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y

R. T.

FISHERIES AND MARINE SERVICE


SERVICE DES PECHES ET DES SCIENCES DE LA MER
TECH ICAL REPORT o. 700
RAPPORT TECH reus 0

977
Environment Environnement
Canada Canada

Fisheries Service des peches


and arine et des sciences
Service . de la mer
Technical Reports

Technical Reports are research documents that are of ufficient importance to


be preserved but which for some reason are not appropriate for primary cientific
publication. Inquirie concerning any particular Report should be directed to the
issuing establishment.

Rapports Techniques

Le rapports techniques ont des documents de recherche qui revetent une assez
grande importance pour etre con erves mais qui, pour une raison ou pour une autre,
ne conviennent pas a une publication scientifique prioritaire. Pour toute demande
de renseignements concernant un rapport particulier, il faut s'adresser au service
responsable.
Department of Fisheries and the Environment Ministere des Peches et de l'Environnement

Pishcries and Marine Service Service des Peches et de Ia mer

Research and Development Directorate Direction de la Recherche at 06veloppemcnt

TECHNICAL REPORT NO. 700 RAPPORT TECHNIQUE NO. 700

(Numbers 1-456 in this series were issued (Les numeros 1-456 dans cette serie furent

as Technical Reports of the Fisheries utilises comme Rapports Techniques de l'office

Research Board of Canada. The series des recherches sur les pecheries du Canada.

name was changed with Les nom de la serie fut change avec Ie

report number 457). rapport numero 457).

Geochemical Analyses of Marine Sediments


and Suspended Particulate Matter

by

D. H. Loring and R. T. T. Rantala

This is the fifty-third Ceci est Ie cinquante-troisieme

Technical Report from the Rapport Technique de la Direction de la

Research and Development Directorate Recherche et Developpement

Marine Ecology Laboratory Laboratoire d'Ecologie Marine

Bedford Institute of Oceanography L'Institut Oceanographique de Bedford

Dartmouth, Nova Scotia Dartmouth, Nouvelle-Ecosse

1977
iii

TABLE OF CONTENTS

Introduction 1

Marine Sediment Classification 2

Sample Collection and Field Observations 4

Surface Samples 5

Subsurface Samples 8

Suspended Particulate Matter 9

Filtration 10

Sources of Error 11

Initial Sample Preparation 13


Apparatus and Equipment 14
Sedimentological Analyses 14
Chemical Analyses 15
Removal of Soluble Sea Salts 16

Removal of the Biologically Available 16


(Acetic Acid Soluble) Fraction
Grain Size Separation 19
Flame Atomic Absorption Analyses 22

Apparatus and Equipment 22

Sample Decompos ion 23

Sediments 23

Suspended Particulate Matter (SPM) 25


v

Page

Standard Preparation 26
Stock Standards 26

Working Standards: Sediments 28


Working Standards: SPM 31
Determination of Elements 33
Interferences 36
Relative Accuracy and Precision 36
Flameless AAS Analyses for Hg 40

Other Chemical Determinations 44

Readily Oxidizable Organic Matter 44


Calcium Carbonate 47
Dithionite Soluble Iron ("Free" Iron) 49
Ferrous Oxide (FeO) 51
Oxygen Activity 52
erences 55
vii

LIST OF TABLES

,
..l. Sediment classification 3

2. Sampling times for size fractions in a 21


beaker or Atterberg cylinder

3. Elements in standard rocks (%) eu and zn (ppm) 31

4. Elements in working solutions from standard 32


rocks (ppm)

5. Sample preparation diagram for silicate rock 33


analyses

6. Standard conditions for atomic absorption 35


analyses

7. Major elements in U.S.G.S. standard rocks (%) 37

8. Trace elements in U.S.G.S. standard rocks (ppm) 38

9. Precision (coefficient of variation) for the 38


determination of trace elements in U.S.G.S.
standard rocks (%)
ix

LIST OF FIGURES

1. Equipment for pressure filtration 10

2. Scheme for grain size separation 19

3. Teflon bomb cross-section 23

4. Chemical tests for ferric and ferrous iron 53


in sediments, indicative of oxygen supply
xi

ABSTRACT

Loring, D. H. and R. T. T. Ranta 1977. Geochemical


analyses of marine sediments and suspended particulate
matter. Fish. Mar. Servo Res. Dev. Tech. Rep. 700, xii +
58 pp.

