o f d a t a n e c e s s a r y f o r
a p p r o p r i a t e assessment o f h a z a r d and r i s k .
U n f o r t u n a t e l y , the i n f o r m a t i o n and d a t a a v a i l a b l e t o a s s e s s o r s
o f hazards and r i s k s a r e not always i d e a l and e v a l u a t i o n s must be
made on available data. Even more unfortunately, those
r e s p o n s i b l e f o r r i s k assessment r e l y t o o f r e q u e n t l y on secondary
and t e r t i a r y d a t a s o u r c e s f o r t h e i r e v a l u a t i o n s . T h i s may l e a d t o
misinterpretation and over interpretations of original
observations.
Finally, it must be remembered that when p e s t i c i d e s are
p r o p e r l y e v a l u a t e d and u s e d , t h e b e n e f i t s o f p e s t i c i d e s g r e a t l y
outweigh the risks associated with their use. The greater
potential for disaster, as is being demonstrated in certain
underdeveloped a r e a s o f t h e w o r l d , i s f a m i n e .
Definitions and Terminology
The EPA (2) has r e c e n t l y produced a good d r a f t document for

assessment o f developmental t o x i c a n t s and t o be c o n s i s t e n t the
same o r e q u i v a l e n t d e f i n i t i o n s and t e r m i n o l o g y a r e u s e d .
Reproductive t o x i c i t y . Adverse e f f e c t s on e i t h e r parent t h a t may

i n t e r f e r e with c o p u l a t i o n , c o n c e p t i o n , g e s t a t i o n , p a r t u r i t i o n or
maturation of the conceptus.
Developmental toxicity. Adverse effects on the developing

organism o c c u r r i n g from the time o f c o n c e p t i o n to the time o f
sexual m a t u r a t i o n .
Embryotoxicity and fetotoxicity. Any toxic effect on the

c o n c e p t u s as a r e s u l t o f p r e n a t a l e x p o s u r e ; t h e d i s t i n g u i s h i n g
f e a t u r e between the terms i s t h e p e r i o d d u r i n g which the i n s u l t
occurred.
A l t e r e d growth. A significant alteration in fetal or neonatal

organ o r body w e i g h t .
Functional teratology. Alterations or delays in functional

competence o f t h e organism o r organ system f o l l o w i n g exposure t o
an agent d u r i n g c r i t i c a l p e r i o d s o f development e i t h e r p r e - o r
postnatally.
Mai f o r m a t i o n s . A permanent s t r u c t u r a l d e v i a t i o n which generally

i s i n c o m p a t i b l e w i t h o r s e v e r e l y d e t r i m e n t a l t o normal postnatal
s u r v i v a l or d e v e l o p m e n t .
Variations. A d i v e r g e n c e beyond t h e usual range o f s t r u c t u r a l

c o n s t i t u t i o n which may not have as s e v e r e an e f f e c t on s u r v i v a l o r
h e a l t h as a m a l f o r m a t i o n .
Hazard Identification
General toxic hazards, reproductive h a z a r d s , and developmental

hazards must be i d e n t i f i e d and c o n s i d e r e d s e p a r a t e l y , y e t t h e
i n t e r r e l a t i o n s h i p s between them must be c l e a r l y u n d e r s t o o d . This
i s p a r t i c u l a r l y d i f f i c u l t when examining t h e e f f e c t s o f p e s t i c i d e s
upon the female s i n c e g e n e r a l t o x i c e f f e c t s may i n d i r e c t l y a f f e c t
t h e a b i l i t y o f t h e female t o c o n c e i v e , c a r r y t h e c o n c e p t u s , o r
c a r e f o r her o f f s p r i n g . To i d e n t i f y t h e p o t e n t i a l o f p e s t i c i d e s
f o r r e p r o d u c t i v e o r developmental h a z a r d s , t h e t o x i c o l o g i s t and
regulatory agencies rely primarily on multigeneration and
teratogenic studies which normally are adequate. Different
p r o t o c o l s and t h e i r s t r e n g t h s , weaknesses, l i m i t a t i o n s , e t c . have
been s u b j e c t o f numerous p u b l i c a t i o n s (3) (4) (5) and as such a r e
not reviewed h e r e . B a s i c a l l y , m u l t i g e n e r a t i o n s t u d i e s examine the
e f f e c t s o f exposure o f both males and females t o p e s t i c i d e s from
b e f o r e mating t h r o u g h weaning over at l e a s t two g e n e r a t i o n s and
teratogenic studies examine the effects of exposure of the
pregnant animal and i t s c o n c e p t u s e s t o the p e s t i c i d e s d u r i n g the
p e r i o d o f major development o f t h e c o n c e p t u s .
R e p r o d u c t i v e Hazards ( E f f e c t s ) . M u l t i g e n e r a t i o n s t u d i e s not o n l y
d e t e c t r e p r o d u c t i v e h a z a r d s , but i n many i n c i d e n c e s t h e y p r o v i d e
d a t a f o r i d e n t i f i c a t i o n o f t h e r e p r o d u c t i v e segment t h a t f a i l e d .
R e p r o d u c t i v e f a i l u r e o r r e p r o d u c t i v e hazards can be c l a s s i f i e d as
impaired mating, impaired c o n c e p t i o n , impaired g e s t a t i o n , impaired
parturition or impaired nursing and c a r e f o r t h e neonate o r
young. Impaired mating or c o n c e p t i o n can be the r e s u l t o f adverse
effects upon t h e m a l e , female, or both. Impaired g e s t a t i o n ,
p a r t u r i t i o n , n u r s i n g and p e r i / p o s t n a t a l c a r e are the r e s u l t s o f
a d v e r s e e f f e c t s upon the f e m a l e . (Note: Some adverse e f f e c t s on

t h e c o n c e p t u s o r o f f s p r i n g may a d v e r s e l y a f f e c t g e s t a t i o n , n u r s i n g
or peri/post natal care.) The e f f e c t s may be d i r e c t o r i n d i r e c t .
Developmental Hazards ( E f f e c t s ) . Over t h e l a s t few y e a r s our

knowledge and concerns f o r developmental hazards have i n c r e a s e d .
We are no l o n g e r concerned only with classical teratogenic
e f f e c t s , i . e . s t r u c t u r a l anomalies induced d u r i n g o r g a n o g e n e s i s ,
but we a l s o r e c o g n i z e t h e p o t e n t i a l f o r e m b r y o / f e t a l t o x i c i t y and
functional teratogenicity. C o n s e q u e n t l y , t h e t o x i c o l o g i s t now
considers structural teratogenic hazards as a subset of
developmental hazards. T h e r e f o r e , not o n l y a r e "teratogenic"
s t u d i e s r e q u i r e d t o i d e n t i f y developmental h a z a r d s , but s t u d i e s
are required where conceptuses are exposed during major
organogenesis and t h e development o f t h e organism i s followed
through sexual maturity. Multigeneration studies fulfill the
requirement.
Developmental hazards may be e x p r e s s e d as death o f c o n c e p t u s ,
live malformed offspring, developmentally delayed/runted
o f f s p r i n g , and f u n c t i o n a l l y i m p a i r e d o f f s p r i n g . Death and a l t e r e d
development may be t h e r e s u l t s o f a poor environment p r e s e n t e d by
t h e dam or a d i r e c t e f f e c t upon o r g a n o g e n e s i s and development o f
the c o n c e p t u s / o f f s p r i n g .
P a r e n t a l Hazards ( E f f e c t s ) . For assessment o f r e p r o d u c t i v e and

developmental r i s k , p a r e n t a l h a z a r d s , both p a t e r n a l and maternal ,
must be i d e n t i f i e d and e v a l u a t e d . Parental hazards can be
e x p r e s s e d as a l t e r e d n u t r i t i o n a l s t a t e , f u n c t i o n a l i m p a i r m e n t , and
s y s t e m i c t o x i c i t y . Because o f p o s s i b l e i n d i r e c t a f f e c t s , knowledge
and evaluation of non-reproductive/non-developmental toxicity
s t u d i e s are u s e f u l . T h i s i n f o r m a t i o n i s a v a i l a b l e by e x a m i n a t i o n
o f s u b c h r o n i c and c h r o n i c t o x i c i t y s t u d i e s .
Hazard Evaluation
Hazard e v a l u a t i o n i s used here t o mean e x a m i n a t i o n and e v a l u a t i o n

o f t h e hazards ( a d v e r s e e f f e c t s ) observed i n t o x i c i t y studies,
i n c l u d i n g r e p r o d u c t i v e , t e r a t o g e n i c , and general t o x i c i t y s t u d i e s
plus other pertinent d a t a . Because o f t h e c o m p l e x i t i e s o f t h e
r e p r o d u c t i v e system as w e l l as embryogenesis and m a t u r a t i o n o f t h e
conceptus, hazard evaluations must go beyond the mere
d e t e r m i n a t i o n o f s t a t i s t i c a l e f f e c t s , no observed e f f e c t levels
(NOELS), relationships between dose and response, dose and
effects, and t h e d e t e r m i n a t i o n o f margins of safety. Most
importantly, for assessment of risk of reproductive and
development toxicity the assessor must determine if the
reproductive system of the parents or development of the
conceptus/offspring are uniquely sensitive to the pesticide.
While i t is p o s s i b l e t o d e t e r m i n e a number o f v a r i a b l e s for
examination, the c o m p l e x i t i e s o f the i n t e r a c t i o n s o f reproduction
preclude a practical set of an all inclusive list for
examination. T h e r e f o r e , h a z a r d e v a l u a t i o n s can be guided most
effectively by a s k i n g a s e r i e s of questions of the observed
results and professionally comparing the answers to known
biological facts, data, theories, etc. Some o f t h e most i m p o r t a n t
q u e s t i o n s a r e l i s t e d below. Not a l l q u e s t i o n s w i l l have answers,

however, t h e e x p e r i e n c e d t r a i n e d i n v e s t i g a t o r s h o u l d be a b l e t o
provide appropriate assessment o f t h e d a t a and statements of
s i g n i f i c a n c e ( t o x i c o l o g i c a l , b i o l o g i c a l or s t a t i s t i c a l ) .
Effect(s). What were t h e t y p e s o f e f f e c t s observed? Did t h e y

i n v o l v e a p a r e n t , both p a r e n t s , o r t h e c o n c e p t u s / o f f s p r i n g ? Were
they reproductive or developmental? What system(s) were
involved? Were t h e e f f e c t s t h e r e s u l t s o f d i r e c t or indirect
toxicity?
Species. What s p e c i e s were a f f e c t e d ? Were a l l s p e c i e s a f f e c t e d

i n t h e same way? Were a l l s p e c i e s a f f e c t e d t o t h e same degree?
Dose-effeet/Dose-response. What were t h e d o s e - e f f e c t and d o s e -

r e s p o n s e r e l a t i o n s h i p s ? (Note: D o s e - e f f e c t s means t h a t t h e t y p e o f
e f f e c t w i l l d i f f e r w i t h d i f f e r e n t d o s e s ; d o s e - r e s p o n s e means t h a t
t h e degree o f r e s p o n s e o r number r e s p o n d i n g w i l l d i f f e r with
different doses.) With increasing doses, were the observed
effects biologically (toxicologically) different, similar,
r e l a t e d , o r an e x t e n s i o n o n l y i n d e g r e e . How s h o u l d l e s i o n s be
t a b u l a t e d t o e x p r e s s i n c r e a s e d e f f e c t s w i t h i n c r e a s e d doses? Does
t h e development o f a p a r t i c u l a r l e s i o n p r e c l u d e the development o f
a different lesion. For example, a heart malformation is
d i f f e r e n t from a m a l f o r m a t i o n o f t h e b r a i n , an anomaly o f t h e long
bones o f t h e f o r e l i m b may be s i m i l a r t o an anomaly o f t h e h i n d
limb, a severe malformation of the CNS may r e s u l t in death
p r e c l u d i n g o b s e r v a t i o n o f a l e s s e r s e v e r e CNS l e s i o n , e t c . What
were the no observed e f f e c t l e v e l s ; t h e minimal e f f e c t levels?
What were t h e s l o p e s and c h a r a c t e r i s i t i c s o f t h e dose r e s p o n s e
curves?
Route(s) o f E x p o s u r e . What r o u t e ( s ) o f exposure were used? What

were t h e d u r a t i o n and c h a r a c t e r i s t i c s o f t h e exposure? Were t h e
r o u t e and d u r a t i o n o f t h e exposure a p p r o p r i a t e f o r e v a l u a t i o n o f
t h e expected exposure o f humans?
E x p e r i m e n t a l D e s i g n ( s ) . What a r e the weaknesses and s t r e n g t h s o f

the experimental designs? What i s t h e u n i t o f a n a l y s i s ? (The
individual conceptus o r o f f s p r i n g , o r the l i t t e r . ) Should the
results be weighted for statistical analysis? What are t h e
appropriate, inappropriate methods of analysis? Should each
experiment be g i v e n t h e same weight o f e v i d e n c e ?
Relative Sensitivity. What are the relationships between,

p a r e n t a l and maternal t o x i c i t y , and r e p r o d u c t i v e e f f e c t s ? What
a r e t h e r e l a t i o n s h i p s between maternal t o x i c i t y and developmental
toxicity? Was t h e r e p r o d u c t i v e system u n i q u e l y s e n s i t i v e t o t h e
pesticide? Was t h e d e v e l o p i n g organism u n i q u e l y s e n s i t i v e t o the
pesticide?
Hazard Extrapolation.
Hazard e x t r a p o l a t i o n i s used here t o mean e x t r a p o l a t i o n both from

t h e observed e f f e c t l e v e l s t o n o n - t e s t e d l e v e l s w i t h i n t h e t e s t e d
s p e c i e s and from t e s t e d s p e c i e s t o n o n - t e s t e d s p e c i e s . Hazard

e x t r a p o l a t i o n beyond t h e observed s h o u l d be attempted o n l y a f t e r
hazard i d e n t i f i c a t i o n , and a f u l l and complete e v a l u a t i o n o f a l l
relevant available toxicity data has been completed. The
reproductive/developmental t o x i c o l o g i s t must be v e r y s p e c i f i c i n
s t a t i n g h i s / h e r c e r t a i n t i e s and u n c e r t a i n t i e s about e x t r a p o l a t i o n
beyond the o b s e r v e d . A g a i n , a s e r i e s o f q u e s t i o n s can g r e a t l y a i d
t h e r e g u l a t o r and t h e i n v e s t i g a t o r i n a r r i v i n g a t judgements o f
the s i g n i f i c a n c e o f the observed data f o r e x t r a p o l a t i o n to the
unobserved. L i s t e d below i s a s e r i e s o f q u e s t i o n s h e l p f u l t o t h e
regulator and the investigator for extrapolation beyond the
observed.
Test M o d e l ( s ) . What was t h e a p p r o p r i a t e n e s s o f t h e t e s t model(s)

used f o r r e p r o d u c t i v e and developmental hazards a s s o c i a t e d w i t h
p e s t i c i d e c o n t a m i n a t i o n o f underground ( d r i n k i n g ) w a t e r . Common
sense t e l l s us t h a t e x t r a p o l a t i o n o f r e s u l t s from a s u b c h r o n i c o r
chronic drinking water study is more appropriate than
extrapolation from some fraction of the LD50 dose given
i n t r a p e r i t o n e a l ^ f o r 5 d a y s . L i k e w i s e , c h r o n i c f e e d i n g i s more
a p p r o p r i a t e than gavage d o s i n g which i s more a p p r o p r i a t e than
dermal e x p o s u r e , e t c . The same c o n c e p t s a p p l y t o r e p r o d u c t i v e and
developmental hazard a s s e s s m e n t s .
Delivered Dose. What was t h e dose d e l i v e r e d t o the target

tissue(s)? V a r i a t i o n s and d i f f e r e n c e s between s p e c i e s , i n d i v i d u a l
a n i m a l s and even u n i t s w i t h i n an animal are common when one
compares response observed t o v a r i o u s exposure r e g i m e n s . However,
examination of delivered dose o f toxicant to target tissues
f r e q u e n t l y reduces t h e v a r i a t i o n s and d i f f e r e n c e s . Kimmel and
Young (8) have r e c e n t l y p u b l i s h e d a paper d e m o n s t r a t i n g improved
p r e d i c t i o n o f t e r a t o g e n i c outcome o f r a t s t o sodium s a l i c y l a t e
when blood l e v e l s were u s e d . The more complete the knowledge and
u n d e r s t a n d i n g o f t h e a b s o r p t i o n , d i s t r i b u t i o n , m e t a b o l i s m , and
e x c r e t i o n w i t h i n the s t u d i e d s p e c i e s and the s p e c i e s o f c o n c e r n ,
t h e g r e a t e r t h e c o n f i d e n c e t h e i n v e s t i g a t o r has i n e x t r a p o l a t i n g
d a t a from one s p e c i e s t o another o r from an observed dose w i t h i n a
s p e c i e s t o a n o n - t e s t e d dose i n t h e same s p e c i e s .
Structural Activity Relationships. Are t h e r e any structural

activity relationships (SAR) between the pesticide under
c o n s i d e r a t i o n and p e s t i c i d e s t h a t have a h i s t o r y o f s a f e uses?
Structural a c t i v i t y r e l a t i o n s h i p s must be u s e d , not misused o r
abused. To be used p r o p e r l y , SAR e v a l u a t i o n s must t a k e into
consideration not only chemical structure class and toxic
c a t e g o r i e s , but s u b t l e chemical s t r u c t u r a l d i f f e r e n c e s as w e l l as
all known b i o l o g i c a l activity and metabolism o f t h e chemical
structure c l a s s .
Mathematical Model s . There are no biological appropriate

mathematical models for evaluation of reproductive or
developmental hazards. The best that can be done is to
mathematically characterize the dose-response curve in the
o b s e r v a b l e range and e s t i m a t e the t h r e s h o l d l e v e l s . The EPA (2)
has r e j e c t e d t h e use o f mathematical modeling f o r estimating
developmental t o x i c i t y r e s p o n s e s below t h e a p p l i e d dose r a n g e .
Statistics. What are t h e s t a t i s t i c a l l i m i t s o f t h e e x p e r i m e n t a l

d e s i g n s and what a r e t h e l i m i t s t o the s t a t i s t i c s t h a t can be
a p p l i e d to r e p r o d u c t i v e studies and e v a l u a t i o n s ? Statistical
evaluations of reproductive and developmental studies present
numerous problems including from whether the litter or the
i n d i v i d u a l conceptus i s t h e e x p e r i m e n t a l u n i t f o r e v a l u a t i o n , t o
t h e e f f e c t s o f w e i g h t i n g o f body w e i g h t s due t o l i t t e r s i z e o r 0
and 100% responses w i t h i n a l i t t e r ( G a y l o r (9) and Nelson and
Holson ( 1 0 ) ) . While i t i s i m p o r t a n t i n a l l t o x i c o l o g i c a l s t u d i e s
to consult a statistician before conducting an experiment,
reproductive and developmental studies a r e more demanding for
proper statistical consultation both before and after the
conducting of a s t u d y ( i e s ) .
Uncertainties. In any hazard or r i s k assessment i t i s e x t r e m e l y

important that uncertainties be expressed. Frequently the
u n c e r t a i n t i e s are expressed only in s t a t i s t i c a l terms. It is

i m p o r t a n t t h a t t h e u n c e r t a i n t i e s a l s o be e x p r e s s e d i n b i o l o g i c a l
terms. S t a t i s t i c a l modeling or modeling s t a t i s t i c s has become
v e r y p o p u l a r i n h e a l t h r i s k a s s e s s m e n t s , p a r t i c u l a r l y f o r "low
dose" extrapolations. As previously stated, there are no
mathematical models w i t h a b i o l o g i c a l b a s i s f o r r e p r o d u c t i o n o r
developmental hazard e v a l u a t i o n .
G a y l o r (11) and Crump (12) have p o i n t e d out some o f t h e
deficiencies of using no-observed-effect-levels (NOELS's) and
minimal e f f e c t l e v e l s (MEL's) i n r i s k management. B a s i c a l l y , they
point out that NOEL's and MEL's are as much a f u n c t i o n of
e x p e r i m e n t a l dose s e l e c t i o n s as t h e t r u e d o s e - r e s p o n s e n a t u r e o f
t h e t e s t animal t o t h e t o x i c a n t s . Both suggest t h a t a s t a t i s t i c a l
a c c e p t a b l e mathematical model be a p p l i e d t o the d a t a i n t h e
observed range and t h a t a c o n s i s t e n t end p o i n t such as a 0.1 o r
0.01 i . e . t h e 10% o r 1% e f f e c t l e v e l be e s t i m a t e d . Examination o f
data from well conducted toxicological studies, including
r e p r o d u c t i v e and t e r a t o g e n i c s t u d i e s suggest t h a t an e s t i m a t e d 10%
e x t r a r i s k c o r r e s p o n d s well t o minimal observed e f f e c t l e v e l s and
an e s t i m a t e d 1% e x t r a r i s k c o r r e s p o n d s w e l l t o a t h r e s h o l d or no-
observed-effect level. Also, consistent end points improve
comparison between effects, studying and in general aid
evaluation. E s t i m a t i o n o f c o n f i d e n t l i m i t s f o r r i s k and doses
about such estimated points help define confidences in a
p a r t i c u l a r s t u d y , but add l i t t l e t o c e r t a i n t i e s o r u n c e r t a i n t i e s
f o r e x t r a p o l a t i o n s t o low doses o r t o o t h e r s p e c i e s . Therefore,
most l i k e l y e f f e c t dose e s t i m a t e s s h o u l d be u s e d .
Unfortunately, certainties and uncertainties cannot be
expressed with mathematical precision and should not be
attempted. C o n f i d e n c e s and u n c e r t a i n t i e s must be expressed as
expert opinions with statements o f s u p p o r t . E x p e r t s can u s u a l l y
agree t h a t above a s t a t e d " h i g h " exposure a g i v e n response is
l i k e l y and t h a t below a s t a t e d "low" exposure t h e response is
unlikely. However, between t h e "low" and " h i g h " exposures t h e r e
i s an a r e a o f u n c e r t a i n t i e s where e x p e r t s w i l l d i s a g r e e about t h e
l i k e l i h o o d o f a g i v e n response t o a p a r t i c u l a r e x p o s u r e .
Risk Characterization
R i s k c h a r a c t e r i z a t i o n i s an e x p e r t , i n t e g r a t e d , summarization o f
hazard identification, evaluation, and extrapolation, plus a
characterization of the population(s) at risk and likely
exposures. It i s t h e c o n c l u s i o n o f t h e s c i e n t i f i c endeavor t o
assess r i s k . It must be p r e c i s e , i n c l u s i v e and s t a t e d i n terms
that can be understood and used appropriately for societal
judgements on the a c c e p t a b i l i t y o f a r i s k .
Risk Acceptability
As a l l m a t e r i a l s a r e t o x i c t o some organisms under some exposure

c o n d i t i o n s , t h e r e i s no " s a f e m a t e r i a l " i n t h e p u r e s t s e n s e , t h e r e
are only "safe handling" or "acceptable handling" procedures, or
risk management techniques. This is particularly true for
pesticides.
In t h i s s e n s e , s a f e t y f a c t o r s , margin o f s a f e t y , low dose
e x t r a p o l a t i o n s , e t c . are not r i s k assessment t o o l s , t h e y a r e r i s k
management t o o l s . Thus w h i l e i t has been noted i n scientific
experiments and o b s e r v a t i o n s t h a t animal t o animal v a r i a t i o n s a r e
seldom g r e a t e r than an o r d e r o f magnitude and s e n s i t i v i t y from one
s p e c i e s t o another i s u s u a l l y w i t h i n a f a c t o r o f t e n , t h e 1/100
s a f e t y f a c t o r f o r e s t a b l i s h i n g a c c e p t a b l e d a i l y i n t a k e (ADI) i s
not a r i s k assessment d e c i s i o n , i t i s a r i s k managerial d e c i s i o n
with s c i e n t i f i c i n p u t .
F o r a c o n t r o l l i n g , r e g u l a t o r y , p e r s p e c t i v e I would l i k e t o
paraphrase Marshall Johnson ( 1 3 ) . It can be c o n c l u d e d t h a t a
pesticide would need to be (regulated) controlled as a
r e p r o d u c t i v e o r developmental hazard o n l y i f the reproductive
system or the embryo/fetus are uniquely susceptible to the
pesticide. Pesticides that are coeffective reproductive or
developmental toxins, that is, adversely affecting the
reproductive system or t h e d e v e l o p i n g c o n c e p t u s o n l y a t dose
l e v e l s t h a t a d v e r s e l y a f f e c t t h e a d u l t , would not n e c e s s a r i l y be
c o n t r o l l e d as r e p r o d u c t i v e o r developmental h a z a r d s . Thus o n l y
n o n - c o e f f e c t i v e r e p r o d u c t i v e o r developmental t o x i n s , which a r e
t h o s e a f f e c t i n g r e p r o d u c t i o n o r t h e d e v e l o p i n g c o n c e p t u s below t h e
dose needed t o a d v e r s e l y a f f e c t the a d u l t would r e q u i r e c o n t r o l .
Conclusion
In c o n c l u s i o n , r e g u l a t o r s must make d e c i s i o n s and i n v e s t i g a t o r s

must e x p r e s s o p i n i o n s based on a v a i l a b l e d a t a and cannot wait f o r
a second o r t h i r d r e c y c l i n g t h r o u g h t e s t i n g and e v a l u a t i o n s . If
hazard i d e n t i f i c a t i o n and p r e l i m i n a r y exposure e s t i m a t e s suggest
the potential o f r e p r o d u c t i v e o r developmental hazard and the
p o t e n t i a l f o r e x p o s u r e , both must conduct a hazard assessment and
hazard e x t r a p o l a t i o n u t i l i z i n g a l l a v a i l a b l e i n f o r m a t i o n and best
science. And, i f t h e assessment demonstrates t h a t r e p r o d u c t i o n o r
development is uniquely s e n s i t i v e , i e , t h a t t h e p e s t i c i d e may
a f f e c t r e p r o d u c t i o n o r t h e d e v e l o p i n g c o n c e p t u s below t h e dose
needed t o a d v e r s e l y a f f e c t t h e a d u l t , then w i t h t h e best e s t i m a t e
o f e x p o s u r e , t h e y must perform a r i s k a s s e s s m e n t . The risk
assessment must be a s c i e n t i f i c endeavor w h i l e the d e c i s i o n s on
risk acceptability and r i s k management should be l e f t to societal

judgement.
Literature Cited
1. "Risk Assessment in the Federal Government: Managing the
Process," National Research Council, National Academy Press,
Washington, D.C., 1983.
2. "Proposed Guidelines for the Health Assessment of Suspect
Developmental Toxicants," Federal Register 49 CFR, November
23, 1984, pp 46325-46331.
3. "U.S. Environmental Protection Agency. 1982. Health effects
test guidelines, Chapter II. Specific organ/tissue toxicity
-teratogenicity." Office of Toxic Substances. Available from:
NTIS, Springfield, VA. PB82-232984.
4. Kimmel, C. .; Holson, J. F.; Hogue C. J.; Carlo, G. L . ;
"Reliability of experimental studies for predicting hazards to

human development." NCTR Technical Report for Experiment No.
6015. 1984; NCTR, Jefferson, Arkansas.
5. "Guidelines for reproduction and teratology of drugs." Bureau
of Drugs. Food and Drug Administration, 1966.
6. Food and Drug Administration. Advisory Committee on Protocols
for Safety Evaluations. "Panel on Reproduction Report on
Reproduction Studies in the Safety Evaluation of Food
Additives and Pesticide Residues." Toxicol. Appl.
Pharmacol. 1970, 16, 264-296.
7. Collins, T. F. X. "Multigeneration Reproduction Studies"; In
"Handbook of Teratology"; Wilson, J. G.; Fraser, F. C., Ed.,
Plenum Press, New York, N.Y., 1978; Chap 7.
8. Kimmel, C. .; Young, J. F. Fundam. Appl. Toxicol. 1983, 3,
250-5.
9. Gaylor, D. W. "Methods and Concepts of Biometrics Applied to
Teratology"; In "Handbook of Teratology 4 Research Procedures
and Data Analysis": Wilson, J. G.; Fraser, F. C., Eds.; Plenum
Press, New York, . Y. 1978; Chap. 14.
10. Nelson, C. J.; Holson, J. F. J. Environ. Pathol. Toxicol.
1978, 2, 187-99.
11. Gaylor, D. W. J. Toxicol. Environ. Health. 1983, 11, 329-36.
12. Crump, K. S. Fundam. Appl. Toxicol. 1984, 4, 854-71. 13.
Johnson, . M. Ann. Rev. Pharmacol. Toxicol. 1981, 21, 417-
29.
13. Johnson, . M. Ann. Rev. Pharmacol. Toxicol. 1981, 21, 417-29.
23
The Toxicological and Epidemiological Effects
of Pesticide Contamination in California Ground Water
Peter E. Berteau and David P. Spath
California State Department of Health Services, Berkeley, CA 94704
The contamination of California groundwater by pes-

ticides is a problem which is becoming more evident
as monitoring programs are being implemented. In a

recent study, 54 pesticides were detected in 2,893
wells in the State. Among the most pervasive toxic
pesticide chemicals found have been 1,2-dibromo-3-
chloropropane (DBCP), ethylene dibromide (EDB) and
1,2-dichloropropane (1,2-D). DBCP alone has resulted
in the closure of about 1,000 drinking water wells.
Toxicological evidence from animal studies indicate
that these substances are carcinogenic and in one
epidemiological study there was an excess of stomach
cancer in census tracts with high DBCP content. An
acutely toxic chemical, aldicarb, has also been
detected in a number of wells in the State. Adverse
reproductive effects and neurotoxicity occur with
several of these pesticides.
Because o f the importance o f a g r i c u l t u r e to the C a l i f o r n i a e c o n o m y ,
w i d e s p r e a d use of p e s t i c i d e s has o c c u r r e d d u r i n g the p a s t f o u r
decades. While t h i s use has l e d t o c o n c e r n s a b o u t p o i s o n i n g s o f
f a r m w o r k e r s , q u e s t i o n s o f r e s i d u e s i n food and the e s t a b l i s h m e n t o f
s a f e l e v e l s , i t has o n l y r e c e n t l y been r e c o g n i z e d t h a t h a z a r d s from
t h e u s e o f p e s t i c i d e s may o c c u r from s o u r c e s o t h e r than o c c u p a t i o n
o r food s u p p l y . Now i t i s e m e r g i n g t h a t t h e c o n t a m i n a t i o n o f
g r o u n d w a t e r i n C a l i f o r n i a by p e s t i c i d e s and i n d u s t r i a l c h e m i c a l s i s
a problem o f p r e v i o u s l y u n f o r e s e e n p r o p o r t i o n s . In t h i s c o n n e c t i o n ,
i t m u s t be r e c o g n i z e d t h a t a b o u t 43% o f the s t a t e o f C a l i f o r n i a o r
a b o u t 10 m i l l 1 on p e o p l e r e l y on g r o u n d w a t e r f o r t h e i r water
supplies.
In T a b l e I an Idea o f the scope o f the p r o b l e m o f p e s t i c i d e

c o n t a m i n a t i o n 1n groundwater i s g i v e n by l i s t i n g some o f the p e s -
t i c i d e c h e m i c a l s which a r e b e i n g most commonly e n c o u n t e r e d . It is
only a p a r t i a l l i s t b u t r e p r e s e n t s the most commonly o c c u r r i n g
c h e m i c a l s , i n p a r t i c u l a r those a r i s i n g from a g r i c u l t u r a l u s e , and
the ones which a r e c o n s i d e r e d i n t h i s s e c t i o n .
0097-6156/ 86/ 0315-0423S06.00/ 0

Table I. Major P e s t i c i d e s Encountered i n C a l i f o r n i a Groundwater
S o i l Fumigants (Nematocides)
l,2-Dibromo-3-chloropropane (DBCP)
E t h y l e n e d i b r o m i d e (EDB)
1,2-Dichloropropane (1,2-D)
Insecticides
A l d i c a r b (Temik)
Herbicides
Atrazine
Simazine
Fungicides
P e n t a c h l o r o p h e n o l (PCP)
D i t h i o c a r b a m a t e s ( e . g . , Maneb, Z i r a m , Thiram)
I n 1 9 8 4 t h e C a l i f o r n i a S t a t e Water Resources C o n t r o l Board

(SWRCB) r e p o r t e d t h a t d u r i n g t h e p a s t 12 y e a r s p e s t i c i d e con-
taminants h a v e b e e n f o u n d i n 2,893 w e l l s ( 1 , 2 ) . A l t h o u g h 54
d i f f e r e n t p e s t i c i d e s have been d e t e c t e d i n these weTls a b o u t 85% o f
t h e c o n t a m i n a t i o n has been caused by l , 2 - d i b r o m o - 3 - c h l o r o p r o p a n e
(DBCP), a s o i l f u m i g a n t t h a t was banned seven y e a r s ago b u t t h a t is
s t i l l b e i n g d e t e c t e d i n i n c r e a s i n g amounts i n w e l l s .
F i g u r e 1 shows a map o f C a l i f o r n i a g i v i n g the l o c a t i o n s o f the
m o s t a b u n d a n t l y o c c u r r i n g p e s t i c i d e s which a r e b e i n g found i n
groundwater. Of c o u r s e , the c o n t a m i n a t i o n i s not l i m i t e d to
a g r i c u l t u r a l c h e m i c a l s such as p e s t i c i d e s ; i n d u s t r i a l c h e m i c a l s have
c o n t r i b u t e d a l m o s t e q u a l l y to o v e r a l l g r o u n d w a t e r contamination,
however, i t 1s p o l l u t i o n by p e s t i c i d e s which we a r e concerned w i t h
here.
Most o f t h i s c o n t a m i n a t i o n a r i s e s from the use o f p e s t i c i d e s i n
a g r i c u l t u r e b u t some p e s t i c i d e c o n t a m i n a t i o n o f g r o u n d w a t e r has
a r i s e n i n the same manner as from i n d u s t r i a l c h e m i c a l s , namely from
c a r e l e s s use and poor housekeeping 1n i n d u s t r i a l p l a n t s . The c o n -
t a m i n a t i o n by p e n t a c h l o r o p h e n o l ( P C P ) 1s thought to a r i s e from the
use o f t h i s chemical f o r t r e a t i n g p o l e s 1n m a n u f a c t u r i n g p l a n t s .
T h e p r e s e n c e o f p e s t i c i d e s and o t h e r c h e m i c a l s i n groundwater
has d e s t r o y e d the l o n g h e l d b e l i e f t h a t g r o u n d w a t e r i s Immune t o
chemical p o l l u t i o n because s o i l would f i l t e r o u t or break down the
chemicals. A l t h o u g h the c o n t a m i n a t i o n has p r o b a b l y been p r e s e n t f o r
years, l a b o r a t o r y t e c h n i q u e s and equipment to d e t e c t low l e v e l s o f
the complex c h e m i c a l s have o n l y been d e v e l o p e d i n r e c e n t years.
S t a t e p r o g r a m s s p e c i f i c a l l y d e s i g n e d to p r o t e c t water from t o x i c
s u b s t a n c e s began l e s s than 10 y e a r s a g o .
Types o f P e s t i c i d e s which Contaminate Groundwater
By f a r the most u b i q u i t o u s p o l l u t a n t s w h i c h a r e contaminating

g r o u n d w a t e r a r e t h e s o i l f u m l g a n t s , p a r t i c u l a r l y DBCP, b u t a l s o
ethylene dibromide (EDB) and 1 , 2 - d i c h l o r o p r o p a n e (1,2-D).
Organophosphorus i n s e c t i c i d e s have n o t been found to any a p p r e c i a b l e
e x t e n t i n groundwater p r o b a b l y because t h e y a r e u s u a l l y readily
BE RTE AU A N D SPATH Pesticide Contamination in California Ground Water
F i g u r e 1. P e s t i c i d e Contamination - C a l i f o r n i a Groundwaters.
broken down i n t o p h o s p h o r i c a c i d d i a l k y l e s t e r s and l o s e t h e i r t o x i c

character. A r e l a t e d c l a s s o f compounds, the c a r b a m a t e s , w h i c h owe
t h e i r t o x i c a c t i o n s to i n h i b i t i o n o f c h o l i n e s t e r a s e , are w i d e l y used
in California. One o f t h e s e i n p a r t i c u l a r i s being found in
g r o u n d w a t e r i n many p a r t s o f the c o u n t r y . T h i s i s the h i g h l y t o x i c
oxime carbamate a l d i c a r b (Temik) w h i c h , i n C a l i f o r n i a , has been
f o u n d a l o n g w i t h i t s s u l f o x i d e i n the extreme N o r t h e r n p a r t o f the
s t a t e c l o s e to the Oregon b o r d e r .
H e r b i c i d e s have a l s o been found i n water a l t h o u g h t h e i r o c c u r -
r e n c e i s more o f t e n seen i n s u r f a c e w a t e r s a r i s i n g from d i r e c t run-
o f f from a g r i c u l t u r a l use as i n r i c e growing. C e r t a i n o f the
t r i a z i n e h e r b i c i d e s have been found i n w e l l s i n N o r t h e r n C a l i f o r n i a
a n d i n t h e L o s Angeles B a s i n . F u n g i c i d e s have a l s o been found i n
groundwater. T h e o c c u r r e n c e o f t h e wood p r e s e r v a t i v e pen-
t a c h l o r o p h e n o l (PCP) has a l r e a d y been m e n t i o n e d . More r e c e n t l y the
metal c o n t a i n i n g d i t h i o c a r b a m a t e s have been e n c o u n t e r e d . Many o f
these a r e the heavy metal s a l t s o f e t h y l e n e - b i s - d i t h i o c a r b a m i c a c i d .

P e s t i c i d e chemicals are r e l a t e d to s p e c i f i c toxic effects.
W i t h the s o i l f u m i g a n t s , r e p r o d u c t i v e e f f e c t s and c a r c i n o g e n i c i t y
a r e the main c o n c e r n . With the c a r b a m a t e s , such as a l d i c a r b , we a r e
c o n c e r n e d w i t h an a c u t e t o x i c e f f e c t on the p e r i p h e r a l nervous
system. With p e n t a c h l o r o p h e n o l high a c u t e t o x i c i t y and t h e poten-
t i a l f o r c a r c i n o g e n i c i t y a r e the main c o n c e r n s .
Soil Fumigants
A s a l r e a d y m e n t i o n e d , t h r e e s o i l f u m i g a n t s , shown below, a l o n g w i t h
t h e i r chemical s t r u c t u r e s , a r e p r e s e n t i n g p r o b a b l y the greatest
p r o b l e m o f g r o u n d w a t e r c h e m i c a l c o n t a m i n a t i o n by p e s t i c i d e s i n
California.
Table II. Chemical Structures of Soil Fumigants
1,2-Dibromo-3-chioropropane (DBCP)
1,2-Dichloropropane (1,2-D)
2 2
Ethylene dibromide (EDB)
T h e s e t h r e e compounds a r e h a l o g e n a t e d as a r e most o f the i n -

d u s t r i a l groundwater p o l l u t a n t s . They are w e l l known a s being
h e p a t o t o x i c a n d h a v e been demonstrated to cause c a n c e r i n one or
23. BE RTE AU A N D SPATH Pesticide Contamination in California Ground Water All
more s p e c i e s o f a n i m a l . Two o f t h e s e , DBCP and EDB, a r e b r o m i n a t e d

c o m p o u n d s a n d these a r e the more p o t e n t animal c a r c i n o g e n s , 1,2-D
b e i n g o n l y weakly c a r c i n o g e n i c . Most s o i l f u m i g a n t s a r e injected
i n t o the s o i l up t o a f o o t i n depth and some o f the chemical i s
c a r r i e d downward i n t o w a t e r - b e a r i n g s t r a t a ( a q u i f e r s ) by i r r i g a t i o n
and r a i n w a t e r . DBCP h a s b e e n the most p e r v a s i v e o f these s o i l
f u m i g a n t s because o f i t s p a s t e x t e n s i v e use s t a r t i n g in the late
1950's. N e a r l y one m i l l i o n pounds per y e a r were b e i n g used by the
time DBCP was banned i n 1977. I n t e r e s t i n g l y , more o f t h i s c h e m i c a l
i s s h o w i n g up now than when i t f i r s t began to be d e t e c t e d i n w e l l s
i n 1979. M i l l i o n s of d o l l a r s have a l r e a d y b e e n s p e n t to drill
w a t e r - w e l l s i n t o d e e p e r , u n t a i n t e d a q u i f e r s i n F r e s n o county i n the
C e n t r a l V a l l e y where most o f the DBCP c o n t a m i n a t i o n h a s occurred.
H o w e v e r , as o f November, 1984, 1,473 w e l l s had been r e n d e r e d unuse-
a b l e f o r d r i n k i n g o r c o o k i n g because they exceeded the a c t i o n level
o f 1 ppb e s t a b l i s h e d by the s t a t e o f C a l i f o r n i a ( 3 ) . (An a c t i o n
l e v e l i s a concentration a t which the C a l i f o r n i a department of

H e a l t h S e r v i c e s recommends, t h a t f o r h e a l t h p r o t e c t i o n , the water
n o t be used f o r d r i n k i n g o r c o o k i n g ) . I f DBCP has a h a l f l i f e in
s o i l s o f more than 100 y e a r s , as some o f the l i t e r a t u r e i n d i c a t e s ,
() i t s p e r s i s t e n c e i s going to be a p r o b l e m .
The t o x i c o l o g i c a l e f f e c t s o f DBCP were i n v e s t i g a t e d i n r a t s i n
the l a t e 1950's n o t long a f t e r i t became c o m m e r c i a l l y a v a i l a b l e {5).
At that time, the t e s t i n g requirements f o r r e g i s t r a t i o n of pes-
t i c i d e s were v e r y much more l i m i t e d than they a r e today and a d v e r s e
f i n d i n g s were o f t e n d i s r e g a r d e d . The study i n c l u d e d s t a n d a r d s k i n
and eye i r r i t a t i o n s t u d i e s a s w e l l as r e p e a t e d v a p o r inhalation
s t u d i e s on r a t s , r a b b i t s and guinea p i g s . The i n h a l a t i o n exposure
c o n c e n t r a t i o n s were 0 ( c o n t r o l ) , 5, 10, 20 and 40 ppm f o r t h e rat.
Exposure times were 7 hours a day, 5 days a week f o r a t o t a l o f 50
e x p o s u r e s (10 w e e k s ) .
T h e m o s t s i g n i f i c a n t f i n d i n g was t h a t a t the l o w e s t l e v e l , 5
ppm, there was a s p e c i f i c h i s t o l o g i c a l a l t e r a t i o n i n the t e s t e s in
the male r a t . I t was r e p o r t e d t h a t t e s t i c u l a r w e i g h t was reduced to
50% o f normal i n h a l f the r a t s a l t h o u g h t h i s r e d u c t i o n was n o t
statistically s i g n i f i c a n t because o f the l a r g e i n t e r n a l v a r i a t i o n
w i t h i n the g r o u p . Changes were a l s o r e p o r t e d i n k i d n e y , l i v e r and
b r o n c h i o l e s a n d w e i g h t g a i n was s i g n i f i c a n t l y r e d u c e d . At higher
c o n c e n t r a t i o n s the e f f e c t i n the t e s t e s o f r a t s was particularly
severe, resulting i n atrophy, degenerative changes, r e d u c t i o n of
s p e r m a t o g e n s i s and the development o f abnormal sperm. Less exten-
s i v e s t u d i e s were done w i t h r a b b i t s and guinea p i g s b u t d e c r e a s e d
t e s t i c u l a r w e i g h t was r e p o r t e d i n both these s p e c i e s a t t h e only
c o n c e n t r a t i o n a d m i n i s t e r e d , 12 ppm. A 90-day f e e d i n g study was a l s o
c o n d u c t e d w i t h r a t s a t dose l e v e l s r a n g i n g from 5 to 1,350 ppm. No
m e n t i o n was made o f any t e s t i c u l a r e f f e c t i n t h i s study and 150 ppm
was judged to be a n o - e f f e c t l e v e l . I t i s n o t known i f t h e testes
were examined.
In g e n e r a l t h i s s t u d y , r e p o r t e d i n 1961, i s w e l l c o n d u c t e d a n d
t h e d a t a a r e s t i l l u s e f u l f o r the s p e c i f i c purposes o f r i s k a s s e s s -
ment t o d a y . The e f f e c t on the t e s t e s a t t h e l o w e s t inhalation
e x p o s u r e i s mentioned s e v e r a l times and the a u t h o r s recommended an
exposure l e v e l below 1 ppm i f p r o l o n g e d exposure i s l i k e l y . No e f -
f o r t was made to r e p e a t the exposure study a t lower l e v e l s i n o r d e r
to determine a n o - e f f e c t l e v e l a s would be r e q u i r e d t o d a y . More i m -

p o r t a n t , however, the study was i g n o r e d f o r a b o u t 15 y e a r s u n t i l the
appearance o f the w e l l p u b l i c i z e d r e p o r t o f s t e r i l i t y i n male
workers a t a DBCP m a n u f a c t u r i n g p l a n t i n L a t h r o p , C a l i f o r n i a ( 6 K
S i n c e t h a t t i m e , e x t e n s i v e t o x i c o l o g i c a l and e p i d e m i o l o g i c a l
s t u d i e s have been conducted w i t h DBCP. These i n c l u d e three s t u d i e s
on h u m a n s . One was a s t u d y on p l a n t w o r k e r s . O f 25 n o n -
v a s e c t o m i z e d men, i n those who had been exposed to DBCP f o r t h r e e
y e a r s , sperm c o u n t s w e r e d r a s t i c a l l y r e d u c e d i n 11 men (< 1
million/ml) a n d n i n e o f these had no d e t e c t a b l e sperm c e l l s . Of
those who had o n l y a s h o r t d u r a t i o n o f e x p o s u r e , sperm c o u n t s w e r e
normal (> 40 m i l l i o n / m l ) (7). In a n o t h e r s t u d y , an i n c r e a s e i n
sperm c e l l s c o n t a i n i n g two Y chromosomes was noted (8). The third
human study was an e p i d e m i o l o g i c a l study i n v o l v i n g s u b j e c t s exposed
t o w e l l - w a t e r c o n t a i n i n g DBCP and w i l l be d i s c u s s e d l a t e r .
Since t h e 1 9 6 1 s t u d y , DBCP has been t e s t e d i n s t a n d a r d l o n g
term r a t and mouse b i o a s s a y s . These s t u d i e s a r e r e v i e w e d i n the

monograph on DBCP i s s u e d by the I n t e r n a t i o n a l Agency f o r Research on
Cancer ( 9 h In the s t u d i e s c o n d u c t e d f o r t h e N a t i o n a l Cancer
Institute, DBCP was h i g h l y c a r c i n o g e n i c a t the l o w e s t doses a d -
m i n i s t e r e d ( a b o u t 10 mg/kg/day f o r mice and 15 mg/kg/day f o r r a t s ) .
Tumors in b o t h s p e c i e s r e s u l t e d in early m o r t a l i t y . Tumors i n
g e n e r a l were squamous c e l l c a r c i n o m a s o f t h e f o r e s t o m a c h w h i c h
m e t a s t a s i z e d i n t o t h e a b d o m i n a l v i s c e r a and l u n g s . Testicular
a t r o p h y was a l s o noted i n the r a t s i n these s t u d i e s . A high in-
c i d e n c e o f adenocarcinomas o f the mammary g l a n d was seen 1n female
r a t s exposed to both the low and high dose l e v e l s ( 1 0 ) .
In s t u d i e s conducted a t the same l a b o r a t o r y T u t sponsored by
the Dow Chemical Company ( 1 1 ) , DBCP was I n c o r p o r a t e d i n t o t h e diet
o f r a t s and m i c e . D i e t a r y " T e v e l s were a d j u s t e d so t h a t both s p e c i e s
r e c e i v e d 0 ( c o n t r o l ) , 0 . 3 , 1.0 and 3.0 m g / k g / d a y . T h e r e w e r e 60
r a t s p e r g r o u p which r e c e i v e d the t r e a t e d d i e t f o r 2 y e a r s and 50
mice per group which r e c e i v e d the d i e t f o r 1 1/2 y e a r s . In the r a t s
a t u m o r l g e n i c e f f e c t was s e e n i n the k i d n e y s and n o n - g l a n d u l a r
r e g i o n o f the stomach w i t h the g r e a t e s t i n c i d e n c e o f n e o p l a s i a b e i n g
o b s e r v e d i n t h e high dose group o f r a t s , w i t h fewer tumors a t the
mid-dose l e v e l and o n l y r a r e l e s i o n s a t t h e l o w - d o s e l e v e l . In
m i c e , a d o s e r e l a t e d i n c r e a s e i n the i n c i d e n c e o f stomach n o d u l e s
was noted In a l l treated animals s a c r i f i c e d at termination.
H i s t o l o g i c a l e x a m i n a t i o n o f c o n t r o l and high dose groups r e v e a l e d a
h i g h i n c i d e n c e o f t r e a t m e n t r e l a t e d n e o p l a s i a (squamous c e l l p a p i l -
lomas and c a r c i n o m a s ) i n the n o n - g l a n d u l a r r e g i o n o f the stomach.
In an i n i t i a t i o n - p r o m o t i o n s k i n b i o a s s a y conducted a t New Y o r k
U n i v e r s i t y Medical C e n t e r ( 1 2 ) , 69.0 mg o f DBCP was a p p l i e d to the
s k i n o f female m i c e , followeoHBy r e p e a t e d a p p l i c a t i o n o f phorbol
m y r i s t a t e a c e t a t e t h r e e times weekly f o r 499 d a y s . The most s i g -
n i f i c a n t f i n d i n g f r o m t h i s s t u d y was t h e o c c u r r e n c e o f lung
p a p i l l o m a s and squamous c e l l carcinomas o f the forestomach i n d i c a t -
i n g t h a t the o c c u r r e n c e o f stomach tumors i n the o r a l s t u d i e s may be
s y s t e m i c and n o t merely r e l a t e d to an I r r i t a n t e f f e c t a t the s i t e o f
application.
B a s e d u p o n t h e s e d a t a accumulated from animal s t u d i e s , the
E n v i r o n m e n t a l P r o t e c t i o n A g e n c y ' s C a r c i n o g e n Assessment Group ( C A G )
23. BE RTE AU A N D SPATH Pesticide Contamination in California Ground Water 429
p e r f o r m e d a r i s k assessment f o r l i f e t i m e exposure to DBCP i n d r i n k -

i n g water ( 1 3 ) . A t a c o n c e n t r a t i o n o f 0.005 ppb the r i s k o f excess
c a n c e r c a s e s would be 1.1 i n 1 m i l l i o n ; a t 0.05 ppb, 11 i n 1 m i l l i o n
and a t 1.0 ppb, 220 i n 1 m i l l i o n . Based on the a v a i l a b l e evidence
on the c a r c i n o g e n i c i t y , s e n s i t i v i t y o f a n a l y t i c a l methods, i m p a c t on
water d e l i v e r y c a p a b i l i t i e s , and a d d i t i o n a l f a c t o r s the California
D e p a r t m e n t o f H e a l t h S e r v i c e s adopted an a c t i o n l e v e l o f 1 ppb f o r
c o n t a m i n a t i o n o f d o m e s t i c d r i n k i n g water by DBCP ( 2 ) . T h i s policy
r e c o m m e n d s t h a t c o n t a m i n a t i o n o f water s u p p l i e s a t t h i s l e v e l or
above i n d i c a t e s t h a t the water s h o u l d n o t be u s e d .
A s t u d y c o n d u c t e d by t h e C a l 1 f o r n i a Department o f H e a l t h
S e r v i c e s i s the o n l y known a c t u a l e p i d e m i o l o g i c a l study that has
b e e n c o n d u c t e d on p e o p l e exposed to water c o n t a m i n a t e d w i t h p e s -
t i c i d e s (14). P o p u l a t i o n groups i n an area o f C e n t r a l C a l i f o r n i a ,
F r e s n o c o u n t y , w h e r e w e l l s had been c o n t a m i n a t e d w i t h DBCP were
studied f o r cancer m o r t a l i t y . The v a r i o u s census t r a c t s under s t u d y
w e r e d i v i d e d i n t o low ( 0 . 0 - 0 . 0 5 p p b ) , medium ( 0 . 0 5 - 1 ppb) and h i g h

(> 1 ppb) l e v e l s o f DBCP i n the d r i n k i n g w a t e r . The c o h o r t s were
examined f o r those c a n c e r s seen i n a n i m a l s which a r e a s s o c i a t e d w i t h
I n g e s t i o n o f DBCP, namely c a n c e r s o f the stomach, e s o p h a g u s , 11 v e r ,
k i d n e y and female b r e a s t . I n c i d e n c e s o f lymphoid leukemia were a l s o
I n c l u d e d because o f a n e c d o t a l r e p o r t s o f t h i s k i n d o f c a n c e r i n the
exposed p o p u l a t i o n . The r e s u l t s o f the s t u d i e s r e v e a l e d a s t a t i s t i -
c a l t r e n d (JD < 0.005) i n male stomach c a n c e r deaths w i t h i n c r e a s i n g
DBCP c o n c e n t r a t i o n s 1n d r i n k i n g water by census t r a c t . A weaker
t r e n d was seen w i t h kidney c a n c e r 1n females ( < 0.01) and l y m p h o i d
leukemia i n males (p < 0 . 0 1 ) .
The r e s u l t s o f t h i s e p i d e m i o l o g i c a l s t u d y , m u s t be regarded
with c a u t i o n . One p l a u s i b l e e x p l a n a t i o n i s t h a t DBCP does t r u l y i n -
c r e a s e the r a t e o f stomach c a n c e r and o t h e r c a n c e r s . However, o t h e r
v a r i a b l e s may be r e s p o n s i b l e . The census t r a c t s c o n t a i n i n g h i g h
l e v e l s o f DBCP w e r e m o r e r u r a l , m o r e H i s p a n i c a n d o f lower
socioeconomic s t a t u s t h a n w e r e t h e l o w DBCP t r a c t s . Low
s o c i o e c o n o m i c s t a t u s has been a s s o c i a t e d w i t h gastrointestinal
c a n c e r s b u t n o t lymphoid l e u k e m i a . Mexican-American e t h n i c i t y may
be a r i s k f a c t o r i n stomach c a n c e r s . Other common r i s k f a c t o r s such
a s s m o k i n g and a l c o h o l consumption s h o u l d be c o n s i d e r e d . In a d d i -
t i o n , p e r s o n s l i v i n g i n r u r a l a r e a s may have more exposure to o t h e r
p e s t i c i d e s some o f which a r e c a r c i n o g e n i c .
Another i m p o r t a n t s o i l f u m l g a n t i s e t h y l e n e d i b r o m i d e (EDB) and
t h e u s e o f t h i s c h e m i c a l was s u s p e n d e d i n s e v e r a l c o u n t i e s 1n
C e n t r a l C a l i f o r n i a when contaminated d o m e s t i c w e l l s were e n c o u n t e r e d
i n the San J o a q u i n V a l l e y . L a t e r i t was banned n a t i o n a l l y by EPA a s
a s o i l fumigant. L e v e l s i n C a l i f o r n i a w a t e r - w e l l s ranged from 70 t o
4800 p p t ( 1 5 , 1 8 ) . S t u d i e s i n a n i m a l s I n d i c a t e t h a t i s has a
similar toxiclogical profile to DBCP. The C a l i f o r n i a State
Department o f H e a l t h S e r v i c e s has recommended t h a t p e r s o n s w i t h EDB-
c o n t a m i n a t e d w e l l s s w i t c h to o t h e r d r i n k i n g w a t e r s u p p l i e s . The
a v a i l a b l e I n f o r m a t i o n on the t o x i c o l o g y o f EDB has been e x t e n s i v e l y
summarized b o t h by the I n t e r n a t i o n a l Agency f o r R e s e a r c h on C a n c e r
( 1 6 ) a n d m o r e r e c e n t l y by t h e O c c u p a t i o n a l S a f e t y and H e a l t h
n i s t r a t i on (0SHA) as a n o t i c e o f proposed r u l e making f o r an o c
cupational workplace exposure c r i t e r i o n (17) and by a l s o the
C a l i f o r n i a Department o f H e a l t h S e r v i c e s a s a basTi" o f r e c o m m e n d i n g
an a m b i e n t a i r s t a n d a r d ( 1 8 ) . In both mice and r a t s g i v e n EDB by

gavage, doses a s low a s 60 mg7kg/day f o r mice and 40 m g / k g / d a y f o r
r a t s r e s u l t e d i n squamous c e l l carcinomas o f the f o r e s t o m a c h which
began to appear e a r l y i n the s t u d i e s . The female r a t s a l s o had s i g
n i f i c a n t increases i n hepatocellular carcinomas. Both sexes o f mice
had s t a t i s i c a l l y s i g n i f i c a n t i n c r e a s e s i n a l v e o l a r / b r o n c h i o l a r
adenomas and t h e r e were s i g n i f i c a n t i n c r e a s e s i n hemangiosarcomas i n
the male r a t s . S i m i l a r i n c i d e n c e s o f c a n c e r were seen w i t h r a t s and
mice i n inhalation studies. T e s t i c u l a r d e g e n e r a t i o n was a l s o seen
i n the male a n i m a l s i n these s t u d i e s . EDB w a s a l s o shown t o be
mutagenic i n s e v e r a l i n v i v o and i n v i t r o s y s t e m s . No e p i d e m i o l o g i
c a l s t u d i e s a r e r e p o r t e d on p e r s o n s e x p o s e d t o d r i n k i n g water
c o n t a i n i n g EDB. In one p u b l i s h e d e p i d e m i o l o g i c a l r e p o r t i n v o l v i n g
161 workers o c c u p a t i o n a l l y exposed t o EDB i t was c o n c l u d e d t h a t t h e
s t u d y c a n n e i t h e r r u l e o u t nor e s t a b l i s h EDB as a human c a r c i n o g e n
because o f the small s i z e o f the p o p u l a t i o n s t u d i e d .
R i s k assessments conducted on the b a s i s o f animal s t u d i e s e s

t i m a t e a l i f e t i m e e x c e s s c a n c e r r i s k from i n h a l a t i o n exposure to EDB
t o r a n g e f r o m 0 . 0 6 to 67 p e r 1000 f o r 0 . 1 ppm and 160 t o 1000 p e r
1000 f o r 20 ppm depending upon the r i s k a s s e s s m e n t models used ( 1 7 ,
18).
One s u b s t i t u t e f o r DBCP i s 1 , 2 - d i c h l o r o p r o p a n e ( 1 , 2 - D ) . This

c o m p o u n d h a s b e e n f o u n d i n s e v e r a l w e l l s i n the extreme N o r t h e r n
p a r t o f C a l i f o r n i a a n d a l s o i n an a r e a b e t w e e n F r e s n o a n d
Bakersfield. In p a r t i c u l a r , 1,2-D has been found i n a r e a s where the
water table i s shallow. U s u a l l y the c o n c e n t r a t i o n s a r e a r o u n d 0 . 1
t o 5 p p b b u t l e v e l s a s high a s 30 ppb have been e n c o u n t e r e d ( 1 9 ) .
S t u d i e s sponsored by the N a t i o n a l T o x i c o l o g y Program have I n d i c a t e d
possible c a r c i n o g e n i c a c t i v i t y 1n l a b o r a t o r y a n i m a l s ( 2 0 ) . The
m a n u f a c t u r e r o f 1,2-D has v o l u n t a r i l y withdrawn D-D, the f o r m u l a t i o n
t h a t c o n t a i n s 1,2-D, from s a l e i n C a l i f o r n i a .
Insecticides
T h e o n l y p r i m a r i l y i n s e c t i c i d a l chemical a r i s i n g from a g r i c u l t u r a l
use which has b e e n e n c o u n t e r e d i n C a l i f o r n i a groundwater is
aldicarb. L e v e l s o f 6 to 26 ppb have been r e p o r t e d i n some w e l l s i n
N o r t h e r n c o u n t i e s o f the s t a t e ( 2 1 ) . The presence o f a l d i c a r b i s a
p r o b l e m i n many o t h e r p a r t s o f t h e c o u n t r y a n d i t s f a t e i n
groundwater i s d i s c u s s e d i n the s e c t i o n o f t h i s s y m p o s i u m dealing
w i t h f i e l d monitoring. The chemical s t r u c t u r e o f a l d i c a r b 1s shown
below.
CH
I II
CH -S-C-CH=N-0-C-NHCH
H 3
Aldicarb
T h e t o x i c o l o g y o f t h i s compound has been summarized by the

N a t i o n a l Academy o f S c i e n c e s / N a t i o n a l R e s e a r c h C o u n c i l ( 2 2 ) a n d by
t h e W o r l d H e a l t h O r g a n i z a t i o n E x p e r t Group on P e s t i c c l R e s i d u e s
(23). The main concern a b o u t t h i s compound i s i t s very h i g h acute
23. BE RTE AU A N D SPATH Pesticide Contamination in California Ground Water 431
toxicity. I t i s a p o t e n t c h o l i n e s te r a s e i n h i b i t o r w i t h an LD50 to
the r a t o f l e s s than 1 mg/kg. However, the compound h a s n o t b e e n
r e p o r t e d t o d i s p l a y a n y a d v e r s e l o n g term e f f e c t s a t s u b - l e t h a l
doses. I t i s n o t c a r c i n o g e n i c , t e r a t o g e n i c , nor does i t d i s p l a y any
a d v e r s e e f f e c t s on r e p r o d u c t i o n i n a t h r e e - g e n e r a t i o n f e e d i n g s t u d y .
Based on s t u d i e s conducted w i t h r a t s a n d d o g s , the World Health
O r g a n i z a t i o n e s t a b l i s h e d an a c c e p t a b l e d a i l y i n t a k e (ADI) o f 0.005
mg/kg f o r a l d i c a r b ( 2 3 ) .
T h e N a t i o n a l A c a d e m y o f S c i e n c e / N a t i o n a l Research C o u n c i l
-
(NAS/NRC) g i v e s a suggested no a d v e r s e response l e v e l (SNARL) for

aldicarb i n d r i n k i n g water o f 7 ppb ( 2 2 ) . The USA E n v i r o n m e n t a l
P r o t e c t i o n Agency (EPA) has recommended a~ealth a d v i s o r y l e v e l of
10 p p b . The C a l i f o r n i a Department o f H e a l t h S e r v i c e s has adopted
E P A ' s l i m i t a s an a c t i o n l e v e l ( 2 4 ) .
Herbicides
The t r i a z i n e h e r b i c i d e s , a t r a z i n e and s i m a z i n e have r e c e n t l y been

e n c o u n t e r e d i n g r o u n d w a t e r i n N o r t h e r n C a l i f o r n i a and i n the Los
A n g e l e s B a s i n a t l e v e l s r a n g i n g f r o m 0 . 4 t o 2 . 0 ppb ( 2 5 . ) The
c h e m i c a l s t r u c t u r e s o f these two compounds a r e shown below:
CI
Simazine
The t o x i c o l o g y o f these compounds has been s u m m a r i z e d by t h e

National Academy o f S c i e n c e s / N a t i o n a l Research Council (26).
A t r a z i n e i s s l i g h t l y t o x i c when g i v e n i n s i n g l e o r a l d o s e s t o rats
and s i m a z i n e i s p r a c t i c a l l y n o n - t o x i c under the same c o n d i t i o n s .
The compounds have been s u b m i t t e d to t e s t s f o r c a r c i n o g e n i c i t y to
m i c e a t t h e h i g h e s t t o l e r a t e d doses and were determined n o t to be

t u m o r i g e n i c under the c o n d i t i o n s o f the t e s t s . S i m a z i n e a t 50 a n d
100 ppb i n the r a t had no a d v e r s e e f f e c t s on r e p r o d u c t i o n o f r a t s o r
t h e i r o f f s p r i n g o v e r three g e n e r a t i o n s . The NAS/NRC r e c o m m e n d s a n
a c c e p t a b l e d a i l y i n t a k e o f 0.0215 mg/kg and 0.215 mg/kg f o r a t r a z i n e
and s i m a z i n e r e s p e c t i v e l y . Recommended l e v e l s i n d r i n k i n g water a r e
7 . 5 ppb f o r a t r a z i n e and 75.25 ppb f o r s i m a z i n e .
Fungicides
T h e o c c u r r e n c e o f the wood p r e s e r v a t i v e p e n t a c h l o r o p h e n o l ( P C P ) , i n
groundwater 1s thought to a r i s e from the m a n u f a c t u r i n g p r o c e s s i n -
v o l v i n g treatment o f p o l e s . The chemical s t r u c t u r e 1s shown below
OH
CI
CI
P e n t a c h l o r o p h e n o l (PCP)
PCP i s a h i g h l y t o x i c compound p r o d u c i n g a v a r i e t y o f t o x i c e f f e c t s ,
I n p a r t i c u l a r h i s t o p a t h o l o g l c a l changes i n the l i v e r . The compound
contains impurities of chlorinated d i b e n z o d i o x l n s , but recently
m a n u f a c t u r e d b a t c h e s do n o t have d e t e c t a b l e l e v e l s o f the h l q h l y
toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin. F o r c h e m i c a l l y p u r e PCP
a no e f f e c t l e v e l o f 3 mg/kg7day was e s t i m a t e d i n the r a t . The
NAS/NRC recommend an ADI o f 0.003 mg/kg and a suggested no a d v e r s e
e f f e c t l e v e l i n d r i n k i n g w a t e r o f 21 ppb ( 2 7 ) .
Another c l a s s o f f u n g i c i d e s r e c e n t l y e n c o u n t e r e d 1n groundwater
a r e t h e e t h y l e n e - b 1 s - d i t h i o c a r b a m a t e s (EBDC's) ( 2 8 ) . These com-
pounds a r e o f t e n s a l t s o f m e t a l s a n d t h e n a m e s a n d c h e m i c a l
s t r u c t u r e s o f some o f them a r e shown:
CH - NH - C - S-Na CH 2 - NH - C - S,
CH.L - NH - C -
II
s
Nabam Maneb
CH,
S
CH.
Ethylenethiourea
23. BE RTE AU AND SPATH Pesticide Contamination in California Ground Water 433
The main t o x i c o l o g i c a l concern a b o u t t h i s c l a s s o f compounds i s

t h e i r b r e a k d o w n to the g o i t r o g e n e t h y l e n e t h i o u r e a ( E T U ) , a p o t e n t
animal c a r c i n o g e n ( 2 9 ) . T e s t i n g f o r ETU i n groundwater i s p r e s e n t l y
being conducted.
Conclusions
An a t t e m p t h a s b e e n made to g i v e an overview o f the s i g n i f i c a n t

t o x i c o l o g i c a l and e p i d e m i o l o g i c a l e f f e c t s t h a t have b e e n reported
f r o m those p e s t i c i d e s which a r e b e i n g e n c o u n t e r e d i n groundwater i n
California. A l t h o u g h a r e l a t i v e l y l a r g e number o f p e s t i c i d e s have
been r e p o r t e d , o n l y a few a r e o c c u r r i n g to such an e x t e n t t h a t t h e i r
e f f e c t s w a r r a n t c o n s i d e r a t i o n from a t o x i c o l o g i c a l p o i n t o f v i e w .
T h e f u m i g a n t s DBCP and EDB comprise by f a r the major p a r t o f the
problem i n C a l i f o r n i a and i t i s p r o b a b l y the o c c u r r e n c e o f these two
c o m p o u n d s t h a t r e p r e s e n t s the g r e a t e s t concern to human h e a l t h .
Both a r e p o t e n t r e p r o d u c t i v e t o x i n s and the e v i d e n c e f o r t h e i r b e i n g

c a r c i n o g e n i c i s overwhelming. The e p i d e m i o l o g i c a l study conducted
i n Fresno county i n census t r a c t s c o n t a i n i n g a p p r e c i a b l e l e v e l s o f
DBCP i s s u g g e s t i v e b u t more data need to be g e n e r a t e d b e f o r e i t can
be c o n f i r m e d o r r e f u t e d t h a t DBCP i n w e l l - w a t e r has been r e s p o n s i b l e
f o r i n c r e a s e d human c a n c e r d e a t h s .
Literature Cited
1. Groundwater Contamination by Pesticides. California State Water
Resources Control Board, Publication No. 83-45 sp, 1983.
2. Cohen, D.B., and Bowers, G.W. Water Quality and Pesticides: A
California Risk Assessment Program (Vol. 1), State Water
Resources Control Board, Toxic Substances Control Program,
Sacramento, CA, November, 1984.
3. Gaston, J.M. to Williams, M. Letter from Sanitary Engineering
Branch, California Department of Health Services to Special
Pesticides Review Division, U.S. Environmental Protection
Agency, May 31, 1979.
4. Burlinson, N . E . ; Lee, L.A.; Rosenblatt, D.H. Environ. Sci.
Technol. 1982, 16, 627-632.
5. Torkelson, T.R.; Sadek, S . E . ; Rowe, V . K . ; Kodama, J.F.;
Anderson, H.H.; Loquvam, C.S.; Hine, C.H. Toxicol. Appl.
Pharmacol. 1961, 3, 545-559.
6. Emergency Temporary Standard for Occupational Exposure to 1,2-
Dibromo-3-chloropropane (DBCP); Hearing. Federal Register 1977,
42 (175), 45536-45543.
7. Whorton, D.; Krauss, R.M.; Marshall, S.; Milby, T.H. Lancet
1977, ii, 1259-1261.
8. Kapp, R.W.; Picciano, D.J.; Jacobson, C.B. Mutat. Res. 1979, 64,
47-51.
9. Evaluation of the Carcinogenic Risk of Chemicals to Humans, Vol.