Accurate and precise sampling and analytical techniques are

required in environmental geochemical studies and to satisfy the

requirements of the Ocean Dumping Act and the Environmental

Contaminants Act. This report provides a detailed description

of the techniques and analytical procedures used for sampling,

grain size determinations, AA analyses of the major elements

(Si, AI, Ti, Fe, Mn, Mg, Ca, Na, and K) and the trace elements

(Zn, Hg, Cu, Pb, Co, Ni, Cr, V, Li, Be, Bar Rb, and Sr) in

marine iments and suspended matter (major elements only) .

In addition it describes procedure for the chemical partition

of the elements (biological availability), the determination

of readily oxidizable organic matter, CaCOg, dithionite soluble

iron, FeO, and a technique for the evaluation of oxygen activity

in sediments. It is written primarily as a laboratory manual

for Marine Ecology Laboratory

but is also a reliable guide for the determination of

certain biologically toxic heavy metals designated under the

Ocean Dumping Act and the Environmental Contaminants Act.


xiii

SOMMAIRE

I,oring, D.H. et R.T.T. Rantala. 1977. Analyses geochimiques de sidiments marins


et de particules suspendues. Fish. Mar. Servo Res. Dev. Tech. Rep. 700,
x i i + 58 pp .

On a besoin de techniques precises d'echantillonnage et d'analyse dans les


etudes geochimiques de l'environnement, pour satisfaire auxexigences de l'Ocean
Dumping Act et de l'Environmental Contaminants Act. Le present rapport decrit
dans Ie detail les techniques et procedures d'analyse employees pour l'echantil-
lonnage, la determination des dimensions granulometriques de particules, l'ana-
lyse AA des elements majeurs (Si. AI, Ti. Fe. Mn. Mg, Ca, Na et K) et des ele-
ments en trace (Zn, Hg, Cu. Pb, Co, Ni, Cr. V. Li. Be, Ba. Rb et Sr) qui se
trouvent dans les sediments marins et dans la matiere suspendue (elements majeurs
seulement). De plus, il decrit des procedures de separation chimique des
elements (disponibilite biologique) et de determination de la matiere organique
facilement oxydable. de CaCo et de fer soluble dans Ie dithionite (FeO), ainsi
3,
qu'une technique d'evaluation de l'activite de l'oxygene dans les sediments. II
a ete redige principalement cornrne manuel du laboratoire de geochimie du Labora-
toire d'ecologie marine. mais il servira aussi de guide pour la determination
de certains metaux lourds toxiques designes par l'Ocean Dumping Act et
l'Environmental Contaminants Act.
1.

INTRODUCTION

In 1961, the Fisheries Research Board of Canada Laboratory

located at the Ins in a series

ological and geochemical studies of marine sediments from the

Gulf of st. Lawrence. The results of these studies have been

published separately from time to time (Loring 1962, Loring and

Lahey 1963, 1965, Nota and Loring 1964, Loring and Nota 1966, 1968,

1969, Loring et aZ. 1970, Loring 1975, 1976, a, b). An overall

report has also been prepared for this region (Loring and Nota

1973). The primary objectives of this work was to provide the

Board's bio ist~ and fishermen in general with quantitative

~HLULHt.ution on the ical characteristics, and mineralogical and

c 1 composition of these sediments. More recently, the data

have been used to establish baseline levels of biologically toxic


metals the environments and define areas of heavy metal

ion (Loring 1975, 1976 a, b). The data have also been used

to the pa by which these elements enter, remain

or leave f system.

In 1963 a (Loring and 1963) was prepared on the

c al techniques used in our laboratory to determine the major

element c i of marine sediments. Since this report was

published, new techniques based on atomic absorption spectrophoto-

me have developed (Rantala and Loring 1973, 1975, 1977) and

our range of st has expanded to include trace elements

(concentrations <1% by weight) and other chemical and physical

characterist s of the sediments as well as the analyses of parti-

culate suspended material.


2.

The purpose of this report is to provide a detailed account

of the techniques used in this laboratory at the present time. It

ludes a description of the ana I procedures used for grain

size determination, the major elements (Si, AI, Ti, Fe, Mn, Ca, K,

Na, Mg) and trace elements (Hg, Zn, Cu, Pb, Co, Ni, Cr, V, , Be,

Ba, Sr, and Rb) in marine sediments and particulate suspended

matter (major elements only). In addition, it describes the proce-

dures for the chemical partition of elements, the determination of

easily oxidizable organic matter, calcium carbonate, dithionite

soluble Fe, ferrous oxide, and the evaluation of oxygen activity in

the sediments. This report written as a laboratory manual for

the Geochemical Laboratory of the Marine Ecology Laboratory and

others who are interested in the techniques used in the physical

and chemical analyses of mar sediments and particulate suspended

matter.

Marine Sediment Classification

Marine sed may be as a mixture of inorganic and

organic mater I that has arrived at the site of deposition as solid

particulate material (detritus) or has been incorporated into the

sediments from solution in a variety of ways (non-detrital material)

They may be classified according to size of the particles (particle

~~U"'lcter making up the sediments), their color, the relative propor-

tion of organic and non-organ components, and their chemical

(siliceous, calcareous, etc.), and mineralogical (quartz-feldspathic,

etc.) composition. In the Gulf of St. Lawrence detrital material

exceeds non-detr 1 mate 1 and determines the broad chemical


3.

features of the sediments as it does for most continental shelf

sediments. For this reason we prefer to classify the sediment

according to size of the particles making up the sediment and its

carbonate content (Table 1). This is the classification used in

mapping the surface sediments of the Gulf of St. Lawrence, (CHS

Chart 8llG, Loring and Nota 1973).

Table 1

SEDIMENT ClASSIFICATION

Sedirnent Size Grades and Particlo Diameters Nomenclature


Critical Limits of the various components are 5% and 30% by weight.
Calcium Particle
- - - - -. . _ - - - - - - - _ . _ - - - - _ . _ - - - -
Size
Grade
Carbonate oiarneter <5% by 5-30% by 5-30% CaC03 >30% by
Equiv. (mm) Weioht Weight by Weight Weight"
------_. "_._----
Pelita Calcipcfite <0-05 Not Named Pelitic Calcareous and Petite Calcipelite
/ or Calclpelitic
Clay <0002
Sill Calcipelito 0-002-0-05 Pelite

Sand Calcarenite 0-05 - 20 Sandy Calcareous and


Sand Calcarenite
/orCalcarenitic
Vory fine Sand 005 -0,125 Very Fine Sand
Fine Snnd 0125 - 0-25 Fine Sand
Medium Sand 0-2.5 - 0-5 Medium Sand
Coarse Sand 0-5 -20 Coarse Sand

GravJC:1 Calcirudite >2-0 Gravelly Calcareous and Gravel Calcirudite


/ or Calciruditic

"If two components represent more than 30% each, the finer grained
component is indicated by its noun, the other with an adjective with
the adverb "vcr/He.g. very sandy pelite and not very pelitic sand. The
term calcipclite is also extended to include calclpelitic petite,

The 1 names the size grades used in this report are:

gravel. particles coarser than 2 mm, sand, for particle diam-

eters between 2 and 0.05 rom (sometimes subdivided into coarse sand

(2~O.5 rom), medium sand (0.5-0.25 rom), fine sand (0.25-.125 mm),

or very fine sand (.125-0.05 rom). For material smaller than 0.05

rom the term pel.ite is used instead of mud. Pelite is composed of

sil.t particles between 0.05 rom and 0.002 rom, and cl.ay particles
less than 0.002 rom in diameter. The term cal.carenite is calcareous

mater 1 of sand size, and Galcareous material smaller than 50~

(0.05 rom) is referred to as calcipel.ite.


4.

The nomenc used to describe the texture of the

iments is similar to that of Nota (1958). Components represen-


ng ss 5% by weight the total sediment are not consid-

ered. Those senting between 5 and 30% are indicated by an

adjec (sandy) se over 30% fy as nouns (sand). If


two components represent more than 30%, the finer-grained component
is icated a noun, the other by an adjective with the adverb
"",0"''' '", e. g. livery sandy peli te" and not "very pelitic sand. II In

s the ipelite is also applied to pelites having

a carbonate content that ranges between 5 and 30% by weight. The

this tem of nomenclature is that the 30% limit can


more easily termined in thin sections or by means of a binocu-
than the 50% limit which is so commonly used.
s of sediments are recorded according to the Munsell

s Geolog Society of America (1971)

Most f the colors are estimated when the samples are fresh and wet,

core s which may dry or partly dry when the

Collect Observations

s ne and particulate suspended matter

re col ted from the sea floor and from the water column using

specif s of apparatus. This is done to ensure that

is of substrate or water

at a ~M,=r';fic geographical location and that is uncontam-

tance that is being analysed for or will

the treatment of the sample.