20. Some Halogenated Hydrocarbons. International Agency for
Research on Cancer, Lyon, France, 1979, pp. 83-96.
10. Bioassay of Dibromochloropropane for Possible Carcinogenicity
(Carcinogenesis Technical Report Series, No. 28), National
Cancer Institute, 78-828, 1978.
11. Dibromochloropropane (DBCP): Final position document. Special
Pesticides Review Division, Office of Pesticide Programs, U.S.
Environmental Protection Agency, September, 1978.
12. Van Duuren, B.L.; Goldschmidt, B.M.; Loewengart, G.; Smith,
A.C.; Melchionne, S.; Selman, I.; Roth, D. J. Natl. Cancer Inst.
1979, 63, 1433-1439.
13. Carcinogen Assessment Group (E.P.A.) review of risk assessment

for DBCP in drinking water in a memo to Jeff Kempter, Special
Pesticides Review Division, U.S. Environmental Protection
Agency, June, 1979.
14. Jackson, R.J.; Greene, C.J.; Thomas, J.T.; Murphy, E.L.; Kaldor,
J. Literature Review on the Toxicological Aspects of DBCP and
An Epidemiological Comparison of Patterns of DBCP Drinking Water
Contamination with Mortality Rates from Selected Cancers in
Fresno County, 1970-1979. Unpublished report to the California
Department of Food and Agriculture from the California
Department of Health Services, June 1, 1982.
15. Smith, C.; Margetich, S.; Fredrickson, A.S. A Survey of Well-
-Water in Selected Counties of California for Contamination by
EDB in 1983. Unpublished report from the California Department
of Food and Agriculture, HS-1123, September 12, 1983.
16. Evaluation of the Carcinogenic Risk of Chemicals to Humans.
Vol. 15. Some Fumigants, the Herbicides 2,4-D and 2,4,5-T,
Chlorinated Dibenzodioxins and Miscellaneous Industrial
Chemicals. International Agency for Research on Cancer, Lyon,
France, 1977, pp. 195-209.
17. Occupational Exposure to Ethylene Dibromide; Notice of Proposed
Rulemaking. Federal Register 1983, 48 (196) 45956-46003.
18. Health Effects of Ethylene Dibromide (EDB). Unpublished report
prepared by the California Department of Health Services, April
15, 1984, 25 pp.
19. Organic Quality of Groundwater in the Fruitvale Area, Kern
County. Unpublished report prepared by the Sanitary Engineering
Branch, California Department of Health Services, January, 1984.
23. E RTE AU AND SPATH Pesticide Contamination in California Ground Wate
20. NTP Technical Report on the Carcinogenesis Bioassay of 1,2-

Dichloropropane (propylene dichloride) in F3441N rats and B6C3F1
mice. National Toxicology Program. Draft Report, February 28,
1983.
21. Klant, R.R. Unpublished information from the California

Regional Water Quality Control Board, North Coast Region, June
17, 1983.
22. "Drinking Water and Health" Vol. 5. Toxicity of Selected

Contaminants, Aldicarb. National Academy Press, 1983, pp. 10-
12.
23. Pesticide Residues in Food, Evaluations 1982. Report of the
Joint Meeting of the FAO Panel of Experts on Pesticide Residues
in Food and the Environment and the WHO Expert Group on
Pesticide Residues, Rome, 1983, pp. 7-15.
24. Spath, D. to Rogers, P. Aldicarb "Action Level". Internal

Memorandum from Sanitary Engineering Branch, California
Department of Health Services, July 25, 1983.
25. Sturm, G., personal communication. Sanitary Engineering Branch,
California Department of Health Services, September, 1984.
26. "Drinking Water and Health" Vol. 4. Organic Solutes, Triazines.
National Academy of Sciences, 1977, pp. 533-537.
27. "Drinking Water and Health" Vol. 4. Organic Solutes,
Pentachlorophenol. National Academy of Sciences, 1977, pp. 750-
753.
28. Bowen, C., personal communication, Sanitary Engineering Branch,
California Department of Health Services, February, 1985.
29. "Drinking Water and Health" Vol. 4. Organic Solutes,
Pesticides: Fungicides, Dithiocarbamates. National Academy of
Sciences, 1977, pp. 650-657.
RECEIVED March 25, 1986
24
Safety Evaluation of Pesticides in Ground Water
D. D. Sumner and J. T. Stevens
Agricultural Division, CIBA-GEIGY Corporation, Greensboro, NC 27419
As tbe sensitivity of analytical methods increases, more

instances of pesticide detection in groundwater will occur. In
order to avoid a series of crisis situations, it is necessary
that standardized procedures for the identification of safe
levels of chemicals in groundwater be established. The same

basic principles used to establish safe levels in food, can be
used to establish safe levels in groundwater. Some methods used
to establish acceptable levels in groundwater are discussed. The
setting of acceptable levels at zero or limits of detection,
should be avoided since practical considerations preclude these
approaches.
The p r e s e n c e o f c h e m i c a l s i n groundwater has become a prominent
and e m o t i o n a l i s s u e . I n t h e past few y e a r s , few i s s u e s have
produced t h e e m o t i o n a l r e s p o n s e s t h a t accompany groundwater contam-
ination. T h i s r e s p o n s e seems i n t e n s i f i e d when t h e c h e m i c a l which
c o n t a m i n a t e s the water i s a p e s t i c i d e [ 1 ] .
Many s c i e n t i f i c and r e g u l a t o r y b o d i e s have c o n s i d e r e d t h e

q u e s t i o n o f groundwater and c h e m i c a l s , and an even g r e a t e r number
are c u r r e n t l y c o n s i d e r i n g t h i s i s s u e . F e d e r a l a g e n c i e s under
s e v e r a l s t a t u e s [2, 3, 4, 5] and s e v e r a l s t a t e r e g u l a t o r y o r l e g i s -
l a t i v e b o d i e s [6, 7, 8, 9] a r e a c t i v e l y i n v e s t i g a t i n g groundwater
q u a l i t y and s t a n d a r d s . I n d u s t r y as w e l l as e n v i r o n m e n t a l groups
are a c t i v e i n d i r e c t i n g a t t e n t i o n t o groundwater.
A l t h o u g h t h e r e i s u n i f o r m i t y i n t h e i n t e r e s t i n groundwater,
c o n s i d e r a b l e d i f f e r e n c e s e x i s t among t h e r e s p e c t i v e groups i n
t h e i r approaches t o s e t t i n g a c c e p t a b l e l i m i t s f o r c h e m i c a l s i n
groundwater. Some groups want no a c c e p t a b l e l e v e l s f o r any
c h e m i c a l i n groundwater, w h i l e o t h e r groups want t o s e t s t a n d a r d s
which ensure s a f e t y o f t h e water [6, 7, 10, 1 1 ] . The l a t t e r a r e
t y p i f i e d by t h e Maximum Contaminant L e v e l s (MCL's) s e t by the EPA
O f f i c e o f D r i n k i n g Water (ODW), which a r e l e g a l l y e n f o r c e a b l e
standards.
0097-6156/ 86/ 0315-0436506.00/ 0

24. SUMNER AND STEVENS Safety Evaluation of Pesticides 437
As d i s c u s s e d w i t h i n t h i s symposium, i t i s not p o s s i b l e to keep a l l

c h e m i c a l s out o f groundwater. As l i m i t s o f d e t e c t i o n are reduced
more c h e m i c a l s w i l l be d e t e c t e d . C l e a r l y t h e r e are many d i f f e r e n t
c h e m i c a l s i n our p o t a b l e water. Some are i n t e n t i o n a l l y i n t r o d u c e d ,
such as c h l o r i n e or f l u o r i d e s a l t s ; some are n a t u r a l p r o d u c t s ; some
are u n i n t e n t i o n a l l y p r e s e n t , such as pathogens, i n d u s t r i a l
c h e m i c a l s , p h a r m a c e u t i c a l s , and p e s t i c i d e s ; and some are s y n t h e -
s i z e d i n s i t u , such as c h l o r o f o r m . A l t h o u g h c l e a r documentation o f
a d v e r s e e f f e c t s i s not common, e p i d e m i o l o g i c a l i m p l i c a t i o n s o f
water q u a l i t y e f f e c t s have been r e p o r t e d [ 1 2 ] . The p r e s e n t paper
w i l l address q u e s t i o n s c o n c e r n i n g the s a f e t y of p e s t i c i d e s i n
groundwater from the p e r s p e c t i v e of human h e a l t h .
S e v e r a l f a c t o r s c o n t r i b u t e to the a t t e n t i o n c u r r e n t l y g i v e n t o
p e s t i c i d e s i n groundwater. One of the most important f a c t o r s i s
the p r o g r e s s which has been made i n a n a l y t i c a l methodology. In the
'oO's, methods were a v a i l a b l e to measure m a t e r i a l s i n the p a r t s per

m i l l i o n (ppm) range. In the '80's, i t i s not uncommon to have
methods which can d e t e c t some m a t e r i a l s i n the p a r t s per t r i l l i o n
( p p t ) range. T h i s c o n s t i t u t e s a one m i l l i o n - f o l d i n c r e a s e i n
sensitivity.
An a d d i t i o n a l f a c t o r c o n t r i b u t i n g to the p r o l i f e r a t i o n o f r e p o r t s
on p e s t i c i d e c o n t a m i n a t i o n o f groundwater i s ease o f p e s t i c i d e
analysis. P e s t i c i d e s are a p r e d e f i n e d a n a l y t i c a l t a r g e t . Federal
r e g u l a t i o n s [2] r e q u i r e the development o f d e f i n e d a n a l y t i c a l
methods which make i d e n t i f i c a t i o n e a s i e r than many o t h e r m a t e r i a l s ,
e s p e c i a l l y natural products. F i n a l l y , the c u r r e n t i n t e r e s t i n
p e s t i c i d e s i n groundwater p r o b a b l y f o c u s e s e f f o r t s which may other-
wise have been d i r e c t e d to o t h e r c h e m i c a l s .
The r e a c t i o n to the p r e s e n c e o f p e s t i c i d e s i n groundwater i s a l s o

i n f l u e n c e d by a m u l t i p l i c i t y o f f a c t o r s . In a d d i t i o n to the
p o t e n t i a l t o x i c i t y o f the m a t e r i a l s or t h e i r p o t e n t i a l e n v i r o n -
m e n t a l e f f e c t s , e m o t i o n a l f a c t o r s seem to c o n t r i b u t e to the
negative response.
F o r example, s i m a z i n e i s i n v o l v e d i n a groundwater i s s u e . Simazine

has an L D b U o f a p p r o x i m a t e l y 5,000 mg/kg [ 1 3 ] . This i s less
a c u t e l y t o x i c than t a b l e s a l t , which has an L D ^ Q o f a p p r o x i m a t e l y
4,000 mg/kg [14], Simazine can be f e d i n the d i e t s o f r o d e n t s f o r
t h e i r l i f e t i m e at 3,000 ppm w i t h o u t any remarkable e f f e c t [15] or
a d m i n i s t e r e d d a i l y at 215 mg/kg/day i n an N a t i o n a l Cancer I n s t i t u t e
(NCI) b i o a s s a y w i t h o u t o n c o g e n i c e f f e c t [ 1 6 ] .
Simazine has r e c e i v e d c o n s i d e r a b l e n o t o r i e t y based upon the f i n d i n g

o f l e v e l s e q u a l t o or l e s s than 3.5 ppb i n s i x out o f 217 w e l l s
e v a l u a t e d i n a study i n C a l i f o r n i a [ 1 7 ] . These s i x w e l l s are
suspected of being point source contaminations [18]. Based upon
the t o x i c i t y d a t a and i t s use i n a l g a e and weed c o n t r o l i n ponds,
s i m a z i n e has a p o t a b l e water t o l e r a n c e o f 10 ppb. I t has a
Suggested No Adverse Response L e v e l [SNARL] e s t a b l i s h e d by the
N a t i o n a l Academy o f S c i e n c e s o f 1,500 ppb. However, because o f the
n o t o r i e t y a s s o c i a t e d with the f i n d i n g s i n the s i x w e l l s , there i s a

move t o r e s t r i c t the product from use on sand and loamy sand s o i l s
[19].
G i v e n t h e e m o t i o n a l i s m aroused by p e s t i c i d e s found i n groundwater,

i t i s d i f f i c u l t t o propose an a c c e p t a b l e s o l u t i o n t o t h e dilemma.
Furthermore, c o n s i d e r i n g the c o m p l e x i t i e s o f the issues i n v o l v e d ,
i t would be presumptuous t o t r y t o a d d r e s s a l l i s s u e s and p o s s i b l e
r e s o l u t i o n s i n a s i n g l e paper. I n s t e a d our d i s c u s s i o n w i l l focus
on some o f t h e approaches t h a t have been t a k e n o r a r e b e i n g taken
to c o n s i d e r the v i t a l q u e s t i o n o f e s t a b l i s h i n g s a f e / a c c e p t a b l e
l i m i t s o f p e s t i c i d e l e v e l s i n groundwater.
The importance o f s e t t i n g a c c e p t a b l e l i m i t s f o r p e s t i c i d e s i n
groundwater cannot be u n d e r e s t i m a t e d . W i t h t h e s e n s i t i v i t y o f
c u r r e n t methods and t h e e x p a n s i o n o f m o n i t o r i n g e f f o r t s , i n s t a n c e s
o f p e s t i c i d e d e t e c t i o n i n water a r e i n e v i t a b l e . Each o f these

i n s t a n c e s w i l l p r e c i p i t a t e a c r i s i s i f t h e a n a l y t i c a l v a l u e s cannot
be p l a c e d i n p e r s p e c t i v e w i t h r e g a r d t o r e l a t i v e h a z a r d .
In t h e absence o f a c c e p t a b l e l i m i t s , i n s t a n c e s o f d e t e c t i o n c o u l d
be e x p e c t e d t o r e s u l t i n o v e r r e a c t i o n t o t r i v i a l e v e n t s . I f false
alarms o c c u r f r e q u e n t l y , t h e consumer may become complacent and
hazardous s i t u a t i o n s c o u l d be i g n o r e d .
The e s t a b l i s h m e n t o f a c c e p t a b l e l i m i t s i s c r i t i c a l from a l e g a l /
p u b l i c r e l a t i o n s p e r s p e c t i v e as w e l l as from a s a f e t y p e r s p e c t i v e .
S e t t i n g a c c e p t a b l e l i m i t s f o r c h e m i c a l s i n water w i l l reduce the
number o f c r i s i s s i t u a t i o n s and a f f o r d o p p o r t u n i t i e s f o r o r d e r l y
d e c i s i o n s c o n c e r n i n g water q u a l i t y and s a f e t y . Hence, i t i s a p p r o -
p r i a t e t o g i v e c o n s i d e r a t i o n t o some o f t h e contemporary approaches
f o r t h e e s t a b l i s h m e n t o f these s a f e l i m i t s .
The N a t i o n a l Academy o f S c i e n c e s (NAS) a d d r e s s e d t h e groundwater

i s s u e i n r e s p o n s e t o t h e Safe D r i n k i n g Water A c t o f 1974 [ 4 ] . The
NAS e x a m i n a t i o n [20] d e a l t w i t h a broad spectrum o f p o s s i b l e
m a t e r i a l s i n c l u d i n g m i c r o b i a l , i n o r g a n i c , o r g a n i c , and r a d i o -
n u c l e o t i d e contaminants; s e v e r a l p e s t i c i d e s i n c l u d e d .
The NAS used t o x i c o l o g y d a t a t o e s t a b l i s h an A c c e p t a b l e D a i l y

Intake (ADl) f o r each o f t h e m a t e r i a l s c o n s i d e r e d . The ADI was
e s t a b l i s h e d u s i n g t h e N o - O b s e r v e d - E f f e c t l e v e l (NOEL) from a n i m a l
s t u d i e s and a s e r i e s o f S a f e t y F a c t o r s r a n g i n g from 10 t o 1,000
depending upon t h e d u r a t i o n o f animal t o x i c i t y s t u d i e s and t h e
nature o f the t o x i c e f f e c t s . F o r oncogens t h e NAS recommended
c o n s i d e r a t i o n o f t h e M u l t i - S t a g e model o f c a r c i n o g e n e s i s . I f the
d a t a a v a i l a b l e were n o t s u f f i c i e n t f o r use o f t h e M u l t i - S t a g e
Model, then t h e One-Hit Model was s u g g e s t e d .
The NAS used t h e ADI t o e s t a b l i s h an a c c e p t a b l e maximum l i m i t

d e s i g n a t e d t h e Suggested No Adverse Response L e v e l (SNARL). The
NAS assumed 20% o f t h e ADI was a v a i l a b l e f o r water c o n t r i b u t i o n
( r e s e r v i n g 80% f o r o t h e r s o u r c e s ) . C a l c u l a t i o n o f the SNARL was

based upon a 70 kg person d r i n k i n g two l i t e r s per day.
NAS SNARL = NOEL (mg/kg/day) SF X 20% 2L/day X 70 kg
The p r o c e d u r e s u t i l i z e d by the NAS i n e s t a b l i s h i n g S a f e t y F a c t o r s

and e v a l u a t i n g the animal d a t a are e s s e n t i a l l y e q u i v a l e n t to the
c u r r e n t s t a n d a r d s [ 2 1 ] , The suggested use o f the M u l t i - S t a g e Model
i s f u r t h e r c o m p a t i b l e w i t h l a t e r recommendations [22, 23]. The NAS
l i m i t e d i t s c o n s i d e r a t i o n o n l y t o p u b l i s h e d d a t a , r e a s o n i n g the
p u b l i s h e d d a t a has undergone peer r e v i e w . However, i n the case o f
p e s t i c i d e s most o f the d a t a r e s i d e s i n c o r p o r a t e and EPA f i l e s and
not i n the l i t e r a t u r e . The r e s t r i c t e d database thus i s a weakness
and a l i m i t i n g f a c t o r a s s o c i a t e d w i t h the NAS approach. Several
s o u r c e s [24, 25] have recommended t h a t a l l a v a i l a b l e d a t a be used
i n s a f e t y e v a l u a t i o n . A l t h o u g h not a l l o f these d a t a w i l l have
been p u b l i s h e d , the d a t a w i l l have undergone r e g u l a t o r y r e v i e w .
F o r t u n a t e l y , o t h e r groups have c o n s i d e r e d an expanded d a t a b a s e .

The N a t i o n a l A g r i c u l t u r a l Chemical A s s o c i a t i o n (NACA) e s t a b l i s h e d a
committee to l o o k i n t o groundwater i s s u e s i n 1983. That committee
made recommendations s i m i l a r t o but not i d e n t i c a l w i t h the NAS
procedures. The NACA committee recommended u s i n g the e x i s i t i n g
database w i t h i n EPA. The database r e q u i r e d f o r p e s t i c i d e s i s v e r y
e x t e n s i v e ( T a b l e I ) and p r o v i d e s c o n s i d e r a b l e i n f o r m a t i o n upon
which to d e v e l o p a s a f e t y e v a l u a t i o n .
T a b l e I. A Partial List o f P e s t i c i d e Data Requirements
Standard Acute S t u d i e s K i n e t i c s of Environmental

90-Day S t u d i e s i n Rats Degradation
1-Year S t u d i e s i n Dogs M o b i l i t y i n the Environment
Teratology i n 2 Species P o t e n t i a l for Bioaccumulation
L i f e t i m e Feeding Studies Avian Acute T o x i c i t y
i n 2 Species Avian Reproductive E f f e c t s
M u l t i g e n e r a t i o n Reproduction A v i a n Acute T o x i c i t y
Studies A q u a t i c C h r o n i c and
Metabolism i n P l a n t s , Reproduction E f f e c t s
A n i m a l s , and S o i l Marine E f f e c t s
Residue D e t e r m i n a t i o n s i n Aquatic Vegetation
Food and Nonfood T o x i c i t y on Earthworms, Bees,
Methods t o Determine and Other B e n e f i c i a l
Residues Invertebrates
In f a c t , p e s t i c i d e s are some o f the most t h o r o u g h l y s t u d i e d

c h e m i c a l s i n our environment. T y p i c a l d a t a needed f o r a food
t o l e r a n c e i n c l u d e : a c u t e , s u b c h r o n i c , r e p r o d u c t i o n , and c h r o n i c ,
as w e l l as o n c o g e n i c i t y , m u t a g e n i c i t y , and e n v i r o n m e n t a l s t u d i e s
[26]. P e s t i c i d e s are unique i n t h a t not o n l y s t u d i e s from the
mammalian h e a l t h p e r s p e c t i v e are completed but a l s o e n v i r o n m e n t a l
i n v e s t i g a t i o n s [27, 28].
I t was the o p i n i o n o f the NACA committee [10] t h a t the e x i s t i n g ADI

e s t a b l i s h e d f o r a l l p r o d u c t s w i t h food t o l e r a n c e s i s adequate t o
e s t a b l i s h maximum s a f e l e v e l s i n groundwater. The ADI e s t a b l i s h e d
by EPA i s based upon the database i n the Agency.
The development o f an ADI i s e s s e n t i a l l y the same i n the NAS proce-

d u r e s , the EPA Food T o l e r a n c e p r o c e d u r e s , and the NACA p r o p o s a l f o r
groundwater. An ADI i s determined by d i v i d i n g the NOEL i n the most
s e n s i t i v e s p e c i e s by a s u i t a b l e S a f e t y F a c t o r ( S F ) . S a f e t y F a c t o r s
f o r s u b c h r o n i c or r e p e a t a d m i n i s t r a t i o n are u s u a l l y 1,000; f o r
c h r o n i c or l i f e t i m e s t u d i e s , 100 i s used. S p e c i e s c o n v e r s i o n s can
be based upon mg/kg, ppm i n the food, or body s u r f a c e a r e a c o n v e r -
s i o n [ 2 9 ] . C u r r e n t l y , non-oncogenic e f f e c t s are c o n s i d e r e d on an
mg/kg b a s i s w i t h o u t attempts to c o r r e c t f o r s p e c i e s d i f f e r e n c e s .
R i s k assessment p r o c e d u r e s f o r oncogenic r i s k employed by the EPA
are based upon s u r f a c e a r e a e x t r a p o l a t i o n s i n an attempt to r e l a t e
to man [ 3 0 ] .
The e s t a b l i s h m e n t o f a maximum a c c e p t a b l e c o n c e n t r a t i o n o f any

c h e m i c a l i n p o t a b l e water s h o u l d not be done i n i s o l a t i o n , but
s h o u l d c o n s i d e r a l l s o u r c e s o f exposure. Intake o f p e s t i c i d e s can
r e s u l t from worker exposure, i n g e s t i o n , and water e x p o s u r e . Work-
r e l a t e d exposure i s time and space l i m i t e d and i s r e s t r i c t e d t o
l i m i t e d p o p u l a t i o n s which are e v a l u a t e d i n s e p a r a t e s t u d i e s and are
not as a l l encompassing as food and water exposure.
I n g e s t i o n o f food i s examined u s i n g T h e o r e t i c a l Maximum R e s i d u e

C o n t r i b u t i o n (TMRC) approach.
The TMRC i s based upon t o l e r a n c e s e s t a b l i s h e d f o r raw a g r i c u l t u r a l

commodities. I t assumes a l l c r o p s are t r e a t e d and t h a t a l l
r e s i d u e s o c c u r at the maximum l e v e l seen i n use s i t u a t i o n s .
T o l e r a n c e s are u s u a l l y s e t at the l i m i t o f a n a l y t i c a l d e t e c t i o n
when r e s i d u e s are not e x p e c t e d to o c c u r . For i n s t a n c e , f r u i t t r e e s
s p r a y e d d u r i n g dormancy w i t h a p r o d u c t t h a t degrades b e f o r e f r u i t
are formed; hence such t o l e r a n c e s i n the f r u i t are m e a n i n g l e s s .
T h e r e f o r e , TMRC g r e a t l y e x a g g e r a t e s p e s t i c i d e i n t a k e .
Market basket surveys have shown a c t u a l r e s i d u e s to be l e s s than

the expected TMRC v a l u e s . F o r most p r o d u c t s the d i e t a r y c o n t r i b u -
t i o n s are l e s s than 10% o f the TMRC. T y p i c a l v a l u e s from the
market basket survey are shown i n T a b l e I I [31, 3 2 ] .
S i n c e the TMRC f o r food r e s i d u e s so v a s t l y exaggerated p e s t i c i d e

i n t a k e , the NACA committee d i d not sponsor t h i s approach i n the
s e t t i n g o f p e s t i c i d e l i m i t s i n water. On the o t h e r hand, they d i d
not want t o i g n o r e the d i e t a r y c o n t r i b u t i o n t o p e s t i c i d e i n t a k e .
The d i e t a r y c o n t r i b u t i o n was e v i d e n t l y r e s o l v e d by a d o p t i n g a
d i f f e r e n t model f o r consumption. The NACA committee recom-
mended use o f a 10 kg c h i l d d r i n k i n g one l i t e r o f water per day;
the TMRC was i g n o r e d . T h i s model p r o v i d e s an a d d i t i o n a l 3.5
SUMNER A N D STEVENS Safety Evaluation of Pesticides 441
TABLE I I
R e l a t i o n s h i p o f " T h e o r e t i c a l Intake" to "Actual Intake" o f

Seven P e s t i c i d e s i n t h e D i e t *
Accept- Relation-
Theore- Relationship able ship of
tical Actual of A c t u a l I n - Daily ADI t o
P e s t i c i d e Intake Intake take t o T h e o r e - Intake Actual
mg/day mg/day^ t i c a l Intake mg/day 3
Intake
DDT 6.79 0.029 230:1 0.300 10:1
dicofol 4.45 0.006 740:1 1.500 250:1

dieldrin 0.23 0.006 40:1 0.006 1:1
lindane 9.21 0.003 >1,000:1 0.750 250:1
malathion 12.56 0.008 >1,000:1 1.20 150:1
parathion 1:18 <1.001 >1,000:1 0.300 >300:1
carbaryl 9:50 0.031 300:1 0.600 20:1
C a l c u l a t e d from USA t o l e r a n c e and 9 t h d e c i l e consumption

f i g u r e s minimum f i g u r e s s i n c e s m a l l consumption commodities
are e x c l u d e d . USA t o l e r a n c e s used f o r c a l c u l a t i o n s were those
i n e f f e c t d u r i n g 1964-1970. T o l e r a n c e s f o r DDT and d i e l d r i n
on c e r t a i n commodities were reduced d u r i n g 1968-69; however,
the h i g h e r t o l e r a n c e s were used i n t h e c a l c u l a t i o n s .
^ D i e t a r y Intake o f P e s t i c i d e C h e m i c a l s i n t h e U n i t e d S t a t e s
( I I I ) , R. E . Duggan and P. E . C o r n e l i u s s e n , P e s t i c i d e M o n i t o r -
ing J o u r n a l , _5, No. 4, March, 1972.
3
P e s t i c i d e R e s i d u e s i n Foods - Report o f t h e 1971 J o i n t FAO/WHO
M e e t i n g , FAO A g r i c u l t u r a l S t u d i e s , Number 88. Based on a 60
kilogram i n d i v i d u a l .
*From FAO/WHO Food Standards Program, 1974. [31]
S a f e t y F a c t o r over the 70 kg p e r s o n d r i n k i n g two l i t e r s . The

o r i g i n a l S a f e t y F a c t o r d e t e r m i n a t i o n s by t h e NAS [33] i n c l u d e d
c o n s i d e r a t i o n o f s u s c e p t i b l e p o p u l a t i o n subgroups so c h i l d r e n i n
some r e s p e c t s had a l r e a d y been c o n s i d e r e d . The NACA committee
suggested t h e term H e a l t h A d v i s o r y (HA) f o r the maximum a c c e p t a b l e
pesticide levels.
A
HACA HA - NOEL (mg/kg/day) SF l L / d a y X 10 kg
L i k e w i s e , ODW a t EPA had used the 10 kg c h i l d as a model i n s e t t i n g

MCL's. By t h e i r a d o p t i o n o f t h e model u s i n g a 10 kg p e r s o n d r i n k -
ing one l i t e r p e r day [ 3 4 ] , i t can be deduced t h a t the NACA commit-
tee compensated f o r d i e t a r y c o n t r i b u t i o n by a d o p t i n g 28.5% o f t h e
ADI f o r water, which a f f o r d s a c o n s i d e r a b l e margin o f s a f e t y
c o n s i d e r i n g t h e market b a s k e t survey d a t a ( T a b l e 2 ) .
F o r o n c o g e n i c m a t e r i a l s the NACA committee recommended a c a l c u l a t e d

r i s k o f one i n a m i l l i o n u s i n g t h e M u l t i - S t a g e model. The NACA
committee f u r t h e r i n d i c a t e d t h a t H e a l t h A d v i s o r i e s a r e not i n t e n d e d
to encourage p r a c t i c e s which w i l l r e s u l t i n h e a l t h a d v i s o r y l e v e l s
[10].
R e c e n t l y t h e S t a t e o f W i s c o n s i n has adopted groundwater l e g i s l a t i o n

which i n t r o d u c e s s e v e r a l i n t e r e s t i n g a s p e c t s . The W i s c o n s i n b i l l
[8] e s t a b l i s h e s a b a s i s f o r n u m e r i c a l s t a n d a r d s based upon t o x i c o l -
ogy d a t a and a v o i d s " l i m i t s o f d e t e c t i o n . " R e g u l a t i o n based upon

l i m i t s o f d e t e c t i o n may seem a t t r a c t i v e on the s u r f a c e , but t o x i -
c o l o g y i s independent o f a n a l y t i c a l t e c h n i q u e . At b e s t , " l i m i t o f
d e t e c t i o n " p r o v i d e s l i t t l e r e l e v a n c e t o b i o l o g y ; at worst, i t
rewards s l o p p y o r i n e p t a n a l y t i c a l development.
The W i s c o n s i n b i l l r e c o g n i z e s the p o s s i b i l i t y o f f u t u r e d e v e l o p -
ments. I t r e c o g n i z e s t h e e x i s t e n c e o f p r e s e n t and f u t u r e f e d e r a l
s t a n d a r d s i n c l u d i n g t h e E P A - e s t a b l i s h e d ADI v a l u e s . I t incorpo-
r a t e s p r o v i s i o n s t o a c c e p t t e c h n i c a l advancements i n t o x i c o l o g y o r
a n a l y t i c a l chemistry.
The W i s c o n s i n b i l l i n t r o d u c e s an i n t e r e s t i n g concept c a l l e d t h e
P r e v e n t i v e A c t i o n L i m i t (PAL). C o n c e p t u a l l y , t h i s c a n be
e n v i s i o n e d as some major p o r t i o n o f the enforcement s t a n d a r d which
c o u l d t r i g g e r i n v e s t i g a t i o n s i n t o s o u r c e s f o r groundwater c o n t a m i -
n a t i o n , i . e . , improper d i s p o s a l , p o i n t s o u r c e s , e t c . In p r a c t i c e
i t i s an a d d i t i o n a l s a f e t y f a c t o r s i n c e t h e s t a t e r e g u l a t o r y
r e s p o n s e i s n e a r l y the same whether a s t a n d a r d o r PAL i s exceeded.
Recent r u l e m a k i n g i n New York has a l s o i n t r o d u c e d another concept

[35]. The s t a t e has proposed t h a t f o r o r d i n a r y t o x i c i t y , t h e water
s t a n d a r d s h a l l u t i l i z e c a l c u l a t i o n s based on a 10 kg c h i l d d r i n k i n g
one l i t e r o f w a t e r . But f o r o n c o g e n i c i t y , a 60 kg p e r s o n d r i n k i n g
two l i t e r s p e r day i s used. This i s l o g i c a l since oncogenicity
s t u d i e s a r e based upon l i f e t i m e f e e d i n g s t u d i e s , thus c o v e r i n g t h e
adult period.
In a d d i t i o n , New York has p r o v i d e d a c l a s s i f i c a t i o n mechanism f o r

groundwater so t h a t a q u i f e r s which a r e u n u s a b l e f o r n a t u r a l r e a s o n s
w i l l n o t need as much p r o t e c t i o n as those which a r e u s e f u l .
I t would, o f c o u r s e , be a s u b s t a n t i a l o m i s s i o n not t o mention EPA.

C o n s i d e r a b l e a c t i v i t y i s i n p r o g r e s s , b u t t h i s has been p r e v i o u s l y
d i s c u s s e d by Dr. S t a r a [36] w i t h i n t h i s symposium.
A l t h o u g h i t would be presumptuous t o attempt t o d e f i n e a program t o

r e s o l v e a l l q u e s t i o n s c o n c e r n i n g p e s t i c i d e s i n groundwater, i t i s
p o s s i b l e t o recommend c e r t a i n elements which would appear t o be
n e c e s s a r y f a c t o r s i n any r e s o l u t i o n . Some o f the most important
a s p e c t s seem t o be:
I n o r d e r t o a v o i d a c r i s i s e v e r y time a p e s t i c i d e i s d e t e c t e d ,
maximum a c c e p t a b l e l e v e l s s h o u l d be s e t b e f o r e samples a r e
analyzed.
S a f e t y e v a l u a t i o n s s h o u l d i n c l u d e use o f the e n t i r e d a t a b a s e .
Data i n t h e p u b l i s h e d l i t e r a t u r e and t h a t i n EPA f i l e s s h o u l d
a l l be c o n s i d e r e d . To do o t h e r w i s e , s h o r t changes the p u b l i c
and t h e i n d u s t r y .
A c c e p t a b l e l e v e l s s h o u l d be based wherever p o s s i b l e on t o x i
c o l o g y d a t a , n o t l i m i t s o f d e t e c t i o n . T o x i c i t y i s independent
of a n a l y t i c a l t e c h n i q u e .
Acceptable l e v e l s should consider environmental as w e l l as

mammalian h e a l t h e f f e c t s .
More p u b l i c e d u c a t i o n t o p r o v i d e i n f o r m a t i o n c o n c e r n i n g t h e
b a s i s f o r s e t t i n g containment l e v e l s and t o c o u n t e r a c t
"emotionalism".
Literature Cited
1. Knudson, T., Groundwater Chemicals Cancer Linked, Pes Moines,

Sunday Register, June 16, 1985.
2. Federal Insecticide Fungicides, Rodenticide Act
3. Toxic Substances Control Act.
4. Clean Water Act.
5. Resources Conservation and Recovery Act.
6. Kim, . K. and D. W. Stone, "Organic Chemicals and Drinking
Water". New York State Department of Health, April 1981.
7. State of Florida Statutes, Chapter 487, 1983.
8. State of Wisconsin, Act 410, 1983.
9. State of California, Pending Legislation, Jones AB2133, 1985.
10. "Groundwater Position Paper," National Agricultural Chemicals
Association: Washington, D.C., 1984.
11. "Groundwater Management by Use Classification," Chemical
Manufacturers Association: Washington, D.C., 1983.
12. Davidson, I. W. F., et. al. Chloroform: A Review of its
Metabolism Teratogenic, Mutagenic and Carcinogenic Potential.
Drug and Chem. Toxicol. 1982, 5, 1-87.
13. "Pesticide Reference Standards and Supplemental Data," Office
of Research and Development, US - EPA Research Triangle Park,
NC, 1973.
14. Loomis, T. A. "Essentials of Toxicology" 2nd Ed.; Lea and
Febiger: Philadelphia, 1974.
15. CIBA-GEIGY Corporation, Internal Communications.
16. Innes, J. R. M., et. al. Bioassay of Pesticides and
Industrial Chemicals for Tumorigenicity in Mice. A
Preliminary Note. J . Nat. Cancer Inst. 1969, 42, 1101-1114.
17. Weaver, D. J., et. al. "Pesticide Movement to Groundwater,

Volume I Survey of Groundwater Basins for DBCP, EDA, Simazine
and Carbofuran"; State of California, Department of Food and
Agriculture": Sacramento, CA, 1983.
18. Roux, P., personal communication.
19. "Partially Closed Meeting of FIFRA Science Advisory Panel,"
Federal Register, 50, 25783, EPA, 1985.
20. "Drinking Water and Health Report of the Safe Drinking Water
Committee," National Academy of Sciences - National Research
Council, Washington, 1977.
21. Hayes, A. W. "Principles and Methods of Toxicology"; Raven
Press: New York, 1982.
22. Crump, K. S.; Guess, H. A. "Drinking Water and Cancer: Review
of Recent Findings and Assessment of Risks." Science Research
Systems, Inc.: Ruston, LA., CEQ Contract No. EQ10AC018.
23. Crump, K. S., et. al. Confidence Intervals and Tests of
Hypothesis Concerning Dose Response Relations Inferred from

Animal Carcinogenicity Data, Biometrics 1977, 33, 437.
24. Mantel, N. and W. R. Bryan. "Safety" Testing of Carcinogenic
Agents. J . Nat'l. Cancer Inst. 1961, 27, 455-470.
25. "Chemical Carcinogens: Review of the Science and its
Associated Principles", Office of Science and Technology
Policy, Fed. Reg. 49, 21595-21661, 1984.
26. "Hazard Evaluation Human and Domestic Animals" Pesticide
Assessment Guidelines Subdivision F, EPA, PB, 82-153916, NTIS
1982.
27. "Chemistry; Environmental Fate" Pesticide Assessment
Guidelines Subdivision N, EPA, 83-153973, NTIS, October,
1982.
28. "Hazard Evaluation: Wildlife and Aquatic Organisms PB"
Pesticide Assessment Guidelines Subdivision E, EPA, 83-153908
NTIS, October, 1982.
29. Casarett, L. F.; Doull, J. "Toxicology the Basic Science of
Poisons" 2nd Ed.; Macmillan: New York, 1975.
30. "Report of the Safe Drinking Water Committee," National
Academy of Sciences, National Research Council Drinking Water
and Health Volume 3, Washington, 1980.
31. "Relationship Between Tolerances and Actual Daily Intake of
Pesticides" FAO/WHO Food Standards Programme, World Health
Organization, Geneva, 1974.
32. Frawley, J. and R. Duggan. "Techniques for Deriving Realistic
Estimates of Pesticide Intakes from Advances in Pesticide
Science", Part 3.; H. Geissbuehler Ed.; Pergamon Press:
Oxford, 1979.
33. Lehman, A. J.; Fitzhugh, O. G. 100-Fold Margin of Safety
Assoc. Food Drug 088. Q. Bull. 1954, 18, 33-35.
34. Lappenbusch, L . ; S. Moskowitz Proc. /EPA Symp. on Drinking
Water and Human Health, Washington, DC, 1984.
35. "Proposed Changes to Subdivision 701", State of New York,
1985.
36. Stara, G. "Evaluation of Pesticides in Groundwater"; Division
of Pesticide Chemistry; American Chemical Society:
Washington, D.C., 1985.
25
Risk Assessment Approaches for Ground Water
Contamination by Pesticides and Other Organic
Substances
J. F. Stara, J . Patterson, and M . L. Dourson
Environmental Criteria and Assessment Office, Office of Research and Development,

U.S. Environmental Protection Agency, Cincinnati, O H 45268
The Environmental Criteria and Assessment Office in

Cincinnati (ECAO-Cin) of the U.S. Environmental
Protection Agency (EPA) has been preparing health
risk assessment documentation and developing methods
useful for assessment of health hazards for single
chemical chronic exposure for several years (1,2).
In addition, ECAO-Cin has been instrumental in devel-
oping new and improving existing methods for health
risk assessments of toxicants and mixtures of toxic
chemicals (3-7). These methodologies are used to
derive "acceptable intakes" for systemic toxicants
or "risk specific intakes" for carcinogens. Sufficient
data are needed in order to develop a satisfactory
program for assessment of the human health risks
associated with ground water contamination by pesti-
cides and other organic and inorganic pollutants.
These data should include the types and concentrations
of pollutants present, the potential and extent of
exposure of the population at risk, and the toxicity
data base on the individual chemicals or their
mixtures.
In t h e U n i t e d S t a t e s , b o t h s u r f a c e waters and ground w a t e r s

are used f o r d r i n k i n g water s u p p l i e s . The use o f ground water as a
s o u r c e o f d r i n k i n g water has been s t e a d i l y i n c r e a s i n g w i t h about
h a l f o f the U.S. p o p u l a t i o n c u r r e n t l y r e l y i n g on ground water f o r
i t s s o u r c e o f d r i n k i n g water. M u n i c i p a l water systems s u p p l y much
of t h e need, but ground water from i n d i v i d u a l l y - o w n e d w e l l s r e p r e -
s e n t s a major d r i n k i n g water r e s o u r c e i n many r u r a l a r e a s . Reliance
on ground water appears t o v a r y w i t h g e o g r a p h i c l o c a t i o n . For
example, the midwest and western s t a t e s tend t o use a g r e a t e r
p r o p o r t i o n o f ground water than do t h e e a s t e r n s t a t e s (J3). Some o f
t h e s e s t a t e s w i t h h i g h ground water usage ( e . g . , Nebraska, Kansas,
Oklahoma) a r e a l s o c h a r a c t e r i z e d by h i g h agricultural activity,
w i t h the expected i n c r e a s e d p o s s i b i l i t y o f c o n t a m i n a t i n g ground wa-
t e r s o u r c e s w i t h p e s t i c i d e s and f e r t i l i z e r s .

Ground water c o n t a m i n a t i o n by e n v i r o n m e n t a l pollutants i s a

growing concern i n t h e U n i t e d S t a t e s t o d a y . Ground water may be
contaminated by a number o f s o u r c e s , such as l a n d d i s p o s a l o f
hazardous w a s t e s , l e a k i n g underground s t o r a g e tanks, land spread-
i n g o f s l u d g e , and Superfund s i t e s , as w e l l as the use o f f e r t i l -
i z e r s and p e s t i c i d e s i n a g r i c u l t u r e .
Three c l a s s e s o f p o l l u t a n t s ( c o n v e n t i o n a l , n o n c o n v e n t i o n a l and
t o x i c ) were e s t a b l i s h e d by the C l e a n Water A c t o f 1977 and a r e
l i s t e d i n T a b l e I . Those t h a t have been t r a d i t i o n a l l y c o n t r o l l e d by
waste water treatment a r e c o n s i d e r e d c o n v e n t i o n a l p o l l u t a n t s . The
t o x i c p o l l u t a n t s a r e t h o s e i d e n t i f i e d i n the 1976 N a t u r a l Resource
D e f e n s e C o u n c i l (NRDC) Consent D e c r e e . P o l l u t a n t s not otherwise
d e s i g n a t e d a r e c l a s s i f i e d as n o n c o n v e n t i o n a l ( 9 ) . A l l t h r e e t y p e s
have been d e t e c t e d i n b o t h ground and s u r f a c e waters.
Table I. Pollutant Classes

CONVENTIONAL POLLUTANTS
B i o c h e m i c a l Oxygen Demand pH
Suspended S o l i d s Fecal Coliforra
O i l and Grease
NONCONVENTIONAL POLLUTANTS
Chemical Oxygen Demand Nitrogen

Ammonia Phosphorus
T o t a l O r g a n i c Carbon Pesticides
Sulfides
TOXIC POLLUTANTS
Heavy M e t a l s Halogenated A l i p h a t i c s
Pesticides Phthalate Esters
PCBs Nitrosamines
Phenol & C r e s o l s P o l y c y c l i c Aromatic Hydrocarbons
Ethers
Source: CEQ, 1982.
T a b l e I I l i s t s t h e h i g h e s t c o n c e n t r a t i o n s o f s e l e c t e d noncon-
v e n t i o n a l and t o x i c o r g a n i c p o l l u t a n t s which have been measured i n
d r i n k i n g water w e l l s and c o n s e q u e n t l y r e f l e c t p o s s i b l e ground water
contamination. F o r comparison purposes, t h i s T a b l e a l s o l i s t s the
h i g h e s t measured s u r f a c e water c o n c e n t r a t i o n s . G e n e r a l l y , t h e l e v e l s
of o r g a n i c s i n s u r f a c e water a r e much lower than i n i n d i v i d u a l w e l l s .
One e x c e p t i o n i s t h e c h l o r i n a t e d compounds t h a t a r e r e l a t e d t o t h e
c h l o r i n a t i o n of s u r f a c e water. Since these values represent the
h i g h e s t c o n c e n t r a t i o n s measured, they may be r e l a t e d t o s p e c i f i c s i t e
contamination i n s t e a d of representing a general trend.
25. STARA ET AL. Risk Assessment Approaches 447
Table I I . T o x i c O r g a n i c Chemicals Found i n D r i n k i n g Water Wells

(With C o r r e s p o n d i n g S u r f a c e Water C o n c e n t r a t i o n s )
Highest D r i n k i n g Highest
Water W e l l S u r f a c e Water
Concentration Concentration
Reported Reported
Chemical (ppb) (ppb)
T r i c h l o r o e t h y l e n e (TCE) 27,300 160

Toluene 6,400 6.2
1,1,1-Trichloroethane 5,440 5.1
Methylene c h l o r i d e 3,000 13
Tetrachloroethylene 1,500 21
Chloroform 490 700
Carbon t e t r a c h l o r i d e 400 30
Benzene 330 4.4

1,2-Dichloroethylene 323 9.8
1,2-Dichloroethane 250 4.8
Xylene 300 24
1, 1 - D i c h l o r o e t h y l e n e 280 0.5
Dibromochloromethane 55 317
Vinyl chloride 50 9.8
Chloromethane 44 12
Bromoform 20 280
1,1-Dichloroethane 7 0.2
Parathion 4.6 0.2
Adapted from 10.
The p o t e n t i a l contamination of d r i n k i n g water sources by

p e s t i c i d e s i s a p r i m a r y concern of the U.S. EPA. The O f f i c e of
P e s t i c i d e Programs and the O f f i c e o f D r i n k i n g Water of the U.S.
EPA a r e now i n the p r e l i m i n a r y s t a g e s of a n a t i o n a l pesticide
s u r v e y t h a t w i l l i d e n t i f y p e s t i c i d e s which are c o n t a m i n a t i n g ground
water s u p p l i e s as w e l l as a s s e s s the e x t e n t of the c o n t a m i n a t i o n .
P e s t i c i d e s have been d e t e c t e d i n the groundwater of numerous s t a t e s ,
o f t e n as a r e s u l t o f a g r i c u l t u r a l use. Some of the major p e s t i c i d e s
t h a t have been i d e n t i f i e d i n c l u d e a l a c h l o r , a l d i c a r b , atrazine,
b r o m a c i l , c a r b o f u r a n , DBCP, DCPA, 1 , 2 - d i c h l o r o p r o p a n e , D i n o s e b , EDB,
Oxamyl and S i m a z i n e . These p e s t i c i d e s have been d e t e c t e d a t l e v e l s
r a n g i n g from 0.02-700 ppb ( 1 1 ) .
The c l e a n - u p of contaminated ground water poses problems t h a t
a r e d i f f e r e n t from contaminated s u r f a c e w a t e r s , p a r t i c u l a r l y because
ground water i s not e a s i l y a c c e s s i b l e . Due t o the t y p i c a l slow
movement of p o l l u t a n t s i n the a q u i f e r and the r e l a t i v e l y low degree
of d i s p e r s i o n , c o n c e n t r a t i o n s of contaminants can remain h i g h and
d e t e c t i o n can be d i f f i c u l t . In the case of p e s t i c i d e s , some of the
f a c t o r s t h a t may c o n t r i b u t e to ground water c o n t a m i n a t i o n i n c l u d e
p h y s i c a l and c h e m i c a l p r o p e r t i e s of the p e s t i c i d e , a p p l i c a t i o n meth-
ods used f o r t h e i r a p p l i c a t i o n , and c h a r a c t e r i s t i c s of the s o i l and
site. Once an a q u i f e r i s contaminated, i t s r e s t o r a t i o n as a u s a b l e

Library
1155 16th St., N.W.
d r i n k i n g water s u p p l y i s e x t r e m e l y d i f f i c u l t o r e x p e n s i v e , o r b o t h .
However, w i t h an i n c r e a s i n g r e l i a n c e on ground water i t i s i m p o r t a n t
to i d e n t i f y and c h a r a c t e r i z e the h e a l t h r i s k from a l l p o l l u t a n t s ,
i n c l u d i n g p e s t i c i d e s , i n d r i n k i n g water t h a t i s d e r i v e d from t h e s e
s o u r c e s . Development o f improved c o n t r o l measures and c l e a n - u p
techniques are a l s o necessary.
Establishing Criteria and Standards
Under the C l e a n Water A c t , the EPA p r e p a r e s c r i t e r i a documents t o be

used i n d e v e l o p i n g water q u a l i t y s t a n d a r d s . The documents c o n t a i n
the l a t e s t s c i e n t i f i c i n f o r m a t i o n on t h e human h e a l t h and e n v i r o n -
mental e f f e c t s of i n d i v i d u a l p o l l u t a n t s or a c l a s s of p o l l u t a n t s .
The c r i t e r i a a r e based on s c i e n t i f i c d a t a and, a t t i m e s , on s c i e n -
t i f i c judgment. C r i t e r i a a r e e s t a b l i s h e d as e i t h e r " s a f e " l e v e l s
f o r c h e m i c a l s where t h e t o x i c i t y i s presumed t o have a t h r e s h o l d ,
or as i n c r e m e n t a l r i s k l e v e l s f o r presumably n o n - t h r e s h o l d c h e m i c a l s
such as c a r c i n o g e n s . These a r e u s u a l l y e s t i m a t e d i n r e g a r d s t o
l i f e t i m e exposure. Ambient water q u a l i t y s t a n d a r d s a r e then s e t
u s i n g these c r i t e r i a and t a k i n g i n t o c o n s i d e r a t i o n m o d i f y i n g f a c -
t o r s , which may i n c l u d e s o c i e t a l f a c t o r s , economic and t e c h n i c a l
considerations such as b e s t a v a i l a b l e t e c h n o l o g y , n a t u r a l back-
ground l e v e l s , and f o r m a l r i s k - t o - b e n e f i t assessments. However, by
n e c e s s i t y some o f these c o n s i d e r a t i o n s cannot involve precise
v a l u e s ; an example i s the d e t e r m i n a t i o n o f the c o s t of a c a s e o f
cancer to s o c i e t y . B a l a n c i n g the c r i t e r i a w i t h m o d i f y i n g f a c t o r s
to e s t a b l i s h s t a n d a r d s i s a p a r t o f t h e r i s k management p r o c e s s .
S i m i l a r c r i t e r i a documents a r e a l s o prepared under t h e Safe
D r i n k i n g Water A c t . These documents s p e c i f y recommended maximum
contaminant l e v e l s (RMCLs) as n o n e n f o r c e a b l e health goals f o r
c h r o n i c exposure and 1-day and 10-day h e a l t h a d v i s o r y levels.
Maximum contaminant l e v e l s (MCLs), the e n f o r c e a b l e s t a n d a r d s , a r e
s e t as c l o s e t o t h e RMCL as i s f e a s i b l e c o n s i d e r i n g t h e b e s t a v a i l -
a b l e t e c h n o l o g y o r treatment t e c h n i q u e s and c o s t s ( 1 2 ) .
The U.S. EPA i s c u r r e n t l y d e v e l o p i n g RMCLs and MCLs f o r more
than two dozen o r g a n i c c h e m i c a l s , i n c l u d i n g many p e s t i c i d e s , t h a t
are b e i n g c o n s i d e r e d f o r c o n t r o l under t h e N a t i o n a l R e v i s e d P r i m a r y
D r i n k i n g Water R e g u l a t i o n s (NRPDWR) T a b l e I I I l i s t s some o f t h e s e
o r g a n i c s and i n c l u d e s RMCLs f o r t h e s i x p e s t i c i d e s t h a t were i n c l u d -
ed i n the N a t i o n a l I n t e r i m P r i m a r y D r i n k i n g Water R e g u l a t i o n s
(NIPDWR). These p e s t i c i d e s a r e those t h a t have e i t h e r been d e t e c t e d
i n d r i n k i n g water, a r e r e g i s t e r e d f o r use i n o r around drinking
water s o u r c e s , o r a r e used i n a way t h a t may r e s u l t i n t h e i r e n t e r -
i n g d r i n k i n g water s u p p l i e s .
R i s k Assessment f o r S i n g l e Chemical C h r o n i c Exposure and C h e m i c a l

Mixtures
In 1980, EPA p u b l i s h e d 64 Ambient Water Q u a l i t y C r i t e r i a Documents

(AWQCDs) c o v e r i n g 128 p r i o r i t y p o l l u t a n t s . Of these 64 documents, 19
were on p e s t i c i d e s such as d i e l d r i n , c h l o r d a n e and DDT. Criteria
25. STARA ETA L . Risk Assessment Approaches 449
Table I I I . Organic Chemicals i n D r i n k i n g Water C o n s i d e r e d

ab
f o r the NRPDWR
0
NIPDWR
RMCL (mg/1) NRPDWR
Endrin 0.0002 Alachlor

Lindane 0.004 Aldicarb
Methoxychlor 0.1 Carbofuran
Toxaphene 0.005 Chlordane

2,4-D 0.1 Chlorobenzene
2,4,5-TP 0.01 c i s - and t r a n s - 1 , 2 - D i c h l o r o e t h y l e n e
Dibromochloroprane (DBCP)
Dichlorobenzenes
Dioxin
ED
Endothall
Epichlorohydrin
E t h y l benzene
Heptachlor
Hexachlorobenzene
1,2-Dichloropropane
PCBs
Pentachlorophenol
Styrene
Toluene
Xylene
a
S o u r c e : Adapted from JL2
b N a t i o n a l R e v i s e d P r i m a r y D r i n k i n g Water R e g u l a t i o n s
c
N a t i o n a l I n t e r i m P r i m a r y D r i n k i n g Water R e g u l a t i o n s , 40 CFR 141.12
were e s t a b l i s h e d i n n i n e o f these p e s t i c i d e documents on t h e b a s i s

of t h e p o l l u t a n t ' s p o t e n t i a l c a r c i n o g e n i c i t y , and i n n i n e documents
c r i t e r i a were established based on t o x i c i t y . C h l o r i n a t e d Benzenes
and C h l o r i n a t e d P h e n o l s were determined t o pose both a c a r c i n o g e n i c
r i s k and t o x i c o l o g i c a l r i s k . I n a d d i t i o n , some o f the c h e m i c a l s
exhibit taste and odor (organoleptic) effects. T a b l e IV l i s t s
1
t h e s e 19 p e s t i c i d e s and E P A s c r i t e r i a l e v e l s .
a
T a b l e IV. Ambient Water Q u a l i t y C r i t e r i a (Human H e a l t h )
Priority Pollutant C r i t e r i o n Based on:
Toxicity Carcinogenicity Organoleptic
Acenaphthene 0.02 mg/1

Aldrin 0.74 ng/1
Arsenic 22 ng/1
Chlordane 4.6 ng/1
3
C h l o r i n a t e d Benzenes* X X
0
Chlorinated Phenols X X
DDT 0.24 ng/1
Dichlorobenzenes 400 ug/1
2,4-Dichlorophenol 3.09 mg/1 0.03 ug/1
Dichloropropene 87 ug/1
Dieldrin 0.71 ng/1

Endosulfan 74 ug/1
Endrin 1.0 ug/1
Heptachlor 2.0 ng/1
Hexachlorocyclohexaneb X
Hexachlorocyclopentadiene 206 ug/1 1.0 ug/1
Naphthalene No criterion
Pentachlorophenol 1.01 mg/1 30 ug/1
Toxaphene 5.1 ng/1
a
As of 3/82
b These documents c o v e r e d a c l a s s or group of c h e m i c a l s , resulting
i n more than one c r i t e r i o n .
The h e a l t h assessment c h a p t e r s o f t h e s e documents c o n t a i n the

a v a i l a b l e dose-response d a t a from a n i m a l experiments and human e p i -
demiology s t u d i e s f o r the c h e m i c a l o r c l a s s of c h e m i c a l s o f c o n c e r n .
By a s s e s s i n g the r i s k s a s s o c i a t e d w i t h v a r i o u s doses, a c c e p t a b l e d a i -
l y i n t a k e s (ADIs - f o r s y s t e m i c t o x i c a n t s ) o r r i s k - s p e c i f i c doses
( f o r carcinogens) were derived. These levels were d i v i d e d by
a p p r o p r i a t e exposure assumptions (e.g., estimated average water
consumption) t o d e r i v e a c r i t e r i o n .
The c r i t e r i a documents, and the r i s k assessment methodologies
used i n the development o f c r i t e r i a , a d d r e s s the need f o r p r o t e c t i v e
standards. " S a f e " l e v e l s are needed t o ensure t h a t p o p u l a t i o n s ex-
posed t o these c h e m i c a l s over a l i f e t i m e w i l l not f a c e p o t e n t i a l
h e a l t h hazards. There i s a l s o a need to be a b l e t o p r e d i c t or
e s t i m a t e the human h e a l t h r i s k i n a p a r t i c u l a r s e t t i n g . The passage
o f Superfund r e f l e c t e d a growing concern with s e r i o u s l o c a l i z e d
c o n t a m i n a t i o n s i t u a t i o n s at hazardous waste s i t e s . A p r i m a r y con-
c e r n a t these s i t e s i s the p o t e n t i a l f o r m i g r a t i o n of t o x i c chemi-
c a l s a t the s i t e i n t o ground and s u r f a c e w a t e r s . Once t h i s has
o c c u r r e d , o p t i o n s f o r c o n t r o l l i n g exposure are s e v e r e l y compromised.
The d i f f i c u l t y i n p r e d i c t i n g the human h e a l t h r i s k from exposure t o
s p e c i f i c m i x t u r e s of c h e m i c a l s on a s i t e - s p e c i f i c b a s i s has become
evident. F o r t h i s r e a s o n , the m e t h o d o l o g i e s developed to e s t a b l i s h
ambient water q u a l i t y c r i t e r i a and d r i n k i n g water c r i t e r i a were
adapted by the ECAO s t a f f t o e s t i m a t e r i s k s from s p e c i f i c c h e m i c a l s
or c h e m i c a l m i x t u r e s a t such s i t e s (_3,4^ F o r example, one a d a p t a -

t i o n i s to c h a r a c t e r i z e i n c r e m e n t a l exposures as a f u n c t i o n of
s i t e - s p e c i f i c f a c t o r s . T h i s approach adds a d d i t i o n a l c o m p l e x i t y t o
the r i s k assessment p r o c e s s , but s h o u l d r e s u l t i n reduced u n c e r t a i n -
ty.
H e a l t h r i s k assessments c o n s i d e r e s t i m a t e s of exposure t o a
t o x i c c h e m i c a l and the h e a l t h hazards a s s o c i a t e d w i t h t h a t c h e m i c a l .
In agreement w i t h the N a t i o n a l Academy of S c i e n c e s and o t h e r s c i e n -
t i f i c r e p o r t s ( 1 3 , 1 4 ) , EPA assumes t h a t c a r c i n o g e n e s i s i s a non-
t h r e s h o l d phenomenon, whereas o t h e r t o x i c e f f e c t s e x h i b i t t h r e s h o l d s
( i . e . , doses below which no adverse e f f e c t s w i l l o c c u r ) . T h e r e f o r e ,
one must determine the p o t e n t i a l c a r c i n o g e n i c i t y or s y s t e m i c t o x i c i t y
o f the c h e m i c a l and then proceed, u t i l i z i n g one of two parallel
methodologies t h a t have been d e s i g n e d t o address n o n t h r e s h o l d o r
threshold e f f e c t s . These assessments i n c l u d e the b a s i c t o x i c o l o g i c
concept of dose-response relationships. F o r c a r c i n o g e n s , o n l y the
incremental r i s k s a s s o c i a t e d with a p o l l u t a n t l e v e l i n a s p e c i f i c
e n v i r o n m e n t a l medium a r e c o n s i d e r e d . F o r s y s t e m i c t o x i c a n t s the
a c t u a l exposure i s compared w i t h l e v e l s t h a t do not p r e s e n t a human
h e a l t h hazard. The next two s e c t i o n s b r i e f l y d e s c r i b e the methodo-
l o g i e s used by EPA t o d e r i v e ADIs and r i s k - s p e c i f i c i n t a k e s . D i e l d r i n
and a l d i c a r b have been used as examples t o i l l u s t r a t e the q u a n t i t a -
t i v e approaches.
Carcinogens (Nonthreshold E f f e c t s ) . A f t e r a compound has been d e t e r -

mined to have the p o t e n t i a l to cause c a n c e r i n humans the r e l a t i o n s h i p
between r i s k and exposure i s e s t i m a t e d . Two types of d a t a a r e used
f o r q u a n t i t a t i v e e s t i m a t e s : human s t u d i e s where excess c a n c e r r i s k
has been a s s o c i a t e d w i t h exposure t o the agent, and a n i m a l b i o a s s a y s .
I f human e p i d e m i o l o g i c d a t a are a v a i l a b l e w i t h s u f f i c i e n t l y v a l i d
exposure i n f o r m a t i o n on the compound, the d a t a are a n a l y z e d by appro-
p r i a t e s t a t i s t i c a l procedures t h a t assume a l i n e a r dose-response
relationship. I f t h e e p i d e m i o l o g i c d a t a show no s i g n i f i c a n t c a r c i n o -
g e n i c e f f e c t when p o s i t i v e animal e v i d e n c e i s a v a i l a b l e , an upper
l i m i t of the c a n c e r i n c i d e n c e i s c a l c u l a t e d , assuming t h a t the t r u e
i n c i d e n c e i s j u s t below the l e v e l of d e t e c t i o n i n the e p i d e m i o l o g i c
studies. Cancer r i s k assessment f o r low exposure l e v e l s i s based on
e s t i m a t e s of the c a n c e r potency, i . e . , t h e s l o p e of the d o s e - r e s p o n s e
c u r v e i n the low dose r e g i o n . The e s t i m a t e d human potency i s d e r i v e d
d i r e c t l y when adequate e p i d e m i o l o g i c d a t a a r e a v a i l a b l e . When a n i m a l
s t u d i e s must be u s e d , the human potency e s t i m a t e i s c a l c u l a t e d u s i n g
the l i n e a r i z e d m u l t i s t a g e model f i t t e d t o the animal d a t a ( 1 5 , 1 ) .
F i r s t , the upper 95% c o n f i d e n c e l i m i t ( q ^ ) of the l i n e a r c o e f f i c -
i e n t i s determined. Then, q^ i s a d j u s t e d f o r exposure d u r a t i o n
and s p e c i e s d i f f e r e n c e s t o g i v e the e s t i m a t e d human potency o r q^
i n (mg/kg/day)"* u s i n g E q u a t i o n 1 :
1 / 3
q i * (A) ( 7 0 ) / W )
A (1)
=
31* (H)
3
(le/Le) ( L e / L )
where :
fc 1
q = a n m a
l (A) ^ l potency (mg/kg/day)
70 = assumed human w e i g h t , kg
W A = a n i m a l weight, kg
l e = l e n g t h of exposure
L e = l e n g t h o f experiment o r o b s e r v a t i o n p e r i o d
L = l i f e s p a n of the a n i m a l .
The cube r o o t o f the r a t i o o f body w e i g h t s i s used t o a d j u s t
f o r s p e c i e s d i f f e r e n c e s on the assumption t h a t m e t a b o l i c r a t e i s
p r o p o r t i o n a l t o body s u r f a c e a r e a , which i s p r o p o r t i o n a l t o t h e 2/3
power of body w e i g h t . The f a c t o r l / L a d j u s t s the a c t u a l dose t o a
e e
d a i l y dose averaged o v e r the l e n g t h o f the experiment. The t h i r d

3
f a c t o r , ( L / L ) , i s used t o e s t i m a t e r i s k from l i f e t i m e exposure
e
when the a n i m a l experiment i s f o r o n l y p a r t i a l l i f e t i m e . This

adjustment i s n e c e s s a r y t o a l l o w f o r p o s i t i v e responses t h a t would
have o c c u r r e d had s u f f i c i e n t time been a l l o w e d f o r the tumors to

develop (J_).
A f t e r the human p o t e n c y has been c a l c u l a t e d , the r i s k - s p e c i f i c
dose (RSD, i n mg/day) a s s o c i a t e d w i t h an upper l i m i t e s t i m a t e o f the
e x c e s s l i f e t i m e c a n c e r r i s k ( e . g . , 10"^ o r 1 i n 100,000 p e o p l e ) i s
determined i n E q u a t i o n 2:
5
RSD = 70 kg ( 1 0 ~ ) (2)
q
i*(H)
T h i s r i s k - s p e c i f i c i n t a k e r a t e i s e a s i l y c o n v e r t e d i n t o a media
c o n c e n t r a t i o n by d i v i d i n g by the a p p r o p r i a t e consumption assump-
t i o n s f o r the exposure medium. F o r example, assuming a daily
i n t a k e o f 2 1 o f c o n t a m i n a t e d water and 0.0065 kg o f c o n t a m i n a t e d
f i s h , the r i s k s p e c i f i c water c o n c e n t r a t i o n ( C , i n mg/1) i s c a l c u -
l a t e d i n E q u a t i o n 3:
C = RSD (mg/day) (3)

2 1/day + 0.0065 kg/day X BCF (1/kg)
where BCF i s the b i o c o n c e n t r a t i o n f a c t o r o f the c h e m i c a l i n f i s h

f l e s h when compared w i t h water i n 1/kg. The EPA has e s t a b l i s h e d an
ambient water q u a l i t y c r i t e r i o n f o r the p e s t i c i d e d i e l d r i n , which i s
a s u s p e c t e d c a r c i n o g e n and p r i o r i t y p o l l u t a n t ( 1 6 ) . In t h e c r i t e -
r i a document f o r d i e l d r i n , the EPA e s t i m a t e d the human p o t e n c y
u s i n g a n i m a l d a t a from a s t u d y by Walker e t . a l ( 1 7 ) . The upper
95% c o n f i d e n c e l i m i t o f the l i n e a r c o e f f i c i e n t was 2.29 (mg/kg/
1
day)" .
U s i n g E q u a t i o n 1:
q = 2 2 9 l 1 / 3
i*(H) (mg/kg/day) ' (70kg/0.030 kg)
(924d/924d) X (924d/924d)3
q = 3 0 3 7 1
i*(H) " (mg/kg/d)"
The r i s k - s p e c i f i c i n t a k e i s c a l c u l a t e d u s i n g E q u a t i o n 2:
RSD = 70kg (1Q-5)

30.37 (mg/kg/d)-l
5
RSD = 2.30 X 10~ mg/d
A c r i t e r i o n was d e r i v e d ( f r o m E q u a t i o n 3) assuming 2 l i t e r s of
water/day, 0.0065 kg of f i s h / d a y and a b i o c o n c e n t r a t i o n f a c t o r of
4670 1/kg:
5
2.30 X I P " mg/d
c 88
2 1/d + 0.0065 kg/d X 4670 1/kg
C = 0.71 ng/1
The p r e d i c t i o n of c a n c e r r i s k at a g i v e n exposure l e v e l uses

the same b a s i c approach o u t l i n e d above and i n v o l v e s s i m i l a r assump-
tions. When human d a t a are adequate, the o b s e r v e d human p o t e n c y i s
used d i r e c t l y t o p r e d i c t the upper bound of r i s k . When a n i m a l d a t a
must be used, and p a r t i c u l a r l y when h i g h e r exposure l e v e l s are
i n v o l v e d , the p o t e n c y a l o n e i s not s u f f i c i e n t , and the complete
m u l t i s t a g e model needs to be used. The r i s k ( r ) a t exposure (d)
u s i n g the m u l t i s t a g e model i s shown i n E q u a t i o n 4 ( 1 5 ) :
z
r(d)=l-exp(-q -q d-q d -...)
0 1 2 (4)
where the q-^s a r e parameters i n the model t o be e s t i m a t e d by c u r v e -

f i t t i n g p r o c e d u r e s . The i n c r e m e n t a l r i s k ( o r "excess r i s k " ) i s then
c a l c u l a t e d i n i n E q u a t i o n 5:
R= r(d)-r(0) ( )
5
l-r(0)
An e s t i m a t e d upper c o n f i d e n c e l i m i t on the excess r i s k (R) i s

used as the l i f e t i m e r i s k p r o j e c t i o n a t exposure l e v e l ( d ) , s u i t a b l y
m o d i f i e d as above f o r s p e c i e s d i f f e r e n c e s and f o r d u r a t i o n i f the
a n i m a l study was f o r o n l y p a r t i a l l i f e t i m e .
Systemic T o x i c a n t s ( T h r e s h o l d E f f e c t s ) . This area i s d i s c u s s e d i n

more d e t a i l elsewhere 0^,2^ To d e r i v e c r i t e r i a based on n o n c a r c i n o -
genic responses, f i v e t y p e s of r e s p o n s e l e v e l s are c o n s i d e r e d :
NOEL - No-Observed-Effect L e v e l
NOAEL - No-Observed-Adverse-Effect L e v e l
LOEL - Lowest-Observed-Effect Level
LOAEL - Lowest-Observed-Adverse-Effect L e v e l
FEL - Frank-Effect Level
A d v e r s e e f f e c t s a r e d e f i n e d as any e f f e c t s t h a t r e s u l t i n f u n c t i o n a l
impairment or p a t h o l o g i c a l l e s i o n s t h a t may a f f e c t the performance
of the whole organism or that reduce an organism's a b i l i t y to
r e s p o n d to an a d d i t i o n a l c h a l l e n g e . F r a n k e f f e c t s are d e f i n e d as
o v e r t l y or g r o s s l y a d v e r s e ( e . g . , s e v e r e c o n v u l s i o n s , l e t h a l i t y ) .
These c o n c e p t s r e p r e s e n t landmarks t h a t h e l p to d e f i n e the
threshold region i n s p e c i f i c experiments. Thus, i f an experiment
y i e l d s a NOEL, a NOAEL, a LOAEL, and a c l e a r l y d e f i n e d FEL i n r e l a -
t i v e l y c l o s e l y spaced d o s e s , the t h r e s h o l d r e g i o n has been r e l a t i v e -
ly well-defined. Such d a t a are v e r y u s e f u l i n d e r i v i n g ADIs. To
d e r i v e an ADI i n w a t e r , the h i g h e s t NOEL or NOAEL, o r the l o w e s t
LOAEL (depending on the d a t a a v a i l a b l e ) i s d i v i d e d by one or more
u n c e r t a i n t y f a c t o r s (I) as i l l u s t r a t e d i n Equations 6 and 7:
H i g h e s t NOAEL o r NOEL (6)

=
AD* Uncertainty Factor(s)
To derive a criterion, the ADI i s divided by exposure a s s u m p t i o n s :

_ ADI (7)
Criterion - Exposure Assumptions
These exposure assumptions may i n c l u d e d a i l y water consumption, d a i -

l y f i s h consumption, b i o c o n c e n t r a t i o n f a c t o r s , e t c .
Some g e n e r a l g u i d e l i n e s have been e s t a b l i s h e d f o r d e r i v i n g
c r i t e r i a from t o x i c i t y d a t a (I). A c l e a r l y d e f i n e d FEL i s of l i t t l e
use i n e s t a b l i s h i n g c r i t e r i a when i t s t a n d s a l o n e , because such a
l e v e l g i v e s no i n d i c a t i o n of how f a r removed i t i s from the t h r e s h o l d
region. S i m i l a r l y , a f r e e s t a n d i n g NOEL has l i t t l e u t i l i t y because
t h e r e i s no i n d i c a t i o n of i t s p r o x i m i t y t o the t h r e s h o l d r e g i o n . If
multiple NOELs are a v a i l a b l e without a d d i t i o n a l d a t a on LOELs,
NOAELs, or LOAELs, the h i g h e s t NOEL i s used to d e r i v e a c r i t e r i o n .
NOAELs, LOELs, and LOAELs are most s u i t a b l e f o r c r i t e r i a d e r i -
v a t i o n . A w e l l - d e f i n e d NOAEL from a c h r o n i c ( a t l e a s t 90-day)
a n i m a l study can be used d i r e c t l y , d i v i d e d by the appropriate
uncertainty factor. A LOEL o f t e n c o r r e s p o n d s to a NOAEL o r a
LOAEL. In the case of a LOAEL, an a d d i t i o n a l u n c e r t a i n t y f a c t o r i s
a p p l i e d ; the magnitude of the a d d i t i o n a l u n c e r t a i n t y factor i s
j u d g m e n t a l and s h o u l d l i e i n the range of 1 t o 10 based on r e v i e w
of a l l s u p p o r t i v e evidence. Caution must be e x e r c i s e d not to
s u b s t i t u t e o t h e r t o x i c e f f e c t s f o r the LOAELs. If, in reasonable
c l o s e l y spaced d o s e s , o n l y a NOEL and a LOAEL of e q u a l q u a l i t y are
a v a i l a b l e , the a p p r o p r i a t e u n c e r t a i n t y f a c t o r i s a p p l i e d t o the
NOEL (J_).
The s e l e c t i o n and justification of u n c e r t a i n t y f a c t o r s are
c r i t i c a l i n u s i n g t h i s approach. The N a t i o n a l Academy o f Science
has p r o v i d e d g u i d e l i n e s f o r u s i n g u n c e r t a i n t y f a c t o r s ( 1 3 ) . "Safety
f a c t o r " or " u n c e r t a i n t y f a c t o r " i s d e f i n e d as a number t h a t r e f l e c t s
the degree or amount of u n c e r t a i n t y t h a t must be c o n s i d e r e d when ADIs
a r e e s t i m a t e d from v a r i a b l e t o x i c i t y d a t a b a s e s . I t i n c l u d e s e x t r a -
p o l a t i o n based on i n t r a s p e c i e s (human p o p u l a t i o n ) as w e l l as i n t e r -
s p e c i e s (from a n i m a l t o human) v a r i a b i l i t y . When the q u a l i t y and
q u a n t i t y of e x p e r i m e n t a l d a t a are s a t i s f a c t o r y , a low u n c e r t a i n t y
f a c t o r i s used; when d a t a are judged t o be inadequate or e q u i v o c a l ,
a l a r g e r u n c e r t a i n t y f a c t o r i s needed. In those cases where the
d a t a do not c o m p l e t e l y f u l f i l l the c o n d i t i o n s f o r one c a t e g o r y , or
appear to be i n t e r m e d i a t e between two c a t e g o r i e s , an i n t e r m e d i a t e

u n c e r t a i n t y f a c t o r i s used. These i s s u e s were reviewed by Dourson
and S t a r a ( 1 8 ) .
The f o l l o w i n g example u s i n g a l d i c a r b i l l u s t r a t e s how t o d e r i v e
an ADI. A l d i c a r b i s a p e s t i c i d e t h a t has been d e t e c t e d i n ground
water i n F l o r i d a and e l s e w h e r e . The EPA i s c u r r e n t l y i n t h e p r o c e s s
of e s t a b l i s h i n g a d r i n k i n g water c r i t e r i o n f o r a l d i c a r b . W e i l and
C a r p e n t e r (19) s t u d i e d the e f f e c t s of a l d i c a r b s u l f o x i d e on r a t s and
d e t e r m i n e d a NOEL o f 0.125 mg/kg/day. T h i s i s s u p p o r t e d by a n o t h e r
r a t study by M i r r o w e t a l . ( 2 0 ) , which r e s u l t e d i n a NOEL e q u a l t o
0.12 mg/kg/day. An ADI i s e s t i m a t e d f o r a l d i c a r b , u s i n g the NOEL
from the W e i l and C a r p e n t e r study and an u n c e r t a i n t y f a c t o r of 100:
0.125 mg/kg/day
0 1
A "
~ 0 . 0 1 2 mg/kg/day ( o r 84 ug/day f o r
a 70 kg a d u l t )
T h i s f a c t o r of 100 a c c o u n t s f o r two 1 0 - f o l d d e c r e a s e s i n dose based

on the expected i n t r a - and i n t e r - s p e c i e s v a r i a b i l i t y t o the t o x i -
c i t y of a l d i c a r b . E q u a t i o n 7 i s used to e s t a b l i s h a c r i t e r i o n f o r
a 70 kg a d u l t :
84 ug/day
=
Criterion 2 1/day
= 42 ug/1
The c a l c u l a t e d c r i t e r i o n assumes t h a t 100% of exposure t o a l d i c a r b

i s from d r i n k i n g water, w i t h an average consumption o f 2 1/day.
Approaches t o R i s k Assessment f o r Chemical M i x t u r e s . The above

m e t h o d o l o g i e s a r e used t o e s t i m a t e the human h e a l t h r i s k from exposure
t o s i n g l e c h e m i c a l s . These methods were d e v e l o p e d f o r use i n d e r i v i n g
c r i t e r i a and e s t a b l i s h i n g p r o t e c t i v e s t a n d a r d s . However, many contam-
i n a t i o n s i t u a t i o n s f r e q u e n t l y do not d e a l w i t h a s i n g l e e n v i r o n m e n t a l
p o l l u t a n t , but i n s t e a d i n v o l v e m i x t u r e s o f c h e m i c a l s i n more t h a n one
e n v i r o n m e n t a l medium ( e . g . , a i r and w a t e r ) . Hazardous waste s i t e s
u s u a l l y i n v o l v e c h e m i c a l m i x t u r e s f o r which the t o t a l h e a l t h r i s k to
the s u r r o u n d i n g p o p u l a t i o n must be d e t e r m i n e d i n o r d e r t o d e c i d e what
c o r r e c t i v e a c t i o n may be n e c e s s a r y . Groundwater c o n t a m i n a t i o n from
the a g r i c u l t u r a l use of p e s t i c i d e s can a l s o i n v o l v e c h e m i c a l m i x t u r e s
t h a t must be e v a l u a t e d i j i t o t o .
Because t h e r e i s r a r e l y a c t u a l d a t a on the m i x t u r e of c o n c e r n ,
an a d d i t i v i t y approach ( a d d i n g a l l the t o x i c e f f e c t s of the i n d i v i d u a l
components) i s sometimes used. T h i s approach i n v o l v e s a number of
assumptions and has c e r t a i n l i m i t a t i o n s due t o the l a c k o f c o n s i d e r a -
t i o n f o r p o t e n t i a l s y n e r g i s m o r antagonism between i n d i v i d u a l c h e m i c a l
compounds. F u r t h e r r e s e a r c h i s needed on human h e a l t h e f f e c t s from
c h e m i c a l m i x t u r e s t o more a c c u r a t e l y p r e d i c t the r i s k s i n v o l v e d i n
t h e s e common e n v i r o n m e n t a l s i t u a t i o n s .
The U. S. EPA has proposed g u i d e l i n e s f o r h e a l t h r i s k assessment

o f c h e m i c a l m i x t u r e s (7) a l o n g w i t h g u i d e l i n e s f o r exposure, c a r c i n o -
gens, mutagens, and t o x i c agents a f f e c t i n g r e p r o d u c t i o n (49 F e d e r a l
R e g i s t e r 46294). G u i d e l i n e s f o r systemic t o x i c a n t s are a l s o being
d e v e l o p e d . For a more complete d i s c u s s i o n of methods f o r the h e a l t h
assessment o f c h e m i c a l m i x t u r e s , see 3^7.
Discussion
R i s k assessment i s a r a p i d l y d e v e l o p i n g s c i e n c e r e p r e s e n t i n g many
d i s c i p l i n e s i n c l u d i n g t o x i c o l o g y , e p i d e m i o l o g y , b i o m a t h e m a t i c s , chem-
i s t r y , and e n g i n e e r i n g . As a r e s u l t , the methods d i s c u s s e d i n t h i s
paper ( i . e . , e s t i m a t i o n s o f ADIs f o r s y s t e m i c t o x i c a n t s and risk-
s p e c i f i c i n t a k e s f o r c a r c i n o g e n s ) are b e i n g c o n s t a n t l y improved based
on new s c i e n t i f i c e v i d e n c e or c o n c e p t u a l i z a t i o n s . The U.S. EPA has
been i n v o l v e d i n t h i s development f o r s e v e r a l y e a r s . Some examples
include uncertainty f a c t o r s ( 1 8 ) , use of epidemiology data (21),

h y p e r s u s c e p t i b l e subgroups ( 2 2 ) , and n o v e l approaches to the e s t i -
m a t i o n of the ADI ( 3 , 4 , 2 3 ) .
Many d o s e / d u r a t i o n gaps e x i s t i n the a v a i l a b l e d a t a base f o r
s y s t e m i c t o x i c a n t s . W e i l and M c C o l l i s t e r (24) , W e i l et a l . (25) , and
McNamara (26) have attempted to d e r i v e e m p i r i c a l r e l a t i o n s h i p s between
l o n g - t e r m and s h o r t - t e r m exposures and the r e s u l t i n g t o x i c e f f e c t s .
However, v a r i a t i o n s among c h e m i c a l a s s e s s m e n t s and the l i m i t e d types
o f c h e m i c a l s c o n s i d e r e d would seem t o p r e c l u d e the development of a
s i n g l e "temporal c o r r e c t i o n f a c t o r " f o r t o x i c e f f e c t s . Two areas
t h a t have been under study i n an attempt t o reduce the u n c e r t a i n t i e s
i n v o l v e d i n h e l a t h r i s k assessment a r e d i s c u s s e d below.
Graphic D i s p l a y . A g r a p h i c d i s p l a y of a l l r e l e v a n t d a t a can be used

t o p e r f o r m r i s k assessments 03,4) For e a c h c h e m i c a l under r e v i e w ,
an e f f e c t - d o s e - d u r a t i o n p l o t i s c o n s t r u c t e d , as shown f o r M i r e x i n
F i g u r e 1. Each symbol i n the f i g u r e r e p r e s e n t s an experimental
o b s e r v a t i o n p l o t t e d on the graph at the exposure d u r a t i o n and average
d a i l y dose of the e x p e r i m e n t . The dose r a t e i n the g r a p h has been
c o n v e r t e d t o an e s t i m a t e d human dose r a t e ( i n mg/day/70 kg) by a
model which assumes t h a t e q u i t o x i c doses among s p e c i e s i s r e l a t e d to
body s u r f a c e a r e a . The exposure d u r a t i o n has been c o n v e r t e d to a
f r a c t i o n of the a n i m a l l i f e s p a n , and t h i s f r a c t i o n has been assumed
to be e q u i v a l e n t to the p o t e n t i a l human e x p o s u r e . Both assumptions
a r e d i s c u s s e d e l s e w h e r e ( 3 , 4 , 2 3 ) . The l a r g e r symbols i n d i c a t e g r e a t e r
c o n f i d e n c e i n the d a t a . L i v e r ( L ) , r e p r o d u c t i v e (RP), and n e r v o u s
system (NS) e f f e c t s a r e a l s o i n d i c a t e d s e p a r a t e l y .
Depending on the c o n s i s t e n c y o f the p a t t e r n , a s t a t i s t i c a l or
j u d g m e n t a l approach ( t h e l a t t e r i s p r e s e n t e d h e r e ) c o u l d be used to
i n t e r p o l a t e or e x t r a p o l a t e to exposure d u r a t i o n s f o r which a c t u a l
d a t a are not a v a i l a b l e . For example, i n F i g u r e 1, an e s t i m a t e of the
b e s t - f i t t i n g , h i g h e s t NOAEL l i n e was made and then a corresponding
ADI l i n e was e s t i m a t e d . (NOTE: T h i s g r a p h i s p r e s e n t e d as an example
only. Mirex i s c o n s i d e r e d to be a c a r c i n o g e n by the o r a l r o u t e and
thus d e r i v a t i o n o f an ADI may not be a p p r o p r i a t e ) T h i s a p p r o a c h p r o -
v i d e s the f l e x i b i l i t y t o e s t i m a t e an a c c e p t a b l e i n t a k e f o r any d u r a -
t i o n once the NOAEL l i n e i s e s t a b l i s h e d . A l t e r n a t i v e l y , by d i v i d i n g
25. ST A R A E T A L . Risk Assessment Approaches 457
I
0.07 0.7 7.0 70
L I F E S P A N (years)
Legend :
Cancer E f f e c t L e v e l ( s t a t i s t i c a l l y o r b i o l o g i c a l l y
s i g n i f i c a n t i n c r e a s e i n tumors o b s e r v e d )
A FEL (Frank-Effect Level)
AEL (Adverse-Effect Level)
NOAEL ( N o - O b s e r v e d - A d v e r s e - E f f e c t Level)
NOEL ( N o - O b s e r v e d - E f f e c t Level)
LV Liver
NS Nervous System
RP Reproductive Effects
F i g u r e 1. E f f e c t - d o s e - d u r a t i o n p l o t f o r a l l r e l e v a n t human
and a n i m a l o r a l t o x i c i t y d a t a f o r m i r e x .
the d a t a p l o t v e r t i c a l l y i n t o f o u r d u r a t i o n segments ( a c u t e , s h o r t -
term, s u b c h r o n i c and c h r o n i c ) one c o u l d a l s o e s t i m a t e an a c c e p t a b l e
i n t a k e f o r each d u r a t i o n u s i n g the c u r r e n t EPA approach t h a t was
d e s c r i b e d e a r l i e r and i s used t o e s t i m a t e d r i n k i n g water h e a l t h
a d v i s o r i e s ; 1-day h e a l t h a d v i s o r i e s c o u l d be e s t i m a t e d from a c u t e
d a t a , and 10-day a d v i s o r i e s from short-terra or subchronic data.
(The O f f i c e o f D r i n k i n g Water o f t h e U.S. EPA c u r r e n t l y uses t h i s
a p p r o a c h but w i t h o u t the d o s e - d u r a t i o n graph.) A n o t h e r advantage
of t h e graph i s t h a t t h e dose a x i s can be d i v i d e d i n t o a r e a s e x p e c t -
ed t o cause: ( a ) g r o s s t o x i c i t y o r d e a t h , ( b ) adverse e f f e c t s , ( c )
t r a n s i t i o n a l e f f e c t s , o r ( d ) no e f f e c t s ( s e e F i g u r e 1 ) . T h i s a l l o w s
f o r the e v a l u a t i o n o f v a r i o u s doses and t h e i r c o r r e s p o n d i n g e f f e c t
l e v e l s a t any exposure d u r a t i o n .
T h i s g r a p h i c a p p r o a c h was p r e s e n t e d a t a workshop sponsored by
U.S. EPA i n J u l y 1983 and a t t e n d e d by over 50 s c i e n t i s t s from
academia, i n d u s t r y , e n v i r o n m e n t a l groups and government. The con-
sensus o p i n i o n was t h a t t h i s approach i s g e n e r a l l y a c c e p t a b l e and

s h o u l d be used (4) The main r e s e r v a t i o n s were t h a t t h e a p p r o a c h
tends t o be somewhat s u b j e c t i v e and t h a t a s t a t i s t i c a l procedure
s h o u l d be d e s i g n e d t o account f o r t h e o v e r a l l q u a l i t y o f d a t a i n an
o b j e c t i v e manner. The U.S. EPA i s c u r r e n t l y engaged i n work on
t h e s e a s p e c t s o f t h e new approach.
V e r i f i c a t i o n o f U n c e r t a i n t y F a c t o r s . As summarized i n s e v e r a l pub-
l i c a t i o n s , u n c e r t a i n t y f a c t o r s a r e c u r r e n t l y recommended t o e s t i m a t e
a c c e p t a b l e i n t a k e s f o r s y s t e m i c t o x i c a n t s (1,13,18). The s e l e c t i o n
of these f a c t o r s i n g e n e r a l r e f l e c t s the u n c e r t a i n t y i n h e r e n t w i t h
the use o f d i f f e r e n t human o r animal t o x i c i t y d a t a ( i . e . , t h e weight
of e v i d e n c e p l a y s a major r o l e i n t h e s e l e c t i o n o f u n c e r t a i n t y
factors). F o r example, an u n c e r t a i n t y f a c t o r o f l e s s than 10 and
perhaps even 1 may be used t o e s t i m a t e an ADI i f s u f f i c i e n t d a t a o f
chronic duration are available on a c h e m i c a l ' s critical toxic
e f f e c t i n a known s e n s i t i v e human p o p u l a t i o n . That i s t o say t h a t
t h i s " i d e a l " d a t a base i s s u f f i c i e n t l y p r e d i c t i v e o f t h e p o p u l a t i o n
t h r e s h o l d dose; t h e r e f o r e , u n c e r t a i n t y f a c t o r s a r e n o t w a r r a n t e d .
An o v e r a l l u n c e r t a i n t y f a c t o r o f 10 might be used t o e s t i m a t e an
a c c e p t a b l e i n t a k e based on c h r o n i c human t o x i c i t y d a t a and would
r e f l e c t the e x p e c t e d i n t r a s p e c i e s v a r i a b i l i t y t o the adverse e f f e c t s
of a c h e m i c a l i n t h e absence o f c h e m i c a l - s p e c i f i c d a t a . An o v e r a l l
uncertainty factor o f 100 might be used t o e s t i m a t e ADIs w i t h
s u f f i c i e n t c h r o n i c animal t o x i c i t y d a t a ; t h i s would r e f l e c t t h e
e x p e c t e d i n t r a - and i n t e r s p e c i e s v a r i a b i l i t y i n l i e u o f c h e m i c a l -
s p e c i f i c data. However, t h i s o v e r a l l f a c t o r o f 100 might be used
w i t h s u b c h r o n i c human d a t a ; i n t h i s case the 1 0 0 - f o l d f a c t o r would
r e f l e c t i n t r a s p e c i e s v a r i a b i l i t y and a s u b c h r o n i c exposure e x t r a p o -
lation.
An o v e r a l l u n c e r t a i n t y f a c t o r o f 1000 i s used t o e s t i m a t e ADIs
w i t h s a t i s f a c t o r y s u b c h r o n i c animal d a t a ( i f adequate c h r o n i c d a t a
a r e unavailable) I t incorporates the u n c e r t a i n t y i n e x t r a p o l a t i n g
t o x i c i t y d a t a from s u b c h r o n i c t o c h r o n i c exposures as w e l l as t h e
two former u n c e r t a i n t y f a c t o r s . Of c o u r s e , a d d i t i o n a l available
e v i d e n c e , even though s c a n t y , i s a l s o c o n s i d e r e d i n t h e s e i n s t a n c e s .
A v a r i a b l e u n c e r t a i n t y f a c t o r between 1 and 10 i s a p p l i e d t o e s t i m a t e
ADIs u s i n g LOAELs ( i f NOAELs a r e u n a v a i l a b l e ) . This uncertainty

f a c t o r d e f i n e s an exposure l e v e l below t h e LOAEL expected t o be i n
the range o f a NOAEL.
Subsequent p u b l i c a t i o n s have f o c u s s e d on t h e u n c e r t a i n t y f a c t o r
t h a t accounts f o r i n t r a - s p e c i e s v a r i a b i l i t y . F o r example, H a t t i s
and B a l l e w (27) i n v e s t i g a t e d the u n c e r t a i n t y a s s o c i a t e d w i t h human
v a r i a b i l i t y and c o n c l u d e d t h a t a 1 0 - f o l d f a c t o r was an a p p r o p r i a t e
d e f a u l t v a l u e but t h a t i n s p e c i a l c a s e s t h i s v a l u e may be i n a d e q u a t e .
E r d r e i c h and S o n i c h - M u l l i n (22) i d e n t i f i e d s e n s i t i v e subgroups and
c o n c l u d e d t h a t such subgroups were not r a r e when exposures t o mix-
tures of chemicals were considered. R e c e n t l y , C a l a b r e s e (23)
p u b l i s h e d a paper i n r e g a r d t o t h e v a r i a b i l i t y o f human r e s p o n s e t o
the t o x i c i t y o f c h e m i c a l s . H i s c o n c l u s i o n was t h a t l a r g e i n t e r i n -
d i v i d u a l v a r i a t i o n i n response t o t o x i c s u b s t a n c e s e x i s t and e x c e e d -
i n g a 1 0 - f o l d f a c t o r i s n o t uncommon.
In a d d i t i o n t o t h e g r a p h i c approach f o r t o x i c i t y d a t a and the
v e r i f i c a t i o n o f u n c e r t a i n t y f a c t o r s , o t h e r areas a r e under s t u d y
such as r o u t e - t o - r o u t e c o n v e r s i o n , h i g h - d o s e t o low-dose e x t r a p o l a -
t i o n , approaches t o a s s e s s the h e a l t h r i s k from l e s s - t h a n - 1 i f e t i m e
e x p o s u r e s , and r e f i n e m e n t o f r i s k assessment approaches f o r c h e m i c a l
m i x t u r e s . A l l o f t h e s e areas r e p r e s e n t p r o g r e s s i n the methods
used f o r r i s k assessment o f s i n g l e c h e m i c a l s and c h e m i c a l m i x t u r e s .
W i t h the new r i s k assessment g u i d e l i n e s c u r r e n t l y b e i n g d e v e l o p e d ,
the U.S. EPA can move forward t o b e t t e r and more c o n s i s t e n t h e a l t h
r i s k assessments.
Literature Cited
1. "Guidelines and Methodology Used in Preparation of Health Ef-
fects Assessment Chapters of the Consent Decree Water Criteria
Documents," U.S. EPA, 1980. Federal Register 45: 79347, November
28, 1980.
2. Stara, J . F . , M.L. Dourson, and C.T. DeRosa. Proc. Environmental
Risk Assessment, "How New Regulations Will Affect the Utility
Industry," Section 3 - Water Quality Criteria: Methodology and
Applications. EPRI Contract No. WS-80-124, 1981.
3. "Approaches to Risk Assessment for Multiple Chemical Exposures."
Summary of a Workshop held in Cincinnati, OH, Sept. 29-30,
1982. Contract No. 68-03-3111, Doc. No. ECAO-CIN-400. U.S.
EPA, Environmental Criteria and Assessment Office, 1984.
4. "Selected Methods for Risk Assessment of Multiple Chemical
Exposures," Summary of a Workshop held in Cincinnati, OH, July
12-13, 1983, Contract No. 68-03-3111, U.S. EPA, Environmental
Criteria and Assessment Office, 1984.
5. Stara, J . F . , Bruins, R.J.F., Dourson, M.L., Edreich, L.S., and
Hertzberg, R.C. "Risk Assessment is a Developing Science:
Approaches to Improve Evaluation of Single Chemicals and Chemi-
cal Mixtures. 1985. In press.
6. Stara, J . F . , Hertzberg, R.C., Bruins, R.J.F., Dourson, M.L.,
Durkin, P.R, Erdreich, L.S., and Pepelko, W.E. "Approaches
to Risk Assessment of Chemical Mixtures." In: "Chemical Safety
Regulation and Compliance." Proceedings of a course held in
Cambridge, MA, Oct. 24-25, 1983; F. Homburger and J.K. Marquis,
Ed., Basel, Switzerland, 1985.
7. "Proposed Guidelines for the Health Risk Assessment of Chemical

Mixtures and Request for Comments," U.S. EPA, 50 FR 1170, Jan.
19, 1985.
8. CEQ (Council on Environmental Quality), 14th Annual Report of
the Council on Environmental Quality, 1983.
9. CEQ (Council on Environmental Quality), 13th Annual Report of
the Council on Environmental Quality, 1982.
10. Pye, V.I., Patrick, R. and Quarles, J . "Groundwater Contamina-
tion in the United States," Philadelphia, PA, University of
Pennsylvania Press, 1983.
11. Cohen, S.Z., Creeger, S.M., Carsel, R.F. and Enfield, C.G.
"Potential for Pesticide Contamination of Ground Water Resulting
from Agricultural Uses." In: Treatment and Disposal of Pesticide
Wastes, American Chemical Society Symposium Series, 1984.
12. Cotruvo, J.A. and Vogt, C. J . of Am. Water Works Assoc., Nov.
1984; p. 34-38, "Development of Revised Primary Drinking Water
Regulations."
13. "Drinking Water and Health," National Academy of Sciences,
1977.
14. Albert, R.E., Train, R.E., and Anderson, E. J. Natl. Cancer Inst.
58: 1537-1541, 1977. "Rationale Developed by the Environmental
Protection Agency for the Assessment of Carcinogenic Risks."
15. Crump, K.S. J . Environ. Path. Toxicol. 5: 675-684, 1981. "An
Improved Procedure for Low-dose Carcinogenic Risk Assessment
from Animal Data."
16. "Ambient Water Quality Criteria for Aldrin/Dieldrin," U.S. EPA,
No.440/5-80-019. 1980.
17. Walker et al. Food Cosmet. Toxicol. 11: 415, 1972. "The Toxi-
cology of Dieldrin (HEOD). Long-term Oral Toxicity Studies in
Mice."
18. Dourson, M.L. and Stara, J.F. Regul. Toxicol. Pharmacol. 3: 224-
238, 1983. "Regulatory History and Experimental Support of
Uncertainty (Safety) Factors.
19. Weil, C.S. and Carpenter, C.P. "Temik Sulfoxide. Results of
Feeding in the Diet of Rats for Six Months and Dogs for 3 Months."
Mellon Inst. Rept. No. 31-141. EPA Pesticide Petition No.
9F0798, 1968.
20. Mirrow, E . J . , DePass, L.R. and Frank, F.R. "Aldicarb Sulfone:
Aldicarb Sulfoxide Twenty-nine Day Water Inclusion Study on
Rats." Mellon Inst. Rept. No. 45-18, 1982.
21. Erdreich, L.S. Envir. Health Persp. 53: 99-104, 1983. "Compar-
ing Epidemiologic Studies of Ingested Asbestos for Use in Risk
Assessment."
22. Erdreich, L.S. and Sonich-Mullin, C. "Hypersusceptible Subgroups
of the Population in Multichemical Risk Assessment." ECAO-Cin-
400. In "Approaches to Risk Assessment for Multiple Chemical
Exposures. Summary of a Workshop" held in Cincinnati, OH,
Sept. 29-30, 1982, under Contract No. 68-03-3111. U.S. EPA,
Environmental Criteria and Assessment Office, Cincinnati, OH,
1983.
23. Dourson, M.D., Hertzberg, R.C., Hartung, R. and Blackburn, K.
Toxicology and Industrial Health, 1985. "Novel Methods for the
Estimation of Acceptable Daily Intakes."
24. Weil, C.S. and McCollister, D.D. Agric. Food Chem. 11(6): 486-
491, 1963. "Relationship Between Short- and Long-term Feeding
Studies in Designing an Effective Toxicity Test."
25. Weil, C.S., Woodside, M.D, Bernard, V.R. and Carpenter, C.P.
Toxicol. Appl. Pharmacol. 14: 426-431, 1969. "Relationship
Between Single Peroral, One-Week and 90-Day Rat Feeding Studies."
26. McNamara, B.P. "Concepts in Health Evaluation of Commercial and
Industrial Chemicals." In "Advances in Modern Toxicology,"
Vol. 1, Part 1, 1976. M.A. Mehlman, R.E. Shapiro and H.
Blumenthal, Ed. Hemisphere Publishing Co., Washington, D.C.
27. Hattis, D. and Ballew, M. "Human Variability in Susceptibility
to Toxic Chemicals." EPA Contract, L.S. Erdreich, Project
Officer, U.S. EPA, Environmental Criteria and Assessment Office,
Cincinnati, OH, 1983.
28. Calabrese, Edward J . Regulatory Toxicology and Pharmacology 5:
190-196, 1985. "Uncertainty Factors and Inter-Individual
Variation."

26
Risk, Uncertainty, and the Legal Process
Sheila Jasanoff
Program on Science, Technology, & Society, Cornell University, Ithaca, NY 14853
Controversies about risk form an important component in

the caseload of the federal courts. These highly tech
nical disputes are decided by judges with no special

expertise in science and technology. Judicial interven
tion in risk management sometimes leads to questionable
results because the courts do not fully appreciate the
complexities of decision-making in this area. However,
the courts more than compensate for their technical
errors by reinforcing the basic values of fairness and
openness in governmental decision-making and by ensuring
that technical evidence and arguments are presented in a
form that is understandable to the general public.
We l i v e i n a w o r l d t h a t i s i n c r e a s i n g l y dependent on s c i e n c e and
t e c h n o l o g y , but o u r i d e a s about how o u r governmental i n s t i t u t i o n s
s h o u l d be s t r u c t u r e d and o r g a n i z e d go back hundreds o f y e a r s b e f o r e
the i n d u s t r i a l r e v o l u t i o n . T h i s i s p a r t i c u l a r l y t r u e o f our c o u r t s
and o u r l e g a l system. We do n o t expect o u r judges t o be t e c h n i c a l
experts. Indeed, t h e i d e a o f an e x p e r t j u d i c i a r y i s a l i e n t o our
common law t r a d i t i o n . U n l i k e t h e c o u n t r i e s o f C o n t i n e n t a l Europe, we
do not have s e p a r a t e a d m i n i s t r a t i v e t r i b u n a l s t o r e v i e w the d e c i s i o n s
o f government a g e n c i e s . W r i t i n g a t t h e end o f t h e n i n e t e e n t h c e n t u r y ,
the g r e a t E n g l i s h c o n s t i t u t i o n a l s c h o l a r D i c e y o b s e r v e d t h a t " t h i s
i d e a i s u t t e r l y unknown t o t h e law o f England, and i n d e e d i s f u n d a
m e n t a l l y i n c o n s i s t e n t w i t h o u r t r a d i t i o n s and customs" ) . While
European n a t i o n s t r a i n t h e i r judges t o become e x p e r t s i n p a r t i c u l a r
f i e l d s o f law, our l e g a l p r a c t i c e s , such as a s s i g n i n g cases by l o t ,
seem d e s i g n e d t o p r e v e n t any undue c o n c e n t r a t i o n o f s p e c i a l i z e d
knowledge. When a judge j o i n s t h e West German F e d e r a l C o n s t i t u t i o n a l
C o u r t , f o r example, he o r she i s a s s i g n e d an a r e a o f competence and
d e a l s w i t h a l l c a s e s a r i s i n g i n t h a t a r e a , such as f a m i l y law, t a x
law, r e l i g i o u s o r c u l t u r a l m a t t e r s , and t h e c i v i l s e r v i c e . By c o n
t r a s t , we expect o u r Supreme Court j u s t i c e s t o d e a l e q u a l l y w i t h a
whole range o f i s s u e s from sex d i s c r i m i n a t i o n t o e n v i r o n m e n t a l
pollution. We demand no s p e c i a l e x p e r t i s e , not even p r i o r j u d i c i a l
experience.
0097-6156/ 86/ 0315-0462$06.00/ 0

26. JASANOFF Risk, Uncertainty, and the Legal Process 463
S p e c i a l i z a t i o n , as we know, has i t s drawbacks. Depth o f knowledge

can be negated by narrowness o r t r i v i a l i t y . Our s o c i e t y has j e s t i n g l y
d e f i n e d a s p e c i a l i s t as someone who knows more and more about l e s s and
l e s s u n t i l he o r she knows e v e r y t h i n g about n o t h i n g . Anyone who works
i n an academic environment knows t h a t t h e r e i s some substance t o t h i s
charge. In s e l e c t i n g our judges, however, we o f t e n seem t o r e a c h f o r
the o p p o s i t e extreme, s e e k i n g the p e r f e c t g e n e r a l i s t who knows n o t h i n g
about e v e r y t h i n g .
U n f o r t u n a t e l y , as the c e n t u r y draws on our problems seem t o demand
d e c i s i o n - m a k e r s who know e v e r y t h i n g about e v e r y t h i n g . Judges are
c o n f r o n t e d w i t h i s s u e s o f i n c r e a s i n g t e c h n i c a l c o m p l e x i t y , and nowhere
more so than i n the a r e a o f c h e m i c a l r i s k management. C o u r t s , i n our
system o f government, are the l a s t r e s o r t f o r answering a h o s t o f
q u e s t i o n s about the r i s k s p r e s e n t e d by t o x i c s u b s t a n c e s t o h e a l t h and
the environment. In d e c i d i n g whether a r e g u l a t o r y d e c i s i o n about a
hazardous c h e m i c a l i s l e g a l l y v a l i d , c o u r t s must c o n s i d e r a v a r i e t y o f
s u b o r d i n a t e i s s u e s , many o f which are h i g h l y t e c h n i c a l . I f the sub-

s t a n c e causes c a n c e r i n l a b o r a t o r y a n i m a l s , does i t a l s o cause c a n c e r
i n humans? Has the r e g u l a t o r y agency l o o k e d a t the b e s t a v a i l a b l e
e v i d e n c e , used the most r e a s o n a b l e assumptions, and made the most
r e l i a b l e estimate of r i s k ? W i l l the proposed s t a n d a r d p r o t e c t o n l y
h e a l t h y p e o p l e , o r a l s o the o l d , the s i c k and the v e r y young? Are the
recommended c o n t r o l s both e c o n o m i c a l l y and t e c h n o l o g i c a l l y f e a s i b l e ?
Our l e g a l system p r o v i d e s e x c e p t i o n a l l y l i b e r a l o p p o r t u n i t i e s f o r
p a r t i e s t o b r i n g such q u e s t i o n s b e f o r e the c o u r t s . I t a l s o ensures
t h a t arguments about such i s s u e s are d e v e l o p e d and p r e s e n t e d a t a
h i g h l e v e l of t e c h n i c a l s o p h i s t i c a t i o n . A g e n c i e s , f o r example, are
r e q u i r e d by law t o compile d e t a i l e d s c i e n t i f i c r e c o r d s and t o engage
i n reasoned d e c i s i o n - m a k i n g . P r i v a t e f i r m s r o u t i n e l y employ l a r g e
s t o r e s o f e x p e r t i s e i n p r e p a r i n g t h e i r c a s e s a g a i n s t governmental
regulation. Congress has even d e s i g n e d laws t h a t t r y t o p l a c e e n v i -
ronmental and p u b l i c i n t e r e s t groups on a more e q u a l f o o t i n g w i t h
i n d u s t r y by f u n d i n g t h e i r use o f e x p e r t s i n r e g u l a t o r y p r o c e e d i n g s .
Yet the c l a i m s and c o u n t e r c l a i m s made by a l l these p a r t i e s e v e n t u a l l y
a r e reviewed by judges who have no f o r m a l t r a i n i n g i n t o x i c o l o g y ,
e n g i n e e r i n g , economics, o r r i s k assessment.
Of c o u r s e , our judges c o u l d e l e c t t o l i g h t e n t h e i r r e s p o n s i b i l i -
t i e s by d e f e r r i n g t o the t e c h n i c a l o p i n i o n s o f a g e n c i e s and o t h e r
expert a u t h o r i t i e s . European c o u r t s have f o l l o w e d j u s t t h i s c o u r s e .
In the European c i v i l law systems, judges e n j o y even g r e a t e r power
than t h e i r common law b r e t h r e n t o second-guess the government's t e c h -
n i c a l d e t e r m i n a t i o n s , but they seldom e x e r c i s e t h i s power. As Ameri-
can a d m i n i s t r a t i v e law has e v o l v e d i n the l a s t f i f t e e n y e a r s , the
f e d e r a l c o u r t s have i n t e r p r e t e d t h e i r duty t o s u p e r v i s e government
a g e n c i e s much more c o n s c i e n t i o u s l y . Under the d i r e c t i o n o f such n o t e d
j u r i s t s as Judge B a z e l o n , Judge S k e l l y W r i g h t , and the l a t e Judge
L e v e n t h a l o f the D.C. C i r c u i t Court o f A p p e a l s , the f e d e r a l c o u r t s
have c o n c l u d e d t h a t they s h o u l d c l o s e l y s c r u t i n i z e the way i n which
a g e n c i e s c o l l e c t and a n a l y z e t e c h n i c a l i n f o r m a t i o n . I t i s a b a s i c
r u l e o f a d m i n i s t r a t i v e law t h a t c o u r t s must not s u b s t i t u t e t h e i r
judgment f o r t h a t o f the a g e n c i e s . Judges, however, can and do make
s e a r c h i n g i n q u i r i e s i n t o the r e c o r d s d e v e l o p e d by r e g u l a t o r y a g e n c i e s
to ensure t h a t a d m i n i s t r a t o r s have taken a " h a r d l o o k " a t a l l the
r e l e v a n t f a c t o r s , based t h e i r f a c t u a l c o n c l u s i o n s on " s u b s t a n t i a l
e v i d e n c e , " and c o n v i n c i n g l y e x p l a i n e d t h e reasons f o r t h e i r p o l i c y

c h o i c e s (2-3)
Many i n t h e s c i e n t i f i c community a r e s k e p t i c a l about t h e a b i l i t y
of t e c h n i c a l l y u n t r a i n e d judges t o c a r r y out t h e s e s u p e r v i s o r y t a s k s .
How c a n judges w i t h no s c i e n t i f i c background hope t o a d j u d i c a t e c o n -
f l i c t s among e x p e r t s i n h i g h l y s p e c i a l i z e d f i e l d s o f knowledge? Can
c o u r t s r e a l l y u n d e r s t a n d t h e c r i t e r i a t h a t s c i e n t i s t s use t o judge the
r e l a t i v e s t r e n g t h s and weaknesses o f s c i e n t i f i c arguments? We know
t h a t t h e f i n e p o i n t s o f r i s k and p r o b a b i l i t y a r e l o s t on most members
of the l a y p u b l i c . There i s e v i d e n c e t h a t judges a r e not l i k e l y t o
f a r e any b e t t e r . They t o o c a n be e a s i l y swayed by p r e c i s e numbers,
f a i l i n g to understand the m u l t i p l e u n c e r t a i n t i e s b u r i e d i n p r o b a b i l -
i s t i c statements about r i s k ( 4 - 5 ) . Indeed, when t e c h n i c a l arguments
become t o o complex, judges may be i n c l i n e d t o r e t r e a t from the s c i e n -
t i f i c a s p e c t s o f d e c i s i o n - m a k i n g and d e c i d e c a s e s p u r e l y on t h e b a s i s
of p o l i c y and p o l i t i c s . These and s i m i l a r f e a r s account f o r t h e c o n -
t i n u i n g p o p u l a r i t y o f t h e i d e a t h a t a " s c i e n c e c o u r t " o r some o t h e r

" o b j e c t i v e " forum s h o u l d a d j u d i c a t e c o n f l i c t s t h a t seem t o l i e beyond
the g r a s p o f our a r c h a i c , g e n e r a l i s t j u d i c i a l system.
In the remainder o f t h i s paper, I would l i k e t o a d d r e s s some o f
these concerns i n the l i g h t o f recent j u d i c i a l d e c i s i o n s i n v o l v i n g
toxic chemicals. There i s no doubt t h a t examples c a n be found t o show
t h a t some f e a r s about the l a y j u d i c i a r y a r e w a r r a n t e d . Judges do g e t
i n t o s e r i o u s muddles and m i s t a k e s when d e a l i n g w i t h h i g h l y t e c h n i c a l
issues. Yet I hope t o show i n the second p a r t o f the paper t h a t these
problems a r e c o u n t e r b a l a n c e d by important s o c i a l and p o l i t i c a l v a l u e s
that g e n e r a l i s t courts preserve i n d e a l i n g with c o n t r o v e r s i e s at the
f r o n t i e r s o f s c i e n t i f i c knowledge. T h i s i s our u l t i m a t e j u s t i f i c a t i o n
f o r r e t a i n i n g the i n s t i t u t i o n s we have i n h e r i t e d from the p a s t .
C o u r t s and S c i e n c e ; A Failed Relationship?
L o o k i n g a t t h e r e c e n t h i s t o r y o f e n v i r o n m e n t a l l i t i g a t i o n , one can
p o i n t t o numerous c a s e s t h a t r a i s e q u e s t i o n s about the j u d i c i a l
c a p a c i t y t o d i s t i n g u i s h good s c i e n c e from bad. I t i s not u n u s u a l
t o f i n d judges a g r e e i n g w i t h agency d e c i s i o n s t h a t s c i e n t i s t s b e l i e v e
1
were based on unsound s c i e n c e . The involvement o f the c o u r t s i n E P A s
e f f o r t s t o r e g u l a t e c h e m i c a l c a r c i n o g e n s i s one example. In the
agency's e a r l i e s t y e a r s , t h e c o u r t s were a major f o r c e i n r e q u i r i n g
EPA t o take a tougher s t a n d on p o t e n t i a l l y c a r c i n o g e n i c p o l l u t a n t s .
The D i s t r i c t o f Columbia C i r c u i t C o u r t , which reviewed a s e r i e s o f
agency d e c i s i o n s c o n c e r n i n g t h e c h l o r i n a t e d h y d r o c a r b o n p e s t i c i d e s ,
i n s t r u c t e d EPA t h a t i t would look v e r y s u s p i c i o u s l y a t d e c i s i o n s n o t
to r e g u l a t e s u b s t a n c e s showing p o s i t i v e r e s u l t s i n animal t e s t s ( 6 ) .
C r i t i c s o f EPA's c u r r e n t r e g u l a t o r y p r i o r i t i e s charge t h a t such j u d i -
c i a l d i r e c t i v e s were r e s p o n s i b l e f o r t h e agency's d i s p r o p o r t i o n a t e l y
heavy investment i n c a r c i n o g e n r e g u l a t i o n d u r i n g the p a s t decade.
I t i s p o s s i b l e t o draw up a p o w e r f u l i n d i c t m e n t o f the j u d i c i a r y ' s
r o l e i n s c i e n t i f i c d e c i s i o n - m a k i n g from t h e s t r i n g o f c a s e s i n v o l v i n g
EPA's r e g u l a t i o n o f DDT, a l d r i n / d i e l d r i n , h e p t a c h l o r / c h l o r d a n e , and
Mirex. F i r s t , by a t t a c h i n g g r e a t weight t o e v i d e n c e o f animal c a r -
c i n o g e n c i t y , the c o u r t s h e l p e d extend t h e p r i n c i p l e o f the Delaney
C l a u s e i n t o t h e a r e a o f p e s t i c i d e c o n t r o l . In so d o i n g , they e n l a r g e d
the a p p l i c a b i l i t y o f a p r o v i s i o n t h a t s c i e n t i s t s c o n s i d e r almost s y n -
onymous w i t h bad s c i e n c e . Second, the c o u r t s a r g u a b l y d e f e r r e d too
f a r t o EPA on some o f i t s more q u e s t i o n a b l e s c i e n c e p o l i c y d e c i s i o n s .

1
For example, the c o u r t s a c c e p t e d E P A s use o f " c a n c e r p r i n c i p l e s " (2)
as a b a s i s f o r making r i s k d e t e r m i n a t i o n s , a l t h o u g h s c i e n t i s t s , then
as now, agreed t h a t the p r i n c i p l e s were c o n c e p t u a l l y s i m p l i s t i c ,
u n s c i e n t i f i c , and d a n g e r o u s l y r i g i d . T h i r d , the j u d i c i a l d e c i s i o n s
r e f l e c t e d and even m a g n i f i e d the p u b l i c ' s f e a r o f c a n c e r , a f f i r m i n g
the s c i e n t i f i c a l l y n a i v e b e l i e f t h a t even the s m a l l e s t c o n t a c t w i t h a
c a r c i n o g e n i s dangerous enough t o m e r i t s t r i c t r e g u l a t i o n . The p e s -
t i c i d e c a s e s thus h e l p e d undermine reasoned debate about c a n c e r r i s k s .
Yet the p u b l i c ' s demand f o r complete p r o t e c t i o n a g a i n s t c h e m i c a l c a r -
c i n o g e n s i s u n r e a l i s t i c , and an e x c l u s i v e f o c u s on i d e n t i f y i n g and
c o n t r o l l i n g t h e s e s u b s t a n c e s d i v e r t s needed r e s o u r c e s from r e g u l a t i n g
more s u b s t a n t i a l r i s k s to p u b l i c h e a l t h .
Another c r i t i c i s m l e v e l e d a g a i n s t the c o u r t s i s t h a t they p e r m i t
p o l i c y c o n s i d e r a t i o n s to o v e r r i d e v a l i d s c i e n t i f i c f i n d i n g s . One
f r e q u e n t l y c i t e d example i s the outcome i n the Agent Orange c a s e ,
which i n v o l v e d a massive l a w s u i t by Vietnam v e t e r a n s a g a i n s t the

m a n u f a c t u r e r s of the h e r b i c i d e ( 8 ) . Judge W e i n s t e i n , who p r e s i d e d
over the l a t t e r s t a g e s o f t h i s l i t i g a t i o n , acknowledged t h a t the p r o o f
o f c a u s a t i o n s u p p l i e d by the v e t e r a n s ' groups was so weak t h a t i t
p r o b a b l y would not support a f i n d i n g o f l i a b i l i t y a g a i n s t the d e f e n -
dant m a n u f a c t u r e r s . Why then d i d the judge encourage and a c c e p t a
s e t t l e m e n t t h a t r e q u i r e d the m a n u f a c t u r e r s t o pay m i l l i o n s o f d o l l a r s
to the v e t e r a n s ? Some have argued t h a t the outcome was d i c t a t e d by
the judge's p e r s o n a l p o l i c y p r e f e r e n c e s . H i s view t h a t some r e p a r a -
t i o n s h o u l d be made t o the Vietnam v e t e r a n s took precedence o v e r h i s
i n t e r e s t i n l e t t i n g s c i e n c e speak f o r i t s e l f .
C r i t i c i s m o f the c o u r t s i n the a r e a o f r i s k management i s by no
means o n e - s i d e d . E n v i r o n m e n t a l and l a b o r groups a r e q u i t e p r e p a r e d t o
j o i n w i t h i n d u s t r y i n c o m p l a i n i n g about j u d i c i a l m i s r e a d i n g s o f s c i -
e n t i f i c i n f o r m a t i o n . One d e c i s i o n t h a t has been r o u n d l y c r i t i c i z e d by
p u b l i c i n t e r e s t groups i s the F i f t h C i r c u i t C o u r t ' s o v e r r u l i n g o f the
attempt by the Consumer Product S a f e t y Commission (CPSC) t o ban u r e a -
formaldehyde foam i n s u l a t i o n (UFFI) ( 9 ) . In the c o u r s e o f i t s r u l e -
making on UFFI, CPSC c o m p i l e d 102 volumes o f s u p p o r t i n g d a t a and
analysis. To f a c i l i t a t e j u d i c i a l r e v i e w , the agency i d e n t i f i e d the
p a r t s o f the r e c o r d i t r e l i e d on, the p a r t s i t r e j e c t e d , and i t s r e a -
sons f o r d o i n g so. Yet the c o u r t c o n c l u d e d t h a t the proposed ban was
not s u p p o r t e d by s u b s t a n t i a l e v i d e n c e .
One o f C P S C s c o m p e l l i n g reasons f o r banning UFFI was a s t u d y done
by the Chemical I n d u s t r y I n s t i t u t e o f T o x i c o l o g y ( C U T ) which showed
t h a t formaldehyde causes c a n c e r i n r a t s a t two exposure doses ( 1 0 ) .
CPSC used the data from the C U T study t o e s t i m a t e the r i s k o f c a n c e r
to p e o p l e l i v i n g i n homes i n s u l a t e d w i t h UFFI, a p r o d u c t t h a t i s known
t o emit gaseous formaldehyde when i t i s i m p r o p e r l y i n s t a l l e d . As i n
any r i s k assessment, CPSC had t o make s e v e r a l assumptions about the
p r o b a b l e d u r a t i o n and i n t e n s i t y o f human exposure t o the t o x i c agent.
Most o f these were c h a l l e n g e d by the formaldehyde i n d u s t r y . To o b t a i n
a n u m e r i c a l e s t i m a t e o f the human r i s k , CPSC a p p l i e d t o the C U T data
a m a t h e m a t i c a l model ( G l o b a l 79) which s t a t i s t i c a l l y c a l c u l a t e s an
upper l i m i t on r i s k and i n c o r p o r a t e s some s t a n d a r d assumptions about
the mechanism o f c a n c e r c a u s a t i o n . Formaldehyde m a n u f a c t u r e r s c h a l -
l e n g e d many o f C P S C s assumptions, as w e l l as the l e g i t i m a c y o f
a p p l y i n g any mathematical r i s k e x t r a p o l a t i o n model t o the a v a i l a b l e
t o x i c o l o g i c a l data on formaldehyde. The c o u r t agreed w i t h the i n d u s

t r y t h a t C P S C s exposure measurements were open t o q u e s t i o n . More
i m p o r t a n t , the c o u r t r e j e c t e d the agency's attempt t o d e r i v e a numer
i c a l l y p r e c i s e e s t i m a t e o f r i s k from i n h e r e n t l y i m p r e c i s e e x p e r i m e n t a l
data.
In t r a c i n g the c o u r t ' s r e a s o n i n g , one can p o i n t to apparent gaps
i n the j u d g e s ' u n d e r s t a n d i n g o f the t h e o r y and p r a c t i c e of r i s k
assessment. For example, the c o u r t took CPSC t o t a s k f o r e s t i m a t i n g
the c a n c e r r i s k to humans on the b a s i s o f a " s i n g l e e x p e r i m e n t , p a r
t i c u l a r l y one i n v o l v i n g o n l y 240 s u b j e c t s . " T h i s o b j e c t i o n suggests
t h a t the c o u r t was u n f a m i l i a r w i t h the p r i n c i p l e s o f animal t e s t i n g ,
which r e c o g n i z e t h a t i t i s a p p r o p r i a t e t o t e s t s m a l l numbers o f a n i
mals a t h i g h doses i n o r d e r to d e t e c t s m a l l i n c r e a s e s i n r i s k caused
by t o x i c c h e m i c a l s . L a r g e r numbers o f a n i m a l s cannot n o r m a l l y be used
i n b i o a s s a y s because o f the p r o h i b i t i v e c o s t s o f r u n n i n g such e x p e r i
ments. The s i z e o f the C U T study was w e l l i n a c c o r d w i t h a c c e p t e d
standards f o r cancer t e s t i n g .
The c o u r t was a l s o on q u e s t i o n a b l e ground i n s u g g e s t i n g t h a t CPSC
s h o u l d have used more than one study i n i t s r i s k assessment. Under
a p p r o p r i a t e c i r c u m s t a n c e s , t o x i c o l o g i s t s a r e p r e p a r e d t o a c c e p t even
one w e l l - d e s i g n e d and w e l l - c o n d u c t e d a n i m a l study as a r e l i a b l e b a s i s
f o r r i s k e x t r a p o l a t i o n . Indeed, the c o u r t ' s s k e p t i c i s m about the CUT
d a t a was not shared by a p a n e l o f e x p e r t s s u b s e q u e n t l y convened by EPA
t o e v a l u a t e the h e a l t h e f f e c t s o f formaldehyde. T h i s consensus work
shop found t h a t the C U T b i o a s s a y r e s u l t s were s u i t a b l e f o r use i n a
r i s k assessment, whereas the a v a i l a b l e e p i d e m i o l o g i c a l s t u d i e s on
formaldehyde were i n a p p r o p r i a t e f o r t h i s purpose ( 1 1 ) .
The F i f t h C i r c u i t ' s d e c i s i o n on formaldehyde has won s u p p o r t from
s c i e n t i s t s who c o n s i d e r C P S C s c h o i c e o f the G l o b a l 79 model i l l -
advised. But even i f one agrees w i t h the case on s u b s t a n t i v e grounds,
one may have t o a c c e p t the f a c t t h a t the c o u r t reached the r i g h t
r e s u l t f o r the wrong r e a s o n s . The formaldehyde o p i n i o n c r e a t e s the
i m p r e s s i o n o f a t e c h n i c a l l y n a i v e c o u r t demanding f a r g r e a t e r c e r
t a i n t y than the a r t o f r i s k assessment i s c u r r e n t l y a b l e t o p r o v i d e .
Moreover, i n r e j e c t i n g C P S C s p r o p o s a l on a p p a r e n t l y s c i e n t i f i c
grounds, the c o u r t o v e r l o o k e d the b l e n d i n g o f s c i e n c e and p o l i c y t h a t
i s i n v o l v e d i n any attempt to a s s e s s c a r c i n o g e n i c r i s k . The p r i n c i p l e
o f j u d i c i a l r e s t r a i n t i n American a d m i n i s t r a t i v e law d i r e c t s t h a t
c o u r t s s h o u l d be v e r y c a r e f u l not to second-guess the r e g u l a t o r y
a g e n c i e s i n the a r e a o f s c i e n c e p o l i c y . Even i f an agency d e c i s i o n
appears t e c h n i c a l l y unsound, c o u r t s s h o u l d r e f r a i n from t r y i n g t o
c o r r e c t the agency u n l e s s t h e r e has been a c l e a r abuse o f d i s c r e t i o n .
Not s u r p r i s i n g l y t h e r e f o r e , most a n a l y s t s o f the formaldehyde case
have c o n c l u d e d t h a t the F i f t h C i r c u i t m i s c o n s t r u e d i t s r o l e i n
r e v i e w i n g r i s k assessment d e c i s i o n s and i m p e r m i s s i b l y s u b s t i t u t e d
i t s own judgment f o r t h a t o f CPSC (3, 12-13).
The Supreme Court has a l s o spoken on the i s s u e o f r i s k assessment
i n ways t h a t a r e troublesome and c o n f u s i n g . The o c c a s i o n f o r the High
C o u r t ' s involvement w i t h c h e m i c a l r i s k s was a l a w s u i t by the p e t r o l e u m
i n d u s t r y c h a l l e n g i n g the new workplace s t a n d a r d f o r benzene p r o m u l
g a t e d by the O c c u p a t i o n a l S a f e t y and H e a l t h A d m i n i s t r a t i o n (OSHA)
( 1). One d i s t u r b i n g a s p e c t o f the c o u r t ' s d e c i s i o n was the f a i l u r e
o f the n i n e j u s t i c e s t o a r t i c u l a t e any c l e a r p r i n c i p l e s to g u i d e
agencies i n f u t u r e cases i n v o l v i n g t o x i c chemicals. J u s t i c e Rehnquist
e x e m p l i f i e d the r e l u c t a n c e o f some judges t o review the t e c h n i c a l
26. JASANOFF Risk, Uncertainty, and the Ingal Process 467
a s p e c t s o f c o n t r o v e r s i e s about r i s k . S i d e s t e p p i n g the complex s c i e n -

t i f i c arguments o f f e r e d by the p a r t i e s , Rehnquist r e s u r r e c t e d a doc-
t r i n e c o n s i d e r e d dead s i n c e the e a r l y days of the New D e a l and
d e c l a r e d t h a t the s t a t u t o r y s e c t i o n under which OSHA had i s s u e d the
benzene s t a n d a r d was u n c o n s t i t u t i o n a l . The a p p r o p r i a t e s o l u t i o n , i n
h i s view, was to r e t u r n the s t a t u t e t o Congress f o r c l e a r e r l e g i s l a -
t i v e guidance.
The r e m a i n i n g e i g h t j u s t i c e s engaged i n a d e t a i l e d e x a m i n a t i o n o f
the r e c o r d , but were u n a b l e t o agree whether o r not OSHA had mustered
an adequate s c i e n t i f i c argument i n support o f the p r o p o s e d benzene
standard. A p l u r a l i t y of f o u r found t h a t OSHA had not made a c r u c i a l
f a c t u a l f i n d i n g . S p e c i f i c a l l y , the agency had f a i l e d t o show t h a t
t h e r e was a s i g n i f i c a n t r i s k to the h e a l t h of workers a t the c u r r e n t
exposure s t a n d a r d . Yet i f we a c c e p t the agency's c o n t e n t i o n t h a t
t h e r e i s no s a f e t h r e s h o l d of exposure t o c a r c i n o g e n s a p o s i t i o n f o r
which t h e r e i s c o n s i d e r a b l e support i n s c i e n c e t h e n i t i s a r g u a b l e
t h a t the agency's showing o f r i s k s h o u l d have been judged s u f f i c i e n t

as a m a t t e r of law. Benzene i s known to cause leukemia i n humans, and
the n o - t h r e s h o l d h y p o t h e s i s i m p l i e s t h a t t h i s r i s k cannot be r u l e d out
at any exposure l e v e l . Whether the r i s k a t the 10 ppm exposure s t a n -
dard i s " s i g n i f i c a n t " i s i n l a r g e p a r t a p o l i c y judgment, and OSHA's
d e t e r m i n a t i o n on t h i s i s s u e was e n t i t l e d t o g r e a t d e f e r e n c e from the
court.
The benzene d e c i s i o n was c o n s t r u e d by the f e d e r a l r e g u l a t o r y
a g e n c i e s as a mandate from the Supreme C o u r t to p e r f o r m q u a n t i t a t i v e
r i s k assessments i n the c o u r s e of s t a n d a r d - s e t t i n g . But i n our p r e s -
ent w o e f u l l y i n c o m p l e t e s t a t e of knowledge about c a n c e r c a u s a t i o n and
about the r i s k s of p a r t i c u l a r c h e m i c a l s , we can ask whether t h i s was a
wise d i r e c t i v e . For many t o x i c s u b s t a n c e s , the data a r e too s k e t c h y
t o p e r m i t q u a n t i t a t i v e a n a l y s i s , and r i s k assessment can o n l y c r e a t e
an a r t i f i c i a l i m p r e s s i o n o f p r e c i s i o n . Indeed, g i v e n the u n c e r t a i n -
t i e s i n v o l v e d i n exposure assessment, h i g h - t o - l o w dose e x t r a p o l a t i o n ,
and e x t r a p o l a t i o n s from a n i m a l t o man, most r e g u l a t o r y d e c i s i o n s based
on m a t h e m a t i c a l models run a s e r i o u s r i s k o f b e i n g d i s m i s s e d by the
c o u r t s as " a r b i t r a r y and c a p r i c i o u s . " Yet t h i s i s j u s t the o p p o s i t e
o f what f o u r members o f the Supreme Court c o n c l u d e d i n the benzene
case.
A Brighter Appraisal
I f we concede t h a t c o u r t s , a t t h e i r b e s t , are unable t o r e s o l v e gen-

u i n e s c i e n t i f i c c o n t r o v e r s i e s , and t h a t they o f t e n are c o n f u s e d or
j u s t p l a i n wrong on t e c h n i c a l m a t t e r s , then why s h o u l d they c o n t i n u e
t o p l a y such a major r o l e i n r i s k management? The answer i s t h a t ,
d e s p i t e t h e i r t e c h n i c a l s h o r t c o m i n g s , c o u r t s u p h o l d v a l u e s t h a t are
c e n t r a l to our t r a d i t i o n s o f p u b l i c d e c i s i o n - m a k i n g and t h a t i t i s
c r u c i a l t o m a i n t a i n t h e s e v a l u e s i n the p r o c e s s o f r e g u l a t i n g t e c h -
nological risks. I would argue, as w e l l , t h a t c o u r t s can s u c c e s s f u l l y
a s s e r t t h e s e v a l u e s even i n c a s e s where they are not i n f u l l command
o f the s c i e n t i f i c and t e c h n i c a l arguments.
The f i r s t of t h e s e v a l u e s i s f a i r n e s s . In the U.S. c o n s t i t u -
t i o n a l t r a d i t i o n , judges a r e s t e e p e d i n the n o t i o n o f due p r o c e s s .
T h i s means t h a t they are a c u t e l y aware o f the i n d i v i d u a l ' s r i g h t t o
be h e a r d b e f o r e b e i n g d e p r i v e d o f an i m p o r t a n t r i g h t or l i b e r t y
t h r o u g h governmental a c t i o n . C o u r t s are s p e c i a l l y s e n s i t i v e t o agency
d e c i s i o n s t h a t seem to c u r t a i l the r i g h t to be h e a r d w i t h o u t p r o v i d i n g
adequate j u s t i f i c a t i o n .
The UFFI case I d i s c u s s e d e a r l i e r seems much l e s s p r o b l e m a t i c i f
we view i t as a j u d i c i a l attempt to ensure f a i r n e s s i n the r e g u l a t o r y
process. Congress a u t h o r i z e d CPSC t o r e g u l a t e t o x i c s u b s t a n c e s under
two major s t a t u t e s , the Consumer Product S a f e t y Act (CPSA) and the
F e d e r a l Hazardous Substances Act (FHSA). The l a t t e r s t a t u t e c a l l s f o r
more formal r u l e m a k i n g p r o c e d u r e s than the former. Under the FHSA,
e v i d e n c e must be p r e s e n t e d a c c o r d i n g to l e g a l r u l e s of e v i d e n c e , and
p a r t i e s have a r i g h t to cross-examine w i t n e s s e s . CPSC, however, chose
to r e g u l a t e UFFI under the p r o c e d u r a l l y l e s s demanding s t a t u t e . The
F i f t h C i r c u i t c o n c l u d e d t h a t t h i s c h o i c e was not p r o p e r l y m o t i v a t e d ,
s i n c e CPSC had not e s t a b l i s h e d t o the c o u r t ' s s a t i s f a c t i o n t h a t the
p u b l i c i n t e r e s t would be b e t t e r s e r v e d by a p r o c e e d i n g under the CPSA.
Lawyers may w e l l d i f f e r as t o whether the c o u r t c o r r e c t l y a s s e s s e d the
r e l a t i o n s h i p between the two s t a t u t e s or the e x t e n t of C P S C s d i s c r e -
t i o n t o choose between them. But the F i f t h C i r c u i t ' s o v e r a l l judgment

t h a t CPSC p a i d i n s u f f i c i e n t heed to the UFFI m a n u f a c t u r e r s ' p r o c e d u r a l
r i g h t s d e s e r v e s a t t e n t i o n . And t h i s p a r t of the c o u r t ' s o p i n i o n can
be t a k e n as a u t h o r i t a t i v e even i f we d i s m i s s the comments on C P S C s
r i s k assessment as t e c h n i c a l l y f l a w e d .
The j u d i c i a l c o n c e r n f o r f a i r n e s s a l s o e x p l a i n s the outcome i n
" t o x i c t o r t " l a w s u i t s such as the Agent Orange c a s e . In such l i t i g a -
t i o n , the r i s k i s not p u r e l y c o n j e c t u r a l , s i n c e the case s t a r t s w i t h
someone who has a c t u a l l y been i n j u r e d . The problem f o r the p l a i n t i f f
i s t o prove t h a t the i n j u r y was caused by an i d e n t i f i a b l e p o l l u t i n g
a c t i v i t y or t o x i c p r o d u c t . But c o u r t s have r e c o g n i z e d t h a t i t i s
almost i m p o s s i b l e f o r p l a i n t i f f s to prove c a u s a t i o n i n t o x i c t o r t
c a s e s w i t h as much c e r t a i n t y as i n more c o n v e n t i o n a l p r o d u c t s l i a b i l -
i t y cases. The l o n g l a t e n c y and u n c e r t a i n e t i o l o g y of d i s e a s e s
i n d u c e d by t o x i c s u b s t a n c e s , as w e l l as the p o s s i b i l i t y of m u l t i p l e
e x p o s u r e s and s y n e r g i s t i c e f f e c t s , enormously i n c r e a s e the p l a i n t i f f ' s
burden o f p r o o f (15-16). For c o u r t s c o n f r o n t e d by c o m p l a i n t s about
t o x i c s u b s t a n c e s , the p r i m a r y c h a l l e n g e i s to f i n d e q u i t a b l e ways of
a l l o c a t i n g the c o s t of the u n c e r t a i n t i e s t h a t p r e v e n t s t r a i g h t f o r w a r d
showings of c a u s a t i o n . F a i r n e s s demands t h a t t h e r e be some c a u s a l
l i n k between the p l a i n t i f f ' s i n j u r i e s and exposure to the i d e n t i f i e d
t o x i c agent. Yet f a i r n e s s a l s o r e q u i r e s t h a t v i c t i m s be compensated
on something l e s s than a w a t e r t i g h t f a c t u a l showing. Otherwise,
p l a i n t i f f s would r a r e l y r e c o v e r , and the c o s t of s o c i e t y ' s i m p e r f e c t
knowledge would always f a l l on those who are i n j u r e d and those who
a r e f i n a n c i a l l y l e a s t p r e p a r e d t o bear the c o s t . The Agent Orange
s e t t l e m e n t i s one d r a m a t i c i l l u s t r a t i o n o f the f a c t t h a t judges must
u n d e r t a k e a complex w e i g h i n g of s c i e n t i f i c and e q u i t a b l e c o n s i d e r a -
tions in t o x i c t o r t cases. I t u n d e r s c o r e s the f a c t t h a t c o u r t s are
i n s t r u m e n t s f o r d o i n g j u s t i c e as w e l l as f o r e s t a b l i s h i n g t r u t h . And
the outcome i n t h a t case t e a c h e s us t h a t , when n e c e s s a r y , c o u r t s may
t r y t o s a t i s f y the demands of j u s t i c e even i f they cannot meet the
demands of t r u t h .
A second fundamental v a l u e t h a t c o u r t s have imposed on government
a g e n c i e s i n the a r e a o f r i s k r e g u l a t i o n i s t h a t s t a t e power s h o u l d not
be used i n a r b i t r a r y f a s h i o n . One important c o r o l l a r y i s t h a t agen-
c i e s s h o u l d not a c t to r e s t r a i n commercial a c t i v i t y u n l e s s i t p r e s e n t s
more t h a n a n e g l i g i b l e r i s k to p u b l i c h e a l t h and s a f e t y . This p r i n -
c i p l e was i n v o k e d by the D.C. Court o f Appeals i n r e v i e w i n g a d e c i s i o n
by the Food and Drug A d m i n i s t r a t i o n (FDA) t o ban p l a s t i c beverage

c o n t a i n e r s made o f a c r y l o n i t r i l e polymer ( 1 7 ) . I n s u p p o r t i n g t h e ban,
FDA c o n s t r u c t e d a t h e o r e t i c a l argument from t h e most b a s i c s c i e n t i f i c
principles. R e l y i n g on the second law o f thermodynamics, o r t h e d i f -
f u s i o n p r i n c i p l e , t h e agency argued t h a t any two s u b s t a n c e s i n c o n t a c t
must d i f f u s e i n t o each o t h e r , whether o r n o t t h e amounts a r e d e t e c t -
able. T h e r e f o r e , FDA assumed t h a t f r e e a c r y l o n i t r i l e from t h e c o n -
t a i n e r w a l l s would m i g r a t e i n t o the beverage and so become a " f o o d
additive." S i n c e a c r y l o n i t r i l e was d i s c o v e r e d t o be an a n i m a l c a r -
c i n o g e n , FDA f u r t h e r argued t h a t such m i g r a t i o n c o u l d n o t be t o l e r a t e d
under t h e Delaney c l a u s e . The o n l y remedy t h e agency saw was t o p r o -
h i b i t the use o f c o n t a i n e r s made o f a c r y l o n i t r i l e .
In h i s famous e s s a y on two c u l t u r e s ( 1 8 ) , C. P. Snow d e f i n e d t h e
c l a s s o f humanists ( o r n o n - s c i e n t i s t s ) as those who do n o t u n d e r s t a n d
the second law o f thermodynamics. I f we a c c e p t Snow's c h a r a c t e r i z a -
t i o n , then we must c o n c l u d e t h a t t h e c o u r t i n the a c r y l o n i t r i l e c a s e
p a t t e r n e d w i t h the h u m a n i s t s , f o r i t remained unpersuaded by FDA's

a b s t r a c t t h e o r e t i c a l argument. W r i t i n g f o r t h e D.C. C i r c u i t , Judge
L e v e n t h a l h e l d t h a t Congress d i d not i n t e n d FDA t o use i t s r e g u l a t o r y
power j u s t because i t c o u l d c i t e a s c i e n t i f i c p r i n c i p l e t o show t h a t
d i f f u s i o n might o c c u r . R a t h e r , L e v e n t h a l reminded FDA t h a t any s t a t -
ute e n a c t e d by Congress i m p l i c i t l y i n s t r u c t s t h e implementing agency
not t o r e g u l a t e i n s i g n i f i c a n t r i s k s t o p u b l i c h e a l t h and s a f e t y . I f
a g e n c i e s do n o t r e f r a i n from a c t i n g i n t h e s e de m i n i m i s s i t u a t i o n s ,
then they a r e i n e f f e c t o v e r e x t e n d i n g t h e power d e l e g a t e d t o them by
the l e g i s l a t u r e .
The Supreme C o u r t ' s benzene d e c i s i o n , mentioned e a r l i e r , c a n a l s o
be read as an i n j u n c t i o n a g a i n s t r e g u l a t i n g i n s i g n i f i c a n t r i s k s . By
a s k i n g OSHA t o q u a n t i f y t h e r i s k a t t h e e x i s t i n g exposure s t a n d a r d ,
the c o u r t was s e e k i n g r e a s s u r a n c e t h a t t h e r e was indeed a genuine
h e a l t h h a z a r d c o n f r o n t i n g workers exposed t o benzene. Without such a
minimal showing, t h e c o u r t c o u l d not countenance OSHA's imposing m i l -
l i o n s o f d o l l a r s o f a d d i t i o n a l c o s t s on i n d u s t r y i n t h e form o f a
s t r i c t e r exposure l i m i t f o r t h e w o r k p l a c e . The agency had a p o s i t i v e
o b l i g a t i o n t o e x p l a i n why i t c o n s i d e r e d benzene worth r e g u l a t i n g , and
i t s e x p l a n a t i o n s h o u l d have been couched i n terms t h a t t h e r e v i e w i n g
court could e a s i l y understand.
The t h i r d and perhaps most important v a l u e t h a t c o u r t s have
i n c o r p o r a t e d i n t o p u b l i c d e c i s i o n s about r i s k i s the p r i n c i p l e t h a t
governmental a c t i o n s s h o u l d be e x p l a i n e d t o the c o n c e r n e d p u b l i c . I t
may be h a r d f o r us t o remember a time when a g e n c i e s d e a l t i n s e c r e t
w i t h t h e i n t e r e s t s they were r e s p o n s i b l e f o r r e g u l a t i n g , and made
s i g n i f i c a n t p o l i c y d e c i s i o n s without n o t i f i c a t i o n or o p p o r t u n i t i e s f o r
the p u b l i c t o comment. Yet t h e e r a o f open government i s not so o l d
even i n t h e U n i t e d S t a t e s and i t s e q u i v a l e n t has y e t t o m a t e r i a l i z e i n
many o t h e r Western d e m o c r a c i e s .
S i n c e Congress e n a c t e d t h e Freedom o f I n f o r m a t i o n A c t and o t h e r
laws mandating openness i n government, t h e c o u r t s have p l a y e d a c r u -
c i a l r o l e i n e n s u r i n g t h a t p u b l i c o f f i c i a l s r e s p e c t the s p i r i t as w e l l
as the l e t t e r o f t h i s l e g i s l a t i o n . Under t h e w a t c h f u l eye o f the
c o u r t s , openness has g r a d u a l l y become a p a r t o f our a d m i n i s t r a t i v e
culture. F o r example, government a g e n c i e s , no m a t t e r what t h e i r
i d e o l o g i c a l o r p o l i t i c a l o r i e n t a t i o n , a r e committed t o t h e i d e a o f
p r o d u c i n g a p u b l i c r e c o r d and e x p l a i n i n g t h e i r d e c i s i o n s i n terms
of t h e m a t e r i a l c o n t a i n e d i n t h a t r e c o r d . I t i s a l s o a c c e p t e d by
d e c i s i o n - m a k e r s both i n and out of government t h a t even s c i e n t i f i c a l l y

complex p r o c e e d i n g s s h o u l d be made a c c e s s i b l e t o the p u b l i c . The
p r o l i f e r a t i o n of r i s k assessment g u i d e l i n e s from EPA and o t h e r r e g u -
l a t o r y a g e n c i e s r e f l e c t s a d e s i r e t o make t e c h n i c a l d e c i s i o n s as
t r a n s p a r e n t as p o s s i b l e . No doubt t h e s e i n i t i a t i v e s impose more
r i g i d i t y on r i s k assessment than s c i e n t i s t s would i d e a l l y w i s h to see.
But such m e t h o d o l o g i c a l g u i d e l i n e s serve two v a l u a b l e purposes i n
return. They i n f o r m the p u b l i c how the agency proposes to make r i s k
management d e c i s i o n s , thus opening a p o t e n t i a l l y arcane p r o c e s s t o
d e m o c r a t i c c o n t r o l . They a l s o i n t r o d u c e r e g u l a r i t y and p r e d i c t a b i l i t y
i n t o agency a n a l y s e s , thus p r o v i d i n g s a f e g u a r d s a g a i n s t a r b i t r a r y
action.
I t i s a t r i b u t e t o the s u c c e s s of the c o u r t s t h a t sudden, unex-
p l a i n e d s h i f t s i n p o l i c y have r e l a t i v e l y l i t t l e chance of s u c c e s s i n
the U.S. a d m i n i s t r a t i v e p r o c e s s . The c o n t r o v e r s i e s g e n e r a t e d by EPA
d u r i n g the f i r s t Reagan term i l l u s t r a t e t h i s p o i n t . Public reaction
was immediate and h i g h l y n e g a t i v e when EPA attempted t o change i t s

p r i n c i p l e s o f c a r c i n o g e n i c r i s k assessment w i t h o u t adequate n o t i c e o r
open d i s c u s s i o n ( 1 9 ) . Some of the most p o i n t e d c r i t i c i s m came from
members o f the s c i e n t i f i c community who r e c o g n i z e d the i d e o l o g i c a l
r a t h e r t h a n s c i e n t i f i c r e a s o n s u n d e r l y i n g the agency's p r o p o s e d
1
changes. A s i m i l a r o u t c r y g r e e t e d the d e c i s i o n by E P A s O f f i c e of
T o x i c Substances not to r e g u l a t e formaldehyde as a p r i o r i t y s u b s t a n c e
under the T o x i c Substances C o n t r o l Act ( 2 0 ) . A g a i n , the major com-
p l a i n t a g a i n s t the agency was i t s apparent d e v i a t i o n from the s c i e n -
t i f i c p r i n c i p l e s p r e v i o u s l y used w i t h i n EPA f o r c a r c i n o g e n i c r i s k
assessment. To make m a t t e r s worse, the d e p a r t u r e from p r i o r p r a c t i c e
o c c u r r e d w i t h o u t p u b l i c e x p l a n a t i o n and a g a i n s t the recommendations of
the agency's own s c i e n t i f i c s t a f f . Under p r e s s u r e from Congress and
independent s c i e n t i s t s , i n t e n s i f i e d by the t h r e a t of a l a w s u i t , EPA
e v e n t u a l l y reopened the formaldehyde c a s e and a g r e e d to r e c o n s i d e r the
s u b s t a n c e a c c o r d i n g t o i t s own e s t a b l i s h e d g u i d e l i n e s .
The c o u r t s have not o n l y i n s i s t e d t h a t r e g u l a t o r y a c t i o n s be
e x p l a i n e d , but have p r e s s e d a d m i n i s t r a t o r s t o improve the q u a l i t y of
t h e i r explanations. C l o s e s c r u t i n y by the c o u r t s was i n s t r u m e n t a l i n
g e t t i n g a d m i n i s t r a t i v e a g e n c i e s to sharpen the concept of a r e c o r d ,
p a r t i c u l a r l y i n the c o n t e x t of i n f o r m a l r u l e m a k i n g ( 2 1 ) . As a r e s u l t ,
t h e r e i s now something a p p r o a c h i n g a common u n d e r s t a n d i n g among f e d -
e r a l a g e n c i e s about what documents and a n a l y t i c a l m a t e r i a l s s h o u l d be
i n c l u d e d i n a r e c o r d and how t h e s e s h o u l d be p l a c e d b e f o r e the p u b l i c
and the r e v i e w i n g c o u r t s . J u d i c i a l i n s i s t e n c e that explanations be
framed i n ways t h a t judges can u n d e r s t a n d has a l s o f o r c e d g r e a t e r
c l a r i t y i n administrative decision-making. Impatience w i t h i n c o n s i s -
t e n c i e s and o m i s s i o n s i n agency r e a s o n i n g can l e a d a c o u r t to i n v a l i -
date a r e g u l a t o r y d e c i s i o n and t o demand f u r t h e r c l a r i f i c a t i o n . In
the benzene c a s e , f o r example, OSHA's somewhat c o n f u s e d p r e s e n t a t i o n
of the arguments i n s u p p o r t of the new exposure s t a n d a r d c l e a r l y
t r o u b l e d the Supreme C o u r t , as d i d the agency's f a i l u r e t o e x p l a i n
why i t had not p r e p a r e d a f o r m a l c h a r a c t e r i z a t i o n o f the r i s k a t the
e x i s t i n g standard (22).
Judges can use the o b l i g a t i o n to e x p l a i n as a p o w e r f u l weapon
a g a i n s t p a s s i v i t y and d e l a y i n the r e g u l a t o r y p r o c e s s . S i n c e the
e a r l y 1970s, f e d e r a l c o u r t s have i n s i s t e d t h a t i t i s important f o r
government o f f i c i a l s not m e r e l y to j u s t i f y p o s i t i v e d e c i s i o n s t o a c t ,
but to e x p l a i n why no a c t i o n has been t a k e n on a t o x i c h a z a r d . In an
e a r l y case i n v o l v i n g the r e g u l a t i o n of DDT, f o r example, the S e c r e t a r y