5.

Surface Samples

Samples of the sediments at the surface of the sea floor and

to a depth not exceeaing 15 cm low the in~orr~~e are collected

by a modified Van Veen grab sampler. The Van Veen grab sampler
2
used in our studies takes a sample of the sea floor of about O.lm

and penetrates up to a depth of 15 cm (depending of course on the

texture of the ). Providing that this sampler is well

designed, no loss of the entrapped sediments and water should occur

the after removal from the sea floor, e.g. leakage of

sediments especially fine-grained material from the grab between

sea surface and the deck will result in erroneous grain size

compositional results. Initially a visual inspection should

be made of samples by means of trap doors in the top of the

bottom grab to ensure that the sample has been collected in an

s state to make an estimate of the texture

of the sediment as 1 as to make certain in situ measurements.

For gravel size material (>2 mm diameter) and sands (2-0.5 mm)

the grab er on s should be done by placing

a non-metal box with a drain and slowly opening the

to let out water. This done to prevent the

loss of any assoc f material, if any, in the sample.

A representa tion of the sample is then collected and placed

a s on the cruise and number have

been written. At least 1-2 kg size mater 1 is collected

if pebble counts are requ ed. Observations noted in a separate log


6.

book include cruise No., station No., geographical location (Lat.,


Long.), water depth, wire angle as well as visual estimate of the

size mater 1. For s of sand, 1 and pelite (mater-

ial < 0.05 mm in diameter); samples of about 1 kg are required if

available. Visual estimates of grain size (coarse, medium or fine

grained), color (according to Munsell color chart code), and the

percentage of other components (gravel, pelite) is made in the log

book. After placement into marked plastic bags, samples of coarse

gra material are placed in marked (cruise No., station No.,

date, time) waxed ice cream containers and stored onboard until

mater 1 is transferred to the laboratory for analyses.

F ined pelites or muds require special attention as

essential components, observations, and measurements may be lost

if not done th certain precautions. The trap doors are opened

f t to see if any water is present on top of the sediment. If

so, the grab is opened slowly, and the water drained off so as

not to wash the sample unduly. Once the top of the sediment is

color of the layer is noted. In our experience,

sediment at interface has a thin oxidized surface layer

usual s from 1 to 10 mm in thickness. It is mostly

yel sh brown (Mun 1 Color Chart Code 10 Y/R 4/2) in color

which is formed by the oxidation of iron compounds in contact with

oxygena sea water. S this layer represents the most recent

sediment it is most representative of the material being deposited

at the present time. Hence, it should be sampled carefully with a

astic spatula and 1-3 grams if possible should be placed in a


7.

numbered plas vial, sea , and frozen for transport to the


laboratory. A sample of the oxidized layer may also be taken to

determine its oxygen activity (see page 52). Before opening

grab, pH and Eh measurements may also be made by placing the


appropriate electrodes into the sample.

After the surface layer has been sampled, the grab is opened

and two samples are taken one of which is representative of both

the surface and subsurface material and the other of the subsurface

material. Obs the material should include colour

(usually dark greenish color because of the reduced state of iron

below the face), gross lithology, and estimate of sand content


made by rubbing fingers to feel any sand grains/or by biting

to assess grittiness of the sample. About 100 grams or more

should be taken to ensure a representative sample. This is placed

a s the contains iron com-


organic compounds are easily oxidized and

s chemical and I composition, the sample


is quick frozen for return to Sometimes fine
gra iments contain ice rafted pebbles. These should be
ram~uorif ident ied if possib , and packaged. Observations ment

oned above should be appropriate places in the log book.

In addition to the Van Veen grab, small surface samples

0.1 kg) may be obta by a ship underway by using a modified

they"mc)q.raph to make a assessment of the texture of the

sea floor (for tails see Loring, et aZ. 1970).


8.