of A g r i c u l t u r e r e f u s e d to respond t o a p e t i t i o n from the E n v i r o n m e n t a l
Defense Fund (EDF) t h a t f e d e r a l r e g i s t r a t i o n f o r the p e s t i c i d e be
suspended ( 2 3 ) . The S e c r e t a r y ' s apparent i n t e n t i o n was to w a i t f o r
the c o m p l e t i o n of a d d i t i o n a l s t u d i e s b e f o r e i n i t i a t i n g f o r m a l r e g u l a -
t o r y p r o c e e d i n g s on DDT. The D.C. C i r c u i t C o u r t , however, h e l d t h a t
d e l a y i n t h i s case e f f e c t i v e l y amounted t o a r e f u s a l of the s u s p e n s i o n
request. Yet t h i s n e g a t i v e d e c i s i o n was e s s e n t i a l l y u n r e v i e w a b l e
because i t was r e a c h e d w i t h o u t e x p l a n a t i o n and w i t h o u t the c r e a t i o n of
a supporting record. A c c o r d i n g l y , the c o u r t remanded the case to the
S e c r e t a r y w i t h i n s t r u c t i o n s e i t h e r to determine the s u s p e n s i o n i s s u e
a f r e s h or t o p r o v i d e reasons f o r h i s s i l e n t r e f u s a l to a c t on EDF's
petition. Such j u d i c i a l mandates have h e l p e d d r i v e home the p o i n t
t h a t governmental a g e n c i e s are a c c o u n t a b l e t o the p u b l i c whether they
choose t o r e g u l a t e or to r e f r a i n from a c t i o n .
The Science Court Reconsidered
I have s u g g e s t e d a number of reasons why c o u r t s s h o u l d r e t a i n a major

r o l e i n s h a p i n g r i s k management d e c i s i o n s . One may w e l l ask, however,
whether the burden on the, g e n e r a l i s t j u d i c i a l i n s t i t u t i o n s we have
today c o u l d not be eased by supplementing them w i t h one or more " s c i -
ence c o u r t s " f o r u m s t h a t would be s p e c i a l l y equipped t o d e a l w i t h
technical controversies. Proponents of the concept note t h a t a
s p e c i a l i z e d s c i e n c e c o u r t would add t o , not r e p l a c e , the o r d i n a r y
h i e r a r c h y of c i v i l c o u r t s ( 2 4 ) . The d u t i e s of the s c i e n c e c o u r t would
be r e s t r i c t e d t o the f a c t u a l s i d e of t e c h n i c a l d i s p u t e s . Legal issues
would s t i l l be d e c i d e d by n o n - s p e c i a l i z e d s t a t e and f e d e r a l t r i b u n a l s ,
as they are at p r e s e n t . A c c o r d i n g to a d v o c a t e s of the s c i e n c e c o u r t ,
the t w o - t i e r a d j u d i c a t i o n of t e c h n i c a l c o n t r o v e r s i e s would have an
entirely beneficial effect. C o u r t s s t a f f e d by e x p e r t s would f i r s t
g i v e a s o p h i s t i c a t e d h e a r i n g to the t e c h n i c a l component of the d i s -
pute. Subsequent a d j u d i c a t i o n of the l e g a l i s s u e s would take advan-
tage o f the u n d e r s t a n d i n g of e q u i t y and due p r o c e s s b u i l t up through
c e n t u r i e s of e x p e r i e n c e i n the o r d i n a r y c o u r t s .
A c l o s e l o o k at modern r i s k c o n t r o v e r s i e s s u g g e s t s why t h i s i d e a ,
d e s p i t e i t s s u r f a c e a p p e a l , i s not l i k e l y to prove w o r k a b l e . To b e g i n
w i t h , the concept of the s c i e n c e c o u r t i s based on the premise t h a t
t e c h n i c a l c o n t r o v e r s i e s can be n e a t l y s e p a r a t e d i n t o f a c t u a l (or
t e c h n i c a l ) and l e g a l components. Yet anyone c o n v e r s a n t w i t h r i s k
d i s p u t e s must q u i c k l y c o n c l u d e t h a t the r e v e r s e i s more o f t e n t r u e .
R i s k assessment, i n p a r t i c u l a r , i s known to be a h i g h l y s u b j e c t i v e
p r o c e s s i n which t e c h n i c a l d e t e r m i n a t i o n s are almost i n v a r i a b l y bound
up w i t h d i s c r e t i o n a r y judgments (25). E x p e r t s engaged i n r i s k
assessment are g u i d e d not m e r e l y by t h e i r s p e c i a l i z e d knowledge, but
by i n t u i t i o n and even p e r s o n a l v a l u e s . I t i s d i f f i c u l t to t r e a t
something so c e n t r a l as the s e l e c t i o n of a h i g h - t o - l o w dose e x t r a p o -
l a t i o n model i n c a r c i n o g e n r i s k assessment as a p u r e l y s c i e n t i f i c
matter. The c h o i c e of a more or l e s s c o n s e r v a t i v e s t a t i s t i c a l model
i s l i k e l y to be g u i d e d by too many e x t r a - s c i e n t i f i c c o n s i d e r a t i o n s ,
such as the d e c i s i o n - m a k e r ' s p e r s o n a l a p p r a i s a l of the o v e r a l l r i s k
t h a t c h e m i c a l s p r e s e n t to p u b l i c h e a l t h or e n v i r o n m e n t a l q u a l i t y .
Under c u r r e n t c o n d i t i o n s of u n c e r t a i n t y , the c h o i c e of a r i s k a s s e s s -
ment model becomes a mixed s c i e n t i f i c and p o l i c y i s s u e . Where s c i -
ence does not u n i q u e l y d i c t a t e the c h o i c e , a g e n c i e s must s e l e c t the
a n a l y t i c a l approach most i n k e e p i n g w i t h t h e i r s t a t u t o r y mandate, and

n o n - s p e c i a l i s t c o u r t s must r e v i e w the d e c i s i o n to make sure t h a t the
law has been c o r r e c t l y u n d e r s t o o d .
Even i f the l i n e s between s c i e n c e and law or f a c t s and v a l u e s were
e a s i e r t o draw, something s i g n i f i c a n t would be l o s t by a s s i g n i n g s c i -
e n t i f i c d i s p u t e s to s p e c i a l i s t c o u r t s . As I mentioned above, one of
the most v a l u a b l e s e r v i c e s the c o u r t s can p e r f o r m i n the r i s k manage-
ment p r o c e s s i s t o cement the i d e a t h a t governmental d e c i s i o n s , how-
e v e r t e c h n i c a l , must be e x p l a i n e d i n ways t h a t judges and p r i v a t e
c i t i z e n s can u n d e r s t a n d . I f t h i s p r i n c i p l e were abandoned, then
o f f i c i a l d e c i s i o n - m a k e r s c o u l d a l l too e a s i l y p r o t e c t themselves from
p u b l i c s c r u t i n y , c o n c e a l i n g i n h e r e n t l y a r b i t r a r y d e c i s i o n s beneath a
v e i l of t e c h n i c a l d i s c o u r s e . By r e q u i r i n g e x p e r t s t o be answerable to
l a y s t a n d a r d s of r a t i o n a l i t y and c o n s i s t e n c y , g e n e r a l i s t c o u r t s p r o -
v i d e an i n d i s p e n s a b l e check a g a i n s t the l o s s of p u b l i c c o n t r o l over
regulatory decisions. A p r o l i f e r a t i o n o f s c i e n c e c o u r t s might t i l t
the b a l a n c e too f a r i n f a v o r o f government by t e c h n o c r a t s who are not

f u l l y a c c o u n t a b l e t o the p u b l i c .
I t i s important to remember, as w e l l , t h a t most of the d i s p u t e s
t h a t come to c o u r t i n the a r e a o f r i s k management have no c l e a r c u t
s c i e n t i f i c s o l u t i o n s . These c o n t r o v e r s i e s a r i s e a t the f r o n t i e r s o f
s c i e n c e where, almost by d e f i n i t i o n , t h e r e are no e s t a b l i s h e d o r
w i d e l y a c c e p t e d answers t o s c i e n t i f i c q u e s t i o n s . Moreover, d i s p u t e s
seldom come t o c o u r t u n t i l they have matured i n forums where the
t e c h n i c a l i s s u e s are t h o r o u g h l y debated: s c i e n t i f i c a d v i s o r y commit-
t e e s , a d m i n i s t r a t i v e h e a r i n g s , i n t e r n a l o r e x t e r n a l p e e r r e v i e w , and
p r e t r i a l negotiations. I f t e c h n i c a l c o n f l i c t s p e r s i s t a f t e r a l l these
p r o c e s s e s are e x h a u s t e d , the r e a s o n v e r y p r o b a b l y i s t h a t the m a t t e r
i n c o n t r o v e r s y cannot be s e t t l e d by s c i e n t i s t s a c c o r d i n g t o p u r e l y
s c i e n t i f i c norms.
F i n a l l y , l e t me suggest t h a t we a v o i d the t e m p t a t i o n t o o v e r r e a d
j u d i c i a l d e c i s i o n s c o n c e r n i n g r i s k management. I t would be s i l l y , f o r
example, to argue as some i n d u s t r y r e p r e s e n t a t i v e s have done t h a t the
UFFI d e c i s i o n i s a p r o h i b i t i o n a g a i n s t w o r s t - c a s e r i s k a n a l y s i s o r the
use o f a l i n e a r i z e d m u l t i s t a g e model f o r h i g h - t o - l o w dose e x t r a p o l a -
tion. S i m i l a r l y , the case s h o u l d not be r e a d as p r o v i d i n g s u p p o r t f o r
any p a r t i c u l a r t e c h n i q u e s o f animal t e s t i n g or exposure assessment.
Judges have no a u t h o r i t y t o i s s u e such h i g h l y t e c h n i c a l d i r e c t i v e s to
administrative agencies. C o u r t s are at t h e i r b e s t i n a p p l y i n g c o n -
c e p t s t h a t have a c q u i r e d meaning through g e n e r a t i o n s of p r i o r j u d i c i a l
i n t e r p r e t a t i o n , such as due p r o c e s s , r e a s o n a b l e n e s s , or de m i n i m i s
harm. T h e i r judgments about r i s k management are most a u t h o r i t a t i v e
when e x p l a i n e d i n terms of t h e s e c o n c e p t s . Let us not f a l l i n t o the
t r a p o f p r e s e r v i n g our g e n e r a l i s t c o u r t s but t r e a t i n g t h e i r l e g a l
d e c i s i o n s as the pronouncements of remote s c i e n t i f i c o r a c l e s .
C o u r t s i n Context
In c r i t i c i z i n g the way c o u r t s handle t e c h n i c a l d i s p u t e s , i t i s easy to

l o s e s i g h t of the w i d e r c u l t u r a l and h i s t o r i c a l c o n t e x t w i t h i n which
courts operate. In c l o s i n g , I would l i k e t o c a l l a t t e n t i o n to two
f e a t u r e s of t h i s c o n t e x t , one i n s t i t u t i o n a l and the o t h e r t e m p o r a l .
We s h o u l d r e c a l l at the o u t s e t t h a t l a c k of e x p e r t i s e i s not
u n i q u e l y a c h a r a c t e r i s t i c of the c o u r t s i n our p o l i t i c a l system. Ours
i s a government of g e n e r a l i s t s . There a r e few t e c h n i c a l e x p e r t s i n
Congress, and i t i s d e b a t a b l e how much i n f l u e n c e i s r e a l l y e x e r c i s e d

by c o n g r e s s i o n a l a d v i s o r y b o d i e s such as t h e O f f i c e o f Technology
Assessment and the G e n e r a l A c c o u n t i n g O f f i c e . L e g i s l a t i o n , even i n
t e c h n o l o g i c a l l y complex a r e a s , emerges through a haphazard p r o c e s s o f
t r a d e o f f s and compromise. The s t a t u t e s e n a c t e d by Congress a r e m e r e l y
frameworks f o r c o n t i n u i n g n e g o t i a t i o n between government and p r i v a t e
interests. They do n o t r e s o l v e a l l r e l e v a n t p o l i c y i s s u e s and they
cannot be r e g a r d e d as b l u e p r i n t s f o r s c i e n t i f i c a l l y exact d e c i s i o n -
making. On the c o n t r a r y , t h e f e d e r a l l e g i s l a t i v e p r o c e s s o f t e n p r o -
duces t e c h n i c a l l y n a i v e f o r m u l a t i o n s , such as the Delaney C l a u s e ,
which c r e a t e s e v e r e problems o f i n t e r p r e t a t i o n and i m p l e m e n t a t i o n f o r
both c o u r t s and a d m i n i s t r a t i v e agencies.
The p r e f e r e n c e f o r g e n e r a l i s t s r a t h e r than t e c h n i c i a n s c a r r i e s
over t o the upper e c h e l o n s o f the e x e c u t i v e b r a n c h . Law i s c o n s i d e r e d
a b e t t e r t r a i n i n g ground f o r h i g h a d m i n i s t r a t i v e o f f i c i a l s than s c i -
1
ence. By 1984, f o r example, seven out o f E P A s e i g h t a c t i n g and p e r -
manent a d m i n i s t r a t o r s had been l a w y e r s . U n l i k e Japan and some E u r o -

pean c o u n t r i e s , we do not seek t o b u i l d r e s e r v o i r s o f s p e c i a l i z e d
knowledge and e x p e r i e n c e by c e n t r a l i z i n g p o l i c y - m a k i n g f o r s c i e n c e and
t e c h n o l o g y w i t h i n a s i n g l e c a b i n e t department. Though our p r e s i d e n t s
have t o d i s p l a y l e a d e r s h i p i n economic, i n d u s t r i a l and defense p o l i c y ,
we do n o t expect them t o approach these t a s k s w i t h e x t r a o r d i n a r y
technical expertise. Jimmy C a r t e r , who was known f o r h i s t e c h n i c a l
knowledge and g r a s p o f d e t a i l , f a r e d much worse i n the White House
than h i s s u c c e s s o r Ronald Reagan.
Our g e n e r a l i s t c o u r t s , then, a r e a n a t u r a l e x t e n s i o n o f t h e much
l a r g e r network o f n o n - t e c h n i c a l i n s t i t u t i o n s t h a t govern the U n i t e d
States. These i n s t i t u t i o n s a c c u r a t e l y r e f l e c t t h i s c o u n t r y ' s p l u r a l -
i s t i c p o l i t i c a l process. Government's r o l e i s n o t t o impose i t s own
p o l i c y c h o i c e s on t h e p e o p l e , but t o a r b i t r a t e among competing i n t e r -
e s t s and t o l e t p o l i c y e v o l v e out o f i n t e r a c t i o n s among d i s p a r a t e
groups f o l l o w i n g t h e i r own s e l f - i n t e r e s t s . I t would be i n c o n s i s t e n t
w i t h t h i s v i s i o n o f government t o have any s i n g l e i n t e r e s t dominate
our p o l i t i c a l o r j u d i c i a l i n s t i t u t i o n s , even so p o w e r f u l an i n t e r e s t
as s c i e n c e and t e c h n o l o g y . A p u b l i c m i s t r u s t f u l o f e l i t e s f e e l s more
c o m f o r t a b l e p l a c i n g s c i e n c e and t e c h n o l o g y on a p a r w i t h o t h e r p r i v a t e
i n t e r e s t s , competing f o r r e s o u r c e s and power, i n s t e a d o f e n t r u s t i n g
them w i t h the r e i n s o f government.
The second p o i n t t o remember about t h e c o u r t s i s t h a t they change
over time i n response t o w i d e r s o c i a l and p o l i t i c a l p r o c e s s e s . Peri-
ods o f a c t i v i s m , i n p a r t i c u l a r , a r e succeeded by p e r i o d s o f r e l a t i v e
p a s s i v i t y , a s , f o r example, d u r i n g and a f t e r t h e New D e a l . The surge
o f e n v i r o n m e n t a l and h e a l t h and s a f e t y l e g i s l a t i o n i n t h e 1970s c a l l e d
f o r t h a s p i r i t o f a c t i v e i n t e r v e n t i o n from t h e c o u r t s , who saw them-
s e l v e s as the i n s t i t u t i o n s b e s t q u a l i f i e d t o e f f e c t u a t e t h e apparent
w i l l of the l e g i s l a t u r e . I n the mid-1980's, however, we a r e d e a l i n g
w i t h an a d m i n i s t r a t i v e c u l t u r e t h a t i s v e r y d i f f e r e n t from t h e one
t h a t p r e d o m i n a t e d b e f o r e t h e e n v i r o n m e n t a l movement began. Agencies
now a r e much more s e n s i t i v e t o the need f o r openness i n t e c h n o l o g y -
r e l a t e d decision-making. I have s u g g e s t e d , t o o , t h a t the o b l i g a t i o n
to e x p l a i n t e c h n i c a l d e c i s i o n s i n terms u n d e r s t a n d a b l e t o t h e p u b l i c
i s now r e c o g n i z e d as an i n t e g r a l p a r t o f our a d m i n i s t r a t i v e p r o c e s s .
I f t h i s i s s o , then the c o u r t s have a c c o m p l i s h e d much t h a t they s e t
out t o do, and we c a n expect them t o p l a y a l e s s a c t i v e r o l e i n s u p e r -
v i s i n g r i s k d e c i s i o n s over the next decade. Yet the p e r i o d o f
474 E V A L U A T I O N O F PESTICIDES I NG R O U N D WATER
a c t i v i s m , d e s p i t e some e r r o r s , f l a w s , and wrong t u r n s , has p l a y e d a

c r u c i a l p a r t i n e n s u r i n g t h a t o u r a d m i n i s t r a t i v e p r o c e s s remains under
democratic c o n t r o l .
Conclusion
The r e l a t i o n s h i p between s c i e n c e and t h e c o u r t s i n t h e U n i t e d S t a t e s

cannot be summed up w i t h a neat f o r m u l a i c p h r a s e . Recent j u d i c i a l
d e c i s i o n s i n t h e a r e a o f r i s k management p r o v i d e numerous examples o f
f a u l t y s c i e n t i f i c a n a l y s i s by c o u r t s u n t r a i n e d i n t h e i n t r i c a c i e s o f
r i s k assessment. There i s r e a s o n t o s u s p e c t t h a t c o u r t s do n o t f u l l y
u n d e r s t a n d c o n c e p t s o f p r o b a b i l i t y and u n c e r t a i n t y and t h a t they w i l l
a v o i d l o o k i n g c l o s e l y a t t e c h n i c a l c o n t r o v e r s i e s i f they c a n f i n d an
alternate basis f o r resolving disputes. Y e t j u d i c i a l r e v i e w has
imported i n t o t h e r i s k management p r o c e s s v a l u e s t h a t we c h e r i s h i n
public administration: a sense o f f a i r n e s s , an a v e r s i o n t o a r b i t r a r y
e x e r c i s e s o f power, and a p r e f e r e n c e f o r openness and u n d e r s t a n d a b l e

reasoning. I would n o t deny t h a t t h e r e a r e c o s t s a s s o c i a t e d w i t h o u r
c u r r e n t approach t o j u d i c i a l d e c i s i o n - m a k i n g . The p r o c e s s i s l o n g and
u n t i d y and does n o t always l e a d t o t h e r i g h t o r t h e b e s t r e s u l t s . But
i n s a c r i f i c i n g e f f i c i e n c y and t e c h n i c a l p e r f e c t i o n , we may have g a i n e d
from o u r c o u r t s something f a r more p r e c i o u s : humanism and an a f f i r
m a t i o n t h a t s c i e n c e and t e c h n o l o g y must be put t o use i n ways c o n s i s
tent with our c u l t u r e ' s democratic v a l u e s .
Literature Cited
1. Dicey, . V. "Introduction to the Study of the Law of the Con
stitution"; St. Martin's Press: New York, 1959; p. 203.
2. Rodgers, W. ., Jr. Georgetown Law J . 1979, 67, 699-727.
3. McGarity, T. 0. Sci., Tech., and Human Values 1984, 9, 97-106.
4. Tribe, L. H. Harvard Law Rev. 1971, 84, 1329-93, 1810-20.
5. Finkelstein, M. O.; Fairley, W. B. Harvard Law Rev. 1971, 84,
1801-9.
6. EDF v. Ruckelshaus, 439 F.2d 584 (D. C. Cir. 1971).
7. Karch, N. In "Decision Making in the Environmental Protection
Agency", IIa; National Academy of Sciences, 1977, pp. 119-206.
8. In Re "Agent Orange" Product Liability Litigation, 597 F.Supp. 740
(E. D. . Y. 1984).
9. Gulf South Insulation v. CPSC, 701 F.2d 1137 (5th Cir. 1983).
10. Kerns, W. D.; Pavkov, K. L.; Donofrio, D. J.; Gralla, E. J.;
Swenberg, J.A. Cancer Res. 1983, 43, 4382-92.
11. "Report on the Consensus Workshop on Formaldehyde"; Little Rock,
Ark., 1983, pp. 138-9.
12. Ashford, . .; Ryan, C. W.; Caldart, C. C. Science 1983, 222,
894-900.
13. Davis, D. L. Columbia J . Env. Law 1985, 10, 67-109.
14. Industrial Union Dept. AFL-CIO v. Amer. Petroleum Inst. 448, U.S.
607 (1980).
15. Yale Law J. 1981, 90, 840-62.
16. Delgado, R. Calif. Law Rev. 1982, 70, 881-908.
17. Monsanto v. Kennedy 613 F.2d 947 (D. C. Cir. 1979).
18. Snow, C. P. "The Two Cultures and the Scientific Revolution";
Cambridge University Press: New York, 1959.
19. Marshall, E. Science 1983, 220, 36-7.
20. "Hearing on Formaldehyde: Review of Scientific Basis of EPA's

Carcinogenic Risk Assessment"; U. S. House of Representatives,
97th Cong., 2nd Sess. 1982.
21. Pedersen, W. F., Jr. Yale Law J. 1975, 85, 38-88.
22. Brickman, R.; Jasanoff, S.; Ilgen, T. "Controlling Chemicals: The
Politics of Regulation in Europe and the United States"; Cornell
University Press: Ithaca, . ., 1985; p. 123.
23. EDF v. Hardin, 428 F.2d 1093 (D. C. Cir. 1970).
24. Kantrowitz, A. Am. Sci. 1975, 63, 505-9.
25. "Risk Assessment in the Federal Government: Managing the
Process"; National Academy of Sciences, 1983.
27
Industry Perspective on Pesticide and Ground Water
Legislation
Loy C. Newby and Charles G. Rock
Agricultural Division, CIBA-GEIGY Corporation, Greensboro, NC 27419
Groundwater must be protected - society is in agree-

ment. It is the focus and level of regulatory pro-
tection which concerns the agricultural chemical

industry. Groundwater is not pure. It contains
many substances, both natural and man-made, for most
of which, minimal safety information is available.
With continually improving analytical capability,
additional products are certain to be detected in
even the most pristine aquifers. A few pesticides
have already been detected and it seems likely that
others will be found. In most cases, these will be
substantially below the levels which could result
in adverse effects. Regulatory efforts should be
directed to establishing acceptable levels, while
industry should act to minimize the movement of all
chemicals to groundwaters. Acceptable levels of
chemicals in groundwater should be uniform throughout
the nation. They should be set at the federal level
or by uniform procedures among the state agencies.
A r e c e n t n a t i o n a l p u b l i c o p i n i o n s u r v e y (_1) conducted by the

N a t i o n a l A g r i c u l t u r a l Chemicals A s s o c i a t i o n (NACA) r e v e a l e d t h a t
47% o f a l l Americans b e l i e v e t h a t p e s t i c i d e s and farm f e r t i l i z e r s
are a "major n a t i o n a l problem;" 55% i n c l u d e c h e m i c a l s i n d r i n k i n g
water i n t h i s c a t e g o r y ; and 48% o f a l l Americans a l s o c o n s i d e r
p o l l u t i o n o f underground water as a "major n a t i o n a l problem."
These r e s u l t s r e i n f o r c e the t i m e l i n e s s and importance o f t h i s
t h r e e - d a y symposium.
The v i e w p o i n t s e x p r e s s e d h e r e i n g e n e r a l l y r e f l e c t those o f
the a g r i c u l t u r a l c h e m i c a l i n d u s t r y as r e p r e s e n t e d by NACA. NACA
i s a n o n - p r o f i t t r a d e o r g a n i z a t i o n l o c a t e d i n Washington, DC and
r e p r e s e n t s those companies who manufacture and f o r m u l a t e pest
c o n t r o l p r o d u c t s employed i n a g r i c u l t u r a l p r o d u c t i o n .
Two and one h a l f y e a r s ago, the a g r i c u l t u r a l c h e m i c a l
i n d u s t r y c o n c l u d e d t h a t groundwater was g o i n g to be t h e i s s u e o f
the decade. C o n s e q u e n t l y , NACA e s t a b l i s h e d an ad hoc Group on
0097-6156/ 86/ 0315-0478$06.00/ 0

27. NEWBY AND ROCK Industry Perspective on Legislation 479
Groundwater P r o t e c t i o n c u r r e n t l y c h a i r e d by the p r i n c i p a l a u t h o r .
1
The c o - a u t h o r i s a member o f NACA s S t a t e A f f a i r s Committee (SAC)
which a d d r e s s e s proposed s t a t e l e g i s l a t i o n and r e g u l a t i o n s
i n c l u d i n g those d e a l i n g w i t h groundwater.
I t seems redundant, almost t r i t e , to say t h a t groundwater i s a
v a l u a b l e n a t i o n a l r e s o u r c e , but i t i s and i t must be p r o t e c t e d
no one d i s a g r e e s ! The degree o f p r o t e c t i o n and the means may not
y i e l d the same consensus, however.
E x c e l l e n t papers have been p r e s e n t e d d u r i n g t h i s symposium on
the r e t r o s p e c t i v e and p r o s p e c t i v e appearance o f a g r i c u l t u r a l
c h e m i c a l s i n groundwater. S u b j e c t matter has i n c l u d e d c o n t r i b u t i n g
f a c t o r s to m o b i l i t y such as s o i l and p e s t i c i d e p h y s i c a l and
c h e m i c a l p a r a m e t e r s , how to i n c o r p o r a t e these i n t o p r e d i c t i v e
models and t o x i c o l o g i c a l s i g n i f i c a n c e and r i s k assessment o f
p e s t i c i d e s i n groundwater. I t i s c e r t a i n l y a p p r o p r i a t e t h a t the
t o p i c o f l e g i s l a t i o n / r e g u l a t i o n f o l l o w s the s u b j e c t o f t o x i c o -
l o g i c a l s i g n i f i c a n c e because any r e g u l a t o r y a c t i o n s h o u l d be
dependent on the former. The mere presence o f a s p e c i f i c c h e m i c a l
i n groundwater does not n e c e s s a r i l y mean t h a t t h e r e i s cause f o r
alarm about h e a l t h e f f e c t s .
I t i s acknowledged t h a t c e r t a i n a g r i c u l t u r a l c h e m i c a l s have
been d e t e c t e d i n groundwater and o t h e r s may be found i n the f u t u r e .
D e t e c t s have been at v e r y low c o n c e n t r a t i o n s and the f i n d i n g s have
g e n e r a l l y been a s s o c i a t e d w i t h unusual combinations o f s o i l t y p e ,
h i g h water t a b l e and o t h e r unique e n v i r o n m e n t a l f a c t o r s . A nation-
wide g e n e r i c groundwater problem as a r e s u l t o f p e s t i c i d e a p p l i c a -
t i o n s f o r r e g i s t e r e d uses seems u n l i k e l y .
A comprehensive d a t a base to support t h i s o r the opposing
p o s i t i o n i s l a c k i n g , however, because a nationwide groundwater
m o n i t o r i n g program has never been undertaken f o r a g r i c u l t u r a l
chemicals. I t s h o u l d be n o t e d , though, t h a t a n a t i o n a l s u r v e y i s
b e i n g planned by EPA a t t h i s t i m e . The a v a i l a b i l i t y o f f u n d i n g
w i l l d i c t a t e when the s u r v e y w i l l b e g i n . Currently, only localized
s t u d i e s are a v a i l a b l e and t h e s e can be s e l e c t i v e l y used to support
or argue a g a i n s t the e x t e n t and s e r i o u s n e s s o f a p e s t i c i d e / g r o u n d -
water problem.
Of the a v a i l a b l e d a t a , one o f the b e t t e r assessments o f
o v e r a l l r u r a l d r i n k i n g water q u a l i t y i s p r o v i d e d by a C o r n e l l
U n i v e r s i t y s t u d y completed f o r EPA i n 1982 ( 2 ) . On a s t a t i s t i c a l
b a s i s , i t r e p r e s e n t s 22 m i l l i o n r u r a l h o u s e h o l d s i n the U.S.
B a s i c a l l y , r e p r e s e n t a t i v e water samples were a n a l y z e d f o r about
30 s e p a r a t e b i o l o g i c a l , p h y s i c a l , c h e m i c a l or r a d i o l o g i c a l p r o p e r -
ties. The s t u d y r e p o r t e d the number o f h o u s e h o l d s where the
a n a l y s e s exceeded the Maximum Contaminant L e v e l s (MCLs) as
e s t a b l i s h e d by the EPA, O f f i c e o f D r i n k i n g Water (ODW). The MCL
i s b a s i c a l l y a s t a n d a r d which d e f i n e s a s a f e l e v e l .
The C o r n e l l s t u d y found t h a t most h o u s e h o l d s had problem
l e v e l s w i t h at l e a s t one o f the c o n s t i t u e n t s f o r which an MCL has
been e s t a b l i s h e d . The presence o f c o l i f o r m b a c t e r i a was the most
common problem and was i n excess o f the s t a n d a r d i n 28.9% o f the
households. I r o n , manganese and sodium l e v e l s were a l s o found to
be h i g h f o r a l a r g e number o f the h o u s e h o l d s . N i t r a t e concentra-
t i o n s above the s t a n d a r d o c c u r r e d among 2.7% of the h o u s e h o l d s ,
l e a d i n 16.6%, selenium i n 13.7%, mercury i n 24.1%, and a r s e n i c
i n 0.8% of the h o u s e h o l d s .
There are s i x p e s t i c i d e s which have MCLs and t h e y were a l s o

a n a l y z e d f o r i n the s t u d y . E n d r i n , Toxaphene, 2,4-D, and 2,4,5-T
were not d e t e c t e d and Lindane and methoxychlor were found o n l y at
e x t r e m e l y low c o n c e n t r a t i o n s a t a few s i t e s . These p r o d u c t s are
no l o n g e r used on c r o p s , so s i g n i f i c a n t r e s i d u e s were p r o b a b l y not
e x p e c t e d and were not found.
In summary, 64% o f a l l households were found t o have e x c e s s i v e
c o n c e n t r a t i o n s o f at l e a s t one c o n s t i t u e n t . Over 30% were too h i g h
on two or more c o n s t i t u e n t s . While these f i n d i n g s are somewhat
s t a r t l i n g and were not e x p e c t e d , widespread w a t e r - r e l a t e d h e a l t h
problems were not apparent throughout the r u r a l U.S., a c c o r d i n g
to the C o r n e l l s t u d y . H e a l t h problems may not be common s i m p l y
because MCLs g e n e r a l l y i n c o r p o r a t e s u b s t a n t i a l s a f e t y margins.
R e s u l t s from a more l i m i t e d s t u d y were r e c e n t l y r e p o r t e d
by K e l l y ( 3 ) . Iowa s c i e n t i s t s a n a l y z e d water samples from
128 w e l l s i n v o l v i n g 58 p u b l i c water s u p p l i e s between May 1984
and March 1985. One o r more s y n t h e t i c c h e m i c a l s were found i n

57 w e l l s r e p r e s e n t i n g 33 water s u p p l i e s . T r i h a l o m e t h a n e s , as a
group, were the most commonly o c c u r r i n g s u b s t a n c e s . The most
f r e q u e n t l y d e t e c t e d s i n g l e p r o d u c t was a t r a z i n e , found i n 24 w e l l s .
O v e r a l l , o n l y 6, o f 34 p e s t i c i d e s a n a l y z e d , were d e t e c t e d . None
were above e s t a b l i s h e d s t a n d a r d s or s t a n d a r d s t h a t c o u l d be s e t by
methodology d i s c u s s e d l a t e r i n t h i s r e p o r t . The h i g h e s t l e v e l
r e p o r t e d f o r any p e s t i c i d e was 16.6 ppb f o r a l a c h l o r .
The most comprehensive i n f o r m a t i o n about the presence o f
p e s t i c i d e s i n groundwater seems to be t h a t c o m p i l e d by the EPA.
D u r i n g t h i s symposium ( 4 ) , the Agency r e p o r t e d t h a t a t o t a l o f
16 d i f f e r e n t p e s t i c i d e s have been found i n a t o t a l o f 23 d i f f e r e n t
states. F i n d i n g s were a t t r i b u t e d to a g r i c u l t u r a l use.
While the p u b l i c may have a p e r c e p t i o n t h a t groundwater s h o u l d
be pure perhaps would be pure i f not f o r a g r o - and o t h e r
s y n t h e t i c c h e m i c a l s many s t u d i e s , i n a d d i t i o n to the C o r n e l l
s t u d y , show the presence o f n a t u r a l s u b s t a n c e s , some at h i g h e r than
desired levels. Groundwater i s not pure! D r i n k i n g water i s not
pure! C h l o r i n a t i o n can form t r i h a l o m e t h a n e s , the most w i d e l y
i d e n t i f i e d t o x i c o r g a n i c c h e m i c a l s i n U.S. water s u p p l i e s (_5).
Page's r e v i e w (5) o f t o x i c contaminants i n d r i n k i n g water noted
t h a t the EPA's water s u p p l y s u r v e y o f f i n i s h e d d r i n k i n g water from
b o t h s u r f a c e and ground waters showed p r a c t i c a l l y a l l systems
c o n t a i n e d c h l o r o f o r m , one o f the t r i h a l o m e t h a n e s .
S h a c k l e f o r d and K e i t h (6) r e p o r t e d i n a 1977 paper t h a t
1,259 d i f f e r e n t compounds had been i d e n t i f i e d i n water s u p p l i e s .
A s i g n i f i c a n t paper (7) on t h i s s u b j e c t was p u b l i s h e d i n 1977
by Dr. B i l l Donaldson o f the Athens, G e o r g i a EPA L a b o r a t o r y .
Dr. Donaldson s a y s , "More than two m i l l i o n o r g a n i c c h e m i c a l s have
been i d e n t i f i e d . The number o f these compounds d e t e c t e d i n a
sample o f water i s r e l a t e d to the s e n s i t i v i t y o f the measurement
t e c h n i q u e : as the d e t e c t i o n l e v e l d e c r e a s e s by an o r d e r o f
magnitude, the number o f compounds d e t e c t e d i n c r e a s e s a c c o r d i n g l y .
Based on the number o f compounds d e t e c t e d by c u r r e n t methods, one
would expect t o f i n d e v e r y known compound at a c o n c e n t r a t i o n o f
10~12 g/i o r h i g h e r i n a sample o f t r e a t e d d r i n k i n g water." Page
(5) i n h i s 1984 a r t i c l e , s u p p o r t s Donaldson's t h e s i s by s u g g e s t i n g
t h a t v i r t u a l l y any substance i n s u f f i c i e n t q u a n t i t y and w i t h
adequate time has the p o t e n t i a l to r e a c h groundwater.
27. NEWBY A N D ROCK Industry Perspective on Legislation 481
T h i s means s y n t h e t i c and c e r t a i n l y n a t u r a l p r o d u c t s cannot be

kept out o f groundwater. In f a c t , the n a t u r a l p r o d u c t s have
p r o b a b l y been t h e r e f o r many l i f e t i m e s a l r e a d y and the s y n t h e t i c s
much l o n g e r than thought.
Many, i f not most, people r e f e r t o some or most o f these
s u b s t a n c e s t h a t have been d e t e c t e d , p a r t i c u l a r l y the s y n t h e t i c s ,
as c o n t a m i n a n t s . I t seems t h a t any a g r i c u l t u r a l c h e m i c a l d e t e c t e d
i n groundwater i s r e f e r r e d to as a contaminant o r p o l l u t a n t . Just
what does i t mean to contaminate o r p o l l u t e ? Webster's (8) says
contaminate means to make u n f i t f o r use by i n t r o d u c t i o n o f unwhole-
some o r u n d e s i r e a b l e elements. A r e c e n t groundwater p u b l i c a t i o n
by the American Chemical S o c i e t y (9) d e f i n e s a p o l l u t a n t as any
s u b s t a n c e , n a t u r a l or human-made, t h a t degrades water q u a l i t y ,
p r e v e n t i n g the use o f water f o r some s p e c i f i c p u r p o s e . Mere
p r e s e n c e , t h e n , s h o u l d not connote c o n t a m i n a t i o n o r p o l l u t i o n .
More o f t e n t h a n not though, i t does, and c o n s e q u e n t l y i m p l i e s
health concerns.
As mentioned at the b e g i n n i n g o f t h i s p r e s e n t a t i o n , the
industry p u b l i c o p i n i o n survey r e v e a l e d t h a t about h a l f o f the
U.S. p o p u l a t i o n b e l i e v e s p o l l u t i o n o f underground water i s a major
n a t i o n a l problem. Seven out o f 10 b e l i e v e f e r t i l i z e r s and p e s t i -
c i d e s used on farms are at l e a s t a minor cause o f such p o l l u t i o n
and 23% t h i n k they are a major c a u s e . What f a c t o r s c o n t r i b u t e to
these b e l i e f s as e x p r e s s e d i n the survey?
Any time a p u b l i c problem a r i s e s , s p e c i a l i n t e r e s t s l i k e to
blame the media, sometimes w i t h r e a l j u s t i f i c a t i o n . In t h i s
i n s t a n c e , they are o n l y one o f s e v e r a l f a c t o r s c o n t r i b u t i n g to the
p u b l i c p e r c e p t i o n s h e l d about p e s t i c i d e s i n groundwater. The media
do not t e l l us what t o t h i n k , but t h e y do i n f l u e n c e what we t h i n k
about. G e n e r a l l y , the d a t a g e n e r a t o r s , i n c l u d i n g those i n
i n d u s t r y , government and academia, must share r e s p o n s i b i l i t y .
The i n v e s t i g a t i v e f o c u s by s c i e n t i s t s , and c o n s e q u e n t l y by
media, may be on p e s t i c i d e s s i m p l y because t h e r e are much more d a t a
a v a i l a b l e on t h i s use c a t e g o r y o f c h e m i c a l s than any o t h e r c l a s s .
C o n t r a r y t o a p o p u l a r p e r c e p t i o n , e x t e n s i v e s a f e t y and e n v i r o n -
mental d a t a are r e q u i r e d f o r a g r i c u l t u r a l c h e m i c a l s b e f o r e r e g i s -
tration. S e n s i t i v e a n a l y t i c a l methodology i s d e v e l o p e d f o r each
p r o d u c t by the r e g i s t r a n t and i s s u b s e q u e n t l y p u b l i s h e d by the
r e g i s t r a n t and/or the r e g u l a t o r y agency. B a s i c a l l y , p e s t i c i d e s
are e a s i e r t o l o o k f o r because methodology i s a v a i l a b l e . It i s
i n t e r e s t i n g t o note t h a t one o f the c r i t e r i a f o r c h o o s i n g p r o d u c t s
to be i n c l u d e d i n the EPA's N a t i o n a l Groundwater Survey i s the
a v a i l a b i l i t y o f good, s e n s i t i v e , a n a l y t i c a l methodology.
In c o n j u n c t i o n w i t h method a v a i l a b i l i t y i s the f a n t a s t i c
p r o g r e s s made by the a n a l y t i c a l c h e m i s t s i n r e c e n t y e a r s . Such
p r o g r e s s i s p a r t i c u l a r l y a p p l i c a b l e to the a n a l y s i s o f p e s t i c i d e s .
To put t h i s i n p e r s p e c t i v e , c h e m i s t s c o u l d r o u t i n e l y d e t e c t a p a r t
per m i l l i o n (ppm) i n the I960's, a p a r t per b i l l i o n (ppb) i n the
1970's and low p a r t s per t r i l l i o n ( p p t ) h e r e i n the 1980's. T h i s
r e p r e s e n t s more than a m i l l i o n f o l d i n c r e a s e over the past 25 y e a r s
i n our a b i l i t y to d e t e c t a g r i c u l t u r a l c h e m i c a l s .
Great p r i d e i s t a k e n i n such p r o g r e s s , but i t has caused a
lot of confusion i n s o c i e t y . Substances have been d i s c o v e r e d
which were not known or thought to be p r e s e n t . Terms o f p a r t s
per m i l l i o n , b i l l i o n and t r i l l i o n are used many times w i t h o u t
c o n s i d e r i n g what they r e a l l y mean to the media and the g e n e r a l

public. They need t o be put i n t o a p e r s p e c t i v e which can be
v i s u a l i z e d by everyone. A m e a n i n g f u l example may be: 1 ppm e q u a l s
1 minute i n two y e a r s , 1 ppb e q u a l s 1 second i n 32 y e a r s , and 1 ppt
e q u a l s 1 second i n 32,000 y e a r s . E s s e n t i a l l y , the a n a l y s t s have
gone from the e q u i v a l e n t o f 1 minute i n 2 y e a r s t o almost 1 second
i n 32,000 y e a r s i n t h e i r a b i l i t y t o r o u t i n e l y d e t e c t .
The media and the p u b l i c more o f t e n f o c u s on the a n a l y t i c a l
f i n d i n g s ( a c h e m i c a l i s p r e s e n t ) and l e s s o f t e n on the a s s o c i a t i o n
of the l e v e l s w i t h any h e a l t h e f f e c t . The p e s t i c i d e d a t a
p r e s e n t a t i o n i n the C o r n e l l Groundwater Study and a subsequent
media r e p o r t p r o v i d e good examples o f these o b s e r v a t i o n s .
The MCLs f o r the s i x p e s t i c i d e s a n a l y z e d and the amounts
detected are:
Method
MCL Sensitivity Detects/No. Detects Level i n
Product (ppb) (ppb) of Samples Over MCL Survey (ppb)
2,4-D 100 * 0/267 0 Not Detected
2,4,5-T 10 * 0/267 0 Not Detected
Toxaphene 5 0.17 0/267 0 <0.17
Lindane 4 0.08 4/267 0 0.08
Endrin 0.2 0.008 0/267 0 <0.008
Methoxychlor 100 0.09 3/267 0 0.09
*Method s e n s i t i v i t y not p r o v i d e d .
An e x a m i n a t i o n o f the p e s t i c i d e d a t a i n the r e p o r t p o i n t s out

t h a t the f o u r Lindane d e t e c t s were i n the s o u t h e r n s t a t e s and the
t h r e e methoxychlor d e t e c t s were i n the western s t a t e s ( 1 0 ) . The
maximum v a l u e found f o r e i t h e r product was never more than 2% o f
the e s t a b l i s h e d MCL. Y e t , the r e p o r t , w h i l e s t a t i n g t h a t n e i t h e r
L i n d a n e nor methoxychlor pose h e a l t h t h r e a t s at the l e v e l s found,
goes f u r t h e r and c o n c l u d e s t h a t s i n c e t h e s e p r o d u c t s a r e p o i s o n s ,
even the presence o f these s m a l l amounts i s u n d e s i r a b l e . Hasn't i t
been known f o r c e n t u r i e s t h a t a l l s u b s t a n c e s can be p o i s o n s ? More
troublesome i s an e x t r a p o l a t i o n r e p o r t e d . From the 1% d e t e c t s i n
the subsamples a n a l y z e d , the statement i s made t h a t 224,000 samples
( 1 % o f the 22,000,000 r u r a l homes) had m e t h o x y c h l o r . While perhaps
s t a t i s t i c a l l y a p p r o p r i a t e , t h i s e x t r a p o l a t i o n seems t o i g n o r e the
f a c t t h a t methoxychlor was o n l y found i n western s t a t e samples.
E q u a l l y troublesome i s what one p u b l i c a t i o n d i d w i t h t h i s
statement ( 1 1 ) . The New Farm r e p o r t on t h i s p a r t i c u l a r p a r t o f
the C o r n e l l s t u d y s a i d , "The water i n more than 200,000 r u r a l
homes c o n t a i n s d e t e c t a b l e amounts o f methoxychlor...While con-
s i d e r e d low i n t o x i c i t y to humans, methoxychlor d i s r u p t e d nervous
and r e p r o d u c t i v e systems i n t e s t a n i m a l s . " No mention was made o f

an MCL, o r the l e v e l s the a n i m a l s were exposed t o i n t h e t e s t , o n l y
the i m p l i c a t i o n t h a t r u r a l water i s u n s a f e t o d r i n k .
From a n o t h e r v i e w p o i n t , i t can be argued t h a t from a p u b l i c
p e r s p e c t i v e , a l l c h e m i c a l s p r e s e n t i n groundwater a r e i n the same
category. P e s t i c i d e s a r i s i n g from a g r i c u l t u r a l use a r e not
d i f f e r e n t i a t e d from i n d u s t r i a l c h e m i c a l s moving from p o i n t s o u r c e s
such as hazardous waste s i t e s . A l l a r e l o o k e d upon as hazardous
chemicals. S i n c e the media f o c u s on hazardous waste s i t e s , the
c o n c e r n about p e s t i c i d e s i n groundwater may be h e i g h t e n e d
unnecessarily.
Is t h e r e , t h e n , a groundwater problem a r i s i n g from t h e use o f
a g r i c u l t u r a l c h e m i c a l s ? One would c o n c l u d e t h a t t h e r e i s - b u t , i t
i s more p r e c e i v e d than r e a l ! In e i t h e r c a s e , the a g r i c u l t u r a l
c h e m i c a l i n d u s t r y must c o n f r o n t i t and must do so b o t h s c i e n t i f -
i c a l l y and from the p u b l i c r e l a t i o n s s t a n d p o i n t . Some c r i t i c s
suggest t h e r e i s a need f o r a d d i t i o n a l l e g i s l a t i o n and/or r e g u l a -

tions. P u b l i c p e r c e p t i o n may demand i t .
A r e v i e w o f s t a t u t e s and r e g u l a t i o n s c u r r e n t l y i n p l a c e t o
address the p r e s e n c e o f p e s t i c i d e s i n groundwater w i l l be u s e f u l .
Based on a r e c e n t r e v i e w (12) by the O f f i c e o f T e c h n o l o g y A s s e s s -
ment (OTA), t h e r e i s no comprehensive p r o t e c t i o n o f groundwater
o f f e r e d by any one f e d e r a l law. Of s i x t e e n e n v i r o n m e n t a l s t a t u t e s
r e v i e w e d , o n l y t h r e e d i r e c t l y or i n d i r e c t l y t o u c h on the s u b j e c t o f
p e s t i c i d e s and groundwater.
The C l e a n Water Act (CWA) o f 1977 has as one o f i t s o b j e c t i v e s
( S e c t i o n 208) the e s t a b l i s h m e n t o f a program t o c o n t r o l n o n - p o i n t
source p o l l u t i o n i n r u r a l a r e a s . T h i s i s a program aimed at con-
t r o l l i n g , f o r example, r u n - o f f from a g r i c u t u r a l f i e l d s . Although
minimal i m p l e m e n t a t i o n has o c c u r r e d , i t c o u l d impact b o t h s u r f a c e
and groundwater.
The F e d e r a l I n s e c t i c i d e , F u n g i c i d e and R o d e n t i c i d e A c t (FIFRA)
which l a r g e l y c o n t r o l s the p e s t i c i d e i n d u s t r y , does n o t c o n t a i n any
d i r e c t r e f e r e n c e t o groundwater. I t does c a l l f o r the c a n c e l l a t i o n
o r s u s p e n s i o n o f p r o d u c t s h a v i n g u n r e a s o n a b l e a d v e r s e e f f e c t s on
the environment, which i n c l u d e s groundwater. The a p p l i c a t i o n o f
t h i s s t a t u t e t o groundwater has r e c e n t l y o c c u r r e d w i t h the r e q u e s t
t h a t " r e s t r i c t e d " l a b e l i n g and groundwater a d v i s o r y s t a t e m e n t s be
added t o c e r t a i n p r o d u c t l a b e l s . Without the e s t a b l i s h m e n t o f a
r e f e r e n c e v a l u e o r s t a n d a r d , t h i s approach w i l l have the e f f e c t o f
banning o r s e v e r e l y r e s t r i c t i n g p r o d u c t use i n some a r e a s .
The o n l y o t h e r a c t t h a t a d d r e s s e s groundwater, though not
e x p l i c i t l y , i s the Safe D r i n k i n g Water A c t (SDWA) o f 1974. I t i s
p r i m a r i l y d e s i g n e d t o a s s u r e t h a t the d r i n k i n g water from p u b l i c
water systems i s s a f e . I t r e q u i r e s the e s t a b l i s h m e n t o f s t a n d a r d s
f o r c e r t a i n s u b s t a n c e s p r e s e n t i n p u b l i c d r i n k i n g water s u p p l i e s ,
the e s t a b l i s h m e n t o f r e g u l a t i o n s f o r underground i n j e c t i o n and the
p r o t e c t i o n o f s o l e source a q u i f e r s . The s t a t u t e i s a d m i n i s t e r e d by
1
the E P A s O f f i c e o f D r i n k i n g Water.
I t i s under the SDWA t h a t s t a n d a r d s have been s e t f o r 22 sub-
s t a n c e s i n d r i n k i n g water whether the s o u r c e i s s u r f a c e o r under-
ground. These s t a n d a r d s a r e r e f e r r e d t o as Maximum Contaminant
L e v e l s (MCLs) and i n c l u d e the s i x p e s t i c i d e s r e f e r r e d t o e a r l i e r
i n t h i s p a p e r . R e g u l a t i o n s a l s o p r o v i d e f o r the e s t a b l i s h m e n t
o f Recommended Maximum Contaminant L e v e l s (RMCLs). RMCLs a r e
n o n - e n f o r c e a b l e h e a l t h g o a l s w h i l e MCLs a r e e n f o r c e a b l e , but must

b a l a n c e h e a l t h p r o t e c t i o n w i t h o t h e r f a c t o r s i n c l u d i n g the a v a i l -
a b i l i t y and c o s t o f treatment t e c h n o l o g i e s t o a t t a i n the s t a n d a r d
(12). The O f f i c e o f D r i n k i n g Water has p l a n s t h i s year t o i s s u e
RMCLs f o r an a d d i t i o n a l 17 or 18 p e s t i c i d e s .
Should a v a i l a b l e t e c h n o l o g y be too c o s t l y f o r a p u b l i c system
to a t t a i n an MCL, the EPA may, i n the v i e w o f some groups ( 1 3 ) ,
employ l a n d use c o n t r o l as a treatment t e c h n o l o g y o p t i o n . A water-
shed o r r e c h a r g e zone c o u l d be d e s i g n a t e d as an a r e a i n which c e r -
t a i n c h e m i c a l s c o u l d n o t be used. The Agency has a p p a r e n t l y n o t
adopted t h i s i n t e r p r e t a t i o n o f the s t a t u t e .
Another r e g u l a t o r y approach t o the presence o f substances i n
d r i n k i n g water has been the e s t a b l i s h m e n t o f H e a l t h A d v i s o r i e s
1
(HAs) by the E P A s O f f i c e o f D r i n k i n g Water ( 1 4 ) . These a r e
numbers which s i m p l y s e r v e as g u i d e l i n e s t o e v a l u a t e the h e a l t h
s i g n i f i c a n c e o f c e r t a i n c h e m i c a l s found i n groundwater o r s u r f a c e
water used f o r d r i n k i n g water and f o r which t h e r e a r e no f e d e r a l

requirements. In g e n e r a l , t h e y a r e e s t a b l i s h e d i n response t o
emergency s i t u a t i o n s and a r e based on s h o r t term - up t o two
y e a r s - exposure t o a p a r t i c u l a r c h e m i c a l . H e a l t h A d v i s o r i e s were
f o r m e r l y known as SNARLs, i . e . , Suggested No Adverse Response
Levels. They a r e n o t e n f o r c e a b l e .
A framework f o r f u r t h e r a d d r e s s i n g c h e m i c a l presence i n
groundwater a t the f e d e r a l l e v e l i s the EPA's groundwater p r o t e c -
t i o n s t r a t e g y (15) i s s u e d i n August 1984. T h i s s t r a t e g y d e a l s w i t h
groundwater from t h e a s p e c t o f the v a r i o u s laws which the Agency
administers. B a s i c a l l y , groundwater i s d i v i d e d i n t o t h r e e c l a s s e s :
1) S p e c i a l groundwaters - those which a r e h i g h l y v u l n e r a b l e

to c o n t a m i n a t i o n because o f h y d r o l o g i c a l c h a r a c t e r i s t i c s
and :
a. a r e i r r e p l a c e a b l e d r i n k i n g water s o u r c e s o r
b. ecologically v i t a l .
2) C u r r e n t and p o t e n t i a l s o u r c e s o f d r i n k i n g water and waters

having other b e n e f i c i a l uses.
3) Groundwaters not c o n s i d e r e d p o t e n t i a l s o u r c e s of drinking

water and a r e o f l i m i t e d b e n e f i c i a l u s e .
The Agency w i l l g i v e d i f f e r e n t l e v e l s o f p r o t e c t i o n t o these

classes.
To prevent c o n t a m i n a t i o n o f c l a s s 1, and presumably c l a s s 2,
EPA " p o l i c y w i l l be d i r e c t e d toward r e s t r i c t i n g o r banning the
use i n these areas o f those p e s t i c i d e s which a r e known to l e a c h
through s o i l s and a r e a p a r t i c u l a r problem i n groundwater." The
g e n e r a l p o l i c y f o r c l e a n u p o f c o n t a m i n a t i o n w i l l be t o background
or a c c c e p t a b l e d r i n k i n g water l e v e l s .
I n d u s t r y does n o t have a b a s i c argument w i t h t h e p o l i c y , but
EPA's i n t e r p r e t a t i o n and e v e n t u a l enforcement remain u n d e f i n e d from
a p r a c t i c a l standpoint. I t i s n o t c l e a r whether the Agency's
i n t e n t i s t o a l l o w no p e s t i c i d e r e s i d u e s i n these c l a s s 1 and 2
a q u i f e r s o r whether c e r t a i n l e v e l s a r e a c c e p t a b l e dependent on the
27. NEWBY AND ROCK Industry Perspective on Legislation 485
s a f e t y of the p r o d u c t . I f the former i s t r u e , r i s k w i l l be managed

by e l i m i n a t i n g i t .
S e v e r a l s t a t e s have r e g u l a t o r y programs i n p l a c e f o r p e s t i -
c i d e s found i n groundwater. These s t a t e s a r e , f o r the most p a r t ,
r e p r e s e n t e d i n t h i s symposium; t h u s , comments h e r e i n w i l l be q u i t e
limited.
L e g i s l a t i v e i n i t i a t i v e s have been put f o r t h by s e v e r a l s t a t e s
to p r o v i d e n e c e s s a r y r e g u l a t o r y a u t h o r i t y f o r e s t a b l i s h i n g s t a n -
dards f o r s u b s t a n c e s t h a t c o u l d e n t e r groundwater. T h i s i s con-
t r a s t e d w i t h the f e d e r a l s i t u a t i o n which i s r e l y i n g upon e x i s t i n g
water q u a l i t y s t a t u t e s f o r s t a n d a r d s e t t i n g .
C e r t a i n s p e c i f i c i n c i d e n t s o f substance appearance i n ground-
water have caused s t a t e l e g i s l a t o r s to move r a p i d l y and d e c i s i v e l y
on t h i s i s s u e . For example, the s t a t e s o f W i s c o n s i n , New York
and F l o r i d a e n a c t e d e n a b l i n g l e g i s l a t i o n t h a t p e r m i t t e d s t a n -
dard s e t t i n g and l a r g e s c a l e m o n i t o r i n g programs to be
established.
Sweeping l e g i s l a t i o n was adopted i n W i s c o n s i n (16) t h a t
e s t a b l i s h e d two p r e c e d e n t s , the A c c e p t a b l e D a i l y Intake (ADI)
methodology and the P r e v e n t i v e A c t i o n L i m i t (PAL) c o n c e p t . The
s t a t e o f New York, under e x i s t i n g s t a t u t o r y a u t h o r i t y ( 1 7 ) , p r o -
posed by r u l e , not o n l y the ADI methodology f o r s t a n d a r d s e t t i n g ,
but went even f u r t h e r to a l l o w the a d o p t i o n o f s t a n d a r d s by chemi-
c a l c l a s s or s i m i l a r i t y i n m e t a b o l i s m , s t r u c t u r e and t o x i c o l o g i c a l
r e s p o n s e f o r o r g a n i c s u b s t a n c e s . W i s c o n s i n and New York p l a c e d
s i g n i f i c a n t weight on the l i k e l i h o o d o f appearance or the a c t u a l
appearance o f a substance i n water as c r i t e r i a f o r s t a n d a r d
setting. These programs u t i l i z e e x i s t i n g t o x i c o l o g y d a t a from
which the ADI and, s u b s e q u e n t l y , the water q u a l i t y s t a n d a r d i s
established.
F l o r i d a , on the o t h e r hand, m a i n t a i n s a zero d e g r a d a t i o n
p h i l o s o p h y which s a y s , i n e f f e c t , t h a t i f no s t a n d a r d i s s e t , then
the mere d e t e c t i o n of a s u b s t a n c e i s a v i o l a t i o n o f the water
q u a l i t y standards (18). U n l i k e the two f o r m e r l y mentioned s t a t e s ,
l e g i s l a t i v e i n i t i a t i v e s i n F l o r i d a d i d not c l e a r l y d e f i n e a s t a n -
dard s e t t i n g methodology o r s p e c i f i c a l l y mandate r u l e p r o m u l g a t i o n
i n t h i s area.
The S t a t e A f f a i r s Committee of the NACA has i d e n t i f i e d
13 s t a t e s as b e i n g l i k e l y to adopt l e g i s l a t i o n i n the a r e a o f water
q u a l i t y t h i s year. Should the F e d e r a l Government c o n t i n u e to d e l a y
i m p l e m e n t a t i o n o f s t a n d a r d s e t t i n g , more and more p r e s s u r e w i l l be
g e n e r a t e d by the p u b l i c f o r a c t i o n by s t a t e l e g i s l a t i v e and r e g u -
latory o f f i c i a l s . The r e s u l t s o f such a c t i o n have p o t e n t i a l f o r
chaos and c o n f u s i o n , p a r t i c u l a r l y when a q u i f e r s t r a v e r s e s t a t e
l i n e s and water q u a l i t y s t a n d a r d s and methodology v a r y from s t a t e
to s t a t e .
At the f e d e r a l l e v e l , the Safe D r i n k i n g Water A c t , the C l e a n
Water Act and FIFRA are a l l up f o r r e a u t h o r i z a t i o n t h i s y e a r .
Groundwater amendments have been proposed f o r the SDWA and some
f e d e r a l l e g i s l a t o r s are even s u g g e s t i n g n a t i o n a l groundwater
legislation.
O b v i o u s l y , the a g r i c u l t u r a l c h e m i c a l i n d u s t r y would p r e f e r to
see f e d e r a l g u i d a n c e on t h i s i s s u e . Adequate f e d e r a l a u t h o r i t y
a l r e a d y e x i s t s to e s t a b l i s h g u i d e l i n e numbers. For the past two
y e a r s , the EPA has been urged to e s t a b l i s h t h e s e numbers f o r a l l
p e s t i c i d e products. A l t h o u g h o n l y a few a g r i c u l t u r a l c h e m i c a l s
have been d e t e c t e d i n groundwater to d a t e , i t seems l i k e l y more
w i l l be i d e n t i f i e d as sampling and a n a l y t i c a l c a p a b i l i t i e s c o n t i n u e
to improve. I t would be a p o s i t i v e s t e p t o have numbers i n p l a c e
p r i o r to d e t e c t i o n .
I r o n i c a l l y , w h i l e the i n d u s t r y p u b l i c o p i n i o n s u r v e y (I)
r e p o r t e d 90% o f the p e o p l e n a t i o n w i d e endorse n a t i o n a l s t a n d a r d s
f o r d r i n k i n g water, 63% do not b e l i e v e t h a t water i s s a f e to d r i n k
j u s t because the government a l l o w s a n a l y t i c a l l y d e t e c t a b l e amounts
of chemicals. I t remains the b e s t way, though, to b e g i n to a d d r e s s
the p u b l i c ' s c o n c e r n about the p e r c e i v e d problem o f a g r i c u l t u r a l
c h e m i c a l s i n groundwater.
G u i d e l i n e numbers, a d v i s o r y l e v e l s or s t a n d a r d s should be s e t
at the f e d e r a l l e v e l not o n l y to a s s u r e u n i f o r m i t y , but because the
d a t a base f o r r e g i s t e r e d p r o d u c t s r e s i d e s i n the EPA's O f f i c e of
P e s t i c i d e Programs. While s t a t e s would p r o b a b l y have the a u t h o r i t y
t o be more s t r i n g e n t than the f e d e r a l g u i d e l i n e , such a c t i o n seems

u n l i k e l y , p a r t i c u l a r l y i f the g u i d a n c e numbers are based on sound
science. D e a l i n g w i t h s e v e r a l d i f f e r e n t groundwater numbers c o u l d
p r e s e n t s i g n i f i c a n t problems f o r r e g i s t r a n t s from a l a b e l i n g s t a n d
point .
Methodology f o r e s t a b l i s h i n g h e a l t h guidance l e v e l s i s t h a t
p r e s e n t e d by Stevens and Sumner (19) i n t h i s symposium. Briefly,
i t i n c o r p o r a t e s the ADI and a 10 k i l o g r a m c h i l d consuming one l i t e r
o f water per day.
ADI (mg/kg/day) 10 kg child

HGL* ( m g / l i t e r ) = "
1 liter/day
*Health Guidance Level
T h i s approach i s not w i t h o u t p r e c e d e n t . I t has been recom

1
mended by E P A s OPP (20) and s u b s e q u e n t l y supported by EPA's
S c i e n t i f i c A d v i s o r y Panel (SAP) ( 2 1 ) . W i s c o n s i n and New York
i n c l u d e d t h i s concept i n t h e i r approach to e s t a b l i s h i n g groundwater
and d r i n k i n g water s t a n d a r d s . The ODW s u g g e s t s t h a t the i n c l u s i o n
o f a 10 kg c h i l d a c t s as a s u r r o g a t e f o r the most s e n s i t i v e sub
group o f the a d u l t p o p u l a t i o n ( 1 4 ) .
T h i s g u i d a n c e number should not reduce the ADI f o r food
intake. The SAP v o i c e d s u p p o r t f o r t h i s concept because o f the
s a f e t y f a c t o r s b u i l t i n t o the food ADI and because groundwater
r e s i d u e s are g e o g r a p h i c a l l y r e s t r i c t e d and i n g e n e r a l , t r a n s i e n t .
In summary, t h e r e i s a problem, more p e r c e i v e d than r e a l ,
a s s o c i a t e d w i t h the p r e s e n c e o f a g r i c u l t u r a l c h e m i c a l s i n ground
water. To p l a c e these f i n d i n g s i n p e r s p e c t i v e r e q u i r e s a g u i d e l i n e
number based on h e a l t h e f f e c t s which would say to the media and the
p u b l i c t h a t t h e r e should not be h e a l t h concerns below a c e r t a i n
level.
The a g r i c u l t u r a l c h e m i c a l i n d u s t r y i s v e r y s e r i o u s about the
importance o f p r o t e c t i n g groundwater and the s a f e use o f a g r i c u l
t u r a l chemicals. S e v e r a l p r o j e c t s are underway to m i n i m i z e the
p r e s e n c e o f t h e s e p r o d u c t s i n groundwater. The i n d u s t r y i s a l s o
v e r y concerned t h a t e f f i c a c i o u s and s a f e p r o d u c t s be m a i n t a i n e d on
the market and new p r o d u c t s r e g i s t e r e d . Groundwater i s a major
i s s u e f o r NACA and i t s member companies. I n i t i a t i v e s have been

taken i n working w i t h government a g e n c i e s - f e d e r a l , s t a t e and
l o c a l - and o t h e r i n t e r e s t e d p a r t i e s t o h e l p prevent problems
involving a g r i c u l t u r a l chemicals.
Literature Cited
1. "Groundwater Contamination: The Measure of Public Concern,"
Center for Communication Dynamics: Washington, DC,
February 1985.
2. "The Cornell Report to ODW, EPA: A National Statistical
Assessment of Rural Drinking Water Conditions," Cornell
University, 1983.
3. Kelley, Richard D. "Synthetic Organic Compound Sampling
Survey of Public Water Supplies," Iowa Department of Water,
Air and Waste Management, 1985.
4. Creeger, S. M. Included in this symposium series, 1985.

5. Page, William G. The Environmentalist, 1984, 4, 131-138.
6. Shackelford, W. M.; Keith, L. H. "Frequency of Organic
Compounds Identified in Water," Environmental Research
Laboratory, NTIS PB-265470, Athens, GA, 1977.
7. Donaldson, William T. Environ. Sci. & Technol., 1977, 4,
348-51.
8. Webster's Seventh New Collegiate Dictionary, 1224 pp.,
G. & C. Merriam Company, Publishers, Springfield, MA, 1971.
9. Groundwater Information Pamphlet. American Chemical Society,
Washington, DC, 1984.
10. Back, Richard. Personal Communication.
11. Zahradnik, Fred, New Farm, 1984, 6, 30-31.
12. "Protecting the Nation's Groundwater from Contamination";
Volume 1, Washington, DC; U.S. Congress, Office of Technology
Assessment, OTA-O-233, October 1984.
13. Gordon, Wendy. In "Citizens Handbook on Groundwater
Protection"; Natural Resources Defense Council, Inc.:
New York, 1984, p. 90.
14. Lappenbusch, William L . ; Moskowitz, Susan B. Proc. AMA/EPA
Symp. on Drinking Water and Human Health, Washington, DC,
1984.
15. "Ground-Water Protection Strategy," U.S. EPA-Office of
Groundwater Protection, Washington, DC, 1984.
16. State of Wisconsin Act 410, 1983.
17. State of Florida Statutes, Chapter 487, 1983.
18. State of New York, Proposed Changes to Subdivision 701, 1985.
19. Stevens, James T.; Sumner, Darrell D. Included in this
symposium series, 1985.
20. Severn, David J.; Offutt, Carolyn K.; Cohen, Stuart Z.;
Burnam, William L.; Burin, Gary J. "Assessment of Groundwater
Contamination by Pesticides," prepared for FIFRA Scientific
Advisory Panel Meeting, June 21-23, 1983.
21. Review of EPA Strategy Paper on: "Assessment of Groundwater
Contamination by Pesticides," Minutes, FIFRA SAP Meeting,
June 21-23, 1983.
28
Ground Water Regulations
Impact, Public Acceptance, and Enforcement
1 2 2
Orlo R. Ehart , Gordon Chesters , and Kari J. Sherman
1
Trade and Consumer Protection, Wisconsin Department of Agriculture, Madison,
WI 53708
2
Water Resources Center, University of Wisconsin-Madison, Madison, WI 53706
Sanctioning pesticides for agricultural use was based

on equating environmental and public health risks to
crop production benefits. More recently, the intro-
duction of groundwater protection into pesticide
regulations has modified the equation by adding other
elements of protection. During the past decade
pesticide issues have been emotionally charged with the
extremists' views most notably reported. The public
believes that groundwater deserves greater protection
than surface water because improving the quality of
contaminated groundwater is more difficult and costly.
This coupled with the users'--particularly rural
residents--concerns that their drinking water is being
polluted, has lead to acceptance of groundwater regula-
tions by pesticide users often opposed to regulation.
Enforcement of regulations, based on acceptable
tolerance levels of pesticides in groundwater, must
rely on quality-assured data. Regulatory mechanisms
include changes in use practices, moratoria and
cancellation of registrations. Mathematical models--
used as an information source--could be helpful in
evaluating the consequences of pesticide use. Enforce-
ment sanctions follow traditional civil and criminal
remedies but innovative cost incentives might be needed
to accelerate protection programs. Mechanisms of
implementation of land management controls vary from
state to state.
The F e d e r a l I n s e c t i c i d e , F u n g i c i d e and R o d e n t i c i d e A c t , as amended,

establishes a policy f o r determining the acceptability of a
p e s t i c i d e use, o r the c o n t i n u a t i o n o f that use, according t o a
r i s k / b e n e f i t assessment. This p o l i c y , administered by t h e U.S.
E n v i r o n m e n t a l P r o t e c t i o n Agency (EPA), r e c o g n i z e s t h a t p e s t i c i d e s
are i n t e n t i o n a l l y p l a c e d i n t h e environment f o r purposes o f p e s t
control. Contrary t o some p u b l i c o p i n i o n , the r i s k / b e n e f i t
assessment does not determine t h a t t h e use i s t o t a l l y " s a f e " n o r
0097-6156/86/0315-0488$06.00/0
28. E H A R T ET AL. Ground Water Regulations 489
suggest t h a t a l l uses of a p e s t i c i d e w i l l not a d v e r s e l y a f f e c t the

environment, including effects on human h e a l t h . As long as
benefits outweigh a d v e r s e e f f e c t s uses of a pesticide can be
r e g i s t e r e d , i . e . , o f f i c i a l l y s a n c t i o n e d by the EPA.
Despite this permissiveness in the law, i t has become
i n c r e a s i n g l y d i f f i c u l t to j u s t i f y the use, or c o n t i n u e d use, of
many p e s t i c i d e s . The a b i l i t y to r e c o g n i z e p o t e n t i a l r i s k s has
improved w i t h advances i n t e c h n o l o g y . The ability to detect
increasingly lower concentrations of pesticides, increased
knowledge of and c o n c e r n about p o t e n t i a l c h r o n i c e f f e c t s , and the
f i n d i n g of low l e v e l s of p e s t i c i d e s i n d r i n k i n g water i n s e v e r a l
a r e a s of the U n i t e d S t a t e s have added more f a c t o r s to the r i s k s i d e
o f the r i s k / b e n e f i t l e d g e r w h i l e the b e n e f i t s i d e has remained
relatively static.
Public P e r c e p t i o n s toward Groundwater P o l i c y and Regulation

A study conducted f o r the N a t i o n a l Academy of S c i e n c e s (1) has

revealed that the average C a l i f o r n i a n i s becoming increasingly
aware of and concerned about t o x i c c h e m i c a l s as a t h r e a t to ground-
water. This important perception i s without regard to the
c o n t a m i n a n t ' s s o u r c e , r e l a t i v e t o x i c i t y or p e r v a s i v e n e s s . The
p u b l i c g e n e r a l l y does not u n d e r s t a n d nor a c c e p t the consequences o f
f e d e r a l p o l i c y , which a l l o w s the p u r p o s e f u l , j u d i c i o u s i n t r o d u c t i o n
of p e s t i c i d e s i n t o the environment, even i f they may have a m i n i m a l
y e t measurable u n d e s i r e d e f f e c t . Thus, i f o n l y minute q u a n t i t i e s
of a pesticide reach groundwater, the federal policy of a
r i s k / b e n e f i t assessment i s r e j e c t e d by much of the p u b l i c r e g a r d -
l e s s of any assessment o f the b e n e f i t o f the p e s t i c i d e i n i m p r o v i n g
c r o p p r o d u c t i o n and q u a l i t y .
When e a s i l y a c c e s s i b l e f a c t s on t e c h n i c a l i s s u e s are u n a v a i l -
a b l e , the p u b l i c f r e q u e n t l y f a v o r s s i m p l e p o l i c i e s . In the case o f
groundwater, t h i s i s the p o l i c y of n o n d e g r a d a t i o n which a l l o w s f o r
no change i n water q u a l i t y . The e s t a b l i s h m e n t o f n u m e r i c a l g r o u n d -
water s t a n d a r d s i s an i m p o r t a n t p o l i c y a l t e r n a t i v e f o r assessing
the s i g n i f i c a n c e of manmade or n a t u r a l l y o c c u r r i n g contamination.
The f e d e r a l government must e s t a b l i s h those l e v e l s i f the p u b l i c i s
ever to p e r c e i v e the d i f f e r e n c e between the mere p r e s e n c e of a
p e s t i c i d e i n groundwater and an a c u t e or c h r o n i c h e a l t h signifi-
cance a s s o c i a t e d w i t h exposure to some l e v e l of c o n t a m i n a t i o n .
The impacted community must a c c e p t r e g u l a t i o n and cooperate
w i t h the r e g u l a t o r y a u t h o r i t y i f a management approach to s o l v i n g
the problem of contaminants i n groundwater i s to s u c c e e d . Regula-
t i o n r e q u i r e s a c c e s s to t e c h n o l o g i c a l i n f o r m a t i o n , the c o o p e r a t i o n
and d e d i c a t i o n of r e s e a r c h e r s and adequate s u r v e i l l a n c e to a s s u r e
v i o l a t o r s are d e t e r r e d . R e g u l a t i o n s have c o s t s a s s o c i a t e d with
them, but they encourage use of those p e s t i c i d e s which create
minimum r i s k s . However, new r e g u l a t i o n s may s u b s t a n t i a l l y modify
the p r e s e n t uses of p e s t i c i d e s . P e s t i c i d e s can a d v e r s e l y a f f e c t
humans or the environment i f not h a n d l e d p r o p e r l y . Because o f
t h e s e d e t r i m e n t a l consequences, a l e r t s u r v e i l l a n c e and speedy and
just enforcement become e s s e n t i a l components of the regulatory
program. O u t r i g h t bans can r e s u l t but they a r e the p r o d u c t of a
d e c i s i o n - m a k i n g p r o c e s s r a t h e r than the f i r s t l i n e of d e f e n s e .
Most Americans a r e c o n c e r n e d about the q u a l i t y of groundwater

and b e l i e v e t h a t i t i s more d i f f i c u l t and c o s t l y t o p r o t e c t and
r e n o v a t e t h a n s u r f a c e water. When t h e i r c o n c e r n s a r e c o u p l e d w i t h
i n a d e q u a t e i n f o r m a t i o n and an u n w i l l i n g n e s s to a c c e p t r e g u l a t o r y
s t a n d a r d s , i t becomes d i f f i c u l t i f not i m p o s s i b l e to e s t a b l i s h
balanced p u b l i c p o l i c y .
Groundwater i s one of the l e a s t t a n g i b l e components of the
t o t a l environment. I t i s the d e c i s i o n to use g r o u n d w a t e r a s a
d r i n k i n g water s o u r c e f o r humans and domestic a n i m a l s , f o r i r r i g a
t i o n and f o r i n d u s t r i a l u s e s t h a t has made i t s c o n t a m i n a t i o n a
r e a l and immediate problem. S i n c e groundwater i s not v i s i b l e and
i t s p r o p e r t i e s and f l o w p a t t e r n s a r e p o o r l y u n d e r s t o o d by laymen,
the p u b l i c i s u n w i l l i n g t o s u p p o r t a p o l i c y p e r m i t t i n g the use of a
p e s t i c i d e t h a t c o u l d be found i n groundwater, even i f the l e v e l s
have no s i g n i f i c a n t e f f e c t on human h e a l t h and the environment.
S i n c e water has d i f f e r e n t uses and q u a l i t i e s , v a r i a b l e s t a n d a r d s
m a t c h i n g s a f e g u a r d s needed f o r p a r t i c u l a r uses now and i n the

f u t u r e would be a p p r o p r i a t e . However, t h i s type o f s t a n d a r d
s e t t i n g would be complex and i t may be d i f f i c u l t t o c o n v i n c e the
p u b l i c o f the need f o r t h i s p o l i c y . N o n e t h e l e s s , such a system
would provide greater flexibility i n devising b e s t management
p r a c t i c e s to p r o t e c t the groundwater r e s o u r c e .
Survey d a t a . The f o l l o w i n g s u r v e y s t a t i s t i c s (2) p r o v i d e some

knowledge o f the p u b l i c ' s p e r c e p t i o n o f groundwater c o n t a m i n a t i o n .
75% of the U.S. p o p u l a t i o n (75% i n W i s c o n s i n ) i s more w o r r i e d

about p o l l u t i o n now t h a n 5 y e a r s ago.
48% o f Americans (58% i n W i s c o n s i n ) c o n s i d e r underground water
p o l l u t i o n t o be a major problem,
91% (91% i n W i s c o n s i n ) endorsed n a t i o n a l s t a n d a r d s f o r s a f e
d r i n k i n g water but o n l y 23% (20% i n W i s c o n s i n ) a r e w i l l i n g t o
accept " s m a l l amounts o f c h e m i c a l s " i n water even i f such
c o n t a m i n a t i o n meets government s t a n d a r d s ,
63% of t h o s e asked (69% i n W i s c o n s i n ) d i s a g r e e d w i t h the i d e a
t h a t i f the government a l l o w s " s m a l l amounts o f c h e m i c a l s i n
w a t e r , " the water i s s a f e t o d r i n k .
When the p u b l i c was q u e s t i o n e d on a g r i c u l t u r a l s o u r c e s o f g r o u n d

water pollutionparticularly from pesticidesthe following
o p i n i o n s were o b t a i n e d .
Asked i f f a r m e r s use too many p e s t i c i d e s , n a t i o n a l l y 59% o f

those s u r v e y e d (57% i n W i s c o n s i n ) answered y e s .
23% of a l l Americans s u r v e y e d (29% i n W i s c o n s i n ) b e l i e v e t h a t
f e r t i l i z e r s and p e s t i c i d e s used on farms a r e a major n a t i o n a l
problem causing water pollution; 76% (82% i n Wisconsin)
c o n s i d e r them t o be a t l e a s t a minor problem.
35% (24% i n W i s c o n s i n ) b e l i e v e f e r t i l i z e r s and p e s t i c i d e s a r e
not a problem i n t h e i r l o c a l d r i n k i n g water w h i l e o n l y 6% ( 3 %
in Wisconsin) believe they a r e not a national problem.
A l t h o u g h some r e s p o n d e n t s thought t h a t t h e i r l o c a l drinking
water s o u r c e was s a f e , t h e y p e r c e i v e d t h a t a problem e x i s t s i n
some o t h e r p a r t s o f the c o u n t r y .
28. EHART ET AL. Ground Water Regulations 491
A survey (3_) showed t h a t 56% o f r e s p o n d e n t s i n d i c a t e d a need

to p r o t e c t farmers when a s k e d : "Do you t h i n k t h a t t h e s o l u t i o n s
f o r water p o l l u t i o n i n W i s c o n s i n s h o u l d be planned so t h a t they do
not i n c r e a s e c o s t s f o r f a r m e r s , o r a r e these problems so s e r i o u s
t h a t we have t o have s o l u t i o n s even i f they mean h i g h e r c o s t s f o r
farmers?" Of those surveyed, 50% i n d i c a t e d that solutions
( r e m e d i a l measures) f o r water p o l l u t i o n s h o u l d be planned n o t t o
i n t e r f e r e w i t h t h e a b i l i t y t o c r e a t e new j o b s ; 6 1 % f a v o r s t a t e
f i n a n c i a l a s s i s t a n c e t o farmers t o c o n t r o l p o l l u t i o n from a g r i c u l
tural activities. I n a n a t i o n a l H a r r i s p o l l ( 4 _ ) , 63% i n d i c a t e d
t h a t c l e a n water was o b t a i n a b l e w i t h o u t a f f e c t i n g j o b s ; however, i f
i t were an e i t h e r / o r p r o p o s i t i o n , t h e p o p u l a t i o n surveyed b e l i e v e d
t h a t h e a l t h i s more important than j o b s . These s u r v e y s and p o l l s
p r o v i d e a snapshot o f p u b l i c o p i n i o n but do not n e c e s s a r i l y r e f l e c t
the t r u e b e l i e f s o f s o c i e t y . However, they do i n d i c a t e t h e p a r a
d o x i c a l elements i n d e a l i n g w i t h t h e p u b l i c ' s p e r c e p t i o n o f complex
policy issues.
A statistical survey study (5_) conducted f o r t h e EPA by
C o r n e l l U n i v e r s i t y r e s e a r c h e r s r e p o r t e d t h a t 63% o f r u r a l homes
have contaminated drinking water; nearly 30% have excessive
bacterial counts but few have d e t e c t a b l e pesticide residues.
Samples from w e l l s a t 2 6 7 s i t e s were s e l e c t e d f o r a n a l y s i s . The
analyses were l i m i t e d to only those s i x p e s t i c i d e s f o r which
maximum contaminant levels (MCLs) a r e n a t i o n a l l y e s t a b l i s h e d .
R e s u l t s o f t h e study showed:
Four out o f 1 2 1 s i t e s i n 1 6 s o u t h e r n s t a t e s c o n t a i n e d lindane

residues. The h i g h e s t l e v e l was 0 . 0 8 p a r t s p e r b i l l i o n (ppb o r
yg/l). The MCL f o r l i n d a n e i s 4 ppb.
Three out o f 3 2 s i t e s i n t h e west c o n t a i n e d m e t h o x y c h l o r with a
maximum l e v e l o f 0 . 0 9 ppb. The MCL f o r m e t h o x y c h l o r i s 1 0 0 ppb
(6).
The executive summary (7_) o f t h e study states: "Endrin,

l i n d a n e , m e t h o x y c h l o r , toxaphene, 2 , 4 - D and 2 , 4 , 5 - T P were v i r t u a l l y
n e v e r d e t e c t e d among r u r a l h o u s e h o l d water s u p p l i e s . " The study
draws no c o n c l u s i o n s on t h e e x t e n t o f c o n t a m i n a t i o n o f r u r a l water
s u p p l i e s by p e s t i c i d e s beyond t h i s l i m i t e d s a m p l i n g . However, t h i s
s m a l l d a t a base was t r a n s l a t e d and e x t r a p o l a t e d t o p r o v i d e a p u b l i c
i n f o r m a t i o n a r t i c l e ( 8 ) which s t a t e s t h a t " l i n d a n e i s p r e s e n t i n
347,000 r u r a l h o u s e h o l d water s u p p l i e s " and "water i n more t h a n
200,000 r u r a l homes c o n t a i n s d e t e c t a b l e amounts o f m e t h o x y c h l o r . "
T h i s type o f p r o j e c t i o n m i s l e a d s and i n f l a m e s t h e emotions o f t h e
public regarding the e x t e n t and s e r i o u s n e s s of contamination.
Editors should respond very forcefully to scare t a c t i c s and
d e c i s i o n - m a k e r s must determine t h e r e l i a b i l i t y o f such s t a t e m e n t s .
Some states have conducted surveys o f water quality.
C u r r e n t l y t h e i n f o r m a t i o n a v a i l a b l e on t h e s t a t u s o f t h e q u a l i t y o f
the n a t i o n a l groundwater r e s o u r c e i s i n a d e q u a t e t o draw any c o n c l u
sions. G e n e r a l l y , assessments o f water q u a l i t y a r e a v a i l a b l e o n l y
for l o c a l i z e d areas. The EPA has proposed a n a t i o n a l groundwater
survey f o r 1 9 8 6 - 8 8 . The p r e l i m i n a r y d r a f t c a l l s f o r sampling 1 5 0 0 -
2000 wells f o r approximately 90 p e s t i c i d e analytes (9). Even
though t h i s i n f o r m a t i o n w i l l be v a l u a b l e , a sample s i z e o f 3 0 - 5 0
w e l l s per s t a t e i s s t i l l i n a d e q u a t e to a s s e s s the q u a l i t y of the

n a t i o n ' s groundwater f o r c o n t a m i n a t i o n by p e s t i c i d e s .
Need f o r S c i e n t i f i c E v a l u a t i o n . Z a k i e t a l . (10) concluded that:
"Our s o c i e t y seems to be w i l l i n g to a c c e p t t a n g i b l e
and measurable r i s k s i n our d a i l y a c t i v i t i e s as a r e s u l t
of c i g a r e t t e smoking, e x c e s s i v e f o o d and a l c o h o l i n t a k e ,
and the use of the a u t o m o b i l e .
The same s o c i e t y , however, i s u n a b l e to t o l e r a t e
p o t e n t i a l , i n t a n g i b l e and unmeasurable r i s k s from food
additives, pesticides, air pollutants, and water
contaminants. As p u b l i c h e a l t h a d m i n i s t r a t o r s , we have a
responsibility not only to m o n i t o r and c o n t r o l these
s u b s t a n c e s but a l s o to h e l p the p u b l i c become f u l l y aware
of t h e i r r i s k s and b e n e f i t s w i t h o u t r e s o r t to r h e t o r i c on
e i t h e r s i d e of the i s s u e . "
I t i s d i f f i c u l t t o p r e v e n t some p e r s o n a l b i a s e s from e n t e r i n g
professional attitudes. However, p r o f e s s i o n a l s s e r v i n g the p u b l i c
i n t e r e s t must r e n d e r an u n b i a s e d p r e s e n t a t i o n of the f a c t s i f the
r o l e of p u b l i c o p i n i o n i n the d e c i s i o n - m a k i n g p r o c e s s i s to be
valid. P r o f e s s i o n a l s must adopt an u n b i a s e d a t t i t u d e , even i n
those c i r c u m s t a n c e s where they have p e r s o n a l b e l i e f s which may
d i f f e r from the f a c t s .
H o l d e n (1_), i n commenting on an, as y e t , u n p u b l i s h e d r e p o r t t o
the N a t i o n a l Academy of S c i e n c e s , s t a t e d t h a t t h e r e i s a l s o c o n s i d -
e r a b l e c o n c e r n t h a t p u b l i c a p p r e h e n s i o n about groundwater contam-
i n a t i o n w i l l grow to the p o i n t where s t a t e w i d e or n a t i o n a l bans
w i l l become p o l i t i c a l l y e x p e d i e n t , even i n c a s e s where p e s t i c i d e
c o n t a m i n a t i o n i s a c o n t r o l l a b l e l o c a l i z e d phenomenon. The r o l e o f
s c i e n t i s t s i n a s s u r i n g the use of r e l i a b l e d a t a i n the d e c i s i o n -
making p r o c e s s has become an i n t e g r a l p a r t of t h e i r p r o f e s s i o n a l
activities. I t i s imperative that unbiased, accurate information
be p r e s e n t e d by t r a i n e d p r o f e s s i o n a l s to s e c u r e p u b l i c a c c e p t a n c e
of sound, r e a s o n a b l e p u b l i c p o l i c y r e g u l a t i n g the presence of
p e s t i c i d e s i n groundwater.
The p u b l i c i s not well informed on technical issues and
frequently provides a r e a c t i o n r a t h e r t h a n an i n f o r m e d opinion.
A l t h o u g h most p e o p l e can d i s t i n g u i s h v o l u n t a r y from involuntary
r i s k , O r l o f f (11) p o i n t s out p e o p l e do not f o c u s on a p a r t i c u l a r
s e t of r i s k s simply to s a f e g u a r d h e a l t h and s a f e t y ; the choice
often r e f l e c t s a moral view. The government o p e r a t e s on the
premise t h a t p u b l i c p o l i c y s h o u l d p r o t e c t a g a i n s t major r i s k s ; the
p u b l i c s h o u l d a c c e p t minor r i s k s . By v i e w i n g an i s s u e from the
moral perspective i t i s u n l i k e l y t h a t p u b l i c consensus can be
reached. I t has not been shown t h a t v o c a l p a r t i c i p a n t s r e p r e s e n t
the spectrum of p u b l i c o p i n i o n . U n l e s s the e f f e c t i v e n e s s of p u b l i c
participation is enhanced, the advisability of direct public
involvement in administrative decisions is debatable (12).
A g e n c i e s a d m i n i s t e r i n g s t a t e p o l i c y must r e n d e r u n b i a s e d d e c i s i o n s
based on the information a v a i l a b l e , use i t s best judgement to
o b t a i n b a l a n c e d p o l i c y , and be a c c o u n t a b l e f o r t h e i r d e c i s i o n s .
28. E H A R T ET AL. Ground Water Regulations 493
Development and A d m i n i s t r a t i o n o f the A l d i c a r b Rule i n W i s c o n s i n
W i s c o n s i n has had a number o f e x p e r i e n c e s i n d e a l i n g w i t h t r a c e s o f

p e s t i c i d e r e s i d u e s i n groundwater; t h e most n o t a b l e i s t h e p r e -
sence o f a l d i c a r b r e s i d u e s i n s h a l l o w a q u i f e r s i n t h e C e n t r a l Sands
region o f the State (Table I ) .
Table I . Major E v e n t s i n t h e Development o f t h e W i s c o n s i n

P o l i c y on P e s t i c i d e s i n Groundwater
Date Event
July 1981 A l d i c a r b c o n f i r m e d i n W i s c o n s i n groundwater
Nov. 1981 WDATCP proposed emergency r u l e
Jan. 1982 L e g i s l a t i v e C o u n c i l Groundwater Management Study
Committee formed
Mar. 1982 Emergency r u l e adopted
Mar. 1982 WDATCP was sued and c o u r t s u p h e l d r u l e

Aug. 1982 WDATCP proposed permanent a l d i c a r b r u l e
Apr. 1983 Permanent a l d i c a r b r u l e adopted
May 1984 1983 W i s c o n s i n A c t 410, Groundwater Law, s i g n e d by
Governor A. E a r l
Nov. 1984 WDATCP proposed permanent f e r t i l i z e r s o r p e s t i -
c i d e s i n groundwater r u l e
Sept . 1985 Permanent groundwater r u l e adopted
Union Carbide Agricultural Products Company, Inc. sells

aldicarbunder t h e t r a d e name T e m i k i n t h e S t a t e f o r use i n
c o n t r o l l i n g i n s e c t p e s t s on p o t a t o e s . I n J u l y 1981, the p r e s e n c e
of a l d i c a r b r e s i d u e s i n W i s c o n s i n groundwater was c o n f i r m e d i n
a r e a s where t h e p e s t i c i d e had been used. The W i s c o n s i n Department
of A g r i c u l t u r e , Trade and Consumer P r o t e c t i o n (WDATCP) promulgated
an emergency r u l e which became e f f e c t i v e p r i o r t o t h e 1982 growing
1
season. The m a n u f a c t u r e r and a g r o w e r s o r g a n i z a t i o n subsequently
sued t h e S t a t e based on whether i t had a u t h o r i t y t o impose such a
r u l e and whether t h e f a c t s s u p p o r t e d t h e d e c i s i o n s made by WDATCP.
The suitonly t r i e d on t h e a u t h o r i t y questionwas decided i n
favor of the State. A t r i a l , based on t h e m e r i t s , would n o t have
been c o n c l u d e d u n t i l a f t e r t h e emergency r u l e had t e r m i n a t e d which
l e d t h e m a n u f a c t u r e r and growers t o drop t h e i r s u i t .
Because a l d i c a r b was d e t e c t e d i n d r i n k i n g water samples i n
W i s c o n s i n d u r i n g 1981, t h e S t a t e w i t h t h e c o n c u r r e n c e and a s s i s -
tance o f the manufacturer amended t h e use d i r e c t i o n s . This
r e s u l t e d i n a f e d e r a l l a b e l amendment which changed t h e time t h a t
a l d i c a r b c o u l d be l e g a l l y a p p l i e d t o p o t a t o e s from time o f p l a n t i n g
to 4 t o 6 weeks a f t e r p l a n t i n g , reduced a p p l i c a t i o n r a t e s from 3 t o
2 pounds o f a c t i v e i n g r e d i e n t per a c r e , l i m i t e d use t o a l t e r n a t e
y e a r s on any p i e c e o f l a n d , p l a c e d an e n v i r o n m e n t a l warning s t a t e -
ment on t h e l a b e l , and made t h e p r o d u c t a r e s t r i c t e d - u s e p e s t i c i d e .
These r e q u i r e m e n t s were p l a c e d i n t h e S t a t e ' s emergency r u l e a l o n g
w i t h p r o v i s i o n s r e q u i r i n g u s e r s t o f i l e a n o t i c e o f i n t e n t t o use
the i n s e c t i c i d e and d e a l e r s to report s a l e s o f t h e Temik 15G
a l d i c a r b f o r m u l a t i o n ; t h e s e r e s t r i c t i o n s a l s o became a p a r t o f a
permanent a l d i c a r b r u l e .
494 EVALUATION O F PESTICIDES ING R O U N D WATER
The emergency r u l e a l s o e s t a b l i s h e d moratorium a r e a s p r o h i b -

iting a l d i c a r b use wherever d e t e c t a b l e residues were found i n
d r i n k i n g water w e l l s . Moratorium a r e a s under the emergency r u l e
were l a n d p a r c e l s on which no a l d i c a r b c o u l d be u s e d . The mora-
torium a r e a s were e s t a b l i s h e d based on known c o n t a m i n a t i o n o f
d r i n k i n g water and on a v a i l a b l e d a t a on d i r e c t i o n o f groundwater
flow, depth t o the water t a b l e , water u s e , and a l d i c a r b u s e .
A p p r o x i m a t e l y 70,000 a c r e s o f l a n d , some o f which was n o t i n a g r i -
c u l t u r a l p r o d u c t i o n , were i n c l u d e d under t h e moratorium. Although
the emergency r u l e e x p i r e d i n J u l y 1982, a m o d i f i e d moratorium a r e a
c o n c e p t was extended under the permanent r u l e . The moratorium on
use remains i n e f f e c t u n t i l a l d i c a r b r e s i d u e s i n well samples
remain below t h e enforcement s t a n d a r d f o r 1 y e a r .
In 1983, WDATCP adopted a permanent r u l e (13) e s t a b l i s h i n g 10
ppb as the " a c t i o n l e v e l " which t r i g g e r s d e s i g n a t i o n o f a morato-
rium a r e a . L e g a l c o n c e r n s over t h e p u b l i c ' s p e r c e p t i o n o f how
moratorium b o u n d a r i e s were e s t a b l i s h e d under t h e emergency r u l e l e d

WDATCP t o e s t a b l i s h the b o u n d a r i e s as a c i r c l e o f 1-mile r a d i u s
( a p p r o x i m a t e l y 2800 a c r e s f o r each moratorium a r e a e s t a b l i s h e d from
a single contamination s i t e ) around l o c a t i o n s where aldicarb
residues exceeded the enforcement s t a n d a r d . The c e n t e r o f the
moratorium a r e a i s t h e c e n t e r o f t h e q u a r t e r / q u a r t e r section of
l a n d on which t h e w e l l i s l o c a t e d .
T h e r e a r e 50 w e l l s l o c a t e d i n 25 q u a r t e r / q u a r t e r s e c t i o n s of
l a n d which were c o n t a m i n a t e d w i t h a l d i c a r b r e s i d u e s above t h e 10
ppb l e v e l and were used t o e s t a b l i s h t h e 1985 a l d i c a r b moratorium
a r e a s ; 33 w e l l s c u r r e n t l y a r e over t h e g u i d e l i n e l e v e l . Because o f
o v e r l a p p i n g , t h e s e s i t e s e s t a b l i s h 11 moratorium a r e a s encompassing
36,500 a c r e s . W e l l owners have been i n f o r m e d o f l e v e l s o f contam-
i n a t i o n and a d v i s e d t o seek a l t e r n a t e water s u p p l i e s u n t i l the
c o n t a m i n a t i o n l e v e l s drop below the g u i d e l i n e l e v e l , o r new w e l l s
can be i n s t a l l e d . Under s e p a r a t e r u l e s o f the S t a t e , some owners
q u a l i f y f o r a compensation fund as a r e s u l t o f t h e p r e s e n c e o f
aldicarb i n their wells. O n l y r e c e n t l y has the a u t h o r i t y been
g r a n t e d t o c l o s e p r i v a t e w e l l s ; t h e a u t h o r i t y has n o t been e x e r -
cised. S i n c e 1982, 12 o f t h e 75 owners whose w e l l s exceeded the 10
ppb l e v e l have t a k e n advantage o f t h e a l d i c a r b m a n u f a c t u r e r ' s o f f e r
t o pay f o r b o t t l e d water. About 40% o f t h e 51 p r i v a t e w e l l owners
who have been o f f e r e d c a r b o n f i l t e r s have a c c e p t e d ( 6 ) .
D e s p i t e t h e WDATCP r u l e , a l d i c a r b r e s i d u e s a r e s t i l l present
i n groundwater a l t h o u g h c o n t a m i n a t i o n l e v e l s o f most w e l l s w i t h i n
moratorium a r e a s a r e d e c r e a s i n g w i t h t i m e . However, s i n c e a l d i c a r b
residues are s t i l l detectable, the S t a t e ' s public intervenora
Wisconsin A s s i s t a n t Attorney General with r e s p o n s i b i l i t y f o r e n v i -
ronmental p r o t e c t i o n a n d some S t a t e l e g i s l a t o r s , environmentalists
and concerned c i t i z e n s b e l i e v e the r u l e i s i n e f f e c t i v e . In their
view, t h e r e m e d i a l a c t i o n taken by WDATCP s h o u l d a l s o r e c t i f y an
already e x i s t i n g c o n d i t i o n , w h i l e WDATCP r e g a r d s the r e m e d i a l
a c t i o n as p r o t e c t i o n f o r t h e f u t u r e , p r o v i d i n g c l e a n s i n g time f o r
the past c o n d i t i o n s but not a c l e a n u p program per se* S t a f f of
WDATCP recognize that protection and c l e a n u p efforts require
decades rather than months. Some members o f the p u b l i c a r e
demanding immediate d e c o n t a m i n a t i o n o f an i n a c c e s s i b l e resource,
and r e t r i b u t i o n i n t h e form o f s t r i c t liability f o r practices
performed b e f o r e t h e e x i s t i n g c o n d i t i o n s were r e c o g n i z e d .
Meanwhile, growers have become more s u p p o r t i v e of proper

r e g u l a t i o n o f p e s t i c i d e p r o d u c t s which have a p o t e n t i a l t o r e a c h
groundwater. They a r e c o n c e r n e d about water q u a l i t y as i t a f f e c t s
t h e i r f a m i l i e s , l i v e s t o c k and economic f u t u r e . They have adopted
i r r i g a t i o n p r a c t i c e s t o reduce e x c e s s i v e water u s e which p r e v i o u s l y
they c o n s i d e r e d u n n e c e s s a r y even though e c o n o m i c a l l y advantageous.
They have, w i t h few e x c e p t i o n s , f i l e d n o t i c e s o f i n t e n t t o a p p l y
aldicarb. They have c o o p e r a t e d w i t h field i n v e s t i g a t i o n s and
s a m p l i n g o f s o i l , groundwater and produce f o r a l d i c a r b r e s i d u e s .
Development, Administration and Enforcement of the Wisconsin

Groundwater Law
For a 2-year p e r i o d , c o n c u r r e n t w i t h t h e development and a d m i n i s -

t r a t i o n o f t h e a l d i c a r b r u l e by WDATCP, t h e W i s c o n s i n L e g i s l a t u r e
s t u d i e d and r e f i n e d the l e g a l framework f o r a S t a t e groundwater
p r o t e c t i o n program. A l t h o u g h d e s c r i b e d by many t o be a comprehen-

sive groundwater protection program, t h e groundwater law (14)
signed i n May 1984 added little authority to existing State
programs; i t merely c o d i f i e d many e x i s t i n g and emerging e f f o r t s o f
S t a t e a g e n c i e s t o p r o t e c t groundwater. The l e g i s l a t i v e a c t i o n i s
important because i t e s t a b l i s h e s the mechanism t o use " h e a l t h
advisory" levels as S t a t e "enforcement standards" not t o be
a t t a i n e d o r exceeded i n groundwater. I t also defines a "preventive
a c t i o n l i m i t " as a f r a c t i o n o f t h e enforcement s t a n d a r d . This i s a
contaminant c o n c e n t r a t i o n f o r s u b s t a n c e s found i n groundwater where
some agency a c t i o n i s r e q u i r e d . The law e f f e c t s a change i n p o l i c y
from t h e s t r i c t n o n d e g r a d a t i o n p h i l o s o p h y o f t h e p a s t w h e r e a c t i o n
was not mandated as a s t a t u t o r y r e q u i r e m e n t t o a new n u m e r i c a l
s t a n d a r d p o l i c y , where an agency d e c i s i o n , even i f i t chooses t o do
n o t h i n g , must be j u s t i f i e d and a r t i c u l a t e d . T h i s i s a major change
in public policy. I t s importance i s t h a t i t a s s u r e s better,
a l t h o u g h not n e c e s s a r i l y a b s o l u t e , p r o t e c t i o n o f t h e groundwater
resource. However, t h i s assurance i s not yet recognized or
a p p r e c i a t e d by t h e g e n e r a l p u b l i c .
The l e g i s l a t i o n was needed t o d e f i n e t h e i n s t i t u t i o n a l r e s p o n -
sibilities o f t h e W i s c o n s i n S t a t e a g e n c i e s w i t h a mandate t o
p r o t e c t groundwater. However, i t s t i m i n g had d e t r i m e n t a l e f f e c t s
1
on WDATCP s e f f o r t s t o conduct an e f f e c t i v e aldicarb control
program. The WDATCP needed answers t o s e v e r a l q u e s t i o n s t o a d d r e s s
the problem o f groundwater c o n t a m i n a t i o n by a l d i c a r b r e s i d u e s i n an
informed, r e s p o n s i b l e f a s h i o n . F o r example, many o f the r e a s o n s
t h a t a l d i c a r b r e s i d u e s move t h r o u g h t h e vadose zone t o groundwater
were n o t u n d e r s t o o d and a r e s t i l l i n a d e q u a t e l y r e s e a r c h e d . The
S t a t e d i d not p r o v i d e adequate r e s e a r c h f u n d i n g because t h e L e g i s -
l a t u r e was g r a p p l i n g w i t h what the S t a t e ' s g e n e r a l groundwater
p o l i c y should be. I r o n i c a l l y , t h e S t a t e modeled i t s groundwater
p o l i c y on the a l d i c a r b r u l e ; no S t a t e d o l l a r s , however, were made
a v a i l a b l e d i r e c t l y f o r r e s e a r c h , even though f r e q u e n t l e g i s l a t i v e
inquiries c o n t i n u e t o demand p r o o f that the a l d i c a r b rule i s
working t o m i n i m i z e o r e l i m i n a t e f u r t h e r i n t r u s i o n o f a l d i c a r b
r e s i d u e s i n t o groundwater.
The c u r r e n t S t a t e program r e q u i r e s each agency t o p r i o r i t i z e
potential groundwater pollutants under i t s jurisdiction. The
W i s c o n s i n Department o f N a t u r a l Resources (WDNR) i s r e q u i r e d t o
m o n i t o r groundwater t o a s s e s s problems caused by these p r i o r i t y

substances. I f p e s t i c i d e r e s i d u e s a r e found i n groundwater, WDNR
w i l l f o r w a r d t h e d a t a t o WDATCP. When WDATCP determines t h a t a
practice r e g u l a t e d by WDATCP i s r e s p o n s i b l e f o r t h e p e s t i c i d e
r e s i d u e s and when t h e l e v e l o f any p e s t i c i d e a t t a i n s o r exceeds a
preventive action limit o r enforcement standard, c e r t a i n site-
s p e c i f i c a c t i o n s must be t a k e n and/or r u l e s must be promulgated t o
modify management p r a c t i c e s . Changes i n p r a c t i c e s must be moni-
t o r e d f o r e f f e c t i v e n e s s t o m i n i m i z e impacts on groundwater q u a l i t y .
The WDATCP w i l l p e r f o r m t h i s f u n c t i o n t o t h e e x t e n t t h a t f i n a n c i a l
resources are a v a i l a b l e .
The WDATCP r u l e ( 1 5 ) e s t a b l i s h i n g a r e g u l a t o r y program f o r
fertilizers or pesticides i n groundwaterbecame effective i n
September 1985. C o n t a i n e d i n t h e r u l e a r e p r o v i s i o n s f o r WDATCP
action following notification o f confirmed pesticide residue
c o n t a m i n a t i o n o f groundwater, a d e s c r i p t i o n o f t h e agency's i n v e s -
t i g a t i o n a l p r o c e d u r e s , methods f o r i d e n t i f i c a t i o n o f w e l l l o c a t i o n s
where n u m e r i c a l s t a n d a r d s w i l l be a p p l i e d , and a s e l e c t i o n o f s i t e -
s p e c i f i c r e s p o n s e s t o be e x p e c t e d when c o n t a m i n a t i o n e x i s t s . The
agency i s also committed t o promulgate specific rules f o r
s u b s t a n c e s f o r which an enforcement s t a n d a r d has been e s t a b l i s h e d .
Memorandum o f U n d e r s t a n d i n g . Another important p r o v i s i o n i n the

r u l e i s t h e e s t a b l i s h m e n t o f a memorandum o f u n d e r s t a n d i n g between
WDATCP and WDNR r e g a r d i n g sample h a n d l i n g and a n a l y s i s . I n the
past, p r e l i m i n a r y , unconfirmed, analytical data intended f o r
program p l a n n i n g was r e l e a s e d t o t h e p u b l i c . In a d d i t i o n the lack
of a specific protocol f o r sample handling raised questions
r e g a r d i n g t h e c o m p a r a b i l i t y and r e l i a b i l i t y o f some d a t a . The
WDATCP and WDNR s t a f f r e c o g n i z e d t h a t l a b o r a t o r y p r o t o c o l s under
p e s t i c i d e r e g u l a t o r y programs d i f f e r from those conducted under
mandatory f e d e r a l water programs. Agreeable, uniform p r a c t i c e s t o
d e a l w i t h t h e s e d i f f e r i n g approaches t o q u a l i t y a s s u r a n c e needed t o
be e s t a b l i s h e d and a r e p a r t o f t h e memorandum o f u n d e r s t a n d i n g .
The memorandum o f u n d e r s t a n d i n g c o n t a i n s a d e s c r i p t i o n o f
a c c e p t a b l e c o l l e c t i o n equipment and c o n t a i n e r s , c o l l e c t i o n p r o c e -
d u r e s , r e c o r d k e e p i n g r e q u i r e m e n t s , use o f c o n t r o l samples, sample
size, storage ( i . e . , temperature and p r e s e r v a t i o n ) and c u s t o d y
requirements. I t e s t a b l i s h e s a r e q u i r e m e n t f o r t h e maintenance o f
a q u a l i t y a s s u r a n c e manual and an a p p r o v a l p r o c e s s f o r a n a l y t i c a l
methods d e t a i l i n g l i m i t s o f d e t e c t i o n ( q u a l i t a t i v e ) and l i m i t s o f
quantification. The memorandum o f u n d e r s t a n d i n g a l s o d e f i n e s when
c o n f i r m a t o r y a n a l y s i s by a n o t h e r method o r c h r o m a t o g r a p h i c column
i s n e c e s s a r y , and r e q u i r e s development o f r e l i a b l e i n f o r m a t i o n on
w e l l c o n s t r u c t i o n and depth i n t h e a q u i f e r and a l l o w s f o r t h e
development o f a l t e r n a t i v e p r o t o c o l s f o r sampling and h a n d l i n g when
s p e c i f i c substances r e q u i r e i t .
T h i s p r o c e s s may seem unduly b u r e a u c r a t i c and u n n e c e s s a r y .
However, i f governmental programs a r e t o be c r e d i b l e , e x a c t i n g
p r o t o c o l s must be e s t a b l i s h e d and adhered t o . E d u c a t i o n o f t h e
p u b l i c on t h e need f o r t h e s e programs and g e n e r a l e d u c a t i o n on
groundwater a r e needed t o i n c r e a s e f a c t u a l awareness. The i n e x p e n -
s i v e method o f c u t t i n g c o r n e r s and n o t a s s u r i n g t h e q u a l i t y o f
program e f f o r t s has c o s t f a r more i n c r e d i b i l i t y than t h e c o s t t o
r u n programs p r o p e r l y . Without such e x p e n d i t u r e s t o s e c u r e q u a l i t y
a s s u r a n c e , the c r e d i b i l i t y o f s c i e n t i f i c data in public decision-

making w i l l not be m a i n t a i n e d .
Mathematical Models. U s i n g models t o a i d i n e v a l u a t i n g the p o t e n -

tial f o r groundwater c o n t a m i n a t i o n has been emphasized. Many
b e l i e v e t h a t models s h o u l d be used as p a r t o f a r e g u l a t o r y approach
to p r e v e n t f u t u r e c o n t a m i n a t i o n . Models are a u s e f u l t o o l f o r
d e t e r m i n i n g p o t e n t i a l p r i o r i t i e s and p o s s i b l e s e n s i t i v e a r e a s and
crop uses and i n d e v e l o p i n g m o n i t o r i n g p l a n s . However, models a r e
not sufficiently reliable and predictive to a l l o w r e g u l a t o r y
a c t i o n s to be taken on the b a s i s of model f i n d i n g s a l o n e . There-
f o r e , a l t h o u g h u s e f u l i n r e s e a r c h and p l a n n i n g , models are not y e t
s u f f i c i e n t l y s o p h i s t i c a t e d to be used as a b a s i s f o r r e g u l a t o r y
programs.
Enforcement. No groundwater p r o t e c t i o n program w i l l be e f f e c t i v e

w i t h o u t p r o p e r enforcement. S u r v e i l l a n c e of p e s t i c i d e uses w i l l
i n c r e a s e as more management c r i t e r i a are added t o l a b e l d i r e c -
tions . Compliance w i l l r e q u i r e improved e d u c a t i o n of u s e r s and
changes i n s o c i a l a t t i t u d e s . C a l i b r a t i o n o f a p p l i c a t i o n equipment,
always a d i f f i c u l t p r o c e d u r e and s u b j e c t t o i n d i v i d u a l e r r o r , w i l l
need more c r i t i c a l a t t e n t i o n . The i n c r e a s e d p o t e n t i a l f o r l e g a l
c h a l l e n g e o f d e c i s i o n s w i l l cause enforcement a g e n c i e s t o spend
more r e s o u r c e s on each investigation. This w i l l entail more
e x t e n s i v e r e c o r d k e e p i n g and more d e t a i l e d r e p o r t i n g .
The r e l i a b i l i t y of c u r r e n t l y a v a i l a b l e t e c h n o l o g y f o r e s t a b -
l i s h i n g and a d m i n i s t e r i n g these p o l i c i e s , must be a s s u r e d o r the
system i s u s e l e s s . There must be a c c u r a t e and r e a d i l y a v a i l a b l e
i n f o r m a t i o n t o e s t a b l i s h enforcement s t a n d a r d s f o r the p e s t i c i d e
p r o d u c t s i d e n t i f i e d as h a v i n g the p o t e n t i a l to r e a c h groundwater.
Enforcement o r r e g u l a t o r y a c t i o n s cannot be f a i r w i t h o u t a c c u r a t e
a n a l y t i c a l data. Knowledge of p e s t i c i d e u s e s , g e o l o g y , hydro-
g e o l o g y and environmental f a t e are needed to p r e d i c t potential
problems, and more i m p o r t a n t l y , t o e s t a b l i s h a r e a s o n a b l e , c o s t
effective monitoring program (16). Programs which provide
i n c e n t i v e s and proper enforcement are needed t o make the system
effective. A system which a s s u r e s t h a t a g e n c i e s tend t o the
b u s i n e s s of a d m i n i s t e r i n g and academic i n s t i t u t i o n s tend t o the
business of r e s e a r c h must be developed; r e s e a r c h e r s must be
r e s p o n s i v e to r e g u l a t o r y i s s u e s . W i s c o n s i n has made some s t r i d e s
a t d e v e l o p i n g a system which i s t e c h n i c a l l y sound and p r a c t i c a l l y
w o r k a b l e but more needs t o be done.
V i o l a t i o n s o f s t a t e laws and r u l e s which r e s u l t i n groundwater
c o n t a m i n a t i o n must be p r o s e c u t e d by t r a d i t i o n a l methods. However,
to a c c e l e r a t e p r o t e c t i o n programs, some i n n o v a t i v e c o s t i n c e n t i v e s
a r e needed. When the i n f o r m e d p u b l i c and a f f e c t e d i n d u s t r i e s a r e
a c t i v e p a r t i c i p a n t s i n the d e c i s i o n - m a k i n g p r o c e s s , the law i s more
s t r i c t l y adhered t o .
The examples detailed i n this paper are from Wisconsin.
Geographical, climatological, legal and political variabilities
exist i n other states which may r e q u i r e m o d i f i c a t i o n of the
Wisconsin procedures before t h e s e methods o f l a n d management
c o n t r o l s can be adopted by o t h e r s t a t e s .
Literature Cited
1. Holden, P., personal communication.
2. "Groundwater Contamination, The Measure of Public Concern";
Center for Communication Dynamics, Washington, D.C., 1985.
3. Wood, D. "Wisconsin Environmental Priorities Survey
Results." Environ. Priorities Conf., Madison, Feb. 14, 1983.
4. Business Week, Jan. 24, 1983. p. 87.
5. Francis, J., personal communication.
6. Back, R., personal communications.
7. Francis, J . ; Larson, O. III. National Statistical Assessment
of Rural Water Conditions. Executive Summary. Cornell Uni-
versity, Ithaca, 1983.
8. Zahradnik, F. The New Farm Jan. 1984, 30-31.
9. Cohen, S., personal communication.
10. Zaki, M.; Moran, D.; Harris, D. Am. J. Public Health 1982,
72, 1391-1395.
11. Orloff, N. "We Scoff at Big Risks and Scotch Small Ones."
Wall Street J., Dec. 3, 1984, p. 34.
12. Schierow, L . - J . ; Chesters, G. Water Resources Bull. 1983, 19,
107-114.
13. WDATCP. Aldicarb Use Restrictions; Reporting Requirements.
Chapter Ag 29.17, Wis. Admin. Code.
14. 83 Wis. Act 410. Laws of Wis., 1983.
15. WDATCP. Fertilizer or Pesticide Substances in Groundwater:
Regulatory Program. Chapter Ag 161, Wis. Admin. Code.
16. Ehart, O. R. Unpublished presentation. Entomol. Soc. Am.,
Detroit, Nov. 29, 1983.
29
Ground Water Contamination by Toxic Substances
A California Assessment
David B. Cohen
Pollutant Investigations Branch, State Water Resources Control Board, Sacramento,

CA 95801
Overoptimistic risk perception, coupled with inadequate

risk assessment, has led to underprotective risk

management of toxic chemicals in ground water. In
California, soil nematicides like DBCP are a parti-
cular concern. DBCP use was banned in 1977, yet it is
s t i l l found in over 2500 wells. An estimated 700,000
people in 32 towns are either drinking water with
measurable levels of DBCP or have had to seek alterna-
tive water supplies. Over 50 other pesticides includ-
ing 1,2-D, EDB, and aldicarb have been found in
California ground water from both point and nonpoint
sources. Future risk management strategies must be
based on a more conservative risk perception approach.
California Water Resources Control Board's ground
water "hot spots" program is an example of such an
approach.
In s e m i - a r i d C a l i f o r n i a , ground water i s a p r e c i o u s r e s o u r c e .
D u r i n g t h e p a s t decade, t h e S t a t e Water Resources C o n t r o l Board,
C a l i f o r n i a ' s e n v i r o n m e n t a l p r o t e c t i o n agency f o r water q u a l i t y , has
l e a r n e d t h a t we have n o t done enough t o p r e v e n t t h e growing problem
of t o x i c c h e m i c a l c o n t a m i n a t i o n o f our ground water.
While both i n d u s t r i a l and a g r i c u l t u r a l c h e m i c a l s have been
found i n C a l i f o r n i a ground w a t e r s , p e s t i c i d e s i n j e c t e d beneath
the s o i l s u r f a c e t o c o n t r o l nematodes a r e a p a r t i c u l a r c o n c e r n . The
n e m a t i c i d e 1,2-dibromo-3-chloropropane (DBCP), which was banned i n
C a l i f o r n i a i n 1977, i s t h e most s e r i o u s example o f t h i s problem i n
C a l i f o r n i a ( 1 - 2 ) . F i g u r e 1 shows t h e i n c r e a s e between 1979 and
1984 i n t h e number o f w e l l s found t o c o n t a i n measurable q u a n t i t i e s
of DBCP. As o f A p r i l 1984, 2522 w e l l s c o n t a i n e d DBCP, w i t h over
h a l f t h e s e w e l l s (1455) h a v i n g c o n c e n t r a t i o n s i n e x c e s s o f 1.0
part per b i l l i o n , the c u r r e n t C a l i f o r n i a "action l e v e l " .
T a b l e I l i s t s over 50 o t h e r p e s t i c i d e s (from both p o i n t and
n o n p o i n t s o u r c e s ) t h a t have been i d e n t i f i e d i n ground water from
28 o f C a l i f o r n i a ' s 58 c o u n t i e s . F i g u r e 2 shows t h e g e o g r a p h i c
0097-6156/ 86/ 0315-0499$08.75/0

500 EVALUATION O FPESTICIDES ING R O U N D WATER
2600
(2522)
2400 -
(2252)
LU
>
2200
2000

1800
LU
1600
(1455)
UJ
< 1400 -
(1292)
i
< 1200 -

LL 1000 -

CO
CC
LU 800 -
m
3
600
400 -
>1.0 p p b
(Action 200 -
Level)
'79 '80 '81 '83 '84
YEAR
F i g u r e 1. DBCP i n C a l i f o r n i a Ground Water - Cumulative Summary

(May 1979 - A p r i l 1984) .
29. COHEN Ground Water Contamination by Toxic Substances 501
Table I. Pesticides Detected in California Ground Water

(Large Water Systems vs. Small Domestic Systems)
No.Verified Pesticide N o
* Verified Pesticide No. Verified
Pesticide
Incidents Incidents Incidents
Aldicarb 27 Dieldrin 4 Omite 2

Aldrin 22 Dimethoate 24 Ordram 3
Atrazine 2 Diphenamid 1 Paraoxon 1
Bentazon 1 Disulfoton 6 P a r a t h i o n , ethyl 4
Benzaldehyde 1 DNBP 11 P a r a t h i o n , methyl 1

Chlordane 4 DNOC 2 PCNB 1
Chlorpropham 1 Dursban 3 PCP 38
Dacthal 4 EDB 32 Phorate 2
DBCP 2522 Endosulfan 23 Phthalates 4
DDD 4 Endrin 1 Sevin 3
DDE 15 Ethion 5 Simazlne 9
DDT 10 Ethylene thiourea 1 TCP 6
DEF 1 Furadan (carbofuran) 2 Toxaphene 5
Delnav 4 Heptachlor 4 Treflen 1
Diazinon 12 Kelthane (dicofol) 3 Zytron 4
Dichlone 1 Lindane 18 2,4-D 10
1,2-Dichloropropane 72 Malathion 5 2,4,5-T 4
1,3-Drchloropropene(cis) 2 Methylene chloride 4 2,4.5-TP 3
1,3-Dichloropropene(tran8) 1 Naled 7 TOTAL 2963
F i g u r e 2. V e r i f i e d I n c i d e n t s o f Ground Water C o n t a m i n a t i o n with

P e s t i c i d e s ( I n c l u d i n g DBC).
d i s t r i b u t i o n o f a l l v e r i f i e d i n c i d e n t s o f ground water c o n t a m i n a -
t i o n by p e s t i c i d e s ( i n c l u d i n g DBCP) as o f November 1984. T h i s
paper f o c u s e s on C a l i f o r n i a ' s e x p e r i e n c e s w i t h p e s t i c i d e s i n ground
water, p o t e n t i a l c a u s e s , and p o s s i b l e s o l u t i o n s .
C a l i f o r n i a ' s Water Q u a l i t y P r o t e c t i o n Program
In 1969, C a l i f o r n i a adopted the P o r t e r - C o l o g n e A c t g i v i n g t h e

S t a t e Water Resources C o n t r o l Board ( S t a t e Board) t h e a u t h o r i t y t o
(1) a s s u r e t h a t a l l water d i v e r s i o n s be p u t t o a b e n e f i c i a l u s e ,
and (2) m a i n t a i n and enhance t h e q u a l i t y o f a l l waters o f t h e
State. One major d i f f e r e n c e between f e d e r a l and s t a t e water
q u a l i t y p r o t e c t i o n programs i n v o l v e s p r o t e c t i o n o f ground water.
The 1972 F e d e r a l C l e a n Water A c t a d d r e s s e d s u r f a c e water q u a l i t y
( " f i s h a b l e and swimmable" by 1985), s p e c i f i c a l l y e x c l u d i n g n o n p o i n t
s o u r c e a g r i c u l t u r a l r e t u r n f l o w s from r e g u l a t i o n . C a l i f o r n i a law
p r o t e c t s a l l waters o f the S t a t e , i n c l u d i n g ground water and g i v e s

the S t a t e Board a u t h o r i t y t o r e g u l a t e a l l s o u r c e s o f c o n t a m i n a t i o n
including pesticides i n a g r i c u l t u r a l runoff. H i s t o r i c a l l y , such
n o n p o i n t s o u r c e s have r a r e l y been r e g u l a t e d by t h e S t a t e and
R e g i o n a l Boards because o f t h e d i f f i c u l t y i n t r a c i n g problem e v e n t s
t o an unknown number o f d i f f u s e s o u r c e s .
The S t a t e i s s u b d i v i d e d a l o n g d r a i n a g e b a s i n b o u n d a r i e s i n t o
n i n e r e g i o n s , each w i t h i t s own R e g i o n a l Water Q u a l i t y C o n t r o l Board
( F i g u r e 3 ) . The r e g i o n a l b o a r d s have t h e a u t h o r i t y t o (1) i s s u e
waste d i s c h a r g e r e q u i r e m e n t s , (2) m o n i t o r water q u a l i t y , (3) take
enforcement a c t i o n s , and (4) adopt n a r r a t i v e o r n u m e r i c a l water
q u a l i t y objectives i n t o basin plans. A t y p i c a l basin plan narra-
t i v e o b j e c t i v e s t a t e s t h a t "the d i s c h a r g e o f p e s t i c i d e s t o waters
o f t h e r e g i o n o r a t l o c a t i o n s where the waste may s u b s e q u e n t l y
r e a c h waters o f t h e r e g i o n i s p r o h i b i t e d " . In o r d e r t o p r o t e c t
ground water, t h e S t a t e Board i n 1972 adopted r e g u l a t i o n s g o v e r n i n g
hazardous waste d i s p o s a l t o l a n d . These r e g u l a t i o n s (Subchapter 15
o f the C a l i f o r n i a Water Code) c l a s s i f i e d both wastes and s i t e s .
Wastes were c a t e g o r i z e d on t h e b a s i s o f t h e r e l a t i v e h a z a r d t o
h e a l t h and t h e environment, w h i l e s i t e s were p r i o r i t i z e d a c c o r d i n g
t o p o t e n t i a l f o r l e a c h i n g and ground water c o n t a m i n a t i o n .
As t h r e a t s from b i o l o g i c a l p o l l u t a n t s i n s u r f a c e waters l e s s e n ,
the awareness o f t h r e a t s from t o x i c c h e m i c a l s i n c r e a s e s . Hardly
a week goes by w i t h o u t a new r e p o r t o f t o x i c o r g a n i c c h e m i c a l s i n
a community water s u p p l y o r o t h e r water r e s o u r c e .
DBCP (1,2-Dibromo-3-chloropropane)
The most w i d e s p r e a d p e s t i c i d e c o n t a m i n a t i o n o f ground water i n

C a l i f o r n i a (and, p o s s i b l y , the n a t i o n ) has o c c u r r e d t h r o u g h use o f
DBCP. The c h e m i c a l was f i r s t d i s c o v e r e d i n C a l i f o r n i a ground water
i n 1979 by t h e C e n t r a l V a l l e y R e g i o n a l Board. Eight years a f t e r
i t s use was banned, more DBCP-contaminated w e l l s a r e s t i l l b e i n g
discovered. DBCP i n some w e l l waters was a t h i g h e r l e v e l s i n 1984
than when f i r s t d i s c o v e r e d i n 1979 ( F i g u r e 4 ) . Many o f t h e s e w e l l s
have been shut down p e r m a n e n t l y , w h i l e o t h e r s a r e o n l y used on an
emergency b a s i s o r when DBCP c o n c e n t r a t i o n s d e c r e a s e below 1 ppb.
F i g u r e 3. R e g i o n a l Water Q u a l i t y C o n t r o l Boards.
Of 8,190 C a l i f o r n i a w e l l s m o n i t o r e d by November 1984, 30.8

p e r c e n t were found t o c o n t a i n DBCP. F r e s n o County had the h i g h e s t
p e r c e n t a g e (41.3 p e r c e n t ) and g r e a t e s t number (1,696) o f DBCP
c o n t a m i n a t e d w e l l s . In some a r e a s o f F r e s n o County, over h a l f the
p r i v a t e w e l l s sampled c o n t a i n e d DBCP above the DHS a c t i o n l e v e l o f
I ppb. C a l i f o r n i a has spent over $10 m i l l i o n i n Fresno County a l o n e
to r e h a b i l i t a t e DBCP-contaminated ground water s u p p l i e s .
Many o f the worst p o l l u t i o n problems were found i n s m a l l or
p r i v a t e r u r a l systems where a w e l l s e r v e s one or more homes. Table
I I compares t h e degree o f DBCP-contamination f o r both l a r g e p u b l i c
water systems (>200 c o n n e c t i o n s ) and s m a l l e r systems (5-200 c o n n e c -
t i o n s ) i n 11 C a l i f o r n i a c o u n t i e s . Large water systems had 14.6
p e r c e n t o f t h e i r w e l l s c o n t a m i n a t e d w i t h DBCP compared t o 33.6
p e r c e n t f o r s m a l l and d o m e s t i c water systems which f r e q u e n t l y pump
from s h a l l o w e r , more v u l n e r a b l e a q u i f e r s . By comparison, a r e c e n t l y
i n a u g u r a t e d s t a t e w i d e m o n i t o r i n g program f o r over 40 t o x i c c h e m i c a l s
i n l a r g e community w e l l s (AB 1803) found t o x i c o r g a n i c c h e m i c a l s i n

82 o f 320 systems (25.6 p e r c e n t ) . (3)
DBCP c o n c e n t r a t i o n s i n some F r e s n o County d o m e s t i c w e l l s
sampled between 1979-1984 have f l u c t u a t e d s e a s o n a l l y by an o r d e r o f
magnitude. F i g u r e 5 shows DBCP c o n c e n t r a t i o n s i n one w e l l f l u c t u -
a t e d between 3 t o 33 p a r t s per b i l l i o n w i t h i n s i x months d u r i n g
1981. Sample c o l l e c t i o n and a n a l y t i c a l methods were unchanged
d u r i n g t h i s p e r i o d . A l t h o u g h the reasons f o r t h i s v a r i a b i l i t y a r e
not y e t c l e a r l y u n d e r s t o o d , t h e s e examples demonstrate the need
t o c o n t i n u e m o n i t o r i n g even a f t e r c o n c e n t r a t i o n s f a l l "below
detection limits". Plumes o f DBCP c o n t a m i n a t e d ground water can
move u n p r e d i c t a b l y through a q u i f e r s t o r e a c h p r e v i o u s l y u n c o n t a m i -
nated monitoring w e l l s .
These r e t r o s p e c t i v e DBCP m o n i t o r i n g d a t a a r e p r e s e n t l y b e i n g
t r a n s f e r r e d t o computer f i l e s . When t h i s work i s completed,
a n a l y s i s o f s p a t i a l and temporal t r e n d s and p o s s i b l e c o r r e l a t i o n s
w i t h s o i l and water p r e d i c t i v e f a c t o r s w i l l be attempted.
C a l i f o r n i a i s f o r t u n a t e i n h a v i n g a mandatory use r e p o r t i n g
system f o r r e s t r i c t e d p e s t i c i d e s . ( 4 ) Computer t a p e s c o n t a i n i n g
the raw d a t a from t h i s program a r e t r a n s f e r r e d t o the U n i v e r s i t y
of C a l i f o r n i a a t D a v i s , which has, w i t h S t a t e Board s u p p o r t ,
d e v e l o p e d a computer program f o r mapping p e s t i c i d e use i n f o r m a t i o n
g e o g r a p h i c a l l y (by c o u n t y , r e g i o n , or the S t a t e ) and t e m p o r a l l y
(by s e a s o n , y e a r , or c u m u l a t i v e y e a r s ) . F i g u r e 6, which shows
r e p o r t e d C a l i f o r n i a use o f DBCP f o r 1972-1977, i s an example o f
that c a p a b i l i t y . U n f o r t u n a t e l y , not a l l p e s t i c i d e use was r e q u i r e d
t o be r e p o r t e d d u r i n g t h i s p e r i o d . DBCP was o n l y r e q u i r e d t o be
r e p o r t e d s h o r t l y b e f o r e i t s use was banned i n 1977. The Department
of Food and A g r i c u l t u r e has t h e r e f o r e e s t i m a t e d a c t u a l use t o be
a p p r o x i m a t e l y t h r e e times r e p o r t e d use. The b e s t e s t i m a t e o f
a c t u a l c u m u l a t i v e DBCP use between 1957 and 1977 i s i n e x c e s s o f
50 m i l l i o n pounds. D e s p i t e the i n c o m p l e t e n e s s o f p a s t p e s t i c i d e
use r e p o r t s , t h i s p e s t i c i d e mapping c a p a b i l i t y i s an i m p o r t a n t t o o l
i n f o c u s i n g S t a t e Board f i e l d m o n i t o r i n g e f f o r t s on a r e a s o f
greatest potential risk.
A p r o s p e c t i v e f i e l d s t u d y o f DBCP movement (both h o r i z o n t a l and
v e r t i c a l ) through s o i l t o ground water has been proposed by
r e s e a r c h e r s a t the U n i v e r s i t y o f C a l i f o r n i a , D a v i s . A particularly
YEAR
F i g u r e 4. DBCP C o n c e n t r a t i o n s i n E s c a l o n M u n i c i p a l W e l l No. 3.
Table . Percent of Wells Contaminated with DBCP

(Point and Nonpoint Source-1884)
Large Small
County TOTAL
Systems Systems
FRESNO 19.1 43.4 41.3
KERN 5.9 23.3 15.9
MADERA 2.7 22.9 20.7

MERCED 22.7 23.5 23.4
TULARE 10.4 29.4 23.8
SAN JOAQUIN 19.9 19.4 19.6
STANISLAUS 16.2 19.9 18.5

RIVERSIDE 2.7 9.1 5.0
SAN BERNADINO 35.8 - 35.8
SUTTER 100.0 44.4 52.4
BUTTE - 33.3 33.3
TOTAL 14.6 33.6 30.8

)
)0
S'
-

<
-

I

F i g u r e 6.
DBCP C a l i f o r n i a Reported Use
(1972-1977).
i n t r i g u i n g s i t e i s t h e c e n t r a l v a l l e y town o f Sanger, near F r e s n o .

DBCP use f o r 25 y e a r s i n t h a t a r e a had caused a s h a l l o w a q u i f e r used
f o r d o m e s t i c purposes t o become c o n t a m i n a t e d . A w e l l 600 f e e t deep
was dug t o o b t a i n b e t t e r q u a l i t y water from t h e presumably uncontam-
i n a t e d deep a q u i f e r . S p e c i a l c a r e was taken t o p r e v e n t t r a n s f e r o f
c o n t a m i n a t e d s u r f a c e s o i l p a r t i c l e s t o t h e depth sample. Traces o f
DBCP were found a t 420 f e e t , t h e g r e a t e s t depth sampled, i n d i c a t i n g
an average v e r t i c a l t r a n s p o r t r a t e o f a p p r o x i m a t e l y 17 f e e t p e r
year (_5). In t h i s c a s e , d i g g i n g deeper was n o t t h e s o l u t i o n t o
pollution.
DBCP appears t o p e r s i s t i n s o i l s f o r decades w i t h a h a l f - l i f e o f
over a c e n t u r y ( 6 ) . A t one C a l i f o r n i a s i t e , DBCP was found t o p e r -
s i s t i n t o p s o i l f o r n e a r l y a decade a f t e r a s i n g l e a p p l i c a t i o n (7_).
T h i s s t u d y conducted i n 1980 i n t h e P a r l i e r a r e a showed DBCP c o n t a m i -
n a t i o n t o a d e p t h o f 30 f e e t throughout t h e s o i l p r o f i l e . The h i g h -
e s t c o n c e n t r a t i o n s o f DBCP were found i n t h e c l a y and s i l t l a y e r s .
DBCP f i n d i n g s i n s o i l and ground water c o i n c i d e d w i t h a r e a s o f h i g h

DBCP use. T h i s has l e d S t a t e Board s t a f f t o c o n c l u d e t h a t p a s t
a g r i c u l t u r a l use i s t h e most l i k e l y s o u r c e o f t h i s widespread
contamination.
DBCP D r i n k i n g Water Standard
EPA has n o t y e t d e v e l o p e d a n a t i o n a l d r i n k i n g water s t a n d a r d f o r

DBCP {8). The 1978 DHS d r i n k i n g water a c t i o n l e v e l o f 1.0 ppb was
adopted b e f o r e c u r r e n t i n f o r m a t i o n on c a r c i n o g e n i c i t y was a v a i l a b l e .
EPA has s i n c e e s t i m a t e d a l i f e t i m e c a n c e r r i s k from consuming 2
l i t e r s p e r day o f water c o n t a i n i n g 1 p a r t p e r b i l l i o n DBCP as 180
e x c e s s c a n c e r i n c i d e n t s p e r m i l l i o n p o p u l a t i o n exposed ( 9 ) . F i g u r e
7 d e p i c t s t h e EPA e s t i m a t e d c a n c e r r i s k a t v a r i o u s DBCP water c o n -
centrations. The S t a t e o f Hawaii i n 1984 adopted a water q u a l i t y
l i m i t o f 0.02 ppb (20 p p t ) ( T O ) . In view o f DBCP's p o t e n t i a l c a n c e r
impacts a t v e r y low c o n c e n t r a t i o n s , SWRCB has recommended t h a t DHS
lower t h e C a l i f o r n i a DBCP a c t i o n l e v e l t o t h e c u r r e n t d e t e c t i o n
l i m i t o f 0.02 p a r t s p e r b i l l i o n ( 1 1 ) .
Population Impacts
Department o f H e a l t h S e r v i c e s s t a f f has e s t i m a t e d t h a t over 700,000

p e o p l e i n 32 towns a r e e i t h e r d r i n k i n g DBCP-contaminated water o r
have had t o seek a l t e r n a t i v e water s u p p l i e s (12). The e s t i m a t e d
breakdown by c o u n t y , town, number o f w e l l s c o n t a m i n a t e d , and popu-
l a t i o n s e r v e d i s shown i n T a b l e I I I .
Large water d i s t r i c t s c a n d i g d e e p e r , s w i t c h t o n o n p o l l u t e d
w e l l s , o r b l e n d t h e i r s u p p l i e s t o meet c u r r e n t p u b l i c h e a l t h
advisories. N e v e r t h e l e s s , a c c o r d i n g t o t e s t i m o n y o f S t a t e Board
C h a i r p e r s o n C. Onorato b e f o r e t h e C a l i f o r n i a Senate A g r i c u l t u r e and
Water Committee on March 5, 1985, "we a r e a p p r o a c h i n g t h e p o i n t
where t o x i c p o l l u t i o n i s b e g i n n i n g t o a f f e c t t h e o v e r a l l a v a i l a b i l i -
t y o f water i n C a l i f o r n i a . I n s t e a d o f moving f o r w a r d t o a n t i c i p a t e
f u t u r e water s h o r t a g e s , we a r e moving backward by l o s i n g some o f
what we a l r e a d y have". Home buyers i n t h e c e n t r a l v a l l e y w i s h i n g t o
o b t a i n a F e d e r a l Farm Home Mortgage l o a n must f i r s t p r o v i d e t h e
l e n d e r w i t h e v i d e n c e t h a t t h e w e l l s u p p l y i n g t h e i r p r o s p e c t i v e home
w i t h d o m e s t i c water i s f r e e o f DBCP ( 1 2 ) .
510 E V A L U A T I O N O F PESTICIDES ING R O U N D WATER
10"
DHS A C T I O N
10* (180)
LIMIT
- 10*-
.

DETECTION
< 20 -<3)-
oc LIMIT
10 'd

6.7 (1)

10 -
(X) = Rlsk per 1 0 population exposed

6
F i g u r e 7. DBCP Water C o n c e n t r a t i o n s V e r s u s Cancer Risk Levels.

Table III. Estimated P o p u l a t i o n A f f e c t e d by DBCP (>1 ppb) i n Large

Water S u p p l i e s ( A p r i l 1983)
Wells Population
County Towns Contaminated Served
Fresno 12 21 290,000
Riverside 3 13 195,000
Stanislaus 3 4 90,000
San B e r n a r d i n o 2 4 50,000
San J o a q u i n 5 17 50,000
Merced 3 6 15,000
Tulare 2 6 10,000
Sutter 1 2 2,000
Kern 1 2 1,000
Total 32 75 703,000
C e n t r a l V a l l e y Ground WaterHow Much i s Contaminated?
Over h a l f (55.6 p e r c e n t ) o f a l l p e s t i c i d e s r e p o r t e d used i n

C a l i f o r n i a were used i n the c e n t r a l v a l l e y . ( 1 3 ) The e a s t e r n San
Joaquin V a l l e y i n p a r t i c u l a r i s vulnerable to chemical contamination
o f ground water because o f a unique c o m b i n a t i o n o f h i g h p e s t i c i d e
use, s h a l l o w water t a b l e s , r e l a t i v e l y porous s o i l s , and s e a s o n a l
irrigation. Schmidt has e s t i m a t e d the volume o f DBCP p o l l u t e d ground
water i n the F r e s n o urban a r e a i n e x c e s s o f 4 m i l l i o n a c r e f e e t
(M.A.F.).(14) S i m i l a r c a l c u l a t i o n s f o r o t h e r h i g h DBCP use a r e a s i n
the San J o a q u i n V a l l e y (8 m i l l i o n a c r e s ) y i e l d an e s t i m a t e d volume
o f DBCP p o l l u t e d ground water a p p r o a c h i n g 30 M.A.F. or over one
q u a r t e r o f the u s a b l e ground water i n the e n t i r e v a l l e y . The c o s t s
f o r pumping and t r e a t i n g such l a r g e volumes o f p o l l u t e d water would
be a s t r o n o m i c a l . Other a l t e r n a t i v e s , such as c a r b o n f i l t r a t i o n ,
b o t t l e d water, or d r i l l i n g d e e p e r , each have t h e i r own t e c h n i c a l or
economic drawbacks. We a r e r e l e a r n i n g the hard way t h a t an ounce o f
p r e v e n t i o n i s b e t t e r than any c u r e .
S t a t e Board P r i o r i t y Chemical I n v e s t i g a t i o n s
In o r d e r t o answer the q u e s t i o n : a r e t h e r e any more DBCP-type

problems o u t t h e r e a w a i t i n g d i s c o v e r y , the S t a t e Board i n May 1980
e s t a b l i s h e d a T o x i c Substances C o n t r o l Program. A major f o c u s o f
t h i s program was development o f an " e a r l y w a r n i n g " p r i o r i t y c h e m i c a l s
p r o j e c t t o (1) a s s e s s r i s k s , (2) recommend water q u a l i t y o b j e c t i v e s ,
and (3) propose a p p r o p r i a t e m i t i g a t i o n measures f o r a g r i c u l t u r a l and
i n d u s t r i a l c h e m i c a l s most l i k e l y t o a d v e r s e l y impact s u r f a c e or
ground water q u a l i t y .
T a b l e IV l i s t s the 13 c r i t e r i a used f o r r a n k i n g t h o s e compounds
(from among hundreds o f p o t e n t i a l c a n d i d a t e c h e m i c a l s ) t h a t posed the
h i g h e s t r i s k t o water q u a l i t y . The 100 h i g h e s t r e p o r t e d use p e s t i -
c i d e s were s c r e e n e d . A s e m i - q u a n t i t a t i v e r a n k i n g s c a l e was d e v e l o p e d
and a p p l i e d i n s e l e c t i n g 12 p r i o r i t y c h e m i c a l s ( F i g u r e 8 ) . Field
m o n i t o r i n g i n p o t e n t i a l "hot s p o t " a r e a s was d e s i g n e d t o document
p r e s e n c e and e x t e n t o f p r i o r i t y c h e m i c a l r e s i d u e s . The v a r i o u s
s t e p s i n t h e p r i o r i t y c h e m i c a l p r o c e s s a r e shown i n F i g u r e 9.
T a b l e IV. SWRCB C r i t e r i a for Selection of Priority Chemicals
1. P o t e n t i a l f o r s u r f a c e water c o n t a m i n a t i o n
2. P o t e n t i a l f o r ground water c o n t a m i n a t i o n
3. Detection i n C a l i f o r n i a
4. Use i n C a l i f o r n i a
5. Fish/wildlife k i l l s
6. P u b l i c c o n c e r n
7. A c t i o n s by o t h e r a g e n c i e s / c o u n t r i e s
8. D e t e c t i o n worldwide
9. B i o a c c u m u l a t i o n p o t e n t i a l
10. P e r s i s t e n c e
11. C a r c i n o g e n i c i t y , m u t a g e n i c i t y , t e r a t o g e n i c i t y
12. A q u a t i c t o x i c i t y , a c u t e / c h r o n i c
13. Human t o x i c i t y , a c u t e / c h r o n i c
1,2- -D/l,3-D ( 1 , 2 - d i c h l o r o p r o p a n e / l , 3 - d i c h l o r o p r o p e n e )
The n e m a t i c i d e s "D-D" and " T e l o n e " , which c o n t a i n 1,2-D/1,3-D, were

s e l e c t e d f o r p r i o r i t y c h e m i c a l i n v e s t i g a t i o n because o f t h e i r r e l a -
t i v e l y h i g h m o b i l i t y i n s o i l . , s o l u b i l i t y i n water, and c h e m i c a l
s i m i l a r i t y t o DBCP.(15) Preliminary information also indicated that
t h e s e c h e m i c a l s might be mutagenic and c a r c i n o g e n i c . Of p a r t i c u l a r
s i g n i f i c a n c e was t h e i n c r e a s e d use o f D-D and T e l o n e i n C a l i f o r n i a
from 4 m i l l i o n pounds i n 1977 (the year DBCP was banned) t o over 16
m i l l i o n pounds i n 1981 ( F i g u r e 1 0 ) .
P r i o r t o 1982 when SWRCB s e l e c t e d t h e s e n e m a t i c i d e s f o r p r i o r -
i t y p e s t i c i d e i n v e s t i g a t i o n , s a m p l i n g e f f o r t s by o t h e r s t a t e o r
l o c a l a g e n c i e s had n o t found 1,2-D i n ground w a t e r . The S t a t e
Board's 1,2-D/1,3-D i n v e s t i g a t i o n documented over 60 w e l l s c o n t a m i -
n a t e d w i t h 1,2-D (25 p e r c e n t o f samples c o l l e c t e d ) . (_15) No 1,3-D
was found i n any o f t h e samples c o n t a i n i n g 1,2-D. SWRCB s u b s e -
q u e n t l y recommended t h a t t h e Department o f Food and A g r i c u l t u r e
(DFA) r e e v a l u a t e a l l s o i l f u m i g a n t s c o n t a i n i n g 1,2-D. DFA a c c e p t e d
t h i s S t a t e Board recommendation.
Use o f D-D ( a p p r o x i m a t e l y 35 p e r c e n t 1,2-D) was s u b s e q u e n t l y
suspended by t h e D e l Norte County a g r i c u l t u r a l commissioner. Shell
C h e m i c a l Company has s i n c e withdrawn D-D from t h e C a l i f o r n i a market.
The S t a t e Board recommended t h a t DHS adopt an a c t i o n l e v e l o f
10 ppb 1,2-D i n d o m e s t i c water s u p p l i e s . County h e a l t h o f f i c i a l s
now a d v i s e p r i v a t e d o m e s t i c w e l l owners t o seek a l t e r n a t i v e s u p p l i e s
f o r water c o n t a i n i n g more than 10 ppb 1,2-D.
A l l o f t h e chemical c o n s t i t u e n t s o f s o i l fumigants, both a c t i v e
and i n e r t , s h o u l d be t e s t e d f o r t h e i r p o t e n t i a l t o l e a c h t o ground
water. The 1,2-D component o f 1,2-D/1,3-D f o r m u l a t i o n s was a non-
e s s e n t i a l contaminant o f t h e major a c t i v e i n g r e d i e n t 1,3-D.
Most o f t h e documented 1,2-D c o n t a m i n a t i o n i n c i d e n t s were i n
private rural wells. A comprehensive ground water m o n i t o r i n g
/ ** /
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AGRICULTURAL CHEMICALS
TOXAPHENE M H M H H M H M M L L M M
1,2-DICHLOROPROPANE
1,3-DICHLOROPROPENE M L M L M L H L L L H L L
E T H Y L E N E DIBROMIDE (EDB) H M H L M L M M L L H L L
ENDOSULFAN H H L L L L M M L H L H L
ARSENICALS H L H H H L M M M L L H L
RICE HERBICIDES
(MOLINATE & THIOBENCARB) M H L M L M H H L H L H L
INDUSTRIAL C H E M I C A L S
P O L Y C H L O R I N A T E D BIPHENYLS
(PCB) H H H H H H H H H L L H H
P E N T A C H L O R O P H E N O L (PCP) M H L M M M H M M M M M 0
TRICHLOROETHYLENE (TCE) H H H M M H H H 0 0 H M 0
CHLORINATED ETHANES H H H M M H H H 0 0 H M 0
CYANIDE H H M M H H H H 0 0 H H 0
CHROMIUM (hexavalent) H H H M H M H H H 0 H M 0
L'LOW RATING
M= M O D E R A T E RATING
H = HIGH RATING
F i g u r e 8. Top Twelve SWRCB P r i o r i t y C h e m i c a l s S e l e c t e d i n 1981.

F i g u r e 9. SWRCB P r i o r i t y Chemical Assessment Process.

COHEN Ground Water Contamination by Toxic Substances
'70 '71 '72 '73 '74 '75 '76 "77 '78 '79 '80 '81 '82 '83
YEAR
B o t h c h e m i c a l s p l a c e d on C a l i f o r n i a Restricted
M a t e r i a l s l i s t in 1 9 7 7 .
F i g u r e 10. DBCP and 1,2-D/1,30-D (D-D) Reported Use (1970 t o 198

program s h o u l d i n c l u d e such w e l l s t o p r o v i d e " e a r l y warning" o f

p o t e n t i a l c o n t a m i n a n t movement from r u r a l a r e a s t o l a r g e urban popu-
lation centers.
The 1,2-D/1,3-D s t u d y d i s c o v e r e d s e v e r a l c a s e s where c h l o r o f o r m ,
c a r b o n t e t r a c h l o r i d e , and TCE were d e t e c t e d t o g e t h e r w i t h DBCP o r
1,2-D i n a s i n g l e sample. Should a r e g u l a t o r y a c t i o n l e v e l f o r a
s i n g l e t o x i c c h e m i c a l be r e v i s e d when o t h e r c h e m i c a l s , p a r t i c u l a r l y
carcinogens, are also present? More s t r i n g e n t s a f e t y f a c t o r s may be
r e q u i r e d f o r d e r i v i n g a d e q u a t e l y p r o t e c t i v e water q u a l i t y s t a n d a r d s
when m u l t i p l e exposure t o a m i x t u r e o f two o r more c h e m i c a l s i s
involved.
I m p l i c a t i o n s o f SWRCB Recommendation f o r 1,2-D
The SWRCB recommendation t o reduce 1,2-D i n s o i l n e m a t i c i d e s t o t h e

l o w e s t p r a c t i c a l l e v e l (<2 p e r c e n t ) was t e c h n i c a l l y f e a s i b l e . DFA
i s p r e s e n t l y d e v e l o p i n g a r e g u l a t i o n t o l i m i t 1,2-D i n n e m a t i c i d e s
t o l e s s than 0.5 p e r c e n t . Of t h e two U. S. m a n u f a c t u r e r s o f t h e s e
n e m a t i c i d e s i n 1982, one was p r o d u c i n g a r e l a t i v e l y c l e a n m a t e r i a l
w h i l e t h e o t h e r was p r o d u c i n g a " h i g h " 1,2-D p r o d u c t . The manu-
f a c t u r e r o f D-D s u b s e q u e n t l y d e c i d e d t o c e a s e p r o d u c t i o n l e a v i n g
o n l y one m a n u f a c t u r e r o f 1,2-D/1,3-D t y p e p r o d u c t s i n t h e U. S.
C o n s e q u e n t l y , t h e c o s t t o a g r i c u l t u r e f o r these t y p e s o f s o i l f u m i -
gants has r e p o r t e d l y i n c r e a s e d . T h i s e x p e r i e n c e h i g h l i g h t s t h e
u r g e n t need t o a c c e l e r a t e t h e s e a r c h f o r n o n c h e m i c a l nematode c o n t r o l
methods which would n o t c o n t a m i n a t e ground water.
E t h e l e n e Dibromide (EDB)
The S t a t e Board's EDB p r i o r i t y p e s t i c i d e s t u d y was i n i t i a t e d i n

1982. (16) In 1983, DFA announced f i n d i n g EDB c o n t a m i n a t i o n i n two
d o m e s t i c w e l l s near F r e s n o . Because a g r i c u l t u r a l use was s u s p e c t e d
as t h e cause o f t h i s c o n t a m i n a t i o n , DFA suspended p e r m i t s f o r EDB
use as a s o i l fumigant i n F r e s n o County. Subsequent f i n d i n g s o f EDB-
c o n t a m i n a t e d w e l l s i n Kern, Merced, San J o a q u i n , and S t a n i s l a u s
C o u n t i e s l e d t o s u s p e n s i o n o f EDB use i n t h e s e c o u n t i e s . The
C a l i f o r n i a Department o f H e a l t h S e r v i c e s i n 1983 d e t e c t e d EDB i n
several private wells i n Bakersfield. The s o u r c e o f t h i s c o n t a m i n a -
t i o n i s s t i l l under i n v e s t i g a t i o n . On t h e b a s i s o f t h e s e and o t h e r
f i n d i n g s n a t i o n w i d e , EPA, on October 11, 1983, p u b l i s h e d an emergency
o r d e r s u s p e n d i n g r e g i s t r a t i o n o f EDB s o i l f u m i g a n t .
1
E P A s emergency s u s p e n s i o n f o r c e d s t a t e s w i t h EDB-contaminated
w e l l s t o scramble f o r an EDB d r i n k i n g water a c t i o n l e v e l . EPA
a d v i s e d Hawaii t h a t EDB r e s i d u e s i n d r i n k i n g water above t h e d e t e c -
t i o n l e v e l o f 20 p p t s h o u l d be c o n s i d e r e d u n s a f e . EPA's S c i e n t i f i c
A d v i s o r y P a n e l (SAP) has c o n c u r r e d w i t h t h i s d e c i s i o n .
The use o f a n i m a l c a r c i n o g e n d a t a t o d e r i v e s a f e l i m i t s f o r
d r i n k i n g water c o n t i n u e s t o be h i g h l y c o n t r o v e r s i a l . Advocates o f
l e s s r e g u l a t o r y s t r i n g e n c y argue t h a t EPA has o v e r - r e g u l a t e d EDB on
the b a s i s o f f l i m s y e v i d e n c e c o n c e r n i n g EDB d i e t a r y e f f e c t s on
humans. Others f e e l t h a t t h e burden o f p r o o f s h o u l d be on t h e r e g -
i s t r a n t s o f p r o d u c t s c o n t a i n i n g a n i m a l c a r c i n o g e n s t o show why
a n i m a l t e s t d a t a a r e i n a p p r o p r i a t e t o d e r i v e human h e a l t h r i s k s .
The SWRCB s e l e c t i o n i n 1982 o f EDB f o r p r i o r i t y p e s t i c i d e i n v e s -

t i g a t i o n h e i g h t e n e d the awareness o f a l l C a l i f o r n i a r e g u l a t o r y agen-
c i e s w i t h r e s p o n s i b i l i t y i n t h i s a r e a t o the p o t e n t i a l f o r EDB c o n -
t a m i n a t i o n o f ground water. I t a l s o l e d t o the r e c o g n i t i o n o f a
g e n e r i c problem w i t h a l l s o i l f u m i g a n t s . The p e r s i s t e n c e o f t h e s e
n e m a t i c i d e s , as w e l l as the unique way t h e y a r e a p p l i e d t o s o i l s ,
i n c r e a s e s the l i k e l i h o o d t h a t t h e y w i l l cause s i m i l a r water q u a l i t y
problems. EPA has s i n c e d e c i d e d t h a t i n o r d e r t o a v o i d the m i s t a k e s
o f t h e p a s t , a l l c u r r e n t l y r e g i s t e r e d s o i l f u m i g a n t s be r e v i e w e d f o r
t o x i c o l o g y , e n v i r o n m e n t a l f a t e , and p r o d u c t c h e m i s t r y d a t a .
SWRCB i n 1984 recommended and DHS e s t a b l i s h e d an a c t i o n l e v e l
f o r EDB i n d r i n k i n g water based on an NCI c a n c e r r i s k assessment t h a t
EDB above the then c u r r e n t d e t e c t i o n l i m i t (50 ppt) would pose an
u n a c c e p t a b l e r i s k t o human h e a l t h . In o t h e r words, any c o n f i r m e d
f i n d i n g o f EDB i n C a l i f o r n i a d r i n k i n g water i s c o n s i d e r e d grounds f o r
recommending the consumer seek an a l t e r n a t e s o u r c e .
A d r a f t c a n c e r r i s k p o l i c y f o r C a l i f o r n i a (17) e x p r e s s e s as a
g o a l t h a t the r i s k from exposure t o a c h e m i c a l c a r c i n o g e n i n d r i n k i n g
water s h o u l d not exceed one p e r s o n a f f e c t e d per m i l l i o n p o p u l a t i o n
exposed. A n a l y t i c a l t e c h n i q u e s f o r known or s u s p e c t e d c a r c i n o g e n s
must be r e f i n e d t o e n a b l e d e t e c t i o n a t l e v e l s t h a t a r e r e l e v a n t t o
t h i s r i s k assessment p o l i c y .
C u r r e n t d r i n k i n g water a c t i o n l e v e l s f o r many t o x i c c h e m i c a l s
a r e based on n o n c a r c i n o g e n i c h e a l t h e f f e c t s d a t a . As soon as p o s s i -
b l e a f t e r new c a n c e r r i s k and o t h e r c h r o n i c e f f e c t s i n f o r m a t i o n
becomes a v a i l a b l e , t h e s e a c t i o n l e v e l s s h o u l d be r e v i s e d .
Aldicarb
A g r i c u l t u r a l use o f a l d i c a r b , a p o s t - p l a n t n e m a t i c i d e , has r e s u l t e d
i n ground water c o n t a m i n a t i o n i n s i x s t a t e s e a s t o f the M i s s i s s i p p i .
The Department o f Food and A g r i c u l t u r e i n 1979 conducted an a l d i c a r b
ground water m o n i t o r i n g s u r v e y i n s e v e r a l C a l i f o r n i a c o u n t i e s . A l l
s u r v e y r e s u l t s were n e g a t i v e . In 1983 the N o r t h Coast R e g i o n a l Water
Q u a l i t y C o n t r o l Board d i s c o v e r e d the f i r s t e v i d e n c e o f a l d i c a r b i n
C a l i f o r n i a ground water (up t o 47 p a r t s per b i l l i o n ) i n Del N o r t e
County. EPA has recommended a l i m i t f o r t o t a l a l d i c a r b i n d r i n k i n g
water o f 10 ppb.
In r e s p o n s e t o the r e g i o n a l board f i n d i n g s , DFA and the c o u n t y
a g r i c u l t u r a l commissioner suspended the use o f a l d i c a r b i n D e l Norte
County. A l t h o u g h the a l d i c a r b c o n t a m i n a t i o n i n D e l N o r t e County was
c o r r e l a t e d w i t h somewhat unique s i t e - s p e c i f i c c o n d i t i o n s , p a r t i c u -
l a r l y low s o i l pH, permeable s o i l , and s h a l l o w ground water, o t h e r
a r e a s w i t h s i m i l a r c o n d i t i o n s might a l s o be v u l n e r a b l e . F i e l d t e s t -
i n g i s b e i n g c o n d u c t e d i n the c e n t r a l v a l l e y by t h e r e g i s t r a n t Union
C a r b i d e Company, t o d e t e r m i n e the p o t e n t i a l f o r ground water contam-
i n a t i o n i n t h i s h i g h use a r e a .
Union C a r b i d e on October 31, 1984 announced a s i g n i f i c a n t ,
unprecedented program t o p r o v i d e a c t i v a t e d c a r b o n f i l t e r s f o r home-
owners whose w e l l s a r e c o n t a m i n a t e d w i t h a l d i c a r b above the recom-
mended a c t i o n l e v e l . T h i s i s the f i r s t time i n C a l i f o r n i a t h a t a
p e s t i c i d e m a n u f a c t u r e r has p r o v i d e d water t r e a t m e n t systems t o c l e a n
up p r i v a t e d o m e s t i c w e l l water c o n t a m i n a t e d by t h e i r p r o d u c t . It
s h o u l d p r o v i d e added i n c e n t i v e f o r o t h e r m a n u f a c t u r e r s t o t h o r o u g h l y
f i e l d t e s t t h e i r p r o d u c t s b e f o r e t h e y a r e marketed f o r p o t e n t i a l to
c o n t a m i n a t e ground water. A l t h o u g h t h i s t e s t i n g i s c o s t l y , the
c o s t s o f c o r r e c t i o n a f t e r c o n t a m i n a t i o n would be f a r g r e a t e r .
Problem Causes
A r e v i e w o f C a l i f o r n i a i n f o r m a t i o n on ground water c o n t a m i n a t i o n
i n d i c a t e s t h a t w h i l e the c a u s e s a r e s i t e s p e c i f i c , most i n c i d e n t s
o c c u r r e d because o f t h r e e i n t e r r e l a t e d problems:
o v e r o p t i m i s t i c r i s k p e r c e p t i o n (RP)
inadequate r i s k assessment (RA)
u n d e r p r o t e c t i v e r i s k management (RM)
The f o l l o w i n g f a c t o r s a r e d i s c u s s e d as r e l e v a n t t o t h e s e problems.
Risk Perception (RP).
" F i l t e r Fantasy"
Inadequate t e s t i n g o f " l e a c h e r s "
R i s k Assessment (RA).
Analytical constraints
Monitoring c o n s t r a i n t s
Toxicological controversy
R i s k Management (RM).
I l l e g a l use
Improper d i s c h a r g e
W e l l s as p o l l u t a n t pathways
High-risk i r r i g a t i o n / i n f i l t r a t i o n practices
N o n e x i s t e n t e a r l y warning systems
S o c i e t y i s i n c r e a s i n g l y c o n c e r n e d t h a t ground water, a s c a r c e
r e s o u r c e , d e s e r v e s much g r e a t e r e f f o r t s toward " f o o l p r o o f " r i s k
management (RM a p p r o a c h i n g 100 p e r c e n t ) . In o r d e r t o a c c o m p l i s h
t h i s g o a l , both (RA) and (RP) must a l s o approach 100 p e r c e n t . The
o p t i m a l r i s k management s t r a t e g y t o meet s o c i e t y ' s e x p e c t a t i o n s
would be (1) t o e r r on the c o n s e r v a t i v e s i d e i n p e r c e i v i n g p o t e n t i a l
r i s k s w h i l e (2) improving r i s k assessment by m o b i l i z i n g i n c r e a s e d
r e s o u r c e s t o a d e q u a t e l y f i l l r i s k and exposure assessment d a t a gaps.
In some c a s e s , economic and t e c h n i c a l c o n s t r a i n t s may r e q u i r e
s o c i e t y t o s e t t l e f o r p r o t e c t i n g l e s s than 100 p e r c e n t o f a p a r t i c u
l a r ground water r e s o u r c e . Even under such c i r c u m s t a n c e s , the c o n
s e r v a t i v e approach t o r i s k p e r c e p t i o n and r i s k assessment s h o u l d not
change. A s i m p l e way o f i l l u s t r a t i n g the i n t e r c o n n e c t e d n e s s o f
t h e s e problems i s t o assume a h y p o t h e t i c a l q u a n t i t a t i v e r e l a t i o n s h i p
where RM = (RP) (RA). Achievement o f o n l y 80 p e r c e n t r i s k manage
ment (RM = 0.8) would s t i l l r e q u i r e n e a r - p e r f e c t r i s k p e r c e p t i o n
and assessment (e.g., RA (0.9) RP ( 0 . 9 ) ) .
Filter Fantasy
F i l t e r f a n t a s y i s a term used t o d e s c r i b e unwarranted t r u s t i n t h e

" m a g i c a l " p r o p e r t i e s o f s o i l t o f i l t e r o u t and p r e v e n t t o x i c chem-
i c a l s from r e a c h i n g ground water. This overoptimistic r i s k percep-
t i o n i s based on t h e b e l i e f t h a t most a g r i c u l t u r a l c h e m i c a l s a r e
u n l i k e l y t o r e a c h ground water because o f t h e i r " i m m o b i l i t y and
r a p i d degradation i n the environment"(18). Mounting e v i d e n c e t h a t
many s o i l c o n d i t i o n s cannot be r e l i e d upon t o p r e v e n t c h e m i c a l move-
ment t o ground water from e i t h e r p o i n t o r n o n p o i n t s o u r c e s i s
l e a d i n g t o a changed p e r c e p t i o n o f t h i s r i s k . Even s o - c a l l e d
"impermeable" C a l i f o r n i a hazardous waste d i s p o s a l s i t e s have been
found t o l e a k . T h i n k i n g o f t h e s o i l as a " s i e v e " r a t h e r than a
" f i l t e r " might h e l p t o c o u n t e r t h i s o v e r o p t i m i s t i c r i s k p e r c e p t i o n .
Inadequate T e s t i n g o f "Leachers"
I n f o r m a t i o n on p e s t i c i d e s o i l m o b i l i t y c a n be d e r i v e d from l a b bench
s c a l e t e s t s , use o f p r e d i c t i v e models, o r f i e l d t e s t s . The f a i l u r e
to p r e d i c t the p o t e n t i a l f o r ground water c o n t a m i n a t i o n o f a number
of p e s t i c i d e s i n d i c a t e s t h e need f o r a change i n t h e r i s k p e r c e p t i o n
toward m u l t i - y e a r f i e l d d i s s i p a t i o n t e s t i n g o f c u m u l a t i v e a p p l i c a -
tions. E x p e r i e n c e w i t h c e r t a i n s o i l a p p l i e d p e s t i c i d e s such as
Oxamyl e x e m p l i f i e s t h e need f o r such t e s t i n g . F i e l d studies with
Oxamyl were c o n d u c t e d a t a s i n g l e C a l i f o r n i a s i t e f o r two y e a r s w i t h
no e v i d e n c e o f a t h r e a t t o ground water. N e v e r t h e l e s s , New York
r e c e n t l y r e p o r t e d f i n d i n g s o f Oxamyl i n S u f f o l k County ground water.
O b v i o u s l y t e s t i n g i s needed a t a wide v a r i e t y o f e n v i r o n m e n t a l s i t e s
under d i f f e r e n t s o i l and c l i m a t i c c o n d i t i o n s t o p r e d i c t l o n g - t e r m
p o t e n t i a l f o r ground water c o n t a m i n a t i o n . The l e n g t h o f time needed
t o c o n d u c t f i e l d t e s t s f o r s o i l i n j e c t e d h e r b i c i d e s and n e m a t i c i d e s
may, i n some c a s e s , have t o exceed two y e a r s . One c a n o n l y s p e c u -
1
l a t e whether m u l t i - y e a r f i e l d t e s t i n g o f DBCP s s o i l m o b i l i t y b e f o r e
i t was r e g i s t e r e d f o r use would have p r e v e n t e d a ground water c o n -
t a m i n a t i o n problem o f unprecedented p r o p o r t i o n s .
Analytical Constraints
Most o f t h e p e s t i c i d e s d e t e c t e d i n C a l i f o r n i a ground water have

n e i t h e r f e d e r a l nor s t a t e d r i n k i n g water s t a n d a r d s . Laboratory
a n a l y t i c a l p r o t o c o l s a r e n o t a v a i l a b l e f o r d e t e c t i n g many o f them
a t o r below one p a r t per b i l l i o n . I n a b i l i t y to routinely detect
many o f t h e s e c h e m i c a l s a t l e v e l s s u s p e c t e d o f h a v i n g l o n g - t e r m
c h r o n i c e f f e c t s i s a s i g n i f i c a n t weakness i n our a b i l i t y t o ade-
quately assess t h e i r r i s k s . Commercial l a b o r a t o r i e s have been
r e l u c t a n t t o d e v e l o p new p e s t i c i d e - s p e c i f i c , a n a l y t i c a l p r o t o c o l s
w i t h o u t a s s u r a n c e t h a t the a n t i c i p a t e d volume o f l a b work would
repay t h e i r investment.
Our a b i l i t y t o f u l l y a s s e s s t h e s e r i s k s depends i n l a r g e p a r t
on c u r r e n t a n a l y t i c a l methods geared towards d e t e c t i n g t h e more
v o l a t i l e o r g a n i c compounds. New, l e s s v o l a t i l e o r g a n i c c o n t a m i n a n t s
w i l l l i k e l y be d i s c o v e r e d w i t h g r e a t e r f r e q u e n c y i n ground water as
t r a c e o r g a n i c a n a l y t i c methods a r e f u r t h e r d e v e l o p e d . Some o f t h e s e
l e s s v o l a t i l e compounds may t u r n o u t t o be o f g r e a t e r t o x i c o l o g i c a l
s i g n i f i c a n c e than t h e c u r r e n t l y d e t e c t e d v o l a t i l e o r g a n i c compounds.
Monitoring Constraints
An i d e a l ground water m o n i t o r i n g network would c o n t i n u o u s l y p r o v i d e

data f o r a l l c o n s t i t u e n t s o f concern i n a l l areas of concern. In
r e a l i t y , most ground water m o n i t o r i n g programs have, u n t i l r e c e n t l y ,
l o o k e d f o r v e r y few t o x i c o r g a n i c c h e m i c a l s i n v e r y few p l a c e s , v e r y
infrequently.
M o n i t o r i n g e x i s t i n g w e l l s f o r t o x i c c h e m i c a l c o n t a m i n a t i o n has
been compared t o s e a r c h i n g b l i n d f o l d e d f o r a n e e d l e i n a h a y s t a c k .
M o n i t o r i n g w e l l s may be t o o deep, t o o s h a l l o w , or i n t h e wrong p l a c e .
Because o f h y d r a u l i c and pumping v a r i a t i o n s i n t h e immediate v i c i n i t y
of a contaminated w e l l , p o l l u t a n t c o n c e n t r a t i o n s vary s i g n i f i c a n t l y
w i t h i n v e r y s h o r t time p e r i o d s . N e v e r t h e l e s s , some a g e n c i e s have
s t o p p e d m o n i t o r i n g f o r DBCP a f t e r a s i n g l e "not d e t e c t e d " r e s u l t . I t
i s i m p o r t a n t t o i n t e r p r e t "not d e t e c t e d " r e s u l t s w i t h c a u t i o n . Moni
t o r i n g f o r p e r s i s t e n t c h e m i c a l s l i k e DBCP i n once contaminated a r e a s
s h o u l d c o n t i n u e f o r s e v e r a l y e a r s a f t e r t h e l a s t "not d e t e c t e d "
r e s u l t before concluding that " a l l i s c l e a n " .
S p e c i a l p r e c a u t i o n s may be needed t o p r e v e n t l o s s o f c e r t a i n
v o l a t i l e o r g a n i c compounds d u r i n g sample c o l l e c t i o n and s t o r a g e .
N o r t h Coast R e g i o n a l Board s t a f f ( 1 9 ) conducted a s t u d y o f 1,2-D l o s s
from a ground water sample as a f u n c t i o n o f sample s t o r a g e t i m e . The
EPA-recommended method (up t o 10 days on i c e ) was used. One sample
was found t o c o n t a i n 250 ppb when a n a l y z e d w i t h i n 24 h o u r s , b u t o n l y
77 ppb when another a l i q u o t o f t h i s sample was r e a n a l y z e d a f t e r 10
days o f s t o r a g e .
Toxicological Controversy
Our c u r r e n t a b i l i t y t o d e t e c t and q u a n t i f y a growing l i s t o f o r g a n i c

c h e m i c a l s i n ground water o u t s t r i p s our a b i l i t y t o i n t e r p r e t t h e t o x
i c o l o g i c a l s i g n i f i c a n c e o f these f i n d i n g s . The l i m i t s o f p r e s e n t
knowledge c o n c e r n i n g p o t e n t i a l l o n g - t e r m damage l e a d s t o c o n t r o v e r s y .
Is i t more p r u d e n t t o e r r on t h e s i d e o f o v e r p r o t e c t i o n o r
unde r pr t e c t i o n ?
F u r r e r (18) s t a t e s t h a t " t h e d e t e c t a b l e l e v e l s o f t r a c e q u a n t i
t i e s o f some p e s t i c i d e r e s i d u e s i n some g e o g r a p h i c a l a r e a s " a r e gen
e r a l l y f a r below t h o s e t h a t may cause any adverse h e a l t h e f f e c t s " .
McCarty(20) s t a t e s : " D i f f i c u l t y i n demonstrating a cause-and-effect
r e l a t i o n s h i p between d r i n k i n g water and c a n c e r i s n o t s u f f i c i e n t
cause t o c o n c l u d e t h a t one does n o t e x i s t . In t h e f a c e o f such
u n c e r t a i n t i e s , prudence d i c t a t e s t h a t e r r o r s h o u l d be on t h e s i d e o f
caution."
F i g u r e 11 shows t h a t f o u r d i f f e r e n t m a t h e m a t i c a l models have a
f i v e o r d e r o f magnitude d i f f e r e n c e i n e s t i m a t e d l i f e t i m e c a n c e r r i s k
when d r i n k i n g water c o n t a i n s 50 ppb TCE. These models were d e s i g n e d
t o e x t r a p o l a t e a n i m a l s t u d y r e s u l t s from h i g h - t o - l o w doses t o c o r r e
spond t o human exposure. The v a l i d i t y o f any o f these models f o r
low-dose r i s k assessment i s q u e s t i o n a b l e . C u r r e n t knowledge does
not a l l o w t h e s e l e c t i o n o f one p a r t i c u l a r model, and e x p e r i m e n t a l
d a t a a r e n o t s u f f i c i e n t t o d i s c r i m i n a t e among competing models. In
l i g h t o f t h i s u n c e r t a i n t y , s h o u l d r e g u l a t o r y a g e n c i e s base t h e i r
p o l i c i e s on t h e most c o n s e r v a t i v e o r t h e most " r e a s o n a b l e " e s t i m a t e ?
F i g u r e 11. E x t r a p o l a t i o n o f Dose-Response Models t o Low Doses o f

TCE. Adapted w i t h p e r m i s s i o n from Ref. 21. C o p y r i g h t 1984
f
R e g u l . T o x i c o l . Pharmacol.
522 EVALUATION O F P E S T I C I D E S IN G R O U N D W A T E R
The U.S. Supreme C o u r t d e c i s i o n on benzene o f J u l y 2, 1980,

d e a l t w i t h the i s s u e w h a t a r e p r u d e n t b o u n d a r i e s f o r a s s e s s i n g
significant risk. The c o u r t c o n c l u d e d t h a t i f the odds f o r exposure
3
are 1 i n 1,000 ( 1 0 ~ ) , a r e a s o n a b l e p e r s o n might c o n s i d e r the r i s k
significant. I f the odds a r e 1-in-1 b i l l i o n (10"~9) t h a t a p e r s o n
w i l l d i e from c a n c e r by t a k i n g a d r i n k o f c h l o r i n a t e d water, the
r i s k c o u l d c l e a r l y be c o n s i d e r e d not s i g n i f i c a n t . Thus, the
Supreme C o u r t has d e f i n e d the bounds o f s i g n i f i c a n c e between 10~3
9
and 10~ . C o t h e r n and Marcus (21) have s u g g e s t e d a scheme f o r
u s i n g the r e s u l t s o f r i s k e s t i m a t e s i n f e d e r a l and s t a t e r e g u l a t o r y
d e c i s i o n making. By assuming t h a t the e n t i r e p o p u l a t i o n o f
C a l i f o r n i a was exposed t o a c h e m i c a l a t the i n d i v i d u a l r i s k r a t e ,
t h r e e d i f f e r e n t r e g u l a t o r y l e v e l s o f p o p u l a t i o n r i s k can be d e r i v e d
for C a l i f o r n i a : (1) 2,000 or more p o t e n t i a l c a s e s per l i f e t i m e a t
r i s k s h o u l d t r i g g e r a n a t i o n a l r e g u l a t o r y d e c i s i o n ; (2) between 20
and 2,000 c a s e s per l i f e t i m e , s t a t e r e g u l a t o r y d e c i s i o n making
s h o u l d be t r i g g e r e d ; and (3) l e s s than 20 per l i f e t i m e r i s k would

be c o n s i d e r e d a l o c a l problem not r e q u i r i n g s t a t e or f e d e r a l a c t i o n .
The c u r r e n t EPA r i s k model f o r DBCP (9) i n d i c a t e s the e x c e s s
c a n c e r r i s k i s 180 per m i l l i o n , or 4,500 C a l i f o r n i a n s a t r i s k . If
t h i s scheme were t o be adopted as n a t i o n a l p o l i c y , C a l i f o r n i a ' s
DBCP i n ground water problem would be d e f i n e d as an u n a c c e p t a b l e
r i s k r e q u i r i n g immediate f e d e r a l a c t i o n .
Illegal Use
EPA's p a s t d e c i s i o n s t o ban c e r t a i n p e s t i c i d e s o f t e n c o i n c i d e d w i t h
a d e c l i n e i n t h e i r demand because o f d e c r e a s i n g e f f i c a c y ( i n c r e a s -
ing pest r e s i s t a n c e ) . DBCP, however, i s s t i l l c o n s i d e r e d t o be
a most e f f i c a c i o u s n e m a t i c i d e . Thus, i l l e g a l use, i f p r o v e n , c o u l d
e x p l a i n some o f the r i s e i n DBCP c o n t a m i n a t e d w e l l s s i n c e i t s use
was banned i n 1977. The e s t i m a t e d h a l f - l i f e o f DBCP i n water i s
3-1/2 y e a r s {8). I f i l l e g a l use were not o c c u r r i n g , one would
e x p e c t a d e c l i n e i n DBCP w e l l water c o n c e n t r a t i o n s a f t e r e i g h t y e a r s
o f nonuse.
On March 11, 1985, the Department o f Food and A g r i c u l t u r e
announced e v i d e n c e o f i l l e g a l DBCP use i n a L o d i a r e a , San J o a q u i n
County v i n e y a r d . The i n v e s t i g a t i o n was s t a r t e d a f t e r a farm worker
c l e a n i n g out equipment became i l l , and a f e l l o w worker r e c o g n i z e d
the d i s t i n c t i v e odor of DBCP. Equipment, s o i l , and w e l l water
from the s u s p e c t e d f i e l d were a n a l y z e d and showed p o s i t i v e DBCP
content. CDFA (22) has c o n c l u d e d t h a t t h i s appears t o be an
isolated incident. I f i l l e g a l use i s s t i l l o c c u r r i n g i n C a l i f o r n i a ,
i t c o u l d not approach the e a r l i e r m i l l i o n pounds-per-year usage.
P e s t c o n t r o l o p e r a t o r s found u s i n g a banned p e s t i c i d e would be
j e o p a r d i z i n g t h e i r l i c e n s e and l i v e l i h o o d . For t h e s e r e a s o n s
i l l e g a l use i s not c o n s i d e r e d t o be a major r e a s o n f o r the s p r e a d
o f DBCP c o n t a m i n a t e d ground water t h r o u g h o u t the San J o a q u i n V a l l e y .
The most l i k e l y s o u r c e i s the l a r g e amount o f r e s i d u a l DBCP,
s t o r e d and c o n t i n u o u s l y moving down the s o i l p r o f i l e .
Improper Discharge
F o r m u l a t i o n , s t o r a g e , and poor d i s p o s a l p r a c t i c e s have r e s u l t e d i n a

number o f p e s t i c i d e ground water c o n t a m i n a t i o n i n c i d e n t s i n
C a l i f o r n i a (2).
One o f t h e most s e r i o u s and c o s t l y o f t h e s e i n c i d e n t s a t the
O c c i d e n t a l Chemical Company P l a n t , L a t h r o p , i n v o l v e d ground water
c o n t a m i n a t i o n by DBCP, EDB, and o t h e r p e s t i c i d e s i n c o n c e n t r a t i o n s
r a n g i n g up t o 1,240 ppb. The C e n t r a l V a l l e y R e g i o n a l Board
determined t h a t the c o n t a m i n a t i o n was the r e s u l t o f w i l l f u l d i s -
c h a r g e o f hazardous wastes and f r a u d u l e n t s e l f m o n i t o r i n g . (The
company i n t e n t i o n a l l y w i t h h e l d i n f o r m a t i o n t h a t t h e y were p r o c e s s -
i n g and d i s c h a r g i n g p e s t i c i d e s i n t o u n l i n e d l e a c h ponds.) This
" p o i n t s o u r c e " d i s c o v e r y prompted the r e g i o n a l board t o i n v e s t i g a t e
the much more widespread n o n p o i n t s o u r c e DBCP problems.
D i s c o v e r y o f p e s t i c i d e c o n t a m i n a t i o n from any s o u r c e s h o u l d be
c o n s i d e r e d e v i d e n c e t h a t i t can o c c u r from a g r i c u l t u r a l use as w e l l .

The d i s c o v e r y i n C a l i f o r n i a ground water o f DBCP, EDB, and 1,2-D
from p o i n t s o u r c e d i s c h a r g e s preceeded subsequent d i s c o v e r y o f
t h e s e same p e s t i c i d e s i n ground water from n o n p o i n t s o u r c e s . Thus,
p o i n t s o u r c e i n c i d e n t s s h o u l d be r e g a r d e d by r e g u l a t o r y a g e n c i e s
as an e a r l y warning o f the p o t e n t i a l f o r c u m u l a t i v e a g r i c u l t u r a l
use o f t h e s e c h e m i c a l s t o a l s o c o n t a m i n a t e ground water. Ground
water m o n i t o r i n g programs s h o u l d be p e r i o d i c a l l y augmented t o
i n c l u d e newly d i s c o v e r e d p e s t i c i d e s i n ground water from any s o u r c e .
W e l l s as P o l l u t a n t Pathways
" I t i s i r o n i c t h a t one way ground water q u a l i t y can d e c l i n e i s

t h r o u g h the w e l l . T h i s o c c u r s when, because o f i n a d e q u a t e c o n s t r u c -
t i o n , w e l l s p r o v i d e a p h y s i c a l c o n n e c t i o n between s o u r c e s o f p o l l u -
t i o n and u s a b l e water. The g e o l o g i c environment has some n a t u r a l
d e f e n s e s a g a i n s t p o l l u t a n t s , but each time we p e n e t r a t e t h a t
environment, we may c a r e l e s s l y e s t a b l i s h avenues f o r t h e i r
uncontrolled introduction."(23)
There a r e over 750,000 w e l l s i n C a l i f o r n i a , most o f which were
d r i l l e d f o r a g r i c u l t u r a l i r r i g a t i o n purposes. There i s no i n v e n -
t o r y o f an e s t i m a t e d one hundred thousand w e l l s t h a t have been
e i t h e r d e l i b e r a t e l y or i n d i s c r i m i n a t e l y abandoned. The Department
o f Water Resources has e s t a b l i s h e d s t a n d a r d s o f water w e l l c o n s t r u c -
t i o n and abandonment. These s t a n d a r d s a r e v o l u n t a r y , however, and
v a r i o u s c o u n t i e s a p p l y them i n d i f f e r e n t ways.
During the drought y e a r , 1977, over 20,000 new w e l l s were
d r i l l e d i n C a l i f o r n i a w i t h n e a r l y h a l f o f t h e s e i n the C e n t r a l
Valley. The r a t e o f w e l l c o n s t r u c t i o n and abandonment i s i n c r e a s -
i n g by a p p r o x i m a t e l y 5 p e r c e n t per y e a r . Current s t a t e standards
do not r e q u i r e s a n i t a r y s e a l s on most a g r i c u l t u r a l w e l l s . Thus,
u n l e s s a c t i o n i s taken t o r e v e r s e t h i s s i t u a t i o n , the problem o f
p o o r l y s e a l e d or r e p a i r e d water w e l l s which a l l o w s u r f a c e p o l l u t a n t s
t o r e a c h ground water i s l i k e l y t o i n c r e a s e .
High Risk I r r i g a t i o n / I n f i l t r a t i o n Practices
The p r a c t i c e o f m e t e r i n g p e s t i c i d e s i n t o i r r i g a t i o n systems
(Chemigation) c a n l e a d t o s o i l and ground water c o n t a m i n a t i o n i f
i r r i g a t i o n pumps f a i l and c h e m i c a l i n j e c t i o n c o n t i n u e s c a u s i n g
chemical backflow i n t o the w e l l . Backflow p r e v e n t i o n d e v i c e s can
m i t i g a t e t h i s problem. In 1982, Kern County was t h e f i r s t t o
adopt an o r d i n a n c e r e q u i r i n g b a c k f l o w p r e v e n t i o n d e v i c e s f o r
c h e m i g a t i o n systems (2).
C a p t u r i n g and d i v e r t i n g storm water t h a t may c o n t a i n p e s t i c i d e s
or o t h e r c h e m i c a l c o n s t i t u e n t s i n t o an a q u i f e r through "dry w e l l s "
may a l s o pose r i s k s t o ground water q u a l i t y . Tens o f thousands
o f such r e c h a r g e w e l l s have been c o n s t r u c t e d i n t h e San J o a q u i n
Valley. S e v e r a l thousand new w e l l s a r e b e i n g c o n s t r u c t e d each
year t o r e p l a c e o l d e r w e l l s c l o g g e d w i t h sediment and d e b r i s .
A l t h o u g h some c o u n t y h e a l t h departments r e q u i r e a 1 0 - f o o t s e p a r a t i o n
d i s t a n c e between t h e d r y - w e l l bottom and t h e u n d e r l y i n g water t a b l e ,

p r o v i s i o n s f o r a s s u r i n g c o m p l i a n c e w i t h t h i s r e q u i r e m e n t a r e vague,
and some d r a i n a g e w e l l s do p e n e t r a t e t h e water t a b l e t o i n c r e a s e
i n f i l t r a t i o n drainage rates. These p r a c t i c e s e x e m p l i f y i n a d e q u a t e
r i s k p e r c e p t i o n which may l e a d t o u n d e r p r o t e c t i v e r i s k management.
N o n e x i s t e n t E a r l y Warning System
Almost e v e r y s i g n i f i c a n t i n s t a n c e o f ground water c o n t a m i n a t i o n i n

C a l i f o r n i a has been d i s c o v e r e d o n l y a f t e r a d r i n k i n g water s o u r c e
has been a f f e c t e d . We need, but do n o t have a r e l i a b l e e a r l y
warning "canary i n t h e c o a l mine" t o warn us a t an e a r l y s t a g e o f
i n c i p i e n t danger from p e s t i c i d e s i n s o i l moving toward ground water.
Improved ground water sampling and a n a l y t i c a l t e c h n i q u e s i s a
n e c e s s a r y s t e p towards t h e " e a r l y warning" g o a l . One p r o m i s i n g
technique c u r r e n t l y being i n v e s t i g a t e d i n C a l i f o r n i a i n v o l v e s
automated l a r g e volume s a m p l i n g , c o n c e n t r a t i n g and q u a n t i t a t i v e l y
e x t r a c t i n g t r a c e amounts o f s y n t h e t i c o r g a n i c c h e m i c a l s i n ground
water u s i n g XAD-type r e s i n s .
M o n i t o r i n g o f t h e vadose ( u n s a t u r a t e d ) zone may, i n c e r t a i n
a r e a s , be another p r o m i s i n g s t e p towards an " e a r l y warning" system.
Ground water c o n t a m i n a t i o n i f d e t e c t e d e a r l y enough from t h i s zone,
c o u l d a l l o w f o r r e m e d i a l measures t o be implemented sooner and
a q u i f e r r e s t o r a t i o n c o s t s s i g n i f i c a n t l y reduced. In a r e a s w i t h a
v e r y s h a l l o w vadose zone ( i . e . , Smith R i v e r w i t h l e s s than 10 f e e t
d e p t h ) , t h e r e may be i n s u f f i c i e n t l e a d time f o r p r e v e n t i v e r e g u l a -
tory action.
Possible Sollutions
The l e a s t c o s t l y and, u l t i m a t e l y , most e f f e c t i v e approach toward

s o l v i n g t h i s problem i s p r e v e n t a t i v e . A t t h e f e d e r a l l e v e l , EPA
must d e v e l o p more r i g o r o u s p e s t i c i d e r e g i s t r a t i o n r e q u i r e m e n t s .
P e s t i c i d e s w i t h a h i g h p o t e n t i a l f o r l e a c h i n g s h o u l d n o t be
r e g i s t e r e d f o r nematode c o n t r o l . Industry can p l a y a lead r o l e i n
p r e v e n t i n g f u t u r e c h e m i c a l c o n t a m i n a t i o n o f ground waters by
d e v e l o p i n g a l t e r n a t i v e b i o t e c h n o l o g i c a l t e c h n i q u e s (e.g., m o d i f y
r o o t b a c t e r i a g e n e t i c codes s p e c i f i c a l l y t o i n d u c e r e s i s t a n c e i n
plants).
1
R o b e r t Kaufman, M o n s a n t o s d i r e c t o r o f p l a n t s c i e n c e s r e s e a r c h ,
i s quoted as s a y i n g , " I t i s c o n c e i v a b l e t h a t i f we're s u c c e s s f u l
w i t h t h i s t e c h n i q u e , c h e m i c a l i n s e c t i c i d e s as we know them c o u l d be
phased out i n the n e x t 25 y e a r s " (24).
A g r i c u l t u r a l e n g i n e e r s can h e l p m i n i m i z e deep p e r c o l a t i o n o f
water s o l u b l e p e s t i c i d e s below the r o o t zone by c o n d u c t i n g r e s e a r c h
t o improve i r r i g a t i o n e f f i c i e n c y ( d r i p method). L o c a l and r e g i o n a l
government a g e n c i e s can promote a d o p t i o n o f b e t t e r management
p r a c t i c e s (BMPs) f o r a p p l y i n g p e s t i c i d e s and water t o s o i l s , as w e l l
as s t e p p i n g up enforcement a c t i o n s a g a i n s t i l l e g a l use and improper
discharge.
The c h a l l e n g e f a c i n g f e d e r a l , s t a t e , and l o c a l a g e n c i e s i s t o
d e v i s e a c o o r d i n a t e d system t h a t e f f e c t i v e l y s a f e g u a r d s water
q u a l i t y w h i l e r e c o g n i z i n g t h a t t h i s complex problem c u t s a c r o s s
j u r i s d i c t i o n a l b o u n d a r i e s o f a l l l e v e l s o f government.
EPA's n a t i o n a l ground water p r o t e c t i o n s t r a t e g y i s based on
p r o m o t i n g s t a t e ground water p r o t e c t i o n programs. California's
S e c r e t a r y o f E n v i r o n m e n t a l A f f a i r s on March 16, 1984, d e s i g n a t e d
SWRCB as t h e l e a d s t a t e agency f o r d e v e l o p i n g a c o o r d i n a t e d ground
water p r o t e c t i o n s t r a t e g y . The S t a t e Board has s u b m i t t e d t o EPA
a p r o p o s e d ground water s t r a t e g y workplan whose elements i n c l u d e :
(1) I n v e n t o r y o f a l l c u r r e n t ground water q u a l i t y p r o t e c t i o n
a c t i v i t i e s by a l l l e v e l s o f government i n c l u d i n g assessment and
p r i o r i t i z i n g o f needs t o c o r r e c t and p r e v e n t problems; (2) a s s e s s -
ment o f EPA ground water b a s i n c l a s s i f i c a t i o n systems and comparison
w i t h C a l i f o r n i a c u r r e n t ground water b a s i n d e s i g n a t i o n and water
q u a l i t y o b j e c t i v e s ; (3) development o f a comprehensive c o m p u t e r i z e d
ground water q u a l i t y d a t a management system; (4) r e f i n e m e n t o f a
ground water "hot s p o t s " r i s k assessment and m o n i t o r i n g methodology.
Ground Water "Hot S p o t s " Program
There i s an u r g e n t need f o r a s y s t e m a t i c methodology t o i d e n t i f y

emerging ground water c o n t a m i n a t i o n problems b e f o r e t h e y become
environmental c r i s e s . The S t a t e Board's ground water "hot s p o t s "
p r o j e c t , which began i n J u l y 1984, i s an attempt t o d e v e l o p such
a p r e d i c t i v e approach. I t i s based on s c r e e n i n g , r a n k i n g , and
a s s e s s i n g c h e m i c a l s and s i t e s l i k e l y t o c o n t a i n c o n t a m i n a t e d s o i l
and ground water b e f o r e an a c t u a l problem i s documented. The
s u c c e s s o f t h i s approach t o p r e d i c t t r o u b l e s p o t s b e f o r e t h e y
assume b a s i n w i d e p r o p o r t i o n s w i l l be a s s e s s e d by comparing
" p r e d i c t e d " v s . " o b s e r v e d " d a t a i n t h r e e r e g i o n s , the C e n t r a l C o a s t ,
C e n t r a l V a l l e y , and Los A n g e l e s B a s i n .
Selection c r i t e r i a include toxicology, physical/chemical
c h a r a c t e r i s t i c s , and e n v i r o n m e n t a l f a t e i n f o r m a t i o n . These d a t a
a r e used t o e v a l u a t e i n d i v i d u a l c h e m i c a l s and e s t i m a t e the degree
o f h a z a r d a s s o c i a t e d w i t h each s i t e . For n o n p o i n t s o u r c e c o n t a m i -
n a t i o n from p e s t i c i d e a p p l i c a t i o n , r a t i n g v a l u e s i n c l u d e the amount
of chemical a p p l i e d . F i n a l r a n k i n g i s based on w e l l l o g s ,
h y d r o g e o l o g y , and o t h e r d a t a d e r i v e d from o n - s i t e r e c o n n a i s s a n c e .
C r i t e r i a may be weighted a c c o r d i n g t o an e s t i m a t e d degree o f

hazard. I f t h e water t a b l e a t a s i t e approaches ground s u r f a c e ,
ground water c o n t a m i n a t i o n i s h i g h l y l i k e l y . The c r i t e r i a "Depth
t o Ground Water" would thus r e c e i v e major emphasis over c e r t a i n
other c r i t e r i a .
T r a n s p a r e n t o v e r l a y s o f s i t e - s p e c i f i c d a t a (e.g., depth t o
ground water) and c h e m i c a l use d a t a (e.g., DBCP, 1,2-D, and a l d i c a r b
c u m u l a t i v e r e p o r t e d use) a l l o w f o r v i s u a l c o r r o b o r a t i o n and f i n e -
tuning o f p r e l i m i n a r y s e l e c t e d hot spot s i t e s .
Other o b j e c t i v e s o f t h e ground water "hot s p o t s " program
i n c l u d e mapping o f g e o l o g i c a l l y s e n s i t i v e a r e a s t o p r o v i d e d a t a
f o r r e g u l a t o r y a c t i o n by c o u n t y a g r i c u l t u r a l commissioners and
r e g i o n a l boards. Such maps c a n be used t o a l l o w r e g u l a t o r y a g e n c i e s
a t t h e l o c a l l e v e l t o d e t e r m i n e where t o a l l o w o r n o t a l l o w
a p p l i c a t i o n o f t h o s e c h e m i c a l s most l i k e l y t o l e a c h t o ground
water ( F i g u r e 1 2 ) .
Is t h e Cup H a l f Empty or H a l f Full?
J a y H. Lehr (25) w r i t i n g about t h e s t a t e o f the n a t i o n ' s ground

water s t a t e s t h a t , "We have p o l l u t e d l e s s than 1 p e r c e n t o f our
ground water which has impacted l e s s than 5 p e r c e n t o f our p o p u l a -
tion. In t h e n e x t 10 y e a r s , t h e s e numbers w i l l i n c r e a s e l e s s than
10 p e r c e n t , and i n t h e f o l l o w i n g decade, t h e y w i l l d e c l i n e . . . .
ground water's g l a c i a l l y slow movement...affords adequate time t o
a c h i e v e t h e most r e a s o n a b l e approach t o managing t h e s e r e s i d u a l
problems o f our p a s t . "
The p e r c e p t i o n o f g l a c i a l l y slow movement i s n o t s h a r e d by
USDA s o i l c h e m i s t Robert Bowman (26). H i s r e s e a r c h i n A r i z o n a o f
p e s t i c i d e p e r c o l a t i o n rates indicates that p e s t i c i d e s applied to
b o t h wet and d r y s o i l s move t h r o u g h t h e s e s o i l s from t h r e e t o f i v e
times f a s t e r than p r e v i o u s s t u d i e s i n d i c a t e d .
P r o f e s s o r P a u l Roberts o f S t a n f o r d U n i v e r s i t y (27) f e e l s t h a t
a l t h o u g h " l e s s than 1 p e r c e n t o f t h e n a t i o n ' s ground water i s
thought t o be c o n t a m i n a t e d by a n t h r o p o g e n i c o r g a n i c p o l l u t a n t s . . . .
t h i s e s t i m a t e i s o n l y a rough a p p r o x i m a t i o n ; our ground water
c o n t a m i n a t i o n may t u r n o u t t o be g r e a t e r than i s now r e a l i z e d . . . I n
the c o n t e x t o f t h e r a p i d e x p a n s i o n i n manufacture and use o f
s y n t h e t i c o r g a n i c c h e m i c a l s s i n c e 1940, l o n g - t i m e l a g s mean t h a t
i n c i d e n c e o f ground water contamint i o n may c o n t i n u e t o be d i s -
c o v e r e d a t an i n c r e a s i n g r a t e i n the y e a r s t o come, even i f
d i s p o s a l p r a c t i c e s a r e m o d i f i e d i m m e d i a t e l y t o a v o i d new s o u r c e s .
In t h a t s e n s e , c o n t a m i n a t i o n by s y n t h e t i c o r g a n i c c h e m i c a l s i s
l i k e a water q u a l i t y time bomb, t i c k i n g away f o r y e a r s under many
communities b e f o r e e r u p t i n g i n t h e form o f a c o n t a m i n a t e d ground
water s u p p l y " .
Perhaps t h e l a s t word on t h i s s u b j e c t s h o u l d be l e f t t o
P r o f e s s o r A b e l Wolman, P r o f e s s o r E m e r i t u s John Hopkins U n i t e r s i t y
(28). P r o f e s s o r Wolman, who has been c a l l e d " t h e c o n s c i e n c e o f
the American water s u p p l y community", reviewed o v e r 3,000 s t u d i e s
on h e a l t h e f f e c t s o f t r a c e o r g a n i c c h e m i c a l s i n d r i n k i n g water f o r
the N a t i o n a l Academy o f S c i e n c e . He c o n c l u d e s t h a t :
COHEN Ground Water Contamination by Toxic Substances
F i g u r e 12. High P e r m e a b i l i t y S o i l s Without Known S h a l l o w

Underlying R e s t r i c t i v e Layers.
We a r e d e a l i n g w i t h an e x t r e m e l y complex u n i v e r s e o f i l l - d e f i n e d
impacts o f o r g a n i c c h e m i c a l s upon man. Disconcerting findings,
i n d i c a t i v e o f l o n g - t e r m g e n e t i c e f f e c t s , appear from day t o day.
We c a n remove p a r t s p e r q u a d r i l l i o n w i t h o u t g r e a t l e a p s o f
technology. E c o n o m i c a l t e c h n i q u e s a r e i n use o r a r e b e i n g
d e v e l o p e d f o r removing o r g a n i c c h e m i c a l s t o n o n d e t e c t a b l e l e v e l s .
I t remains t h e p a r t o f wisdom t h a t we reduce as much as p o s s i b l e
the d e l e t e r i o u s e f f e c t s o f o r g a n i c s on our water r e s o u r c e s .
When i n doubt, t a k e i t o u t .
Those o f us who now s u g g e s t t h e s e f u t u r e r e s p o n s i b i l i t i e s and
a c t i o n s a r e sometimes accused o f s u r r e n d e r i n g t o p u b l i c c o n c e r n
and f e a r r a t h e r than i n s i s t i n g on w a i t i n g upon s c i e n t i f i c
v a l i d a t i o n o f t h e impact o f t o x i c c h e m i c a l s upon man.
I am f u l l y aware o f what t h e c o s t s w i l l be. I am f u l l y aware
t h a t what I have s a i d i s d i s t u r b i n g , b u t I don't b e l i e v e we c a n
s i t around and w a i t u n t i l a l l the e v i d e n c e i s i n . I t never w i l l
be.
L e t ' s s t o p demanding p r o o f . We c a n ' t w a i t .
I f we, as stewards o f our n a t i o n ' s ground water r e s o u r c e adopt
P r o f e s s o r Wolman's p e r c e p t i o n o f t h i s r i s k , f u t u r e g e n e r a t i o n s
l o o k i n g back on t h e problem we a r e g r a p p l i n g w i t h today w i l l be
a b l e t o s a y ( p a r a p h r a s i n g W i l l Shakespeare's Hamlet s e a r c h i n g f o r
h i s f a t h e r ' s g h o s t ) , "T'was h e r e , t'was t h e r e , t ' i s gone!".
Literature Cited
1. "Water Quality and Pesticides: A California Risk Assessment
Program (Volume 1)", California State Water Resources Control
Board, 1984.
2. "Groundwater Contamination by Pesticides--A California
Assessment", California State Water Resources Control Board,
1983.
3. Spath, D., personal communication.
4. "Pesticide Use Report: Annual 1983", California Department of
Food and Agriculture, 1984.
5. Vonder Hass, S., personal communication.
6. Burlinson, N.E., Lee, L.A.; Rosenblatt, D.H. Environ. Sci.
Technol. 1982, 16, 627.
7. "Investigation of Groundwater Contamination by Dibromochloro
propane", California Department of Health Services, 1980.
8. Kim, V., personal communication.
9. "Dibromochloropropane; Intent to Cancel Registrations of
Pesticide Products Containing Dibromochloropropane (DBCP)",
Federal Register, January 9, 1985 (50 FR1122).
10. Koizumi, .., personal communication.
11. Onorato, C.A., personal communication.
12. Redlin, G., personal communication.
13. "Report on Environmental Assessment of Pesticide Regulatory
Programs: State Component (Volume 1)", California Department
of Food and Agriculture, 1978.
14. Schmidt, K.D. Proc. NWWA: Western Regional Conference on
Groundwater Management, 1983.
15. "1,2-Dichloropropane (1,2-D) 1,3-Dichloropropene (1,3-D)",
California State Water Resources Control Board, 1983.
29. COHEN Ground Water Contamination by Toxic Substances
529
16. "Ethylene Dibromide (EDB): A Water Quality Assessment",

California State Water Resources Control Board, 1984.
17. "Carcinogen Policy. Section 3: A Policy for Reducing the
Risk of Cancer", California Department of Health Services,
1982.
18. "Value of Good Agricultural Practices for Avoidance of
Detectable Pesticide Residues in Groundwater", National
Agricultural Chemical Association, 1984.
19. Warner, S., personal communication.
20. McCarty, P.L. Proc. National Conf. on Environ. Engineering,
1979.
21. Cothran, C.R.; Marcus, W.L. Regul. Toxicol. Pharmacol. 1984,
4,265.
22. Wells, J., personal communication.
23. "Water Well Standards: State of California", California
Department of Water Resources, 1981.
24. "Designer Genes for Field Use: Monsanto Seeking Permit to

Test Revolutionary Pesticide", Sacramento Bee, December 23,
1984.
25. Lehr, J.H. Groundwater Monitoring J. 1984.
26. Bowman, R. Groundwater Monitor, 1985, 1,27.
27. Roberts, P.V. JAWWA. 1982, 74, 161.
28. Wolman, A. Engineering News Record, 1983.

30
Two Ground Water Contamination Problems
Case Studies
Nancy K. Kim, Anthony J. Grey, Ronald Tramontano, Charles Hudson, and

Geoffrey Laccetti
Bureau of Toxic Substance Assessment, New York State Department of Health,

Rockefeller Empire State Plaza, Albany, NY 12237
In New York State, three types of chemicals are

found to cause most groundwater contamination:
solvents, petroleum products, and pesticides. Two
different contamination scenarios involving sandy
soil and pesticides are described. In Fort Edward,
an investigation of drinking water contamination
near an industrial plant was conducted. During
sampling, chemicals not associated with the
industrial plant were detected. This
identification resulted in another sampling program
which showed drinking water wells and springs
contaminated with atrazine and alachlor; the highest
levels were 260 ug/1 and 660 ug/1 respectively. In
Suffolk County following the removal of aldicarb
from the Long Island market, oxamyl was used as an
alternative pesticide under an experimental use
permit. After several years of use, monitoring
indicated increasing levels of oxamyl contamination
in groundwater, and by January 1984, oxamyl was
removed from the Long Island market.
F o r t Edward. N.Y.
The p e s t i c i d e c o n t a m i n a t i o n i n t h i s s m a l l , u p s t a t e New York town

was d i s c o v e r e d i n March, 1984, b u t t h e events l e a d i n g t o t h e s e
f i n d i n g s began t o u n f o l d i n 1983. In 1983, t h e s t a t e r e c e i v e d
t a s t e and odor c o m p l a i n t s about d r i n k i n g water o b t a i n e d from
p r i v a t e ' w e l l s i n t h e v i c i n i t y of a l o c a l i n d u s t r i a l p l a n t (See
F i g u r e 1 ) . The p l a n t , l o c a t e d i n a r e s i d e n t i a l a r e a n o t s e r v i c e d
by p u b l i c w a t e r , used l a r g e q u a n t i t i e s o f s o l v e n t s , p a r t i c u l a r l y
t r i c h l o r o e t h y l e n e and PCBs. A l t h o u g h water samples taken s e v e r a l
y e a r s e a r l i e r from t h e r e s i d e n c e s near t h e p l a n t had n o t
c o n t a i n e d PCBs, because o f t h e c o m p l a i n t s , water samples were
t a k e n a g a i n from houses on Park Avenue ( s e e map) and a n a l y z e d f o r
0097-6156/ 86/ 0315-0530S06.00/ 0

Figure
1.
Map
o f study
a r e a i n F o r t Edward,
NY.
PCBs and v o l a t i l e c h l o r i n a t e d h y d r o c a r b o n s . The samples were

found t o c o n t a i n PCBs, t r i c h l o r o e t h y l e n e p l u s o t h e r r e l a t e d
solvents.
Because of t h e s e f i n d i n g s , groundwater a t t h e p l a n t s i t e
was sampled and found t o c o n t a i n t r i c h l o r o e t h y l e n e . Apparently,
improper h a n d l i n g and s p i l l p r o c e d u r e s l e d t o t h e b u i l d - u p of a
pool of h i g h l y contaminated groundwater o n - s i t e .
The S t a t e began an o f f - s i t e m o n i t o r i n g program. As
c o n t a m i n a t i o n was f o u n d , t h e a r e a l e x t e n t f o r sampling p r i v a t e
w e l l s was i n c r e a s e d . S i n c e l i t t l e was known about groundwater
f l o w , water samples were taken from most of t h e s u r r o u n d i n g homes
and a n a l y z e d f o r v o l a t i l e s o l v e n t s and PCBs. The groundwater and
w e l l depths were not a v a i l a b l e f o r most l o c a t i o n s . Generally,
the groundwater i s a t 15 t o 20 f e e t i n a s h a l l o w a q u i f e r . Well
depths ranged from about 10 t o 200 f e e t .
A f t e r s e v e r a l rounds of s a m p l i n g , w i t h most of t h e sampling
c o n c e n t r a t e d i n t h e a r e a w e s t , s o u t h w e s t , and south of t h e p l a n t
( s e e F i g u r e 1 - t h e a r e a c l o s e s t t o t h e Hudson R i v e r ) , d r i n k i n g
w a t e r from homes on Stevens Lane were found t o be h i g h l y
c o n t a m i n a t e d w i t h t r i c h l o r o e t h y l e n e , w i t h the most contaminated
w e l l s h a v i n g c o n c e n t r a t i o n s g r e a t e r than 50 m i l l i g r a m s p e r
liter. The homeowners were a d v i s e d not t o use t h e w a t e r .
Because of t h e h i g h l e v e l s and c o n c e r n s about i n h a l a t i o n and
dermal e x p o s u r e , a l i m i t e d e x p e r i m e n t was undertaken i n an
attempt to q u a n t i f y i n h a l a t i o n exposure.
F i v e a i r samples (1) were c o l l e c t e d a t a r e s i d e n c e on

S t e v e n s Lane a t d i f f e r e n t times o r l o c a t i o n s ( s e e T a b l e I ) .
(1) Taken on k i t c h e n c o u n t e r p r i o r t o t u r n i n g on the

f a u c e t s ; doors and windows c l o s e d .
(2) Taken on bathroom s i n k c o u n t e r w i t h d o o r and window

c l o s e d ; no w a t e r use d u r i n g t e s t . Taken c o n c u r r e n t l y
w i t h number 1.
(3) Taken on uncovered p a t i o i n r e a r of house c o n c u r r e n t l y

w i t h number 1.
(4) Taken on k i t c h e n c o u n t e r (same l o c a t i o n as number 1)

between d o u b l e s i n k and s t o v e . Water t a k e n from t h e
home's w a t e r s u p p l y was b o i l e d on t h e s t o v e d u r i n g
sample c o l l e c t i o n . A p p r o x i m a t e l y two i n c h e s of t a p
water was p l a c e d i n a 12 i n c h s a u c e - r o a s t i n g pan which
was not c o v e r e d . Make-up w a t e r was added once d u r i n g
the sampling p e r i o d . S t a f f attempted t o s i m u l a t e
d i s h w a s h i n g by c o n t i n o u s l y s c r u b b i n g and r i n s i n g a pot
i n t h e double s i n k . T h i s sample ran f o r 57 m i n u t e s .
Towards the end of t h i s time p e r i o d , one member of t h e
s t a f f commented s e v e r a l times t h a t he " f e l t f u n n y . "
(5) Taken i n bathroom/shower and run c o n c u r r e n t l y w i t h

number 4. Sample head was hung i n s i d e shower
30. KIM ET AL. Two Ground Water Contamination Problems 533
enclosure. The shower was run on a " h o t " s e t t i n g . The

i n i t i a l f l o w r a t e was t h r e e l i t e r s / 2 5 seconds a t 42oc
and f i n a l f l o w r a t e was t h r e e l i t e r s / 2 7 seconds a t
390c. The shower ran c o n t i n u o u s l y and t h e door
remained c l o s e d d u r i n g s a m p l i n g . T h i s sample ran f o r
22 m i n u t e s . When r e - e n t e r i n g bathroom t o remove t h e
sample, a v e r y s l i g h t sweet odor was d e t e c t e d . This
sample would s i m u l a t e c o n d i t i o n s i n a bathroom w i t h
showers b e i n g t a k e n s e q u e n t i a l l y by two r e s i d e n t s .
The f o l l o w i n g water samples were c o l l e c t e d (see T a b l e I):
(1) Taken a t k i t c h e n s i n k before a i r sampling. Cold water.
(2) Taken a t bathroom tub s p i g o t b e f o r e a i r sampling.

Water a t " h o t " shower t e m p e r a t u r e .
(3) Taken by s a m p l i n g water i n tub t h a t remained a f t e r

r u n n i n g shower f o r a i r sample. Taken a f t e r a i r
sampling.
A h e a r i n g was h e l d t o o b t a i n p u b l i c water f o r t h e p e o p l e on
Stevens Lane. T h i s s t r e e t i s j u s t n o r t h of t h e n e a r e s t p u b l i c
water so an e x t e n s i o n was f a i r l y easy t o o b t a i n . The i n d u s t r y
agreed t o pay t o have t h e s e f a m i l i e s hooked up t o t h e p u b l i c
water s u p p l y and t o u n d e r t a k e a sampling program t o d e t e r m i n e i f
any o t h e r l o c a l i z e d " h o t s p o t s " e x i s t e d i n t h e a r e a ; t h e S t a t e
a n a l y z e d a s m a l l number of d u p l i c a t e samples.
T a b l e I. T r i c h l o r o e t h y l e n e C o n c e n t r a t i o n s i n Micrograms
Per L i t e r (ug/1) o r Micrograms Per Cubic Meter (ug/m3)
Kitchen Cold Bathroom Hot Bathroom Tub

Water 34,000 ug/1 29,000 ug/1 13,000 ug/1
Air
ambient Kitchen Bathroom Ambient
background 35 ug/m3 230 ug/m3 35 ug/m3
a f t e r water use 2000 ug/m 3

38,000 ug/m *3
^ b r e a k t h r o u g h on c a r t r i d g e ; minimum l e v e l
During t h e sampling program, s e v e r a l w e l l s from homes on

Ethan A l l e n and Putnam S t r e e t s were found t o be c o n t a m i n a t e d w i t h
PCBs. Along w i t h t h e PCBs, t h e gas chromotograph p i c k e d up
several u n i d e n t i f i e d peaks. On March 2, 1984, one w e l l was found
t o be c o n t a m i n a t e d w i t h 35 ug/1 of PCBs, an u n u s u a l l y h i g h
level. F o l l o w - u p samples were taken from the same r e s i d e n c e and
nearby r e s i d e n c e s . By March 8, 1984, t h e o r i g i n a l PCB r e s u l t was
c o n f i r m e d and t h e samples w i t h unknown peaks had been a n a l y z e d by
a mass s p e c t r o p h o t o m e t e r . The compounds p r e s e n t a t h i g h

c o n c e n t r a t i o n s were i d e n t i f i e d as a l a c h l o r and a t r a z i n e ,
chemicals not a s s o c i a t e d with the i n d u s t r y . The p o t e n t i a l s o u r c e
f o r t h e s e compounds was a l o c a l a g r i c u l t u r a l s u p p l y s t o r e .
L a b o r a t o r y s t a n d a r d s were o b t a i n e d f o r t h e s e new compoundsand
t h e sampling a r e a was expanded. By March 2 1 , 1984, s i x p r i v a t e
w e l l s were found t o be c o n t a m i n a t e d , two w i t h PCBs and f o u r w i t h
pesticides. By t h e m i d d l e of May, 15 w e l l s had been found t o be
c o n t a m i n a t e d w i t h p e s t i c i d e s , s i x w i t h PCBs a n d / o r c h l o r i n a t e d
h y d r o c a r b o n s o l v e n t s and one w i t h both p e s t i c i d e s and PCBs. In
a d d i t i o n t o d r i n k i n g water w e l l s , s p r i n g s i n t h e a r e a s were found
t o be c o n t a m i n a t e d . The h i g h e s t l e v e l s found f o r t h e p e s t i c i d e s
were 260 ug/1 f o r a t r a z i n e and 660 ug/1 f o r a l a c h l o r .
Atrazine
A t r a z i n e i s a w i d e l y used p r e - and post-emergency h e r b i c i d e f o r

s e l e c t i v e l y c o n t r o l l i n g b r o a d l e a f and g r a s s y weeds i n c o r n ,
sorghum, a s p a r a g u s , m i l l e t , p i n e a p p l e , f r u i t t r e e s , s u g a r c a n e ,
and summer f a l l o w ; i t i s a l s o used t o c o n t r o l v e g e t a t i o n i n land
not used f o r c r o p s . Sugar b e e t s , t o b a c c o , o a t s and many o t h e r
vegetable crops a r e very s e n s i t i v e t o a t r a z i n e .
T r i a z i n e h e r b i c i d e s a r e m o d e r a t e l y p e r s i s t e n t i n s o i l s and
w a t e r (10-18 months) w i t h a t r a z i n e b e i n g one of t h e more
p e r s i s t e n t of t h e g r o u p . L a b o r a t o r y and f i e l d d a t a have shown
t h a t t h e d i s a p p e a r a n c e of a t r a z i n e from s o i l i s i n f l u e n c e d by
t e m p e r a t u r e , pH, m o i s t u r e c o n t e n t , and o r g a n i c m a t t e r c o n t e n t ;
t h e e f f e c t of t e m p e r a t u r e and pH on t h e h a l f - l i f e of a t r a z i n e i n
s o i l ( s i l t loam - l a b o r a t o r y s t u d y ) i s as f o l l o w s ( 2 ) :
Temperature pH[ Half-life (days)

250C 4.9 35
250C 7.0 72
50C 4.9 250
50C 7.0 439
R e s p i r a t o r y d i f f i c u l t i e s , loss of muscular c o o r d i n a t i o n ,
c o n v u l s i o n s , and t h y r o i d d y s f u n c t i o n have been observed i n
l a b o r a t o r y a n i m a l s g i v e n h i g h l e v e l s of a t r a z i n e . The o r a l
LD50 i s 2,090 mg/kg f o r r a t s , 1,750 mg/kg f o r m i c e , and
750 mg/kg f o r r a b b i t s . In one a c u t e experiment (3) w i t h sheep
and c a t t l e , symptoms of a t r a z i n e p o i s o n i n g i n c l u d e d m u s c u l a r
spasms, s t i f f g a i t , and i n c r e a s e d r e s p i r a t i o n r a t e s ; a t
n e c r o p s y , compound d e g e n e r a t i o n and d i s c o l o r a t i o n of t h e
a d r e n a l g l a n d s , and c o n g e s t i o n of t h e l u n g s , l i v e r and k i d n e y s
were o b s e r v e d . No cases of p o i s o n i n g i n humans were found i n
the l i t e r a t u r e .
A t r a z i n e appears t o have a r e l a t i v e l y low c h r o n i c t o x i c i t y
v i a t h e o r a l r o u t e , but t h e d a t a base i s l i m i t e d . The
N a t i o n a l Academy of S c i e n c e s (4) c a l c u l a t e d an a c c e p t a b l e
d a i l y i n t a k e (ADI) u s i n g a n o - o b s e r v e d ~ e f f e e t l e v e l (NOEL)
from an 80 week mouse ( d i e t a r y ) t u m o r i g e n i c i t y s t u d y (5.) and
an u n c e r t a i n t y f a c t o r of 1,000; a suggested g u i d e l i n e of
30. KIM ETAL. Two Ground Water Contamination Problems 535
150 ppb f o r a t r a z i n e i n d r i n k i n g water was c a l c u l a t e d ,

assuming a human weight of 70 k g , consumption of two l i t e r s of
water p e r day and 20% of t h e ADI a l l o t t e d t o d r i n k i n g w a t e r .
Review of t h e e x p e r i m e n t a l p r o t o c o l f o r t h e mouse s t u d y
i n d i c a t e s , however, t h a t the average d a i l y dose of a t r a z i n e
was c a l c u l a t e d i n c o r r e c t l y ; t h e r e v i s e d d r i n k i n g
w a t e r g u i d e l i n e would be 60 ppb. Because o n l y one dose l e v e l
was used and t h e s t u d y was d e s i g n e d as a s c r e e n i n g s t u d y f o r
c a r c i n o g e n i c i t y , i t i s i n a d e q u a t e t o d e r i v e a NOEL f o r
non-carcinogenic e f f e c t s .
In 1981, t h e U.S. EPA (6) e v a l u a t e d u n p u b l i s h e d
t o x i c o l o g i c a l d a t a s u b m i t t e d i n s u p p o r t of a proposed
t o l e r a n c e f o r a t r a z i n e i n o r on o r c h a r d g r a s s and o r c h a r d g r a s s
hay, which i n c l u d e d :
(1) 2-year r a t chronic feeding/oncogenic study

NOEL = 100 ppm (5 mg/kg/day)
(2) 2 - y e a r dog c h r o n i c f e e d i n g s t u d y
NOEL = 150 ppm (3.75 mg/kg/day)
(3) Three-generation rat reproduction study

NOEL = 100 ppm (5 mg/kg/day)
The c h r o n i c r a t s t u d y i s c o n s i d e r e d i n a d e g u a t e (some e f f e c t s
observed a t 100 ppm) and i s b e i n g r e p e a t e d by t h e m a n u f a c t u r e r .
Data l a c k i n g f o r t h i s p e s t i c i d e i n c l u d e d t e r a t o l o g y s t u d i e s i n
two s p e c i e s ( p r e f e r a b l y r a t and r a b b i t ) and an o n c o g e n i c i t y s t u d y
in mice.
Most of t h e t o x i c o l o g i c a l s t u d i e s on a t r a z i n e were conducted
i n t h e I960*s and t h e r e g u i r e m e n t s f o r an adeguate s t u d y have
become much g r e a t e r o v e r t h e l a s t 10 y e a r s , p a r t i c u l a r l y w i t h
r e g a r d t o p a t h o l o g i c a l , h i s t o p a t h o l o g i c a l , and b i o c h e m i c a l
parameters. Some of t h e s t u d i e s were conducted by I n d u s t r i a l
B i o t e s t L a b o r a t o r i e s and a r e c o n s i d e r e d i n a d e g u a t e o r a t b e s t
supplemental f o r r e g u l a t o r y purposes. In a d d i t i o n t o c o n c e r n s
regarding the c h r o n i c t o x i c i t y data base, another concern
i n v o l v e s the p o s s i b l e a d v e r s e e f f e c t s of c h r o n i c i n g e s t i o n on
c a r b o h y d r a t e m e t a b o l i s m and DNA, RNA and p r o t e i n s y n t h e s i s .
U n t i l t h e r e s u l t s of t h e r e p e a t c h r o n i c r a t f e e d i n g s t u d y and
r a t t e r a t o l o g y s t u d y a r e a v a i l a b l e , t h e 70 ppm d i e t a r y l e v e l ( r a t
f e e d i n g s t u d y , i n p r o g r e s s ) o r t h e 2 - y e a r dog c h r o n i c f e e d i n g
s t u d y and an u n c e r t a i n t y f a c t o r of 1,000 can be used t o c a l c u l a t e
t h e ADI. A d r i n k i n g water g u i d e l i n e of 25 ug/1 i s c a l c u l a t e d
assuming a human weight of 70 k g , consumption of two l i t e r s of
w a t e r p e r day and t h a t 20% of t h e ADI can come from d r i n k i n g
water.
Alachlor
A l a c h l o r i s a h e r b i c i d e used t o c o n t r o l annual g r a s s e s and

c e r t a i n b r o a d l e a f weeds i n soybeans, c o r n , p e a n u t s , d r y beans,
s u n f l o w e r s , m i l o , and p o t a t o e s . The pure i n g r e d i e n t i s a s o l i d
which melts a t about 4 0 c e n t i g r a d e (C) and i s s o l u b l e i n water

t o about 240 m i l l i g r a m s p e r l i t e r ( m g / ) a t 25<>c.
The body of t o x i c o l o g i c a l d a t a on a l a c h l o r c o n s i s t s of
unpublished manufacturer-sponsored s t u d i e s (Monsanto A g r i c u l t u r a l
Products). No l o n g - t e r m animal s t u d i e s were a v a i l a b l e i n t h e
p u b l i s h e d l i t e r a t u r e which would c o n t r i b u t e i n f o r m a t i o n on
r e p r o d u c t i v e e f f e c t s o r c a r c i n o g e n i c p o t e n t i a l of a l a c h l o r . The
i n f o r m a t i o n used by t h e New York S t a t e Department of H e a l t h was
o b t a i n e d from t h e U.S. EPA summary ( 7 - 8 ) and Monsanto ( 9 ) .
A l a c h l o r does not appear t o be h i g h l y t o x i c on an a c u t e
basis. The o r a l LD50 v a l u e f o r r a t s was r e p o r t e d t o be
930 mg/kg and t h e dermal LD50 was 13,300 mg/kg i n r a b b i t s .
A l a c h l o r was r e p o r t e d t o be o n l y s l i g h t l y i r r i t a t i n g t o r a b b i t
skin.
The U.S. EPA O f f i c e of P e s t i c i d e Programs (7) reviewed and
e v a l u a t e d t h e t o x i c o l o g i c a l d a t a base submitted by Monsanto i n
s u p p o r t of a p e t i t i o n f o r t o l e r a n c e l e v e l s f o r a l a c h l o r i n o r on
raw a g r i c u l t u r a l c o m m o d i t i e s * . Data c o n s i d e r e d i n s u p p o r t of t h e
p e t i t i o n and summarized i n t h e F e d e r a l R e g i s t e r , i n c l u d e d :
0) Rat t e r a t o l o g y s t u d y
No observed t e r a t o g e n i c i t y a t 400 mg/kg [ h i g h e s t dose
tested]
NOEL = 150 mg/kg f o r maternal t o x i c i t y and f e t o t o x i c i t y
(2) 3-generation r a t reproduction study

NOEL = 10 mg/kg/day
(3) 18-month mouse c h r o n i c f e e d i n g / o n c o g e n i c i t y study

P o s i t i v e oncogenic response i n females ( b r o n c h i o l a r
alveolar
tumors) a t 260 mg/kg/day
(4) 2 - y e a r r a t c h r o n i c f e e d i n g / o n c o g e n i c i t y study
P o s i t i v e o n c o g e n i c response a t 42 mg/kg/day
(both sexes - n a s a l t u r b i n a t e tumors) and 126 mg/kg/day
(both sexes - n a s a l and stomach tumors; males - t h y r o i d
f o l l i c u l a r t u m o r s ) ; no c a r c i n o g e n i c e f f e c t s were observed
a t 14 mg/kg/day.
* R e c e n t l y t h e U.S. EPA (10) i n i t i a t e d a s p e c i a l r e v i e w of

a l l p e s t i c i d e p r o d u c t s c o n t a i n i n g a l a c h l o r based on t h e
oncogenic f i n d i n g s .
A c c o r d i n g t o EPA, d a t a l a c k i n g i n c l u d e d a 2 - y e a r c h r o n i c
f e e d i n g s t u d y ( r a t s ) , a 1 - y e a r f e e d i n g study ( d o g s ) , a t e r a t o l o g y
study ( r a b b i t s ) , a metabolism study ( r a t s ) , a s k i n s e n s i t i z a t i o n
s t u d y ( g u i n e a p i g s ) , and m u t a g e n i c i t y s t u d i e s . The Agency a l s o
s t a t e d t h a t a l a c h l o r had been d e t e r m i n e d t o be an oncogen i n mice
and r a t s . In a d d i t i o n t o m u l t i - s i t e o n c o g e n i c i t y , c o n c e r n has
a l s o been r a i s e d r e g a r d i n g e f f e c t s on t h e eyes o f r a t s . An
a c c e p t a b l e d a i l y i n t a k e has not been e s t a b l i s h e d f o r a l a c h l o r .

In New York S t a t e , n o t i f i c a t i o n i s r e q u e s t e d i f d r i n k i n g water
l e v e l s exceed 1 u g / 1 .
In Summary
As a r e s u l t of t h e s e groundwater contamination findings, actions

were t a k e n .
(1) Homes w i t h p r i v a t e w e l l s contaminated w i t h PCBs a n d / o r

s o l v e n t s were hooked up t o p u b l i c water s u p p l i e s by t h e
company.
(2) Wells contaminated with p e s t i c i d e s a r e on a l t e r n a t e

water s o u r c e s .
Suffolk County. Long I s l a n d . N.Y.
By 1978, a l d i c a r b had been a p p l i e d t o p o t a t o f i e l d s i n t h e n o r t h

and south f o r k s of Long I s l a n d f o r s e v e r a l y e a r s . Approximately
200 farms c o n s i s t i n g of 22,000 a c r e s a r e l o c a t e d i n t h e a r e a .
F i v e t o t e n thousand water s u p p l y w e l l s a r e e s t i m a t e d t o be n e a r
these potato farms.
In 1978, a t t h e u r g i n g of a t e c h n i c a l a d v i s o r y committee of
t h e N a s s a u / S u f f o l k p l a n n i n g b o a r d , Union C a r b i d e a n a l y z e d samples
from skimming w e l l s b e f o r e and a f t e r t h e a p p l i c a t i o n of a l d i c a r b
t o t h e p o t a t o f i e l d s on f o u r d i f f e r e n t f a r m s . Samples were
c o l l e c t e d i n t h e s p r i n g and a l d i c a r b was d e t e c t e d i n 20 of 31
samples. A d d i t i o n a l samples were c o l l e c t e d i n A p r i l of 1979 and
s i m i l a r r e s u l t s were f o u n d . In A u g u s t , 1979, 14 w a t e r samples
were taken from p r i v a t e w e l l s a t farm homes near t h e p o t a t o
f i e l d s , o t h e r s h a l l o w water w e l l s and somewhat deeper m u n i c i p a l
water supply w e l l s . S i x of n i n e farm w e l l s showed a l d i c a r b
l e v e l s between 4 and 140 u g / 1 .
These f i n d i n g s l e d t o an e x t e n s i v e s u r v e y f o r a l d i c a r b
c o n t a m i n a t i o n (H). Once e x t e n s i v e c o n t a m i n a t i o n was f o u n d ,
a l d i c a r b was removed from t h e Long I s l a n d market.
With a l d i c a r b b e i n g withdrawn from t h e m a r k e t , Long I s l a n d
p o t a t o f a r m e r s needed an a l t e r n a t e i n - g r o u n d use p e s t i c i d e .
S e v e r a l thousand a c r e s of farm land a r e g u a r a n t i n e d f o r growing
p o t a t o e s because of t h e Golden Nematode. A suggested a l t e r n a t i v e
was oxamyl which was b e i n g used f o r f o l i a r a p p l i c a t i o n s . The
i n - g r o u n d use of t h i s p e s t i c i d e o c c u r r e d under an e x p e r i m e n t a l
use p e r m i t and w i t h a m o n i t o r i n g program t o d e t e r m i n e i f t h i s
compound would c o n t a m i n a t e groundwater.
A s o i l and water m o n i t o r i n g program was c a r r i e d out
t h r o u g h o u t t h e summer of 1980. I n i t i a l r e s u l t s looked
promising. The compound was not d e t e c t e d i n groundwater. The
s o i l sampling r e s u l t s a l s o i n d i c a t e d t h a t oxamyl was decomposing
r a p i d l y i n t h e t o p s o i l l a y e r s and o n l y one s i t e showed a low
l e v e l of c o n t a m i n a t i o n i n t h e 20 i n c h c o r e s .
F o r t h e 1981 s e a s o n , oxamyl was a l l o w e d t o be used on t h e

p o t a t o f i e l d s a g a i n w i t h a m o n i t o r i n g program. The program was
t o address s e v e r a l concerns r a i s e d the previous y e a r .
(1) S o i l samples were t a k e n f u r t h e r i n t o t h e f a l l because

some c o r e l e v e l s i n c r e a s e d d u r i n g t h e l a t t e r h a l f of t h e
summer.
(2) R a i n f a l l was 6" l e s s than normal i n 1980 which may have

d e c r e a s e d t h e m i g r a t i o n compared t o normal y e a r s .
(3) Deeper s o i l c o r e s were needed because oxamyl was

d e t e c t e d i n t h e d e e p e s t c o r e sampled.
The 1981 r e p o r t (12.) c o n c l u d e d , " T h a t under normal use

c o n d i t i o n s oxamyl does not c o n t a m i n a t e w e l l water on Long I s l a n d . "
Oxamyl was used a g a i n d u r i n g t h e 1982 growing s e a s o n .

However, i n 1982, t h e S u f f o l k County H e a l t h Department took o v e r
t h e Union C a r b i d e ( m a n u f a c t u r e r o f a l d i c a r b ) sampling program f o r
a l d i c a r b i n d r i n k i n g water and surveyed a r e a s not p r e v i o u s l y
covered. The County a l s o began m o n i t o r i n g f o r oxamyl. By
November, 1982, 27 homeowner w e l l s had been found t o c o n t a i n
oxamyl a t c o n c e n t r a t i o n s l e s s than t h e New York S t a t e H e a l t h
Department g u i d e l i n e of 50 u g / 1 .
In 1983, t h e d e c i s i o n was a g a i n t o a l l o w oxamyl t o be used i n
p o t a t o f i e l d s and f o r above ground a p p l i c a t i o n s because t h e
g u i d e l i n e had n o t been e x c e e d e d . By November, 1983, t h e County
H e a l t h Department (H) had d e t e c t e d oxamyl ( d e t e c t i o n l i m i t - 1
ug/1) a t 75 of 3,000 sampling s i t e s . C a l c u l a t i n g the percentage
of p o s i t i v e s i t e s u n d e r e s t i m a t e s t h e p o t e n t i a l c o n t a m i n a t i o n
because t h e sampling program was o r i g i n a l l y d e s i g n e d f o r a l d i c a r b
and t h e sampling s i t e s were g e n e r a l l y n o t c l o s e t o farm a r e a s .
Oxamyl c o n t a m i n a t i o n was p r o b a b l y w i d e s p r e a d c l o s e t o use a r e a s
as e x e m p l i f i e d by t h e m o n i t o r i n g r e s u l t s from t h e Town of
Laurel. In 1983 f o r t h i s town, p o s i t i v e r e s u l t s (16 s i t e s , 23
samples) ranged from 1 ug/1 t o 106 ug/1 w i t h two s i t e s (6
samples) equal t o o r e x c e e d i n g t h e 50 ug/1 g u i d e l i n e . Oxamyl's
c o n t i n u e d use was p r o d u c i n g i n c r e a s i n g l e v e l s i n groundwater.
Most of t h e c o n t a m i n a t e d w e l l s were s h a l l o w , but oxamyl was found
i n w e l l s d e e p e r than 100 f e e t . In a d d i t i o n , a t L a u r e l , oxamyl
had been found t o have m i g r a t e d s e v e r a l hundred f e e t from t h e
s i t e of a p p l i c a t i o n . By J a n u a r y 1984, t h r e e w e l l s had been found
t o c o n t a i n oxamyl above t h e g u i d e l i n e s and t h e m a n u f a c t u r e r
removed i t from t h e market on Long I s l a n d .
Oxamyl
Oxamyl i s a s y s t e m i c o r c o n t a c t i n s e c t i c i d e , m i t i c i d e and
nematocide. The h a l f - l i f e f o r oxamyl i n s o i l r e p o r t e d l y ranges
from 1-6 weeks depending on s o i l t y p e , pH, m o i s t u r e c o n t e n t , and
t e m p e r a t u r e ( 1 4 ) . Some c h e m i c a l and p h y s i c a l p r o p e r i t i e s a r e :
Physical State crystalline solid

Vapor P r e s s u r e 2.3 10-4 mm Hg a t 25<>c
7.6 10-3 mm Hg a t 70<>C
Specific Gravity 0.097
S o l u b i l i t y i n Water . . 280 g/1 a t 25oc
Melting Point 100O-102OC changing t o a
d i f f e r e n t c r y s t a l l i n e from which
from which m e l t s a t 1 0 8 0 - n o o c
Oxamyl has a h i g h a c u t e t o x i c i t y d i s p l a y i n g t h e t y p i c a l
e f f e c t s of carbamate i n s e c t i c i d e s , e . g . r a p i d o n s e t of
c h o l i n e s t e r a s e i n h i b i t i o n f o l l o w e d by r a p i d r e c o v e r y . Symptoms
of a c u t e i n t o x i c a t i o n i n a n i m a l s i n c l u d e d t r e m o r s , s a l i v a t i o n ,
l a c r i m a t i o n , b u l g i n g e y e s , and m u s c u l a r t w i t c h i n g . The o r a l
LD50 f o r oxamyl i n t h e r a t i s t h e range of 5 t o 15 mg/kg.
The World H e a l t h O r g a n i z a t i o n (WHO) ( 1 5 ) , i n 1981, s e t a

temporary ADI f o r oxamyl based on a n o - e f f e c t l e v e l from a 2 - y e a r
dog s t u d y . The Committee e x p r e s s e d c o n c e r n , however, t h a t the
dog i s somewhat l e s s s e n s i t i v e t o oxamyl than the r a t and t h a t a
c l e a r n o - e f f e c t l e v e l had not been e s t a b l i s h e d i n t h e r a t .
A d d i t i o n a l c o n c e r n was e x p r e s s e d o v e r t h e l a c k of i d e n t i f i c a t i o n
of 50% of t h e t i s s u e r e s i d u e s of oxamyl. The WHO was r e q u i r i n g
t h a t by 1983 t i s s u e r e s i d u e s be i d e n t i f i e d and t h a t the n o - e f f e c t
l e v e l i n t h e r a t be c l a r i f i e d . Based on t h e WHO temporary ADI, a
d r i n k i n g water g u i d e l i n e of 70 ug/1 can be c a l c u l a t e d .
The U.S. EPA has used an ADI based on a 2 - y e a r c h r o n i c r a t
d i e t a r y study. A d r i n k i n g water g u i d e l i n e of 175 ug/1 was
c a l c u l a t e d u s i n g t h i s ADI.
The New York S t a t e Department of H e a l t h e s t a b l i s h e d a
p r e l i m i n a r y g u i d e l i n e of 50 ug/1 because of u n c e r t a i n i t i e s i n t h e
n o - e f f e c t l e v e l i n r a t s and l a c k of d a t a on c h o l i n e s t e r a s e
i n h i b i t i o n i n humans. A d d i t i o n a l c o n c e r n s c e n t e r e d on the
r e s u l t s of a r a b b i t t e r a t o l o g y s t u d y which i n d i c a t e d NOELs f o r
e m b r y o t o x i c i t y and f o r m a t e r n a l body weight changes which a r e
lower than t h e e s t i m a t e d NOEL from c h r o n i c r a t d a t a .
Literature Cited
(1) "Air Sample collection technique for aromatic hydrocarbons,
and related volatile organic compounds," Wadsworth Center
for Laboratories and Research, New York State Department of
Health, 1981.
(2) Nearpass, D.; Edwards, W.M.; Taylor, A.W. Agronomy Journal
1978, 70, 937-40.
(3) Palmer, J.; Radeleff, R. Ann. N.Y. Acad. Sci. 1964, 111(2),
729-36.
(4) "Drinking Water and Health," National Academy of Sciences,
1977, Volume 1.
(5) Innes, J.; Ulland, B.; Valerio, M.; Petrucelli, L.;

Fishkein, L.; Hart, E.; Pallotta, .; Bates, R.; Falk, H.;
Gart, J . ; Klein, M.; Mitchell, I.; Peters, J. J. Natl. Canc.
Inst. 1969, 42, 1101-14.
(6) "Atrazine: Proposed Tolerance," U.S., Food and Agriculture
Organization of the United Nations, Rome, Report Number 56,
1984.
(7) "Tolerances and Exemptions from Tolerances for Pesticide
Chemicals in or on Raw Agricultural Commodities: Alachlor,"
U.S. Environmental Protection Agency, Federal Register,
48(62):13173-4, 1983.
(8) U.S. Environmental Protection Agency, Office of Drinking
Water, personal communication, April, 1984.
(9) Monsanto Agricultural Products, Alachlor, Information sheets
submitted to the New York State Department of Health, April,
1984.
(10) "Alachlor: Special Review of Certain Pesticide Products,"

U.S. Environmental Protection Agency, Federal Register,
50(6):115-19, 1985.
(11) Zaki, M.H.; Moran, D.; Harris, D. Am. J. Publ. Hlth. 1982,
72, 1291-95.
(12) E.I. duPont de Nemours and Co., Inc., Biochemicals
Department, January 1982, Data supporting the use of Vydate
L insecticide/nematicide on potatoes. Groundwater analyses
and soil residue determination of oxamyl, Long Island, New
York, 1981.
(13) Mr. Baire, November 15, 1983, Oral presentation to Oxamyl
Task Force. Suffolk County Department of Health Services,
Hauppauge, NY 11788.
(14) Harvey, J.; Han, J. J. Agric. Food Chem. 1978. 26, 536-41.
(15) "Pesticide Residues in Food," FAO/WHO, Food and Agriculture
Organization of the United Nations, Rome, Report Number 56,
1984.
Two recent reviews of the toxicological effects of
trichloroethylene and PCBs have been published:
Safe, S. CRC Critical Rev. Toxicol. 1984, 13, 319-395.
Kimbrough, R.; Mitchell, F.; Hunk, V. J. Toxic. and
Environ. Health 1985, 15, 369-383.

31
The Emerging Role of Pesticide Regulation in Florida
Due to Ground Water Contamination
Howard L. Rhodes
Florida Department of Environmental Regulation, Tallahassee, F L 32301
This paper describes the sequence of events that led

to a stronger environmental pesticide program in the
State of Florida. Prior to 1983, the State of Flori-

da did not have an active pesticide program. There
was very little impetus to protect the groundwater
from the effects of pesticide contamination. The
technical findings, the news media publications and
the resultant political actions changed the climate
in the state to one of serious concern over ground-
water contamination by pesticides. In 1983, the
State Legislature made broad, major inroads into
legislation and funding of programs that provided the
state with a comprehensive pesticide program that
looked at the environmental impacts of a wide range
of pesticide activities. The discoveries of aldicarb
and EDB in the groundwater were the two pesticides
that made these programs possible.
The process chosen for presenting this paper is one of a story-

t e l l i n g nature as opposed to a rigorous s c i e n t i f i c t r e a t i s e . It
t r i e s to show a t r a i l of science, risk-assessment and public p o l i -
cy. It is not meant to show or j u s t i f y the actions taken nor to
detract from them, but rather to portray a series of events leading
to a regulatory conclusion.
The nature of pesticides is one of a poison deliberately being
applied to plants and animals for the benefit of man. Much work
has been done on the methods to do this most e f f i c i e n t l y and e f -
f e c t i v e l y . Finding pesticides to accomplish this task has been
rewarding and has increased both the quality and quantity of man-
kind's food supply. This is c l e a r l y the beneficial and good side
of the coin and is a f a i r l y well-known fact in the agricultural
community, but much less well-known and appreciated by the con-
sumers in our society.
The reverse side of the coin is what pesticides do to our en-
vironment and more s p e c i f i c a l l y to man. While much study in some
0097-6156/ 86/ 0315-0541 $06.00/ 0

aspects of this issue has been done, i t is beginning to appear that

we w i l l never f u l l y understand a l l the complex impacts of the i n -
troduction of a foreign material into our environment or i t s r e s u l -
tant impacts on man. Because of a changing p o l i t i c a l climate and
improved s c i e n t i f i c technology for detection of pesticides, we can
do a better job than has previously been done. Knowledge of people
and our environment has expanded our understanding of the i n t e r -
relationship among various elements within our environment. The
role of the media is also extremely e f f e c t i v e at setting public
opinion that sometimes is otherwise shaped by the status quo.
These forces came together in F l o r i d a in the last two or three
years and forced the state to look more closely at the "other side
of the c o i n . "
In mid-1982 on the program "60 Minutes," CBS presented a some-
what frightening story of how water wells on Long Island, New York
had been contaminated by the pesticide Temik, and that i t s use was
p r o l i f e r a t i n g , especially in F l o r i d a . The story parenthetically

added that no one in F l o r i d a was monitoring for pesticides in
groundwater, nor was anyone r e a l l y aware of the pesticide Temik's
contamination p o t e n t i a l .
You can be assured that the following Monday, the state news
media and p o l i t i c a l community were c a l l i n g to ask what the F l o r i d a
Department of Environmental Regulation (FDER) proposed to do to
test groundwater. Needless to say, the state was not prepared for
the on-slaught. We were not testing groundwater to any s i g n i f i c a n t
degree at the time and had only just passed rules to regulate the
discharge of pollutants to groundwater. In addition, our labora-
tory chemist did not even know how to analyze for the chemical.
What CBS did not mention was that their " i n v e s t i g a t i v e " r e -
porter had called this speaker some two months e a r l i e r inquiring
about the s t a t e ' s pesticide program. When queried about any poten-
t i a l problem we should be aware of, he merely stated that there was
no problemhe just wanted to find out about the pesticide program
in the state. This appears to have been the major contact with the
state when i t was found l i t t l e was being done in the area of
groundwater contamination caused by pesticides. This deception was
responsible for several months delay in finding the pesticides in
F l o r i d a ' s groundwater.
Within days, staff was detailed to study at least two or three
sites in the state. During the interim, a contingent of the manu-
f a c t u r e r ' s agricultural chemicals division met with the staffs of
the F l o r i d a Department of Agriculture and Consumer Services (FDACS)
and the FDER. Assurances were made that there was no way for the
material to be found in groundwater in F l o r i d a because of i t s warm
climate and more alkaline waters. In retrospect, we believe these
highly technically oriented people r e a l l y believed these state-
ments, but their c r e d i b i l i t y suffered when our laboratory reported
positive findings a few weeks l a t e r .
News reporters called my staff d a i l y for reports on findings
and l i t e r a l l y started getting results and wanting my comments be-
fore I had seen the r e s u l t s . This led to a requirement that r e -
sults not be released before I read them, which meant I would be
the f i r s t contact with the media, but not the l a s t . To have im-
posed a restraint requiring staff not to talk to the media in a
31. RHODES The Emerging Role of Pesticide Regulation in Florida 543
state l i k e F l o r i d a that has an open records policy would have led

to accusations of censorship, which was not the intended purpose.
This did lead to various "quotes" of the day by various staff mem-
bers interpreting the positive finds over the next two or three
months. It is quite l i k e l y that no one r e a l l y knew the s i g n i f i -
cance of the positive findings except that a pesticide was present
in groundwater.
In early December 1982, the Commissioner of Agriculture, under
some pressure from the media, held a hearing for several state
agencies. The Commissioner stated that he would l i k e to have some
recommendations on how to address this contamination event. The
FDER and the Florida Department of Health and Rehabilitative Serv-
ices (FDHRS) suggested several constraints, including that the
material not be applied within 1,000 feet of drinking water wells.
It was f e l t that with the unknowns surrounding the pesticide Temik
a response was called f o r , but not a complete ban. Four agencies
were represented.
When a vote was called for on the health and environmental
recommendations, the agricultural community had disproportionate
voting power and got f i v e of the seven votes on the committee.
Each subsequent substantive environmental recommendation was voted
down 5-2. The following day there was much news coverage on this
meeting. Most of the coverage was not very complimentary to the
agricultural portion of the committee.
Several weeks later when an actual drinking water well was
found p o s i t i v e , not the groundwater positives found at the test
s i t e , the Commissioner of Agriculture banned the use of the p e s t i -
cide in the state for one year.
Some people f e l t that the environmental and health agencies
had pressured the Commissioner to take such an action. They had
not. It was more l i k e l y that the press coverage, as well as a
desire by the Commissioner that no c i t i z e n in the state be allowed
to drink water contaminated with p e s t i c i d e s , prompted the action.
Such is the case in the p o l i t i c a l arena when nothing seems to
be c l e a r l y black and white. Such action c l e a r l y alienated some in
the agricultural community for depriving them of an e f f e c t i v e pes-
t i c i d e . Some environmental groups were upset that action had not
taken place sooner. The press got good coverage of these actions.
There were a couple of exceptions to the ban: 1) totally
self-contained plants in nurserys, and 2) a small potato growing
area of North F l o r i d a . This potato area was i n i t i a l l y in the ban,
but after extensive testing by the health and agricultural agencies
found no pesticide in any well in the area, the exemption was
granted.
Concurrent with the announcement of the ban, the Commissioner
requested the manufacturer, the University of F l o r i d a Agricultural
Research Branch and the FDER to research the effects of the p e s t i -
cide on groundwater in F l o r i d a and to make recommendations to him
on what should be done.
As a r e s u l t , the manufacturer set up two virgin research sites
in conjunction with the University and the FDER during the next
seven to eight months to study the effects of the pesticide on
groundwater. These sites had never had previous applications of
aldicarb. Thus, there could not be a source of unknown application
time and rate to interfere with the study. The manufacturer also
volunteered to monitor the other three state sites where contamina-
tion had been found. Test applications of aldicarb were conducted
at these virgin sites to determine the length of time for contami-
nation to occur and also the rate of movement in the groundwater
and degradation rates.
Recommendations resulting from the study were nearly unanimous
to allow the p e s t i c i d e ' s use again in September 1983, with the only
discussion being how f a r from drinking water wells the material
should be applied. This resulted from the research showing the
material did get in the shallow groundwater and except for the
central ridge area of the state, the material hydrolized quickly
and no trace could be found after a few weeks. In the central
ridge, the degradation was much slower. Models developed by the
manufacturer, and concurred with by the University, suggested a 300
foot buffer. The FDER f e l t a safety factor of 100 percent should
be added based on data collected from two of the s i t e s . The Com-
missioner chose to go with the 300 foot buffer.

Sometime later i t became clear that one of the virgin sites
which had an application of aldicarb in the ridge area showed
leaching to groundwater took almost a year and then spread slowly
and e r r a t i c a l l y . After the model was shown to be incorrect, the
manufacturer requested the Commissioner to change the buffer to
1,000 feet.
During the whole process, the state was v i s i t e d by many high
ranking o f f i c i a l s of the company, including the president of the
agricultural chemicals d i v i s i o n on two or three occasions. Even
today, the manufacturer is continuing to monitor the site with the
contamination to learn more of what happens in groundwater in the
Highland ridge area.
In late 1982, the new Speaker of the Florida House of Repre-
sentatives had assumed duties, and quickly appointed a blue ribbon
task force on water quality. Many of these previously reported
events happened during the time the task force was holding hear-
ings. Other chemicals were also being found in drinking water
during this time. This led to a report that became a partial blue-
print for the 1983 Florida Legislature on a b i l l later known as the
Water Quality Assurance Act.
These and other events relating to water contamination became
the major b i l l during the session, putting many l e g i s l a t o r s in the
position of supporting l e g i s l a t i o n that would have been impossible
to support without the attendant p u b l i c i t y and without the strong
desires of the House leadership. Included as one provision was a
section setting up a data product evaluation bureau in the FDACS, a
pesticide section in the FDER and a toxicologist in the FDHRS. In
addition, a Pesticide Review Council was abolished and then recon-
stituted to include more environmental and health representatives.
The Legislature went into extended session to pass the b i l l ,
by which time the Senate and House had become f u l l y committed. The
l e g i s l a t i o n was the most comprehensive environmental l e g i s l a t i o n in
twelve years and set the course for many new i n i t i a t i v e s in not
only pesticides and groundwater but also hazardous waste and a
state grant program for sewage plants.
The story could end at this point except that EDB was discov-
ered in Hawaii's and C a l i f o r n i a ' s groundwater in early 1983. The

FDACS by now was f u l l y sensitized to the problems of groundwater
contamination by pesticides. The agency knew that i t had an on-
going program for applying large quantities of EDB to the s o i l in
and around citrus groves and had done so for years to control nema-
todes. It tested t h i r t y or forty wells in early July 1983 and
found EDB contamination. The FDER and FDHRS were promptly notified
of the r e s u l t s . The news media was not far behind. The p u b l i c i t y
was widespread, and the results predictable.
The Chairman of the F l o r i d a House Community A f f a i r s Committee,
whose d i s t r i c t previously had a groundwater contamination event
caused by a F l o r i d a Department of Transportation testing laboratory
disposal area, was very interested in the whole a f f a i r . He as-
signed staff to interview the affected well owners and ask ques-
tions such as "Are you s a t i s f i e d with the way the state has treated
you?" "What do you think the state should do to make you happy?"
"Are you s a t i s f i e d with the answers you are getting from the
state?" Needless to say, most answers were negative.
The Governor, the Commissioner of Agriculture and the House
Community A f f a i r s Chairman met to discuss the problem. The result
was the appointment of an EDB Task Force composed of the health
agency, the agricultural agency, the community a f f a i r s committee
and the environmental agency with charges to provide tests for a l l
the wells that were contaminated, an information newsletter and an
"800" h o t - l i n e , and then to find a solution and provide i t for
inclusion in the budget in January 1984. The task force met and
worked on the l o g i s t i c s .
The l o g i s t i c a l problems were legion. The state has between
500-700,000 private wells in addition to public water supplies.
With a number of exceptions, these d i f f i c u l t i e s were worked out.
The most d i f f i c u l t exceptions were finding and plotting locations
where the material was applied and getting enough people to sample
and analyze the samples. No extra provisions were made for new
s t a f f in any of the agencies to accomplish this and as a r e s u l t , a
number of a c t i v i t i e s suffered.
We could find nothing in the l i t e r a t u r e that offered e f f e c t i v e
ways to remove EDB. Research was done under contract with a p r i -
vate firm in cooperation with the U.S. Environmental Protection
Agency to determine the best way to remove the material from the
water. This research indicated that activated carbon was the most
effective technique.
Through the f a l l of 1983, the media continued to give wide
coverage to the constant number of findings of EDB in the wells.
This translated into continued p o l i t i c a l awareness of groundwater
contamination right to the top of the p o l i t i c a l structure in F l o r i -
da. At the same time, the FDER had elected not to use i t s labora-
tory for EDB work, but to concentrate on toxic dumps and the analy-
sis of groundwater at these s i t e s . Each one of these sites then
became a media event when positives were found.
The task force requested funds to correct contaminated wells
in areas where the EDB had been state applied. The Governor's
Office accepted the request in January 1984, only weeks before the
state budget was to be presented to the state Legislature.
The request for funds passed through the House e a s i l y , but
faulted in a very conservative Senate until the President of the

Senate found his own d i s t r i c t had some of the most contaminated
wells. Some 3.1 m i l l i o n dollars was ultimately made available, but
only after a proviso was attached that the well owners had to r e -
lease the state from property l i a b i l i t y in exchange for the r e l i e f .
This provision has caused about half the well owners to refuse to
sign the release, and thus no f i l t e r can be provided.
The EDB situation is s t i l l present in F l o r i d a today with the
l o g i s t i c s of sampling, analysis, n o t i f i c a t i o n of well owners and
r e t r o f i t of wells continuing. New contamination is found every
week with a total of 7,729 wells having been tested and 817 p o s i -
tives having been found as of February 27, 1985.
While the day-to-day issues of EDB have dominated many hours,
weeks and months of my staff and other agencies' staff time, a
greater good has evolved. For a year-and-a h a l f , weekly meetings
of a l l concerned agencies have resulted in decisions being made on
how things are done in the state. The close working relationships
developed among the f i v e agencies mean resources are used to their
f u l l e s t and the agencies' d i r t y laundry is aired weekly. Also, the
decisions of one agency are subject to intense scrutiny by another
agency. This has led to a tremendous amount of informed decision
making. The environmental and health agencies have learned a l o t
about agriculture and pesticide use. The agricultural community
has learned s i g n i f i c a n t facts about chemical toxicology, ground-
water movement and means of contamination and about drinking water
supply sources in the state. This open discussion in the various
agencies has led to a better appreciation of the concerns of af-
fected interests.
The result has been a s i g n i f i c a n t concern in the agricultural
agency for groundwater and surface water contamination potential of
p e s t i c i d e s . This is manifested by a bureau being created to deal
with pesticide registration in the state and the hiring of hydrolo-
g i s t s , biologists and toxicologists in the agricultural agency to
question the potential impacts of new pesticide registrations and
renewals of pesticides on the environment in the state.
There has been a commensurate impact at the environmental
agency, which had not given much p r i o r i t y to pesticide contamina-
tion until the Temik and EDB situations. The agency now has a
pesticide section that is systematically looking at groundwater in
areas of high pesticide use and in areas with s o i l l i k e l y to allow
pesticide migration. The purpose is to determine i f any other
pesticides are leaching into F l o r i d a ' s f r a g i l e groundwater.
Contrary to the media's implications, EDB is a f a i r l y l o c a l -
ized phenomena in certain areas of the state. The whole water
supply is not contaminated. The media's i n t e r e s t , and therefore
much of the p o l i t i c a l i n t e r e s t , has waned; but due to the sensitive
nature of this issue, the least amount of a toxic substance find
can create considerable consternation among the public as a whole.
The state level agencies are cooperating in a style not expe-
rienced in recent F l o r i d a history. Many agricultural meetings that
had previously been closed are being opened to environmental agency
personnel. While there is s t i l l a degree of mistrust, these groups
now recognize that in addition to food production, there is a
growing awareness of the stewardship role that the agricultural
community must play in protecting the earth's resources.
In the state Legislature, discussions on pesticides are no

longer the solely vested interest of the agricultural committees.
Discussions now occur in natural resource committees where most
environmental l e g i s l a t i o n is discussed. This a c t i v i t y causes a l l
points of an issue about pesticides to be analyzed.
Recently, we were advised that the main university research
i n s t i t u t e in F l o r i d a has decided i t w i l l no longer do e f f i c a c y
testing for new pesticides unless environmental fate studies unique
to F l o r i d a are done concurrently or have already been completed.
This w i l l have s i g n i f i c a n t impacts on the registration process, but
will go a long way toward ensuring that new pesticides w i l l not
have a detrimental impact on F l o r i d a ' s environment.
While regulation can never f u l l y be the answer to problems, in
Florida i t has begun to assist with the basic issue a l l of us must
grapple with t h e protection of this planet earth and i t s inhabi-
tants. Food, f i b e r , housing, clean air and water are v i t a l to our
existence.

32
Considering Pesticide Potential for Reaching
Ground Water in the Registration of Pesticides
Samuel M. Creeger
Office of Pesticide Programs (TS-769C), U.S. Environmental Protection Agency,

Washington, D C 20460
Ground water was once thought immume from chemicals

applied on the soil's surface, but current evidence

shows the presence of at least 1 of 16 different
pesticides in the ground water of 23 different
states. This paper describes procedures the U.S.
Environmental Protection Agency is using in consid-
ering the potential of pesticides to reach ground
water in the pesticide registration process.
About 379,500 metric tons of pesticide active ingredients were
I n t h
applied a g r i c u l t u r a l l y i n the United States i n 1984 ( 1). e
case of i n s e c t i c i d e s , i t has been estimated that 1 % of a t y p i c a l ,
a g r i c u l t u r a l i n s e c t i c i d e a p p l i c a t i o n i s responsible for the i n -
s e c t i c i d a l effect on the insect (2). The remaining 99+% of the
application does not d i r e c t l y perform i t s intended p e s t i c i d a l
function since i t misses the target insect, degrades, or moves from
the treatment area due to d r i f t and other transport mechanisms.
One can deduce that s i g n i f i c a n t portions of t y p i c a l herbicide and
fungicide applications are s i m i l a r l y not d i r e c t l y responsible i n
c o n t r o l l i n g their target p e s t ( s ) . It i s a portion of this 99+% of
pesticide applications that i s available for leaching through s o i l
and reaching ground water.
The complexity involved i n detecting pesticide residues i n
ground water and i n monitoring and cleaning up ground water con-
taining a g r i c u l t u r a l l y applied pesticides i s a factor that c o n t r i -
butes to the p u b l i c ' s fear for the loss of purity of the nation's
ground water supplies; water that i s used for drinking, bathing,
and i r r i g a t i n g / w a t e r i n g food and feed commodities. Pesticides are
i n t e n t i o n a l l y applied to crops for the purpose of pest control and
a tolerance i s set allowing an acceptable l e v e l of residues to
remain on the treated crop at the time of use/consumption of the
raw a g r i c u l t u r a l commodity (3). If the tolerance i s exceeded or
i l l e g a l pesticide residues are found i n a food or feed commodity,
the residue-containing food or feed can be removed from the market.
In contrast to t h i s , pesticide residues i n ground water are not put
there i n t e n t i o n a l l y , serve no useful purpose there and may not
dissipate from the ground water system f o r decades.

32. CREEGER Pesticide Potential in the Registration of Pesticides 549
Table l a . SUMMARY OF ENVIRONMENTAL FATE DATA REQUIREMENTS

FOR TERRESTRIAL USE PATTERNS
TERRESTRIAL USES
FIELD
AND
DOMESTIC GREEN- NON- ORCHARD VEGE. FORES-
DATA REQUIREMENTS* OUTDOOR HOUSE CROP CROP CROP TRY
DEGRADATION
HYDROLYSIS
PHOTOLYSIS
-WATER R R R
-SOIL CR CR CR
METABOLISM
AEROBIC SOIL R
ANAEROBIC SOIL R
MOBILITY
LEACHING R R R R R R
AGED LEACHING R R R R R R
FIELD DISSIPATION
SOIL
FOREST
ACCUMULATION
ROTATIONAL CROP CR
FISH CR CR CR CR
AQUATIC NONTARGET CR
* STUDIES REQUIRED ONLY UNDER CERTAIN CONDITIONS (SUCH AS PHOTOLY-

SIS IN AIR, VOLATILITY STUDIES, TANK MIX STUDIES AND IRRIGATED CROP
STUDIES) ARE NOT INCLUDED IN THIS TABLE.
R - REQUIRED; CR = CONDITIONALLY REQUIRED; UNDERLINE (R, CR) INDI-

CATES DATA REQUIREMENTS WHEN AN EXPERIMENTAL USE PERMIT IS SOUGHT.
Table l b . SUMMARY OF ENVIRONMENTAL FATE DATA REQUIREMENTS

FOR AQUATIC AND AQUATIC IMPACT USE PATTERNS
AQUATIC USES
DATA REQUIREMENTS* FOOD CROP NON-CROP
DEGRADATION
HYDROLYSIS
PHOTOLYSIS
-WATER
METABOLISM
AEROBIC AQUATIC R R
ANAEROBIC AQUATIC R R
MOBILITY
LEACHING**
FIELD DISSIPATION
SOIL (SEDIMENT) R R
WATER R R
ACCUMULATION
ROTATIONAL CROP CR
IRRIGATED CROP CR CR
FISH CR CR
AQUATIC NONTARGET CR
* STUDIES REQUIRED ONLY UNDER CERTAIN CONDITIONS (SUCH AS

PHOTOLYSIS IN AIR, VOLATILITY STUDIES AND TANK MIX STUDIES)
ARE NOT INCLUDED IN THIS TABLE.
* * A BATCH EQUILIBRIUM (ADSORPTION/DESORPTION) STUDY.
R = REQUIRED; CR - CONDITIONALLY REQUIRED; UNDERLINE (R, CR)

INDICATES DATA REQUIREMENTS WHEN AN EXPERIMENTAL USE PERMIT
IS SOUGHT.
The n a t i o n ' s ground w a t e r s u p p l y was once c o n s i d e r e d t o be

i s o l a t e d and immune from a c t i v i t i e s occurring on the Earth's
surface. The b e l i e f t h a t o r g a n i c c h e m i c a l s would c o m p l e t e l y degrade
i n s o i l and t h a t ground water cannot be d i r e c t l y o b s e r v e d s u p p o r t e d
t h a t p o s i t i o n (4) However, ground w a t e r m o n i t o r i n g done i n the
p a s t 10 y e a r s does show ground water i n many a r e a s t o be v u l n e r a b l e
to organic chemicals, such as p e s t i c i d e s , a p p l i e d a t the soil
surface. E v i d e n c e (5) p u b l i s h e d i n 1984 r e c o r d e d the ground water
o f 18 s t a t e s t o c o n t a i n a t l e a s t 1 of 12 a g r i c u l t u r a l l y a p p l i e d
pesticides; information r e c e i v e d s i n c e t h a t 1984 publication now
shows the ground w a t e r of 23 d i f f e r e n t s t a t e s to c o n t a i n a t l e a s t
1 of 16 a g r i c u l t u r a l l y a p p l i e d p e s t i c i d e s ( 6 ) .
How does the E n v i r o n m e n t a l P r o t e c t i o n Agency now determine
p o t e n t i a l f o r p e s t i c i d e s t o r e a c h ground water and how i s that
knowledge used i n the p e s t i c i d e r e g i s t r a t i o n process? In the
r e g i s t r a t i o n p r o c e s s , t h e r e a r e t h r e e mechanisms t h a t b r i n g p e s t
i c i d e c h e m i c a l s under c o n s i d e r a t i o n f o r p o t e n t i a l t o r e a c h ground
w a t e r . They a r e : (1) New c h e m i c a l r e g i s t r a t i o n , (2) R e r e g i s t r a -
t i o n ( a l s o known as the R e g i s t r a t i o n S t a n d a r d s P r o c e s s ) , and (3)
An Amendment t o an E x i s t i n g R e g i s t r a t i o n .
1. A new c h e m i c a l r e g i s t r a t i o n i n v o l v e s s u b m i s s i o n of a d a t a
package by the r e g i s t r a n t t o EPA. That package c o n t a i n s , i n p a r t ,
s t u d i e s on the e n v i r o n m e n t a l f a t e of the a c t i v e i n g r e d i e n t . The
number of s t u d i e s t o be s u b m i t t e d depends on the proposed use
p a t t e r n as shown by i n f o r m a t i o n p r e s e n t e d i n T a b l e s l a and l b t a k e n
from t h e S u b d i v i s i o n G u i d e l i n e s ( 7 ) . 2. These t a b l e s can a l s o
be used to determine the data needed under the Registration
Standards p r o c e s s , which i s the second of the t h r e e r e g i s t r a t i o n
p r o c e s s e s mentioned i n the p r e v i o u s p a r a g r a p h .
Of the s t u d i e s r e q u i r e d i n s u p p o r t of the r e g i s t r a t i o n o r r e -
r e g i s t r a t i o n of a p e s t i c i d e p r o d u c t , the r e s u l t s from t h e f o l l o w i n g
s t u d i e s have the g r e a t e s t impact on d e t e r m i n i n g a p e s t i c i d e ' s po
t e n t i a l t o r e a c h ground w a t e r ( T a b l e I I ) . D a t a on the t o p i c s i n
T a b l e I I a r e a l s o r e q u i r e d as p a r t of the Ground Water D a t a C a l l In
d i s c u s s e d a t the end of t h i s p a p e r .
Table I I . ENVIRONMENTAL FATE STUDIES USED IN DETERMINING A

PESTICIDE'S POTENTIAL TO REACH GROUND WATER
Hydrolysis
Photolysis i n Water
Photolysis on Soil
Aerobic S o i l Metabolism
Anaerobic S o i l Metabolism
Anaerobic Aquatic Metabolism
Leaching
F i e l d D i s s i p a t i o n ( T e r r e s t r i a l , Aquatic or Forestry)
3. The o t h e r r e g i s t r a t i o n mechanism t h a t b r i n g s p e s t i c i d e s under

c o n s i d e r a t i o n f o r p o t e n t i a l t o r e a c h ground water i s an amendment
t o an e x i s t i n g r e g i s t r a t i o n . The f o l l o w i n g amendments t o a p e s t -
i c i d e p r o d u c t may change the p e s t i c i d e ' s p o t e n t i a l t o r e a c h ground
water ( T a b l e I I I ) :
Table I I I . TYPES OF AMENDMENTS TO EXISTING REGISTRATIONS
Increased A p p l i c a t i o n Rates
Change i n A p p l i c a t i o n Timing
Change i n F o r m u l a t i o n
New Use Site

When a r e g i s t r a n t wishes t o amend an e x i s t i n g r e g i s t r a t i o n by

a d d i n g a new crop use, t h e n d a t a needed t o s u p p o r t t h a t new use
must be s u b m i t t e d . F o r example, i f a f u n g i c i d e p r o d u c t i s used on
greenhouse-grown e g g p l a n t s e e d l i n g s and the r e g i s t r a n t wants t o
e x t e n d use o f t h a t p r o d u c t t o f i e l d grown tomatoes, green peppers
and e g g p l a n t s , then the d i f f e r e n c e s i n t h e d a t a r e q u i r e m e n t s (as
g i v e n i n T a b l e l a ) between greenhouse use and f i e l d v e g e t a b l e c r o p
use w i l l have t o be s a t i s f i e d ( T a b l e I V ) :
T a b l e IV. ADDITIONAL DATA TO SUPPORT CHANGE IN USE

FROM GREENHOUSE TO TERRESTRIAL FIELD CROP
P h o t o l y s i s i n Water
P h o t o l y s i s on Soil
Anaerobic Soil Metabolism
Field Dissipation
R o t a t i o n a l Crop
Fish Accumulation
(The u n d e r l i n e d s t u d i e s a r e used i n determining p o t e n t i a l to reach

ground w a t e r ) .
I n t h i s example, the r e s u l t s of the u n d e r l i n e d s t u d i e s i n

T a b l e IV w i l l be c o n s i d e r e d w i t h the p r e v i o u s l y s u b m i t t e d h y d r o l y -
s i s , a e r o b i c s o i l metabolism and l e a c h i n g s t u d i e s which s u p p o r t e d
the grenhouse-grown e g g p l a n t s e e d l i n g use, t o determine the p o t e n -
t i a l f o r the p e s t i c i d e t o r e a c h ground w a t e r when used i n the f i e l d
as p r o p o s e d . The r e s u l t s of t h e s t u d i e s , a l o n g w i t h water s o l u b i l -
i t y , v a p o r p r e s s u r e and o c t a n o l - w a t e r p a r t i t i o n i n g d a t a a r e used t o
determine p o t e n t i a l f o r the p e s t i c i d e t o r e a c h ground w a t e r . If
t h e r e v i e w of the s t u d i e s shows the p e s t i c i d e t o meet a t l e a s t one
of t h e c r i t e r i a ( 5 ) i n T a b l e V when used as proposed, then t h e
p e s t i c i d e i s c a t e g o r i z e d as h a v i n g p o t e n t i a l t o r e a c h ground w a t e r .
T a b l e V. CRITERIA FOR POTENTIAL TO REACH GROUND WATER
Water S o l u b i l i t y - G r e a t e r than about 30 ppm
- L e s s than 5
Hydrolysis h a l f - l i f e - Greater than about 25 weeks
Soil half-life (field) - Greater than about 2-3 weeks

D e s i g n a t i n g p e s t i c i d e s as p o t e n t i a l l e a c h e r s based on o n l y one
c r i t e r i a may appear t o be an o v e r l y s t r i c t a p p r o a c h . F o r example,
would not one e x p e c t a p e s t i c i d e w i t h a water s o l u b i l i t y of 50 ppm
but a s o i l h a l f - l i f e of l e s s t h a n 2 weeks t o degrade i n s o i l b e f o r e
l e a c h i n g deep enough t o r e a c h ground w a t e r ? However, t h e Agency's
c o n c e r n about such c h e m i c a l s i s t h a t t h e y may be s u b j e c t e d t o a
heavy r a i n f a l l o r i r r i g a t i o n so soon a f t e r a p p l i c a t i o n t h a t they
w i l l l e a c h t h r o u g h the t o p p o r t i o n (2-3 f e e t ) of the s o i l w i t h t h e
h i g h e s t p o p u l a t i o n s of m i c r o b i a l p e s t i c i d e d e g r a d e r s , reach the
deeper s o i l l a y e r s where t h e y w i l l p e r s i s t and be a v a i l a b l e f o r
f u r t h e r l e a c h i n g and e v e n t u a l r e a c h i n g of the ground w a t e r .
I f the r e g i s t r a n t chooses t o pursue r e g i s t r a t i o n of a p e s t i -
c i d e d e s i g n a t e d as h a v i n g p o t e n t i a l t o r e a c h ground w a t e r , t h e n
a d d i t i o n a l i n f o r m a t i o n and sometimes e x t e n s i v e f i e l d s t u d i e s under
r e p r e s e n t a t i v e but worst case use c o n d i t i o n s w i l l have t o be p e r -
formed t o determine whether o r not l e a c h i n g w i l l a c t u a l l y o c c u r .
The r e s u l t s of t h e s e f i e l d s t u d i e s w i l l have t o d e s c r i b e t h e l e v e l
of p e s t i c i d e r e s i d u e s i n the ground water, i f any, t h a t can be
e x p e c t e d when used as p r o p o s e d . A l t e r n a t i v e l y , t h e r e g i s t r a n t may
propose l a b e l r e s t r i c t i o n s o r l a b e l changes ( s u c h as a change i n
a p p l i c a t i o n r a t e s and/or t i m i n g , g e o g r a p h i c a l r e s t r i c t i o n s a g a i n s t
use i n sandy s o i l s o r a r e a s w i t h s h a l l o w o r u n c o n f i n e d a q u i f e r s )
that w i l l remove the p o t e n t i a l f o r ground water contamination.
T h i s i n f o r m a t i o n w i l l be s u b j e c t e d t o a r i s k - b e n e f i t a n a l y s i s t o
d e t e r m i n e i f r e g i s t r a t i o n s h o u l d be g r a n t e d .
Below a r e some d e s c r i p t i o n s of p e s t i c i d e s w i t h p o t e n t i a l f o r
r e a c h i n g ground water o r t h a t have a l r e a d y been found i n ground
water and how t h e i r l e a c h i n g c h a r a c t e r i s t i c s have ( i n p a r t ) a f f e c t -
ed t h e i r r e g i s t r a t i o n s t a t u s . The f i r s t two examples i n v o l v e s u s -
p e n s i o n and/or c a n c e l l a t i o n and the l a s t f i v e d e s c r i b e r e q u e s t s
t h a t a r e i n " o b j e c t s t a t u s " . O b j e c t s t a t u s means t h a t the p a r t i c u -
l a r r e q u e s t has not been g r a n t e d b u t t h e r e g i s t r a n t may resubmit
the r e q u e s t w i t h new i n f o r m a t i o n and t h e Agency w i l l r e c o n s i d e r i t s
position. The r e g i s t r a n t s i n v o l v e d i n the l a s t 5 examples have a l l
e l e c t e d t o do a d d i t i o n a l work w h i c h may a l l e v i a t e the Agency's
ground w a t e r c o n c e r n s .
(1) DBCP ( l , 2 - d i b r o m o - 3 - c h l o r o p r o p a n e ) , a soil nematicide/

f u m i g a n t , was found i n ground water and found t o pose s i g n i f i c a n t
health risks. In 1979, a l l uses o f DBCP i n t h e c o n t i n e n t a l U.S.
were suspended ( 8 ) and t h e r e m a i n i n g u s e i n p i n e a p p l e f i e l d s i n
H a w a i i was c a n c e l l e d i n 1985 ( 9 ) .
( 2 ) EDB (1,2-dibromoethane), a s o i l n e m a t i c i d e / f u m i g a n t , was
found i n ground water and found t o pose s i g n i f i c a n t h e a l t h r i s k s .
I t s uses were suspended i n 1983 ( 1 0 ) .
( 3 ) C a r b o f u r a n i s a s o i l n e m a t i c i d e / i n s e c t i c i d e and has been
found i n t h e ground water o f NY, WI and MD due t o a g r i c u l t u r a l u s e
(60. The r e g i s t r a n t s u b m i t t e d r e q u e s t s a t d i f f e r e n t times f o r a
change i n a p p l i c a t i o n t i m i n g on c o t t o n t o "at p l a n t i n g " , f o r u s e
on n o n - b e a r i n g c i t r u s and r a s p b e r r i e s (new c r o p s ) , and f o r u s e on
sorghum a t i n c r e a s e d r a t e s . These amendments have n o t been g r a n t e d
b a s e d on ground w a t e r c o n c e r n s ( 1 1 ) .
( 4 ) C a r b o s u l f a n i s a new s o i l n e m a t i c i d e / i n s e c t i c i d e . The
r e g i s t r a n t has r e q u e s t e d u s e on n o n - b e a r i n g f r u i t , nut and c i t r u s

and on a l f a l f a , sorghum and c o r n . Based on ground w a t e r c o n c e r n s ,
none o f t h e s e new uses have been g r a n t e d and t h e f i r s t p r o d u c t
c o n t a i n i n g c a r b o s u l f a n as an a c t i v e i n g r e d i e n t h a s y e t t o r e c e i v e
a r e g i s t r a t i o n (11).
(5) Oxamyl i s a s o i l n e m a t i c i d e / i n s e c t i c i d e and h a s been
found i n t h e ground water o f NY and RI due t o a g r i c u l t u r a l u s e ( 6 ) .
The r e g i s t r a n t has proposed amending i t s p r o d u c t l a b e l t o i n c l u d e
uses on l e t t u c e , e n d i v e , e s c a r o l e , cabbage, mint and b e a n s . Based
on ground w a t e r c o n c e r n s , t h e s e amendments have n o t been g r a n t e d
up.
(6) A l d i c a r b i s a s o i l n e m a t i c i d e / i n s e c t i c i d e and has been
found i n the ground water o f 15 s t a t e s due t o a g r i c u l t u r a l u s e (p.
The r e g i s t r a n t has proposed amending i t s p r o d u c t l a b e l s t o i n c l u d e
uses on c o r n , tomatoes and t o b a c c o . Based on ground water c o n c e r n s ,
t h e s e amendments have n o t been g r a n t e d ( 11). Use i n New J e r s e y on
e g g p l a n t s e e d l i n g s i n greenhouses was g r a n t e d u n d e r S e c t i o n 18 o f
the F e d e r a l I n s e c t i c i d e , F u n g i c i d e , and R o d e n t i c i d e A c t (FIFRA)
(12) s i n c e d a t a showed t h e a l d i c a r b r e s i d u e s t o r a p i d l y degrade i n
t h e s o i l d u r i n g t h e two week p o s t - a p p l i c a t i o n p e r i o d i n t h e g r e e n -
house b e f o r e b e i n g t r a n s p l a n t e d t o t h e f i e l d , and t h e S e c t i o n 18
was t o l a s t o n l y 1 y e a r ( 1 1 ) .
(7) A l d o x y c a r b i s a s o i l n e m a t i c i d e / i n s e c t i c i d e . Registration
of a p r o d u c t f o r u s e on t o b a c c o , peanuts, sweet p o t a t o e s and c o l e
c r o p s was pursued by t h e r e g i s t r a n t b u t r e g i s t r a t i o n was n o t g r a n t -
ed based on ground water c o n c e r n s . The r e g i s t r a n t was g r a n t e d a
r e g i s t r a t i o n f o r a p l a n t f e r t i l i z e r spike product c o n t a i n i n g the
p e s t i c i d e based on t h e Agency's c o n c l u s i o n t h a t such a low pound
p e r a c r e use would n o t r e s u l t i n s i g n i f i c a n t residues reaching
ground water ( 1 1 ) .
T h i s ends a b r i e f d e s c r i p t i o n o f how t h e Agency c o n s i d e r s
p o t e n t i a l f o r p e s t i c i d e s t o r e a c h ground water i n t h e p e s t i c i d e
r e g i s t r a t i o n p r o c e s s . T h i s paper w i l l c l o s e w i t h a d e s c r i p t i o n of
the Ground Water Data C a l l I n i n i t i a t e d by t h e Agency i n 1984 f o r
t h e purpose o f d e t e r m i n i n g w h i c h o f t h e 600 most w i d e l y used a c t i v e
i n g r e d i e n t s have p o t e n t i a l t o r e a c h ground water when a p p l i e d under
use c o n d i t i o n s . A Data C a l l In i s t h e means by which EPA a c q u i r e s
a d d i t i o n a l d a t a r e l e v a n t t o e x i s t i n g r e g i s t r a t i o n s and i s a u t h o r -
i z e d by S e c t i o n 3 ( c ) ( 2 ) ( B ) o f FIFRA (12). C r i t e r i a f o r s e l e c t i n g
t h e c a n d i d a t e s from the 600 most h i g h l y used a c t i v e i n g r e d i e n t s

a r e g i v e n i n T a b l e V. I f one o r more of t h e c r i t e r i a were met,
t h e n t h e p e s t i c i d e was p l a c e d on t h e Ground Water Data C a l l In
list. The r e s u l t a n t l i s t c o n t a i n e d 141 c h e m i c a l s ( s e e A p p e n d i x ) .
However, 51 of those c h e m i c a l s were on a d i f f e r e n t d a t a c a l l - i n
l i s t c a l l e d t h e R e g i s t r a t i o n S t a n d a r d s development l i s t and t h e
d a t a needed t o a s s e s s ground water c o n t a m i n a t i o n p o t e n t i a l had
a l r e a d y been o r I s t o be s u b m i t t e d s h o r t l y w i t h t h a t d a t a c a l l i n .
T h e r e f o r e , 90 c h e m i c a l s remained f o r which the Agency asked f o r t h e
d a t a i n T a b l e I I p l u s water s o l u b i l i t y , vapor p r e s s u r e and o c t a n o l -
water p a r t i t i o n i n g data. Those p e s t i c i d e s w i t h use p a t t e r n s n o t
r e q u i r i n g a s t u d y ( i e s ) i n support of t h e i r r e g i s t r a t i o n (consult
T a b l e s l a and l b ) w i l l n o t n o r m a l l y need t h a t s t u d y ( i e s ) i n a s s e s -
sing i t s leaching potential. In some c a s e s , t h i s would be t h e
f i r s t time e n v i r o n m e n t a l f a t e d a t a a s s e s s i n g t h e l e a c h i n g p o t e n t i a l
of t h e p e s t i c i d e would be s u b m i t t e d t o EPA s i n c e t h e r e g i s t r a t i o n
of some p e s t i c i d e p r o d u c t s p r e - d a t e t h e e n v i r o n m e n t a l f a t e d a t a
r e q u i r e m e n t s i n s t i t u t e d i n 1970 ( 1 3 ) .
A p e s t i c i d e reviewed under the ground w a t e r d a t a c a l l - i n and
d e s i g n a t e d as a l e a c h e r w i l l be s u b j e c t t o t h e f o l l o w i n g r e s p o n s e s
as p r o v i d e d by FIFRA (J_l) (Table V I ) :
Table VI. REGULATORY OPTIONS FOR PESTICIDES FOUND TO

HAVE POTENTIAL TO REACH GROUND WATER
(1) Suspension
(2) Cancellation
(3) Restricted Use(s) including geographic restrictions
(4) Advisory Labels
(5) Field S t u d i e s and f u r t h e r study
APPENDIX
The 141 P e s t i c i d e s
to be E v a l u a t e d Under t h e Ground Water Data Call-in
GW - Data t o be s u b m i t t e d under t h e Ground Water D a t a C a l l - i n

RS - D a t a t o be s u b m i t t e d under t h e R e g i s t r a t i o n Standards Data
Call-in
Acephate - RS A n i l a z i n e - RS
A c i f l u o r f e n - GW Aspon - RS
A l a c h l o r - RS Asulam - GW
A l d i c a r b - RS A t r a z i n e - RS
Ametryn - GW B e n d i o c a r b - GW
Ami no car b - GW Bentazon - RS
A m i t r o l e - RS B r o m a c i l - RS
Ammonium s u l f araate - RS Broraoxynil - GW
Amobam - GW Bufencarb - GW
(continued)
EVALUATION OF PESTICIDES IN GROUND WATER
APPENDIX ( c o n t i n u e d )
B u t y l a t e - RS Ferbam - GW
C a c o d y l l c a c i d - GW Fluometuron - GW
C a l c i u m a r s e n a t e - GW Formetanate - RS
C a r b o f u r a n - RS F o s t h l e t a n - GW
C a r b o p h e n o t h i o n - RS G u t h i o n - GW
C a r b o x i n - RS Hexazinone - RS
CDAA - GW Imidan - GW
Chloramben - RS Karathane - GW
4 - C h l o r o p y r i d i n e N-oxide - GW K r e n i t e - GW
C h l o r d i m e f o r m - RS Lead a r s e n a t e - GW
C h l o r d i m e f o r m HC1 - RS L i n u r o n - RS
Chlormequat - GW M a l e i c h y d r a z i d e - GW
Chlorpropham - GW Mancozeb - GW
C h l o r p y r i f o s - RS Maneb - GW
C h l o r o p i c r i n - RS MCPA - RS
C h l o r o t h a l o n i l - RS Mecoprop - GW
Crotoxyphos - GW M e f l u i d i d e - GW
C r y o l i t e - RS M e s u r o l - GW
C y a n a z i n e - RS Me tarn-sodium - GW
C y c l o a t e - GW M e t h i d a t h i o n - RS
Dalapon - GW Methomy1 - RS
D a c t h a l - GW M e t h y l bromide - GW
Daminozide - RS M e t h y l i s o t h i o c y a n a t e - GW
Dazomet - GW M e t o l a c h l o r - RS
DC A - RS M e t r i b u z i n - GW
Deroet o n - GW Mob am - GW
Desmedipham - GW M o l i n a t e - GW
D i a l i f o r - RS Monocrotophos - GW
D i a l l a t e - RS Monuron - RS
D i a z i n o n - GW MSMA - GW
Dicamba - RS Nabam - GW
D i c h l o b e n i l - GW Napropamide - GW
DIchlone - RS Naptalam - GW
1 , 3 - D i c h l o r o p r o p e n e - GW Ne bur on - GW
D i c l o f o p methyl - GW O f t a n o l - GW
D i c r o t o p h o s - RS Oxamyl - GW
D i f e n z o q u a t - GW Oxydemeton-methyl - GW
D i f l u b e n z u r o n - GW Paraquat - GW
Dimethoate - RS P e b u l a t e - GW
Dinoseb - GW Fhenraedipham - GW
Diphenamid - GW P h o r a t e - RS
D i p r o p e t r y n - GW Phosalone - RS
D i q u a t - GW P h o s d r i n - GW
D i s u l f o t o n - RS Phosphamidon - GW
2 , 2 - D i t h i o b i s b e n z t h i a z o l e - GW P i c l o r a m - RS
D i u r o n - RS Polyram - GW
DSMA - GW Pro me t o n - GW
Dyfonate - RS Prometryn - GW
E n d o t h a l l - GW Proamide - GW
EPTC - RS P r o p a c h l o r - GW
E t h i o f e n c a r b - GW P r o p a z i n e - GW
Ethoprop - RS Prop h am - GW
F e n a m i n o s u l f - RS P r o p a n i l - GW
Fenamiphos - GW S i d u r o n - GW
F e n s u l f o t h i o n - RS Simazine - RS
T e b u t h i u r o n - GW T r i a d i m e f o n - GW
T e r b a c i l - RS Trichlorobenzoic acid - GW
T e r b u t o l - GW T r i c h l o r f o n - RS
T e r b u t r y n - GW V e r n o l a t e - GW
T h i a b e n d a z o l e - GW Zineb - GW
T h i d i a z u r o n - GW Zirara - GW
T r i a l l a t e - GW
Literature Cited
1. "Pesticide Industry Sales and Usage - 1984 Market Estimates,"
U.S. Environmental Protection Agency, 1985.
2. von Rumker, R.; Lawless, E.W.; Meiners, G. In "A Study of
the Efficiency of the Use of Pesticides in Agriculture," von
Rumker, R.; Kelso, G.L. U.S. Environmental Protection Agency,
Contract # 68-01-2608, 1975, p. 10.

3. Federal Food, Drug and Cosmetic Act, approved June 25, 1936,
52 Stat. 1040 et seq., as amended.
4. Parfit, M. "Ground Water: Out of Sight, Out of Mind",
Smithsonian 1983, 13, p. 51-61.
5. Cohen, S.Z.; Creeger, S.M.; Carsel, R.F.; Enfield, C.G.
"Potential Pesticide Contamination of Groundwater Resulting
from Agricultural Uses"; In Treatment and Diposal of Pesticide
Wastes, Eds. Krueger, R.F.; Seiber, J.N., ACS Symposium Series
259, Washington, DC, 1984. p. 297-325.
6. Cohen, S.Z.; Eiden, C.; Lorber, M.N. "Monitoring Ground Water
for Pesticides in the U.S.A." (in press, this volume).
7. "Pesticide Assessment Guidelines Subdivision N, Chemistry:
Environmental Fate," EPA 540/9-82-021, U.S. Environmental Pro-
tection Agency, 1982.
8. Federal Register, October 29, 1979, p. 65161.
9. Federal Register, January 1985, p. 1122-1130.
10. Federal Register, October 11, 1983, p. 46228.
11. Registration files maintained by the U.S. Environmental Pro-
tection Agency.
12. Federal Insecticide, Fungicide and Rodenticide Act, as amend-
ed, 1978; U.S. Environmental Protection Agency.
13. PR Notice 70-15, Notice to Manufacturers, Formulators, Distri-
butors, and Registrants of Economic Poisons. United States
Department of Agriculture, June 23, 1970.

Author Index
A l l e r , L i n d a , 141 K o s k i n e n , W. C , 2
Anderson, Mary P., 396 K r a s k a , Susan, 311
B e n n e t t , Truman, 141 K r o l l , David G., 219
B e r t e a u , P e t e r ., 423 K u r t z , David A., 256
Cheng, . ., 2 L a c c e t t i , G e o f f r e y , 530
C h e s t e r s , Gordon, 488 L e h r , Jay H., 141
C l e n d e n i n g , L. D e n i s e , 384 Lemley, A. T., 61
Cohen, David ., 499 L i u , C. C. ., 366
Cohen, S. Z., 170 L o p e z - A v i l a , V i o r i c a , 311
Cooper, Sandra C , 78 L o r b e r , M. N., 170,342
Coy, David W., 39 Melancon, Sue, 311
Creeger, Samuel ., 548 Moon, Ralph ., 159
Publication Date: July 17, 1986 | doi: 10.1021/bk-1986-0315.ix001
De Rose, N i c h o l a s , 118 Moye, . ., 294

Dourson, M. L., 445 M u l l i n s , M i c h a e l E., 39
Duncan, D. W., 282 Newby, Loy C , 478
Dzantor, E. Kudjo, 219 N k e d i - K i z z a , P.. 100
Edvardsson, K. S. V., 100 O f f u t t , C a r o l y n ., 342
E h a r t , O r l o R., 488 Oshima, R. J . , 282
E i d e n , C., 170 Ou, L. T., 100
E l a b d , Hesham, 384 P a r i z e k , R i c h a r d R., 256
F a t h u l l a , Riyadh ., 219 P a t t e r s o n , J . , 445
F l a n a g a n , M i c h a e l , 311 P e t t y , Rebecca, 141
G i s h , Timothy J . , 14 P i s e r c h i a , P h i l l i p V., 39
Green, R. E., 366 P o l l a r d , J i m , 311
Grey, Anthony J . , 530 Rao, P. S. C , 100
H a r k i n , John ., 219 Resketo, Margaret, 384
H e l l i n g , C h a r l e s S., 14 Rhodes, Howard L., 541
Henry, C a r o l D., 159
Rock, C h a r l e s ., 478
Hern, Stephen C., 311
Sherman, K a r i J . , 488
H i r a t a , P a t , 311
S m i t h , J e r r y ., 414
Hornsby, A. G., 100
Spath, David P., 423
Hudson, C h a r l e s , 530
S t a r a , J . F., 445
J a s a n o f f , S h e i l a , 462
S t e v e n s , J . T., 436
J e s s u p , R. E., 100
Sumner, D. D., 436
Jex, G. W., 294
Tamrakar, ., 366
Jones, Frank A., 219
T a y l o r , John H., J r . , 311
Jones, R u s s e l l L., 197
Tramontano, Ronald, 530
J u r y , W i l l i a m A., 384
Kew, Gregory A., 39 Wagenet, R. J . , 61,330
Kim, Nancy ., 530 Weintraub, R. ., 294
Zhong, W. Z., 61
Subject Index
A c r y l o n i t r i l e polymer, FDA
ban, 468-469
A c c e p t a b l e D a i l y I n t a k e (ADI) Adsorption
a l d i c a r b , 455 disadvantages of s i m p l i s t i c
a t r a z i n e , 534-535 models, 6-7
b a s i s , 438 k i n e t i c s r o l e , 24
oxamyl, 539 l e a c h i n g r e l a t i o n s h i p , 26
u n c e r t a i n t y f a c t o r used f o r l i n e a r isotherm explained i n
e s t i m a t i o n , 458-459 s c r e e n i n g model, 20-21
water, 454 mechanisms i n v o l v e d , 6-7
W i s c o n s i n l e g i s l a t i o n , 488 parameters, c r o s s - c o r r e l a t i o n s , 389t
558
Author Index
A l l e r , L i n d a , 141 K o s k i n e n , W. C , 2
Anderson, Mary P., 396 K r a s k a , Susan, 311
B e n n e t t , Truman, 141 K r o l l , David G., 219
B e r t e a u , P e t e r ., 423 K u r t z , David A., 256
Cheng, . ., 2 L a c c e t t i , G e o f f r e y , 530
C h e s t e r s , Gordon, 488 L e h r , Jay H., 141
C l e n d e n i n g , L. D e n i s e , 384 Lemley, A. T., 61
Cohen, David ., 499 L i u , C. C. ., 366
Cohen, S. Z., 170 L o p e z - A v i l a , V i o r i c a , 311
Cooper, Sandra C , 78 L o r b e r , M. N., 170,342
Coy, David W., 39 Melancon, Sue, 311
Creeger, Samuel ., 548 Moon, Ralph ., 159
De Rose, N i c h o l a s , 118 Moye, . ., 294

Dourson, M. L., 445 M u l l i n s , M i c h a e l E., 39
Duncan, D. W., 282 Newby, Loy C , 478
Dzantor, E. Kudjo, 219 N k e d i - K i z z a , P.. 100
Edvardsson, K. S. V., 100 O f f u t t , C a r o l y n ., 342
E h a r t , O r l o R., 488 Oshima, R. J . , 282
E i d e n , C., 170 Ou, L. T., 100
E l a b d , Hesham, 384 P a r i z e k , R i c h a r d R., 256
F a t h u l l a , Riyadh ., 219 P a t t e r s o n , J . , 445
F l a n a g a n , M i c h a e l , 311 P e t t y , Rebecca, 141
G i s h , Timothy J . , 14 P i s e r c h i a , P h i l l i p V., 39
Green, R. E., 366 P o l l a r d , J i m , 311
Grey, Anthony J . , 530 Rao, P. S. C , 100
H a r k i n , John ., 219 Resketo, Margaret, 384
H e l l i n g , C h a r l e s S., 14 Rhodes, Howard L., 541
Henry, C a r o l D., 159
Rock, C h a r l e s ., 478
Hern, Stephen C., 311
Sherman, K a r i J . , 488
H i r a t a , P a t , 311
S m i t h , J e r r y ., 414
Hornsby, A. G., 100
Spath, David P., 423
Hudson, C h a r l e s , 530
S t a r a , J . F., 445
J a s a n o f f , S h e i l a , 462
S t e v e n s , J . T., 436
J e s s u p , R. E., 100
Sumner, D. D., 436
Jex, G. W., 294
Tamrakar, ., 366
Jones, Frank A., 219
T a y l o r , John H., J r . , 311
Jones, R u s s e l l L., 197
Tramontano, Ronald, 530
J u r y , W i l l i a m A., 384
Kew, Gregory A., 39 Wagenet, R. J . , 61,330
Kim, Nancy ., 530 Weintraub, R. ., 294
Zhong, W. Z., 61
Subject Index
A c r y l o n i t r i l e polymer, FDA
ban, 468-469
A c c e p t a b l e D a i l y I n t a k e (ADI) Adsorption
a l d i c a r b , 455 disadvantages of s i m p l i s t i c
a t r a z i n e , 534-535 models, 6-7
b a s i s , 438 k i n e t i c s r o l e , 24
oxamyl, 539 l e a c h i n g r e l a t i o n s h i p , 26
u n c e r t a i n t y f a c t o r used f o r l i n e a r isotherm explained i n
e s t i m a t i o n , 458-459 s c r e e n i n g model, 20-21
water, 454 mechanisms i n v o l v e d , 6-7
W i s c o n s i n l e g i s l a t i o n , 488 parameters, c r o s s - c o r r e l a t i o n s , 389t
558
INDEX 559
AdsorptionContinued AldicarbContinued
pesticides leaching
c o r r e l a t i o n t o s o i l o r g a n i c matter assessment r e s u l t s , 362t
c o n t e n t s , 6-7 assessment u s i n g PRZM, 358-359
t e c h n i q u e s used t o e s t i m a t e , 5 f a c t o r , 209,211-212,2l4f
sandy loam study d e s c r i b e d , 314 W i s c o n s i n ground water, 226
s p a t i a l v a r i a b i l i t y , 387-392 measured and c a l c u l a t e d e f f l u e n t
Adsorption c o e f f i c i e n t c o n c e n t r a t i o n s , 69-71
e q u a t i o n used, 21 m i n e r a l i z a t i o n i n ground water
measurement f o r p e s t i c i d e s , 20-21 samples, 246t
PRZM p r o d u c t i o n f o r a l d i c a r b , 357 model
Agent Orange, p o l i c y c o n s i d e r a t i o n s c a l i b r a t i o n f o r W i s c o n s i n ground
overriding s c i e n t i f i c water s t u d y , 252
f i n d i n g s , 465 e f f o r t s i n W i s c o n s i n ground water
Alachlor s t u d y , 249
ground water presence, 190 moratorium on use i n W i s c o n s i n , 494
ground water presence i n Iowa, 480 movement, 207-209
NOEL, 536 o x i d a t i o n d e s c r i b e d by f i r s t - o r d e r
o n c o g e n i c i t y , 536-537
k i n e t i c s , 62
t o x i c i t y d a t a , 535-537 p r e d i c t e d v s . observed
Aldicarb c o n c e n t r a t i o n s , 406-407f,409f
ADI, 455 r a i n f a l l e f f e c t on l e a c h i n g , 210
amount leached i n t o W i s c o n s i n ground r e g i s t r a t i o n h i s t o r y , 554
water, 241 r e l a t i o n t o a l k a l i n i t y , 242
application rates relation to microbial
frequencies i n Wisconsin a c t i v i t y , 246-249
study, 222t r e s e a r c h programs, 201t-206t
PRZM s t u d y , 359 residue a n a l y s i s i n Wisconsin
c a l i b r a t i o n parameters f o r PRZM s t u d y , 225-226
study, 347t residue concentrations
C a l i f o r n i a , ground water i n l y s i m e t e r l e a c h a t e , 236t
presence, 426,517-518 i n the s o i l o f W i s c o n s i n p o t a t o
c o n c e n t r a t i o n s i n W i s c o n s i n water f i e l d s , 234-235t
samples, 228-229t i n W i s c o n s i n ground water samples
c o n t a m i n a t i o n i n U.S. ground withdrawn through m u l t i l e v e l
water, 32-33 samplers, 230-233t
c u r r e n t s t a t u s i n ground water, 188 residue d i s t r i b u t i o n
data f o r degradation study, 72t i n W i s c o n s i n ground water
degradation study, 227-228,238
h a l f - l i f e v a r i a t i o n , 110t w i t h depth, 241
pathway, 199f residues i n lysimeter
r a t e s , 76t,208t l e a c h a t e , 238-240
t r a n s p o r t f o r r e s i d u e s , 197 r e t a r d a t i o n f a c t o r , 405
e f f e c t o f W i s c o n s i n ground water s a t u r a t e d zone movement, 209
law, 495 simultaneous t r a n s p o r t and
exposure assessment PRZM t r a n s f o r m a t i o n e q u a t i o n , 64
s i m u l a t i o n s , 360t s o i l p r o p e r t y i n f l u e n c e , 32
f a t e i n W i s c o n s i n ground water, 219 sorption coefficient
f e d e r a l l a b e l amendment, 493 v a r i a b i l i t y , 103
Florida s p a t i a l v a r i a t i o n s in. o r g a n i c carbon
ground water s t u d y , 543-544 c o n t e n t , 109f
response t o ground water s t r u c t u r e , 430
presence, 543 t o x i c o l o g y , 430-431
half-life transport
decreases w i t h a p p l i c a t i o n c a l i b r a t i o n s c e n a r i o s i n PRZM
d a t e s , 353 study, 352
e f f e c t on PRZM model o u t p u t , 251t results f o r c a l i b r a t i o n scenarios
PRZM s t u d y , 352 i n s t u d y , 353t
h i s t o r y , 220 use, 220,554
h y d r o l y s i s r a t e s , 242 use and presencence i n ground
i r r i g a t i o n i n f l u e n c e on water, 554
l e a c h i n g , 362 w e l l s a f f e c t e d i n W i s c o n s i n , 494
A l d i c a r b s u l f o n e , d e g r a d a t i o n , 200
Aldicarb sulfoxide
d e g r a d a t i o n , 200
measured and c a l c u l a t e d e f f l u e n t B a c t e r i a , enumeration i n a q u i f e r
c o n c e n t r a t i o n s , 69-71 sediments by pour p l a t e counts on
Alkalinity ground w a t e r - y e a s t e x t r a c t
e f f e c t on a l d i c a r b i n W i s c o n s i n agar, 247
ground water, 242 B a c t e r i a l a n a l y s i s , Wisconsin a l d i c a r b
measured and c a l c u l a t e d f o r s t u d y , 226
W i s c o n s i n ground water B a t c h e q u i l i b r i u m method
samples, 245 c o r r e l a t i o n w i t h f l o w - t h r o u g h method
W i s c o n s i n ground water s t u d y , 243f for distribution coefficient
A l t e r e d growth, d e f i n i t i o n i n r i s k d e t e r m i n a t i o n , 392
assessment, 416 d i s t r i b u t i o n c o e f f i c i e n t , 386
A n t o i n e e q u a t i o n , 45-47 measurement o f a d s o r p t i o n
Apparent d i f f u s i o n c o e f f i c i e n t , c o e f f i c i e n t , 20-21
d e t e r m i n a t i o n , 67 Benzene
Aquifer boundaries f o r a s s e s s i n g r i s k , 522
d e f i n i t i o n , 148
d i s t r i b u t i o n o f s i m u l a t e d vapor
i n s t a l l a t i o n o f m o n i t o r - c e l l s , 162 pressure, 49f
parameter e s t i m a t i o n , 398-399 workplace s t a n d a r d s ,
use a f t e r c o n t a m i n a t i o n , 447-448 l a w s u i t , 466-467
A q u i f e r media Beta density functions, 44f
ranges and r a t i n g s , 151t B r o m a c i l , a d s o r p t i o n parameters, 388t
r o l e i n ground water Bromide
c o n t a m i n a t i o n , 148 a d s o r p t i o n parameters, 388t
A r d i l l a s o i l s , d e s c r i p t i o n , 88 a n a l y s i s o f EDB d e g r a d a t i o n p r o d u c t s
A r i z o n a , ground water i n water, 299
c o n t a m i n a t i o n , 33 variations i n concentration i n
Arrhenius plot s o i l , 105f
EDB h y d r o l y s i s , 302f Buckingham-Darcy e q u a t i o n ,
hydrolysis rate constants v s . d e s c r i b e d , 18-19
pH, 302f
Atrazine
ADIs, 534-535 C
amount l e a c h e d i n sandy loam a f t e r
30-day t e s t , 324f
a n a l y t i c a l methodology f o r sandy Cable t o o l r i g , d r i l l i n g
loam s t u d y , 315 m o n i t o r - c e l l s , 164-165
concentration p r o f i l e s , increased California
b u l k d e n s i t y e f f e c t , 22 C e n t r a l V a l l e y ground water
c o n t a m i n a t i o n i n the U n i t e d c o n t a m i n a t i o n , 511
S t a t e s , 30-32 ground water c o n t a m i n a t i o n , 33
d i s t r i b u t i o n i n s o i l a f t e r 30-day p e s t i c i d e c o n t a m i n a t i o n e f f e c t s and
t e s t , 317f-319f e x t e n t , 423-433
ground water p r e s e n c e , 190 p e s t i c i d e s found, 499
ground water presence i n Iowa, 480 use r e p o r t i n g f o r r e s t r i c t e d
leaching, 23f p e s t i c i d e s , 505
l e a c h i n g experiment i n sand Cape Cod, s m a l l - s c a l e r e t r o s p e c t i v e
loam, 313-314 s t u d y , 189
l e a c h i n g i n sandy loam Carbamate i n s e c t i c i d e s , h i s t o r y , 79
s t u d y , 316-327 C a r b o f u r a n , ground water
l e a c h i n g through sandy loam, 326 presence, 190,554
mass b a l a n c e and d e g r a d a t i o n Carbon d i o x i d e , p a r t i a l p r e s s u r e
h a l f - l i f e i n sandy loam, 325t e f f e c t i n ground water, 245
movement, h y d r a u l i c c o n d u c t i v i t y C a r b o n a t e S e e K a r s t system
e f f e c t , 24 C a r b o s u l f a n , r e g i s t r a t i o n h i s t o r y , 554
physicochemical p r o p e r t i e s , 312t C a r c i n o g e n s , r i s k and exposure
s t r u c t u r e , 431 r e l a t i o n s h i p , 451
t o x i c i t y , 534-535 Chemical parameters, v a r i a b i l i t y i n
t o x i c o l o g y , 431-432 W i s c o n s i n a l d i c a r b s t u d y , 249
INDEX 561
Chemical-soil interaction, DegradationContinued

e q u a t i o n , 333 f i r s t - o r d e r rate c o e f f i c i e n t
Chemicals, r e g i s t r a t i o n by EPA, 549 d e f i n e d , 336
Chemigation, d e f i n i t i o n , 524 h a l f - l i v e s , measurement, 108
Chloride pathway o f a l d i c a r b , 198-200
a d s o r p t i o n v a r i a b i l i t y , 390 r a t e c o e f f i c i e n t , DBCP, 373
measured and c a l c u l a t e d e f f l u e n t r a t e measurement, 22
c o n c e n t r a t i o n s , 69-71 See a l s o P e s t i c i d e s
Chlorobenzene, d i s t r i b u t i o n o f See a l s o Ground water
s i m u l a t e d vapor p r e s s u r e , 5 0 f Delaney Clause
Chromatography, used i n k a r s t system a c r y l o n i t r i l e polymer ban, 469
s t u d y , 259 p e s t i c i d e c o n t r o l e x t e n s i o n , 464
Clarendon s o i l s , d e s c r i p t i o n , 88 Depth t o water
C l a y , t y p e s and r e l a t i v e p r o p o r t i o n s ranges and r a t i n g s , 151t
i n EDB s t u d y , 289t r o l e i n ground water
Clean Water Act c o n t a m i n a t i o n , 147
1972, o b j e c t i v e s , 503 D e t e r m i n i s t i c models
1977, o b j e c t i v e s , 483 boundary c o n d i t i o n s , 20
C l i n c h f i e l d sand, d e s c r i p t i o n i n Lee d e f i n i t i o n , 331-332

County, G e o r g i a , 85 d e s c r i p t i o n , 17-20
C o l i f o r m b a c t e r i a , presence i n ground d i s a d v a n t a g e s o f c u r r e n t models, 339
water, 479 Developmental hazards
C o l l u v i u m , N i t t a n y Mountain, 265 e f f e c t s , 417
Column method mathematical models, 419-420
d i s t r i b u t i o n of simulated Developmental s t u d i e s , s t a t i s t i c s , 420
s o l u b i l i t y , 44f Developmental t o x i c i t y , d e f i n i t i o n i n
octanol-water p a r t i t i o n r i s k assessment, 416
c o e f f i c i e n t , 45 Diazinon
Contaminant, d e f i n i t i o n , 481 a n a l y t i c a l methodology f o r sandy
C o n t a m i n a n t - t r a n s p o r t models loam s t u d y , 315
a p p l i c a t i o n to a l d i c a r b i n Wisconsin d i s t r i b u t i o n i n s o i l a f t e r 30-day
ground water, 400-410 t e s t , 317f,3l8f
c a l c u l a t i o n d i f f i c u l t y , 404 p h y s i c o c h e r a i c a l p r o p e r t i e s , 312t
c a l i b r a t i o n procedure i n W i s c o n s i n 1,2-Dibromo-3-chloropropane (DBCP)
ground water s t u d y , 404 average l a t e r a l c o n c e n t r a t i o n s i n
c a l i b r a t i o n questions i n Wisconsin Hawaiian s o i l s
ground water s t u d y , 408 C a l i f o r n i a ground
description,397,399-400 water, 500f,506-508f,510f,515
factors influencing discrepancies i n C a l i f o r n i a ground water
r e s u l t s , 408 c o n t a m i n a t i o n , 503-509
f l o w modeling f o r a l d i c a r b i n C a l i f o r n i a population
W i s c o n s i n ground water a f f e c t e d , 511t
s t u d y , 402 presence i n C a l i f o r n i a ground
two-dimensional e q u a t i o n , 399-400 water, 499
C o n v e c t i o n , d e f i n e d f o r p e s t i c i d e s , 21 C a l i f o r n i a w e l l s m o n i t o r e d , 505
Convection-dispersion equation, c o n t a m i n a t i o n h i s t o r y , 427
assumptions i n use, 381 c r o s s - s e c t i o n a l diagram o f
C o n v e c t i o n - d i s p e r s i o n model, use, 385 s h a n k - i n j e c t e d , 370f
Courts d r i n k i n g water s t a n d a r d , 509
g e n e r a l i s t s advantages, 472-473 dual a n a l y t i c a l one-dimensional
r e g u l a t o r y d e c i s i o n i s s u e s , 463 model, 377
r e l a t i o n s h i p w i t h s c i e n c e , 464-467 e p i d e m i o l o g i c a l study on
Cyanazine, ground water p r e s e n c e , 191 people, 429
Hawaiian ground water
c o n t a m i n a t i o n , 367
D Hawaiian s o i l c o n c e n t r a t i o n s , 378f
model b a s i s f o r Hawaiian ground
Darcy's law, f l o w model use, 399 w a t e r s , 366-367
Degradation n u m e r i c a l one-dimensional model
first-order kinetics r e s u l t s , 377-37
d e s c r i p t i o n , 336-337 n u m e r i c a l s i m u l a t i o n s , 380f
1,2-Dibromo-3-chloropropane (DBCP) 1,2-Dibromoethane ( E D B ) C o n t i n u e d

Continued p r o d u c t s o f h y d r o l y s i s , 306f
one-dimensional movement purgeable brominated d e g r a d a t i o n
s i m u l a t i o n , 376 p r o d u c t s , 299
p o p u l a t i o n impact i n regression analysis i n s o i l
C a l i f o r n i a , 509 p r o f i l e s t u d y , 290t
presence i n C a l i f o r n i a ground review o f l i t e r a t u r e , 295
water, 499 s o i l and sludge d e g r a d a t i o n
r e s i d u e s i n Hawaiian f i e l d experiments, 298,305-308
s o i l s , 374 s o i l l e a c h i n g a b i l i t y , 291
s i m u l a t e d d u a l model approach s t a t i s t i c a l analysis i n s o i l
concentrations, 3 p r o f i l e s t u d y , 289-290
s o r p t i o n i n Hawaiian ground water s t r u c t u r e , 426
s t u d y , 375t,376t t o x i c o l o g y , 429-430
s o r p t i o n on s o i l and two s o i l p r o f i l e s , 282
s a p r o l i t e , 375-376 1.2- D i c h l o r o p r o p a n e (1,2-D)
s t r u c t u r e , 426 C a l i f o r n i a ground water
s u b s t i t u t e , 430 presence, 430
t o x i c o l o g i c a l e f f e c t s , 426-427 ground water presence, 191

two-dimensional n u m e r i c a l i m p l i c a t i o n s o f C a l i f o r n i a SWRCP
model, 376-377 recommended l e v e l s , 516
use and presence i n ground s t r u c t u r e , 426
water, 554 1.3- Dichloropropene, C a l i f o r n i a
1,2-Dibromoethane (EDB) ground water c o n t a m i n a t i o n , 512
analysis o f degradation products Dieldrin
i n water, 299 e s t i m a t e d human potency, 452
a n i m a l c a r c i n o g e n d a t a , 516-517 r i s k - s p e c i f i c i n t a k e , 453
application i ns o i l profile Dinoseb, ground water p r e s e n c e , 191
s t u d y , 284 D i s c r i m i n a n t a n a l y s i s , EDB s t u d y , 290t
a p p l i c a t i o n s i t e s and D i s p e r s i o n parameters, W i s c o n s i n
contamination s i t e s i n ground water s t u d y , 405
F l o r i d a , 296f D i s p e r s i v i t y , relationship with
C a l i f o r n i a , 516-517 diffusion-dispersion
c h e m i c a l and m i c r o b i a l d e g r a d a t i o n c o e f f i c i e n t , 21
i n F l o r i d a ground water Distribution coefficient
c o n c e n t r a t i o n s i n water batch e q u i l i b r i u m method and
samples, 289t f l o w - t h r o u g h method
contamination extent i n F l o r i d a compared, 392
ground water, 295 e q u a t i o n , 74
d e g r a d a t i o n dependence on pH, 300 Diuron, s p a t i a l v a r i a t i o n s i n organic
d e g r a d a t i o n i n methanogenic carbon c o n t e n t , 109f
s l u d g e , 306f-307f D o l o m i t e , N i t t a n y mountain, 262
d e g r a d a t i o n t o e t h y l e n e , 305 Dose-response models, e x t r a p o l a t i o n t o
F l o r i d a ground water d e t e c t i o n and low doses o f TCE, 5 2 1 f
response, 544-5456 DRASTIC
F l o r i d a ground water p r e s e n c e , 546 d e f i n i t i o n , 173
gas chromatographic a n a l y s i s o f d e s c r i p t i o n o f f a c t o r s , 147-150
F l o r i d a ground water, 297 e v a l u a t i n g p o l l u t i o n p o t e n t i a l by
gaseous p r o d u c t s from s o i l pesticides o f hydrogeologic
d e g r a d a t i o n , 298 s e t t i n g s , 141-156
ground water p r e s e n c e , 189,191,283 factors
h i s t o r y and use, 282,294 a s s i g n e d w e i g h t s , 150t
hydrolysis e v a l u a t e d o r weighted, 150
degradation product ranges, 150-153
s t u d i e s , 303-305 r a t i n g s o f ranges, 153-156
i n b u f f e r e d s o l u t i o n s , 301t index computation, 154t
i n F l o r i d a ground water, 296f index e q u a t i o n , 153
r a t e c o n s t a n t s v s . pH, 302f p a r t s l i s t e d and d e s c r i b e d , 150-156
mechanism o f h y d r o l y s i s , 306f system d e s c r i p t i o n , 144
o r g a n i c matter used t o p r e d i c t D r i l l i n g , hollow-stem auger, 181
r e s i d u e s , 289-290 D r i l l i n g logs, information
pH dependence o f d e g r a d a t i o n , 299 contained, l67t
INDEX 563
D r i n k i n g water, o r g a n i c c h e m i c a l s F
c o n s i d e r e d f o r t h e NRPDWR, 449t
Dual a n a l y t i c a l model, s i m u l a t i o n f o r
Hawaiian ground water s t u d y , 371 Fairness
Dyfonate, ground water p r e s e n c e , 191 t o x i c t o r t l a w s u i t s , 468
UFFI c a s e , 468
F e d e r a l I n s e c t i c i d e , F u n g i c i d e , and
R o d e n t i c i d e A c t (FIFRA)
ground water a p p l i c a t i o n , 483
o b j e c t i v e , 488
Fetotoxicity, definition i n risk
Effective diffusion coefficient, assessment, 416
d e f i n i t i o n , 369 F i e l d l y s i m e t e r s , use i n W i s c o n s i n
Effective retardation factor, a l d i c a r b s t u d y , 224
e q u a t i o n , 386 F i e l d s i t e s , used i n parameter
Electrical resistivity v a r i a b i l i t y experiment, 101-102
d e s c r i b e d , 120-122 F i l t e r f a n t a s y , d e s c r i p t i o n , 519
f i e l d a p p l i c a t i o n uses a l t e r e d , 122 Florida
use i n ground water s t u d i e s , 122 EDB d e g r a d a t i o n i n ground

E l e c t r i c a l r e s i s t i v i t y survey water, 294-308
c r o s s - s e c t i o n a l view, 123f present regulations f o r p e s t i c i d e
p l o t s f o r l a t e r a l p r o f i l e and c o n t a m i n a t i o n , 547-548
v e r t i c a l sounding, 123f Water Q u a l i t y Assurance A c t , 544
Electromagnetic conductivity z e r o d e g r a d a t i o n p h i l o s o p h y , 488
advantage over e l e c t r i c a l Flow models
r e s i s t i v i t y , 124 c a l i b r a t i o n p r o c e s s , 398
d e s c r i p t i o n , 122-124 output c h a r a c t e r i s t i c s , 399
Electromagnetic c o n d u c t i v i t y surveys recharge i n W i s c o n s i n ground water
contour map, 134f-135f s t u d y , 402-404
cross-sectional plot of conductivity Formaldehyde
v a l u e s , 125f a n a l y s i s o f EDB d e g r a d a t i o n p r o d u c t s
c r o s s - s e c t i o n a l view o f t r a n s m i t t e d i n water, 299
e l e c t r o m a g n e t i c f i e l d , 125f EDB c o n v e r s i o n , 303-305
ground water a p p l i c a t i o n , 133 EPA r e g u l a t i o n s , 470
E l e c t r o m a g n e t i c s u r v e y s , u s e s , 124 F r a g i p a n , d e s c r i p t i o n , 86
Embryotoxicity, d e f i n i t i o n i n r i s k
assessment, 416
E n d r i n , summary, 491 G
E n v i r o n m e n t a l P r o t e c t i o n Agency
determining p o t e n t i a l f o r p e s t i c i d e s
to reach ground water, 549-552 Gas chromatography, used f o r a l d i c a r b
formaldehyde r e g u l a t i o n , 470 r e s i d u e a n a l y s i s , 225
E s t i m a t e d human potency, c a r c i n o g e n s , Gas s a t u r a t i o n method, vapor p r e s s u r e
e q u a t i o n s , 451 d e t e r m i n a t i o n , 47
Ethylene Generator column method, water
detection during incubation o f s o l u b i l i t y d e t e r m i n a t i o n , 42
EDB, 307f G e o l o g i c maps
EDB d e g r a d a t i o n , 305 proposed f i e l d - a p p l i c a t i o n
E t h y l e n e - b i s - d i t h i o c a r b a m a t e s (EBDCS) s i t e , 137f,139f
s t r u c t u r e s , 432 s i t e showing k a r s t f e a t u r e s , 139f
t o x i c o l o g i c a l c o n c e r n , 433 Geology
Ethylene g l y c o l ground water c o n t a m i n a t i o n
a n a l y s i s o f EDB d e g r a d a t i o n p r o d u c t s i d e n t i f i c a t i o n , 160-161
i n water, 299 N i t t a n y Mountain, 260
EDB c o n v e r s i o n , 303 Geophysical surveys
t o x i c o l o g i c a l c o n c e r n , 433 advantages i n ground water
Exposure assessment, d e f i n i t i o n , 343 a p p l i c a t i o n , 128-130
E x t r a c t i o n , procedures used i n k a r s t selected i l l u s t r a t i v e
system s t u d y , 259 models, 130-138
Extrinsic variability Geophysics
d e s i g n used t o e v a l u a t e , 104f a p p l i c a t i o n o f t e c h n i q u e s t o ground
s o i l properties i n s p a t i a l water contaminant
v a r i a b i l i t y s t u d y , 102-103 i n v e s t i g a t i o n s , 138
GeophysicsContinued
h i s t o r y and development, 118-119 Ground w a t e r C o n t i n u e d
investigation at a potential F l o r i d a government concern over
p e s t i c i d e c o n t a m i n a t i o n , 546
f i e l d - a p p l i c a t i o n s i t e , 136-138
l e a k d e t e c t i o n systems, 138 flow
use i n ground water c o n t a m i n a t i o n importance, 179
s t u d i e s , 119 two-dimensional e q u a t i o n , 398
Ground p e n e t r a t i n g r a d a r geology use, 160
c r o s s - s e c t i o n a l view o f t r a n s m i t t e d history of classification
e l e c t r o m a g n e t i c s i g n a l , 127f systems, 142
d e s c r i p t i o n , 124-126 "hot s p o t s " program i n
f i e l d s u r v e y s , 126 C a l i f o r n i a , 525-526
l i m i t a t i o n s o f p r o f i l e s , 126 important a s p e c t s o f p e s t i c i d e
p r o f i l e r e c o r d , 127f presence, 443
Ground water induced f l o w i n k a r s t system
acceptable l i m i t s f o r s t u d y , 278-279
p e s t i c i d e s , 438 large-scale retrospective
a g r i c u l t u r a l c h e m i c a l problem, 483 s t u d i e s , 173-177
a n a l y t i c a l methodology, 481 mathematical models
applications o f geophysical c h a r a c t e r i s t i c s , 397

methods, 128-130 W i s c o n s i n law, 497
b a c t e r i a , enumeration by pour p l a t e memorandum o f u n d e r s t a n d i n g i n
counts on ground water-yeast W i s c o n s i n law, 496
e x t r a c t agar, 247t models
California basis f o r pesticide
assessment o f t r a n s p o r t , 9-12
c o n t a m i n a t i o n , 499-528 c l a s s i f i c a t i o n , 397
work p l a n s t r a t e g y , 525 v a l i d a t i o n d i f f i c u l t i e s , 396
c h a r a c t e r i z a t i o n o f contamination See a l s o Models
e x t e n t , 173 m o n i t o r i n g , 170-328
c h e m i c a l parameter measurement, 183 movement i n N i t t a n y Mountain, 262
cleanup problems o f contaminated need f o r s c i e n t i f i c e v a l u a t i o n , 492
s i t e s , 447-448 o v e r a l l r u r a l q u a l i t y , 479
compounds i d e n t i f i e d , 480 pesticide
contamination a n a l y s i s ease, 437
a e r i a l photograph use, 160 contamination
case s t u d i e s i n New York, 530-539 C a l i f o r n i a , 423-433,504f
f i e l d reconnaissance p e r c e p t i o n , 490
t e c h n i q u e s , 161 c o n t a m i n a t i o n s o u r c e s , 159
from s u r f a c e water i n k a r s t leaching potential i n
system, 268 r e g i s t r a t i o n , 548-557
h e a l t h and s a f e t y monitoring i n the United
requirements, 161 S t a t e s , 170-193
h y d r o g e o l o g i c c o n s i d e r a t i o n s , 161 o c c u r r e n c e , 187-192
p o i n t source o r i g i n s , 160 r e g u l a t i o n i n F l o r i d a , 541-547
problem i d e n t i f i c a t i o n , 160-161 pollution
s o l u t i o n s , 524-525 applications o f surface
U n i t e d S t a t e s , 30-33 g e o p h y s i c a l methods, 118-139
degradation DRASTIC index r e l a t i o n s h i p , 153
k i n e t i c s o f EDB, 297,300 positive results of pesticide
p e s t i c i d e s a f t e r sampling, 184 monitoring i n the United
dispersal i n a karst aquifer S t a t e s , 172t
system, 269-272 proposed survey, 491-492
enforcement o f W i s c o n s i n p u b l i c p e r c e p t i o n s toward p o l i c y and
law, 495-497 r e g u l a t i o n , 489-492
e x i s t i n g systems t h a t e v a l u a t e recommended c o l l e c t i o n
p o l l u t i o n p o t e n t i a l , 142-144 procedure, 182
extent o f contamination regions
problem, 188,526-527 s t u d i e d by DRASTIC system, 144-145
factors contributing to pesticide U n i t e d S t a t e s , 146
a t t e n t i o n , 437 r e g u l a t i o n s , 488-497
f i e l d v a l i d a t i o n models, 396-410 renewable r e s o u r c e b a s i s , 3
INDEX 565
Ground w a t e r C o n t i n u e d Hydraulic conductivityContinued

r i s k assessment and i t s ranges and r a t i n g s , 153t
t o x i c o l o g i c a l b e n e f i t , 414-476 residuum w a t e r - t a b l e a q u i f e r , 89
sampling r o l e i n ground water
v o l a t i l e o r g a n i c s , 183-184 c o n t a m i n a t i o n , 149-150
Wisconsin a l d i c a r b upper F l o r i d a n a q u i f e r , 93
s t u d y , 224-225 Hydrogeologic s e t t i n g
survey d a t a o f p u b l i c p e r c e p t i o n o f d e f i n i t i o n , 144-145
c o n t a m i n a t i o n , 490 format, I 4 6 f
t h r e e c l a s s e s , 484 sample i n A t l a n t i c and G u l f c o a s t a l
time frame f o r comparison movement p l a i n , 155f
o f s u r f a c e water, 272 Hydrogeology, c h a r a c t e r i z a t i o n , 178
W i s c o n s i n p o l i c y on p e s t i c i d e s , 493t Hydrology, d e s c r i b e d f o r Lee County,
Ground Water Data C a l l - i n , p e s t i c i d e s G e o r g i a , 88-97
t o be e v a l u a t e d , 555-556 Hydrolysis
a l d i c a r b i n R i v e r h e a d s o i l , 75
F l o r i d a ground water, 301f
r a t e c o n s t a n t s v s pH, 302f
H a l f - l i f e , a l d i c a r b , 405 I
H a w a i i , c h e m i c a l and h y d r a u l i c i n p u t s
i n ground water s t u d y , 371 Instrinsic variability
Hazard e x t r a p o l a t i o n degradation h a l f - l i v e s o f p e s t i c i d e s
d e f i n i t i o n , 418 i n s o i l , 108-112
d e l i v e r e d dose, 418 o r g a n i c carbon c o n t e n t , 103-108
structural activity s o r p t i o n c o e f f i c i e n t s , 103-108
r e l a t i o n s h i p s , 419 Iowa
t e s t models, 418 ground water c o n t a m i n a t i o n , 311
Hazards s y n t h e t i c c h e m i c a l s found, 480
d o s e - e f f e c t and dose-response, 418 I r r i g a t i o n , i n f l u e n c e on a l d i c a r b
e v a l u a t i o n , 417-418 l e a c h i n g , 362
Head d i s t r i b u t i o n , t w o - d i m e n s i o n a l Isoteniscope, 48f
model study o f W i s c o n s i n ground
water, 404
Health advisories, regulatory
approach, 484
Health advisory l e v e l ,
a l d i c a r b , 358-359
H e a l t h guidance l e v e l s , e q u a t i o n , 486 K a r s t system
Henry's law c o n s t a n t , c a l c u l a t i o n i n a q u i f e r s , 265
Hawaiian ground water s t u d y , 374 c o m p l e x i t y o f contaminant
Herbicides d i s p e r s a l , 256
C a l i f o r n i a ground water, 426 d e f i n i t i o n , 260
movement through sand loam, 311-327 d i s p e r s i o n pathways o f l a n d d i s p o s e d
Hierarchial analysis of variance, wastes, 266-279
d e s c r i p t i o n , 184-185 h y d r o g e o l o g i c a l s e t t i n g , 259-266
Hollow-stem auger m i g r a t i o n o f contaminants i n t o
cross-contamination of d r i l l e d a q u i f e r , 266-279
m a t e r i a l s , 181 s u r f a c e r u n o f f and s o i l e r o s i o n , 276
d e s c r i p t i o n i n Wisconsin a l d i c a r b s u r f a c e water t o ground water
s t u d y , 223 f l o w , 268-269
d r i l l i n g t e c h n i q u e d i s c u s s e d , 181 Kinetics, pesticide degradation, 8
l o c a t i o n s and d i s t r i b u t i o n o f
a l d i c a r b residues i n Wisconsin
ground water s t u d y , 239f
Hollow-stem auger r i g s , d r i l l i n g L
m o n i t o r - c e l l s , 165
Hydraulic conductivity Large-scale retrospective studies
d e t e r m i n a t i o n , 187 ground water, 173-177
p e s t i c i d e movement a f f e c t e d , 24 o b j e c t i v e , 173
Le Grand system, e v a l u a t i n g Magnetic p r o f i l e , l o c a l anomaly

l a n d f i l l s , 143 c r e a t e d by b u r i e d drums, 129f
L e a c h a t e , e x t r a c t i o n i n sandy loam Magnetometry, d e s c r i p t i o n , 126-128
s t u d y , 315 Malformations, d e f i n i t i o n i n r i s k
Leaching assessment, 416
aldicarb Management-educational models,
i n PRZM s t u d y , 361-362 d e f i n i t i o n and p e s t i c i d e
i n W i s c o n s i n ground water, 226 a p p l i c a t i o n s , 332
assessment Manometric methods, vapor p r e s s u r e
f o r a l d i c a r b u s i n g the d e t e r m i n a t i o n , 45
PRZM, 359-363
Marker compound
s i m u l a t i o n s i n PRZM s t u d y , 361
c o n c e n t r a t i o n i n home water s u p p l i e s
a t r a z i n e , 316-327
i n k a r s t system s t u d y , 271f
e f f e c t o f r a i n f a l l on a l d i c a r b , 210 c o n c e n t r a t i o n i n stream and homes i n
e x t e n t , 15 k a r s t system s t u d y , 274-275f
i r r i g a t i o n i n f l u e n c e on c r o s s - s e c t i o n a l stream a n a l y s i s i n
a l d i c a r b , 362 k a r s t system s t u d y , 276t
l i n d a n e , 316-327 dispersion
PCP, 316-327 k a r s t system s t u d y , 270

p r o c e s s e s a f f e c t i n g , 17 pathways near p l a n t s i t e i n k a r s t
r o l e o f recharge water, 148 system s t u d y , 263f
s o i l c h a r a c t e r i s t i c s h i e r a r c h y , 34 h e i g h t - o f - l a n d p r o f i l e o f domestic
s o i l p r o p e r t y i n f l u e n c e , 26 water s u p p l i e s , 2 7 1 f
t e s t s d e s c r i b e d , 25-26 long-term p e r s i s t e n c e i n k a r s t
See a l s o P e s t i c i d e s system, 270
L e g i s l a t i o n , i n d u s t r y p e r s p e c t i v e on r e c o v e r y from s p i k e d t a p water, 260t
p e s t i c i d e and ground s p r e a d i n g v i a s u r f a c e water f o r
water, 478-487 k a r s t system, 272-276
Lindane s u r f a c e r u n o f f and s o i l e r o s i o n i n
amount leached i n sandy loam a f t e r k a r s t system s t u d y , 276-278
30-day t e s t , 324f s u r f a c e - w a t e r measurements i n k a r s t
a n a l y t i c a l methodology f o r sand l o a n system s t u d y , 277f
s t u d y , 315 t o p o g r a p h i c map showing
d i s t r i b u t i o n i n s o i l a f t e r 30-day c o n t a m i n a t i o n a r e a , 258f
t e s t , 320f,321f,322f u t i l i t y l i n e s as contaminant r o u t e s
l e a c h i n g i n sandy loam i n k a r s t system s t u d y , 278
s t u d y , 313-327 Maximum Contaminant L e v e l s (MCLs)
mass b a l a n c e and d e g r a d a t i o n d e f i n i t i o n , 479
h a l f - l i f e i n sandy loam, 325t e n d r i n , 482
p h y s i c o c h e m i c a l p r o p e r t i e s , 312t l i n d a n e , 482
summary, 491 methoxychlor, 482
L i n e a r a d s o r p t i o n i s o t h e r m , assumption p e s t i c i d e s , 482
i n transport screening toxaphene, 482
model, 19-20 Memorandum o f u n d e r s t a n d i n g , W i s c o n s i n
L i s b o n f o r m a t i o n , d e s c r i p t i o n i n Lee ground water law, 496
County, G e o r g i a , 83 Metolachlor
Loading r a t e , W i s c o n s i n ground water degradation h a l f - l i f e
s t u d y , 405 v a r i a t i o n s , 108,110t
Lysimeter leachate, a l d i c a r b ground water p r e s e n c e , 192
r e s i d u e s , 238-240 s p a t i a l v a r i a t i o n s i n o r g a n i c carbon
c o n t e n t , 109f
M e t r i b u z i n , ground water presence, 192
M Middle ordovician limestone u n i t s ,
N i t t a n y Mountain, 262
Macropore f l o w M i n i m a l E f f e c t L e v e l s (MELs), r i s k
d e f i n i t i o n f o r s o i l s , 357 assessment, 420
d e t e r m i n a t i o n , 187 Mirex, effect-dose-duration plot f o r
Madison a r e a computer c e n t e r (MACC) o r a l t o x i c i t y d a t a , 457f
subroutines, contour p l o t s M i s c i b l e displacement theory
c o n s t r u c t e d , 249-250 o r g a n i c m o l e c u l e , 63
Magnetic a n o m a l i e s , u s e , 128 s t e a d y - s t a t e c o n d i t i o n s , 63
INDEX 567
Models
advantages, 343
calibration
c o n s i d e r a t i o n , 400 Napropamide
d e f i n i t i o n , 397 adsorption
classification criteria for parameters, 388t
u n s a t u r a t e d zone, 331 v a r i a b i l i t y , 390
compared i n Hawaiian ground water average c h e m i c a l c o n c e n t r a t i o n s o f
s t u d i e s , 379-381 f i e l d p l o t experiment, 391f,393f
d i m e n s i o n a l i t y , 398 c o n c e n t r a t i o n v s . s o i l depth, 391f
field validation c u m u l a t i v e p r o b a b i l i t y curve f o r
d e f i n i t i o n , 397 p l o t average, 393f
ground water, 396-410 f i e l d experiment r e s u l t s , 390
g e n e r a l c l a s s i f i c a t i o n s , 397 f i e l d study f o r model
parameters t h a t r e p r e s e n t p e s t i c i d e e v a l u a t i o n , 386-387
o r g a n i c matter i n t e r a c t i o n , 335 o r g a n i c carbon p a r t i t i o n c o e f f i c i e n t
r i s k assessment, 520 o b t a i n e d , 387
s p a t i a l v a r i a b i l i t y o f water, 338 N a t i o n a l A g r i c u l t u r a l Chemicals
w e l l s necessary f o r A s s o c i a t i o n (NACA), purpose, 478

c a l i b r a t i o n , 408-410 N a t i o n a l Revised P r i m a r y D r i n k i n g
See a l s o C o n t a m i n a n t - t r a n s p o r t Water R e g u l a t i o n s (NRPDWR),
models p e s t i c i d e s considered f o r
See a l s o Flow models c o n t r o l , 448-449
Monitor-wells N a t u r a l environment, d e f i n i t i o n and
advantages o f d r i l l i n g l o g s , 167 l i m i t s , 3-5
a q u i f e r i n s t a l l a t i o n , 162 Nebraska, ground water
c o n s t r u c t i o n , 180-182 c o n t a m i n a t i o n , 30
d e s i g n i n ground water Net recharge
i n v e s t i g a t i o n s , 162-164 ranges and r a t i n g s , 151t
d i m e n s i o n s , 163 r o l e i n ground water
d r i l l i n g , 164 c o n t a m i n a t i o n , 147-148
d r i l l i n g and w e l l i n s t a l l a t i o n New York
t e c h n i q u e s , 164-167 a l d i c a r b presence i n ground
d r i l l i n g methods comparison, I 6 6 t water, 537-538
installation ground water c o n t a m i n a t i o n , 32
and development, 165 p e s t i c i d e contamination
W i s c o n s i n a l d i c a r b s t u d y , 222-223 F o r t Edward, 530-534
l o c a t i o n and number, 162,179 S u f f o l k County, 537-539
m a t e r i a l , 164 N i t t a n y Mountain, g e o l o g y , 259-262
o b j e c t i v e s o f d r i l l i n g program, 180 Nittany Valley, regional geological
problems, 520 cross s e c t i o n , 261f
recommended, 182 No-Observed-Effect L e v e l s (NOELs),
s a m p l i n g , 182-184 r i s k assessment, 420
s l o t s i z e s o f t h e s c r e e n s , 163 N o n t h r e s h o l d e f f e c t s , d e f i n i t i o n , 451
Monte C a r l o s i m u l a t i o n Normalized s o r p t i o n c o e f f i c i e n t ,
assumptions f o r v o l a t i l i z a t i o n from d e f i n i t i o n , 74,335
water, 56 North C a r o l i n a , s i t e d e s c r i p t i o n f o r
h i s t o r y , 40 PRZM s t u d y , 345-348
r e s u l t s f o r v o l a t i l i z a t i o n from
water, 57t
uncertainty i n physical
parameters, 39-59 0
Mud r o t a r y r i g , d r i l l i n g
m o n i t o r - c e l l s , 164-165
Multigeneration studies, O c a l a l i m e s t o n e , d e s c r i p t i o n i n Lee
d e f i n i t i o n , 416 County, G e o r g i a , 85
M u l t i l e v e l samplers, d e s c r i p t i o n i n O c c u p a t i o n a l S a f e t y and H e a l t h
W i s c o n s i n a l d i c a r b s t u d y , 223-224 A d m i n i s t r a t i o n (OSHA), benzene
M u l t i - s t a g e model s t a n d a r d , l a w s u i t , 466-467
development and u s e , 439 Octanol-water p a r t i t i o n c o e f f i c i e n t
oncogenic m a t e r i a l r i s k , 442 d i s t r i b u t i o n from t h e s h a k e - f l a s k
r i s k , e q u a t i o n , 453 method, 4 6 f
Octanol-water p a r t i t i o n c o e f f i c i e n t Pentachlorophenol (PCP)Continued

Continued mass b a l a n c e and d e g r a d a t i o n
methods and e r r o r h a l f - l i f e i n sandy loam, 325t
d e t e r m i n a t i o n , 43-45 p h y s i c o c h e m i c a l p r o p e r t i e s , 312t
s h a k e - f l a s k method, 43
P e r i s t a l t i c pump, recommended
Octanol-water p u r i f i c a t i o n
use, 182-183
c o e f f i c i e n t , Monte C a r l o
Permeable zones
s i m u l a t i o n a p p l i e d , 39-60
head d i f f e r e n t i a l i n Upper F l o r i d a n
One-dimensional a n a l y t i c a l model,
a q u i f e r , 95
Hawaiian ground water s t u d y , 368
h y d r a u l i c s e p a r a t i o n , 95
One-dimensional n u m e r i c a l model
p r e c i p i t a t i o n e f f e c t s i n t h e upper
d i f f u s i v e vapor l o s s , Hawaiian
F l o r i d a n a q u i f e r , 97
ground water s t u d y , 369-371
Hawaiian ground water s t u d y , 371 PESTANS, p e s t i c i d e model, 342
O r g a n i c carbon c o n t e n t Pesticides
s p a t i a l v a r i a t i o n s i n s o i l , 109f a d d i t i o n a l d a t a t o support change i n
variations i n concentration i n use from greenhouse t o
s o i l , 107f t e r r e s t r i a l f i e l d c r o p , 552t
adsorption
Oxamyl
ADI, 539 e x p e r i m e n t a l methods f o r
d e s c r i p t i o n , u s e , and t o x i c i t y q u a n t i f i c a t i o n s t u d y , 65
s t u d i e s , 538-539 quantifying during
ground water presence, 192 t r a n s p o r t , 61-76
l e a c h i n g , 26,27f amendments t o e x i s t i n g
Long I s l a n d , NY, w e l l water, 538 r e g i s t r a t i o n s , 552t
use and presence i n ground atmospheric r o u t e a s d i s p e r s i o n
water, 554 mode, 279
Oxygen r e a e r a t i o n r a t e c o n s t a n t b i o t a a s d i s p e r s i o n mode, 279
e q u a t i o n , 53-55 C a l i f o r n i a p l a n f o r reduced ground
95-percent c o n f i d e n c e l i m i t , 55 water c o n t a m i n a t i o n , 283
r e l a t e d t o v o l a t i l i z a t i o n from c r i t e r i a f o r p o t e n t i a l t o reach
water, 53 ground water, 553t
s i m u l a t i o n mean and s t a n d a r d c u r r e n t modeling approaches, 338-339
d e v i a t i o n s , 57t d a t a requirements f o r s a f e t y
e v a l u a t i o n , 439t
degradation
assumption o f f i r s t - o r d e r
k i n e t i c s , 22
b a s i s o f knowledge, 8
Palmyra s o i l factors, 8
aldicarb k i n e t i c s , 7-8
a d s o r p t i o n and d e g r a d a t i o n , 73 quantifying during
t r a n s f o r m a t i o n , 73 t r a n s p o r t , 61-76
d i s t r i b u t i o n c o e f f i c i e n t and s o i l - w a t e r c o n t e n t and
normalized s o r p t i o n c o e f f i c i e n t temperature, 111
values, 75t spatial variability of
P a r e n t a l h a z a r d s , e f f e c t s , 417 parameters, 100-112
P a r t s p e r b i l l i o n , p e r s p e c t i v e , 482 environmental f a t e data requirements
P a r t s p e r m i l l i o n , p e r s p e c t i v e , 482 a q u a t i c impact use p a t t e r n s , 551t
P a r t s p e r t r i l l i o n , p e r s p e c t i v e , 482 t e r r e s t r i a l use p a t t e r n s , 550t
P e n n s y l v a n i a , ground water ground water o c c u r r e n c e i n U n i t e d
c o n t a m i n a t i o n , 31 S t a t e s , 187
P e n t a c h l o r o p h e n o l (PCP) ground water t r a n s p o r t , 2-13
a n a l y t i c a l methodology f o r sandy interactions o f factors affecting
loam s t u d y , 315 f a t e i n s o i l , 11f
d i s t r i b u t i o n i n s o i l a f t e r 30-day l e a c h i n g , 25-26
t e s t , 320f,321f migration
ground water o c c u r r e n c e , 426 a l t i t u d e o f water t a b l e i n t h e
leaching residuum a t study
experiment i n sand loam, 313-314 s i t e , 92f,94f
sandy loam s t u d y , 316-327 borehole geophysical logs f o r t e s t
through sandy loam, 326-327 hole, 84f
INDEX 569
PesticidesContinued PesticidesContinued
f i e l d methods f o r geohydrology U . S . a p p l i c a t i o n , 3,548
study, 81-83 u t i l i t y l i n e s as d i s p e r s i o n
f i e l d s i t e selected f o r mode, 278
geohydrology, 79-81 v o l a t i l i z a t i o n process, 9
geohydrology o f a f i e l d P e s t i c i d e Root Zone Model (PRZM)
s i t e , 78-98 base case u s i n g F l o r i d a r i d g e
geology o f study s i t e , 83-86 c o n d i t i o n s , 213t
l o c a t i o n o f study s i t e , 8 0 f c a l i b r a t i o n , 344-349
major s o i l s e r i e s i n study model s t u d y , 349-358
s i t e , 87f parameters f o r a l d i c a r b use, 347t
topography o f study s i t e , 8 2 f r e s u l t s , 350-351f,354-356f
m o b i l i t y c h a r a c t e r i z a t i o n , 392 run summary, 348t
modeling movement i n the u n s a t u r a t e d s c e n a r i o s i n PRZM s t u d y , 349-358
zone, 330-340 d e s c r i p t i o n , 209-210,343
movement e v a l u a t i o n d e s c r i p t i o n , 311
f i n e , moist s o i l , 291 r e s u l t s i n W i s c o n s i n ground
through sand loam, 311-327 water, 252
n o n v o l a t i l e , model assumptions f o r s o i l and crop parameters f o r

s c r e e n i n g , 20-22 c a l i b r a t i o n , 346t
p e r s i s t e n c e i n s o i l s , model, 111 u n s a t u r a t e d zone, 342
p l a n t uptake c o n s i d e r e d i n pH, EDB d e g r a d a t i o n dependence, 300
modeling, 337-338 P h y s i c a l and c h e m i c a l
p o t e n t i a l f o r r e a c h i n g ground parameters, 2-116
water, 553-554,555 P l a n t uptake, modeling
relationship o f theoretical intake c o n s i d e r a t i o n , 337
to a c t u a l i n t a k e , 441t P l i n t h i t e , d e s c r i p t i o n , 86
r o u t e t o ground water, 3-5 Plume c o n c e n t r a t i o n , d e f i n i t i o n f o r
s a f e t y e v a l u a t i o n i n ground a l d i c a r b , 361
water, 436-443 Pollutants
sewage sludge d i s p o s a l as d i s p e r s i o n c l a s s e s , 446t
mode, 279 p o s s i b l e ground water
s i m u l a t i o n model h i s t o r y , 385-386 c o n t a m i n a t i o n , 446-447
sorption, spatial v a r i a b i l i t y of water q u a l i t y c r i t e r i a , 450t
parameters, 100-112 Pollution
s p i l l s , hydrogeologic factors affecting potential i n
i n v e s t i g a t i o n s , 159-167 ground water, 145-147
s t u d i e s used t o determine p o t e n t i a l systems t h a t e v a l u a t e p o t e n t i a l i n
t o reach ground water, 549t ground water, 142-144
s u r f a c e r u n o f f and s o i l e r o s i o n as P o r t e r - C o l o g n e A c t , 503
d i s p e r s i o n mode, 276 P r e v e n t i v e A c t i o n L i m i t (PAL)
s u r f a c e water as d i s p e r s i o n W i s c o n s i n ground water
mode, 272 l e g i s l a t i o n , 442
t r a n s f o r m a t i o n p r o c e s s e s , 7-9 W i s c o n s i n l e g i s l a t i o n , 488
transport Primary sampling u n i t s ,
c l a s s i f i c a t i o n of nonsoil d e f i n i t i o n , 175
factors, I8t P r o b a b i l i t y surveys
d e t e r m i n i s t i c approach advantages, 175
d e s c r i b e d , 17-20 d e s c r i p t i o n , 174-177
model d i f f i c u l t i e s , 10 e x p e r i m e n t a l d e s i g n s , 174
p r o c e s s e s a f f e c t i n g water Prometryn, a d s o r p t i o n parameters, 388t
movement, 4 f Propham, l e a c h i n g , 26,27f
s i m u l a t i o n s , 22-24
soil characteristics affecting
movement i n t o ground
water, 14-35
s o l u t e t r a n s p o r t e q u a t i o n i n one R
dimension, 19
processes, 9
s c r e e n i n g models, 384-394 Random sampling
types t h a t contaminate ground d e s c r i p t i o n , 175
water, 424-426 weakness, 176
Random walk model Risk assessmentContinued

a l d i c a r b movement through s a t u r a t e d u n c e r t a i n t y , and the l e g a l
zone, 250-252 p r o c e s s , 462-474
r e s u l t s i n W i s c o n s i n ground R i s k c h a r a c t e r i z a t i o n , d e f i n i t i o n , 421
water, 252 R i s k management
use i n two-dimensional model, 402 C a l i f o r n i a ground water
Recharge c o n t a m i n a t i o n , 518
a q u i f e r parameter c r i t i c i s m o f c o u r t s , 464-465
e s t i m a t i o n , 398-399 high-risk i r r i g a t i o n practices i n
Hawaiian ground water s t u d y , 372 C a l i f o r n i a , 524
s i t e l o c a t i o n s i n PRZM i l l e g a l use o f p e s t i c i d e s i n
s t u d y , 360-361 C a l i f o r n i a , 522
w e l l s i n C a l i f o r n i a , 524 improper d i s c h a r g e o f p e s t i c i d e s i n
Recommended Maximum Contaminant L e v e l s C a l i f o r n i a , 523
(RMCLs), d e f i n i t i o n , 483-484 n o n e x i s t e n t e a r l y warning system i n
R e g i s t r a t i o n standards process, C a l i f o r n i a , 524
r e r e g i s t r a t i o n w i t h EPA, 549 r e g u l a t i o n s u c c e s s , 488-490
R e g r e s s i o n a n a l y s i s , EDB s t u d y , 290t s c i e n t i f i c s o l u t i o n s , 472
R e p r o d u c t i v e h a z a r d s , e f f e c t s , 416-417 w e l l s as p o l l u t a n t pathways i n
R e p r o d u c t i v e t o x i c i t y , d e f i n i t i o n , 415 C a l i f o r n i a , 523
Research models, d e f i n i t i o n and Risk perception
p e s t i c i d e a p p l i c a t i o n s , 332 C a l i f o r n i a ground water
Residuum, d e s c r i p t i o n i n Lee County, c o n t a m i n a t i o n , 518
G e o r g i a , 85-86 f i l t e r f a n t a s y , 519
Residuum w a t e r - t a b l e a q u i f e r inadequate t e s t i n g o f l e a c h e r s , 519
e v a p o r a t i o n d a t a i n Lee County, R i s k - s p e c i f i c dose, c a r c i n o g e n s ,
G e o r g i a , 90 e q u a t i o n , 452
g e o l o g i c d e s c r i p t i o n , 89-93 Riverhead s o i l
p r e c i p i t a t i o n i n f l u e n c e , 90 a l d i c a r b d e g r a d a t i o n and
Retardation factor a d s o r p t i o n , 74
a l d i c a r b , 405 d i s t r i b u t i o n c o e f f i c i e n t and
d e f i n i t i o n , 387 normalized s o r p t i o n c o e f f i c i e n t
d e t e r m i n a t i o n , 187 v a l u e s , 75t
Retention processes h y d r o l y s i s o f a l d i c a r b , 75
definition, 5
p e s t i c i d e s , 5-7
t e c h n i q u e s used t o c h a r a c t e r i z e , 5
R i s k a c c e p t a b i l i t y , d i s c u s s i o n , 421 S
R i s k assessment
a n a l y t i c a l c o n s t r a i n t s , 519
approaches f o r ground water Safe D r i n k i n g Water A c t , 1974,
c o n t a m i n a t i o n by c r i t e r i a documents, 448
p e s t i c i d e s , 445-459 ground water a p p l i c a t i o n s , 483
C a l i f o r n i a ground water MCLs, 483
c o n t a m i n a t i o n , 518 San J o a q u i n V a l l e y , ground water study
c h e m i c a l m i x t u r e s , 455-456 l o c a t i o n , 284
c o u r t s demanding g r e a t e r Sandy loam
u n c e r t a i n t y , 466 movement c o r r e l a t i o n w i t h o r g a n i c
c r i t i c i s m o f c o u r t s , 466 carbon n o r m a l i z e d a d s o r p t i o n
graphic d i s p l a y of r e l e v a n t data c o e f f i c i e n t , 325t
used, 456-458 p e s t i c i d e and h e r b i c i d e
g u i d e l i n e s , 415 movement, 311-327
minimal e f f e c t l e v e l s , 420 S a t u r a t e d zone
m o n i t o r i n g c o n s t r a i n t s , 520 a l d i c a r b s t u d i e s , 198
n o - o b s e r v e d - e f f e c t l e v e l s , 420 degradation
p u b l i c d e c i s i o n f a c t o r s , 468-469 a l d i c a r b , 200
r e p r o d u c t i v e and a l d i c a r b r e s i d u e s , 208t
developmental, 414-422 model under F l o r i d a r i d g e
s i n g l e c h e m i c a l c h r o n i c exposure and c o n d i t i o n s , 216f
c h e m i c a l m i x t u r e s , 449-456 model used t o s i m u l a t e a l d i c a r b
s u b j e c t i v e n e s s , 471 c o n c e n t r a t i o n s , 215
t o x i c o l o g i c a l c o n t r o v e r s y , 520 modeling d i f f i c u l t i e s , 343
INDEX 571
Saturation zoneContinued S o i l OM c o n t e n t
models, 210-215 a t r a z i n e movement a f f e c t , 24
movement o f a l d i c a r b , 209 e f f e c t s on the PRZM model, 251t
S c i e n c e c o u r t , r e c o n s i d e r e d , 471-472 importance on p e s t i c i d e movement, 22
S c r e e n i n g models, d e f i n i t i o n and used t o measure a d s o r p t i o n
p e s t i c i d e a p p l i c a t i o n s , 332 c o e f f i c i e n t , 21
S e a s o n a l s o i l compartment model, S o i l properties
e v a l u a t i o n d e s c r i p t i o n , 311 background, 15
S e i s m i c r e f r a c t e d waves, time v s . c l a s s i f i c a t i o n , 15t-l6t
d i s t a n c e p l o t a t geophones, 121f Soils
Seismic r e f r a c t i o n a l d i c a r b d e g r a d a t i o n and
d e s c r i p t i o n , 119-120 t r a n s p o r t , 197
l i m i t a t i o n s t o ground water c h a r a c t e r i z a t i o n , 178
method, 120 c o n t e n t s d e s c r i b e d , 25
Seismic r e f r a c t i o n survey, core
c r o s s - s e c t i o n a l view, 121f s a m p l i n g , 184-185
S e i s m i c v e l o c i t y , s o i l and rock t y p e s s p l i t t i n g and a n a l y s i s f o r
c h a r a c t e r i z e d , 120 EDB, 285-286
S h a k e - f l a s k method c o r i n g , EDB, 284

d i s t r i b u t i o n o f s i m u l a t e d aqueous EDB d e g r a d a t i o n by m i c r o f l o w , 298
s o l u b i l i t y , 44f e l e c t r i c a l c o n d u c t i v i t y measurement
water s o l u b i l i t y d e t e r m i n a t i o n , 42 f o r EDB, 285-286
S h o r t - c i r c u i t i n g , d e f i n i t i o n , 339 experiments conducted i n a d s o r p t i o n
Simazine q u a n t i f i c a t i o n s t u d y , 68t
ground water presence, 192 e x t r a c t i o n i n sandy loam s t u d y , 316
leaching, 29f high permeability without shallow
s o i l pH e f f e c t s , 26 underlying r e s t r i c t i v e
s t r u c t u r e , 431 l a y e r s , 527f
t o x i c i t y , 431-432,437-438 macropore f l o w d e s c r i b e d , 357
Sinkholes parameters d e f i n e d i n Hawaiian
described i n p e s t i c i d e migration ground water s t u d y , 374
s t u d y , 81 property
ground water c o n t a m i n a t i o n r o l e , 32 s p a t i a l v a r i a b i l i t y t y p e s , 102
Site characterization, small-scale v a r i a b l e s i n EDB s t u d y , 286-289
r e t r o s p e c t i v e s t u d i e s , 178 sampling i n s m a l l - s c a l e
Site selection, criteria for r e t r o s p e c t i v e s t u d i e s , 184-186
small-scale retrospective s o u t h e a s t e r n Lee County,
s t u d i e s , 177-178 G e o r g i a , 86-88
Small-scale prospective studies t e x t u r a l a n a l y s i s f o r EDB, 285-286
Cape Cod, 189 Solute diffusion-dispersion
d e s c r i p t i o n , 186-187 c o e f f i c i e n t , Hawaiian ground water
s i t e s e l e c t i o n and s t u d y , 373
c h a r a c t e r i z a t i o n , 186 Sorption
s o i l and water sample d i s t r i b u t i o n c o e f f i c i e n t i n Hawaiian
c o l l e c t i o n , 186 ground water s t u d y , 373
Small-scale retrospective studies e q u a t i o n , 334
d e s c r i b e d , , 177-186 Sorption c o e f f i c i e n t ,
number and l o c a t i o n o f o b s e r v a t i o n u s e f u l n e s s , 381-382
w e l l s , 179-180 Spatial variability
s i t e s e l e c t i o n , 177 s o i l s , 24-25
s o i l s a m p l i n g , 184 t y p e s , 102
S o i l c o n s e r v a t i o n s e r v i c e curve number S p i l t b a r r e l sampler, use i n EDB
approach, water b a l a n c e a l g o r i t h m s t u d y , 289
b a s i s , 344 S t o c h a s t i c models
S o i l core d a t a , evidence o f p e s t i c i d e d e f i n i t i o n , 332
l e a c h i n g , 283 d e s c r i p t i o n , 17
S o i l d i s t r i b u t i o n c o e f f i c i e n t , organic u n s a t u r a t e d zone d e s c r i p t i o n , 340
m a t t e r c o n t e n t used t o S t o r a g e c o e f f i c i e n t , a q u i f e r parameter
c a l c u l a t e , 250 e s t i m a t i o n , 398
S o i l erosion, pesticide transport, 9 S t r a t i f i e d random s a m p l i n g ,
S o i l media, 148-149,152t d e s c r i p t i o n , 175-176
S t r a t i f i e d random survey Transformation processes

advantages f o r l a r g e t a r g e t defined, 7
p o p u l a t i o n s , 176-177 p e s t i c i d e s , 7-9
example, 176 Transmissivity
Structural A c t i v i t y Relationships a q u i f e r parameter e s t i m a t i o n , 398
(SAR), p e s t i c i d e s , 419 hydraulic conductivity
Subsurface zones, avenues o f l o s s i n r e l a t i o n s h i p , 399
the PRZM, 344 Transport
Suggested-No-Adverse-Response L e v e l s mechanisms f o r p e s t i c i d e s i n t h e
(SNARL) u n s a t u r a t e d zone, 333
c a l c u l a t i o n , 438-439 processes f o r p e s t i c i d e s , 9
r e g u l a t o r y approach, 484 Trichloroethylene
S u r f a c e g e o p h y s i c a l survey c o n c e n t r a t i o n s i n F o r t Edward,
t e c h n i q u e s , 119-128 NY, 533t
S u r f a c e impoundment assessment ( S I A ) , ground water presence, 532
e v a l u a t i n g l a n d f i l l s , 143 q u a n t i f y i n g i n h a l a t i o n exposure
Surface runoff, p e s t i c i d e transport, 9 experiment, 532-533
S u r f a c e zone, avenues o f l o s s i n t h e water samples c o l l e c t e d , 533
PRZM, 344 T r i c h l o r o p r o p a n e , ground water

Systemic t o x i c a n t s , v e r i f i c a t i o n o f presence, 192
u n c e r t a i n t y f a c t o r s , 458-459 T r i h a l o m e t h a n e s , ground water presence
i n Iowa, 480
Two-dimensional n u m e r i c a l model,
Hawaiian ground water study, 369
Target p o p u l a t i o n s , examples f o r
p r o b a b i l i t y , 174 U
T e r a t o g e n i c s t u d i e s , d e f i n i t i o n , 416
Terbacil
leaching, 29f U.S. l e g a l system, s p e c i a l i z e d
s o i l pH e f f e c t s , 26 knowledge, 462
T h e o r e t i c a l Maximum Residue U l t i s o l s , s o u t h e a s t e r n Lee County,
C o n t r i b u t i o n (TMRC), i n g e s t i o n o f G e o r g i a , 86
food examined, 440 Uncertainty factor
T h r e s h o l d e f f e c t s , d e f i n i t i o n , 451 d e f i n i t i o n f o r systemic
T h r e s h o l d r e g i o n , d e f i n i t i o n and t o x i c a n t s , 454
c a l c u l a t i o n f o r systemic v e r i f i c a t i o n f o r systemic
t o x i c a n t s , 454 t o x i c a n t s , 458-459
T i f t o n s o i l , d e s c r i p t i o n , 88 Unsaturated zone
Toluene, d i s t r i b u t i o n o f s i m u l a t e d a l d i c a r b s t u d i e s , 198
vapor p r e s s u r e , 4 9 f d e g r a d a t i o n o f a l d i c a r b , 200
Topography depth, 359
ranges and r a t i n g s , 152t h i s t o r y o f s t u d i e s , 330
r o l e i n ground water modeling approaches, 331-332
c o n t a m i n a t i o n , 149 modeling p e s t i c i d e movement o f
Toxaphene Hawaiian s o i l s , 366-382
r u r a l household water s u p p l i e s , 491 models, 209-210
summary, 491 p r i n c i p l e s o f modeling p e s t i c i d e
T o x i c h a z a r d s , i d e n t i f i c a t i o n , 416-417 movement, 330-340
T o x i c Substances C o n t r o l Program, processes a f f e c t i n g p e s t i c i d e
C a l i f o r n i a , 511 f a t e , 332-338
Toxic t o r t lawsuits, d i f f i c u l t i e s o f See a l s o Vadose zone
p r o o f , 468 Upper F l o r i d a n a q u i f e r
Toxicants, systemic d a i l y mean water l e v e l s , 96f
t h r e s h o l d e f f e c t s , 453-455 d e s c r i b e d i n Lee County,
t y p e s o f response l e v e l s , 453 G e o r g i a , 93-97
T o x i c i t y , r e l a t i v e s e n s i t i v i t y , 418 permeable zones d e s c r i b e d , 93-94
T r a c e r s , d e f i n i t i o n and water l e v e l s and head
advantages, 187 differences, 95t
INDEX 573
Urea-formaldehyde foam i n s u l a t i o n Waste d i s p o s a l C o n t i n u e d

( U F F I ) , ban attempt, 465-466 p r a c t i c e s , 160
U t i l i t y l i n e s , c o n d u i t o f ground Water
water, 267f e s t a b l i s h i n g c r i t e r i a and
s t a n d a r d s , 448
l a t e r a l s u b s u r f a c e movement, 2 7 f
Water b a l a n c e
V c a l i b r a t i o n r e s u l t s i n PRZM
study, 352t
Vadose zone l e a c h i n g assessment s i m u l a t i o n s i n
aldicarb residue concentrations i n PRZM s t u d y , 361t
W i s c o n s i n , 238 Water q u a l i t y , r e g i o n a l c o n t r o l boards
d e f i n i t i o n , 149 i n C a l i f o r n i a , 504f
ranges and r a t i n g s , 152t Water Q u a l i t y Assurance A c t ,
r o l e i n ground water F l o r i d a , 544
c o n t a m i n a t i o n , 149 Water s o l u b i l i t y
s o i l sample d e s c r i p t i o n i n p o t a t o d e t e r m i n a t i o n d e s c r i b e d , 40-41
f i e l d s , 234-235 d e t e r m i n a t i o n methods, 41-42
See a l s o U n s a t u r a t e d zone Monte C a r l o s i m u l a t i o n

Vapor p r e s s u r e a p p l i e d , 39-60
d e t e r m i n a t i o n methods, 45-51 sources o f e r r o r i n
Monte C a r l o s i m u l a t i o n d e t e r m i n a t i o n , 42
a p p l i e d , 39-60 Water t a b l e
Vapor p r e s s u r e s i m u l a t i o n s , contour map near p l a n t s i t e i n k a r s t
distribution of relative system s t u d y , 264f
e r r o r , 50f simulated contours i n Wisconsin
Variations, definition i n risk ground water s t u d y , 403f
assessment, 416 W a t e r - t a b l e c o n t o u r s , maps, 237f,239f
Vertical electrical resistivity Water v e l o c i t y , r e l a t i o n s h i p t o
sounding (VES) c o n v e c t i o n s , 21
d e s c r i p t i o n and ground water Water w e l l s , t o x i c o r g a n i c c h e m i c a l s
a p p l i c a t i o n , 130-133 found, 447t
f i v e layer, three-dimensional WellsSee Monitor-wells
i s o m e t r i c p r o j e c t i o n , 132f Wisconsin
s i t e l o c a t i o n i n Northhampton a l d i c a r b f a t e i n ground water, 219
County, V i r g i n i a , 131f contaminant t r a n s p o r t model used i n
V o l a t i l i z a t i o n f l u x , determined f o r ground water s t u d y , 400-410
p e s t i c i d e s , 337 f a c u l t a t i v e anaerobic bacteria
V o l a t i l i z a t i o n from water c h a r a c t e r i s t i c i n ground
e r r o r a n a l y s i s , 54-56 water, 248f
e s t i m a t i o n d e s c r i b e d , 51-58 g r i d used i n the modeling s i m u l a t i o n
e x p e r i m e n t a l p r o t o c o l s , 52-53 o f a l d i c a r b , 403f
h i g h - v o l a t i l i t y compounds ground water law, 495-497
p r o t o c o l , 52-53 l o c a t i o n o f C e n t r a l Sand P l a i n , 4 0 1 f
r e s u l t s , e r r o r e s t i m a t i o n , 56 mean a i r and s o i l temperatures and
V o l a t i l i z a t i o n process, pesticides, 9 p r e c i p i t a t i o n i n study
V o l a t i l i z a t i o n rate constant a r e a , 240f
95-percent c o n f i d e n c e s i t e d e s c r i p t i o n f o r PRZM
l i m i t , 54 s t u d y , 348-349
e q u a t i o n , 54 site selection for aldicarb
s i m u l a t i o n mean and s t a n d a r d s t u d y , 221
d e v i a t i o n s , 57t v a r i a t i o n i n temperature w i t h depth
i n ground water, 244f
Waste d i s p o s a l
ground water c o n t a m i n a t i o n r a t i n g X e n o b i o t i c compounds, ground water t o
scheme, 143 s u r f a c e water f l o w , 272

(ACS Symposium Volume 315) Willa Y. Garner, Richard C. Honeycutt, and Herbert N. Nigg (Eds.) - Evaluation of Pesticides in Ground Water-American Chemical Society (1986)

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ACS SYMPOSIUM SERIES 315

Richard C. Honeycutt, EDITOR

Herbert N. Nigg, EDITOR

Developed from a symposium sponsored by

American Chemical Society, Washington, DC 1986

Richard C., 1945- . III. Nigg, Herbert N.,

Harvey W. Blanch Donald E. Moreland

Marye Anne Fox W. D . Shults

Rudolph J . Marcus Douglas B. Walters

THE INTENSE PUBLIC INTEREST IN C H E M I C A L CONTAMINATION of O u r

T h i s v o l u m e explores a l l aspects of the factors that impinge o n g r o u n d

The process of transporting pesticides down through the

The t o p i c o f t h i s symposium i s b o t h t i m e l y and o f s p e c i a l c o n c e r n t o

0097-6156/ 86/ 0315-O002$06.00/ 0

Some 68% o f the p e s t i c i d e s was used f o r a g r i c u l t u r a l p u r p o s e s ,

It i s not always o b v i o u s t h a t groundwater i n most c a s e s is a

ENVIRONMENTAL ZONES WATER PROCESSES PESTICIDE PROCESSES

Atmosphere Evaporation Precipitation A p p | i c a t i o n Photodecomposition

^ * '^' Drift Condensation

Movement Transport Degradation

F i g u r e 1. P r o c e s s e s a f f e c t i n g water movement and p e s t i c i d e

die. Once i n t h e s o i l , t h e c h e m i c a l must be t r a n s p o r t e d , u s u a l l y by

range of c o n c e n t r a t i o n s . However, a p l o t t i n g o f v a l u e s t a k e n from

Many s t u d i e s have shown t h a t p e s t i c i d e a d s o r p t i o n can be

bonding, l i g a n d and i o n exchange, charge t r a n s f e r , i o n - d i p o l e and

i n v o l v e d i n a d s o r p t i o n , many of which a r e not r e a d i l y r e v e r s i b l e by

The term ' t r a n s f o r m a t i o n ' i s used h e r e t o encompass a l l changes i n

c h a r a c t e r i z e the mechanisms and k i n e t i c s of p e s t i c i d e d e g r a d a t i o n in

A l t h o u g h the downward t r a n s p o r t of p e s t i c i d e s by water i s of u l t i m a t e

t e m p e r a t u r e , and a i r movement (39-41). A model a c c o u n t i n g f o r most

A number of m o d e l i n g approaches a t t e m p t i n g t o d e p i c t the p r o c e s s of

II. Soil factors:

S o i l p r o p e r t i e s : type and amount of o r g a n i c m a t t e r , c l a y , and

This l i s t i s by no means an e x h a u s t i v e one, but i t r e v e a l s the

Inputs Processes Output

the groundwater? Perhaps we have n o t y e t a t t a i n e d n e a r l y t h e l e v e l

J o i n t c o n t r i b u t i o n from Department o f Agronomy and S o i l s , Washington

1. Storck, W. J. Chem. Engin. News 1984, 62(15), 35-59.

22. Alexander, M. Science 1981, 211, 132-8.

31. Frehse, H.; Anderson, J. P. E. In "Pesticide Chemistry";

Charles S. Helling and Timothy J. Gish

Agricultural Research Service, U.S. Department of Agriculture, Beltsville, M D 20705

Processes that modify convective transport of pesti-

tion/desorption, degradation, volatilization, runoff,

This chapter not subject to U.S. copyright.

12 p e s t i c i d e s were found i n groundwaters o f 18 s t a t e s as a c o n s e -

l a b o r a t o r y and f i e l d experiments t h a t focus on a d s o r p t i o n and l e a c h -

Background: Soil Properties

S o i l s c a n be c h a r a c t e r i z e d i n many ways, depending, f o r example, on

Background: Other R e l a t e d Properties

Table I. Classification o f Some S o i l Properties

Table II. Classification o f Some Macro S o i l Properties

Table I I I . C l a s s i f i c a t i o n of Nonsoil Factors P o t e n t i a l l y Affecting

The d i s t r i b u t i o n o f p e s t i c i d e s throughout the s o i l p r o f i l e , as a

c o n v e c t i o n and d i f f u s i o n , w h i l e at the same time a c c o u n t i n g f o r the

F r e q u e n t l y termed the Buckingham-Darcy e q u a t i o n , E q u a t i o n 1 may

VJ W = 0 mass b a l a n c e f o r water (2a)

Here, i s the s o i l bulk d e n s i t y , i s the f i r s t - o r d e r d e g r a d a t i o n

s o i l d e p t h , S i s t h e adsorbed c o n c e n t r a t i o n p e r u n i t o f mass, and

o f E q u a t i o n 4a, s u b j e c t e d t o a p p r o p r i a t e i n i t i a l and boundary c o n d i

e q u i v a l e n t u n i f o r m water f l u x and water c o n t e n t ( 2 5 - 6 ) .

The model p r e s e n t e d can be used f o r s c r e e n i n g n o n v o l a t i l e p e s t i c i d e s

A d s o r p t i o n . The s o l u t i o n used t o e v a l u a t e the p e s t i c i d e t r a n s p o r t