Subsurface Sampling

Samples of the subsurface sediments are often taken to

determine the change in lithology and composition with depth


in order to assess environmental changes in the depositional

conditions with time. They are usually taken in areas having fine

grained sediments but specialized corers are available for coarse

grained sediments. We have used two types: the gravity corer which

free-falls from the ship and penetrates the sea floor by gravity,

and the piston corer which is dropped from a set distance above the

floor, penetrates the sediment by free fall, and the sediment is

sucked into the core barrel by an upward moving piston as the core

is retreived. To avoid problems of extrusion and contamination,

plastic core 1 are placed inside the core barrels. After the

corer is brought on board, the liners are capped at the bottom, the

1 removed, the top, is capped and stored in a vertical position

until. all the water inside the liner has risen to the top. The

core liner is then cut off at the sediment water interface, capped

a deep zer transport to the laboratory.

observat s and measurements should include the usual data

ruise No., S~.No. ,depth, time) along with core length, general

1 and changes in lithology, evidence of methane losses

etc. and recorded in the appropriate places in the log book. In

the Gulf, core samples to 20 m have been obtained using standard

piston corers with weights of 160 kg and 545 kg; plastic 1 1/2"

1 rs up to 6 m were used with the 160 kg core weight and 3 1/2"

liners up to 25 m were used with the 545 kg core weight. Short

cores of about 2 m were also obtained using a light weight gravity

corer. In our experience the greater the diameter of the core


9.

liner, the less will be the amount of distortion of the subsurface

sediment by the corer penetrating the sediments. We have found

the core liners with diameters greater than 2" are satisfactory for

analyses of changes in the rate heavy metal deposition in the

environment (see Loring and Bewers, 1976 for details) .

Suspended Particulate Matter

Suspended particulate matter samples are ~ollected to deter-

mine the concentration and distribution in the water column as well


as the inorganic and organic composition.

matter is commonly defined with reference to a

imum diameter depending on the pore size of the filter being

us However, since a Id-up of particles modifies the effective

pore size of a filter, mater 1 caught on a filter includes


t 1 part les smaller than the original pore size (Sheldon

and Sutcliffe 1969). In pract e, suspended matter is defined

1 as that is reta by the type of filter being

u For s work, there , suspended matter is defined as

reta a 0.4 ~m pore-size Nuclepore filter.

n to obta a sentat sample SPM from water

columns ly c sen an STD cast (sal

ture ). The ing method, and fil

is that descr Sundby (1974) . Typically samples are

taken at each loca : a surface sample (~ 1m), a at the

minimum (i.e., the intermediate cold layer), a th

e in the warmer water, and a fourth 3-5 m above bottom.


10.

Samples are taken with 12 litre Niskin bottles which have been

modified by substituting the internal rubber spring with a PTFE-

sheathed shock spring (Bewers, Hall, and Macaulay 1974) .

Filtration

The Niskin bottles containing samples are placed in wooden

racks after they are retrieved. A pair of wooden wedges placed

between the top of the rack and the top end-cap of the Niskin

bottle prevents the end-caps from leaking during the pressurization

of the bottles. The air-vent is removed from the bottle, and

replaced with a gas inlet vent, made from polypropylene, through

which the Niskin bottle could be pressurized, using compressed dry

nitrogen gas (Figure 1) .

7\ih~itl bo r rle

""ilara''''
FIG. 1 Equipment for pressure filtration.
(From Sundby 1974)
The samples are f tered through Nuclepore filters (47 rom

diameter, 0.4 ~m pore size). The filters are preweighed on

a Cahn RTL electrobalance, In the presence an ionizing source

to minimize the effects of static electricity. The filters are

held in Mill in-l fi ho s made of glass-filled

polypropylene. The f holders are connected to the Niskin

bottle outlet with Tygon tubing. The sample is filtered at

pressures up to 5 p.s.i. until either the filter clogs or all of

the sample has been passed through the f ter.

The filters are rinsed with 50 ml of distilled, deionized,

membrane-filte water 11 in the filter holder using a

slight vacuum produced by an a pump. The filters are

12 h at 60C, cooled in a desiccator, and then

weighed.

Source of Error

The errors affect the measurement of SPM (material> 0.4

~m pore size of Nuc f ters) are:

Errors that arise the sample. The

may become , particles may be generated or

Such errors 1 t the accuracy the

measurement, but are kept to a minimum by the

1 pressure filtration procedure.

(b) Errors the exper 1 pro(~e(1ure. Sources of

systemat errors, if know'n, can be eliminated. For

tance, Ba or and Sutclif (1963) demonstrated that

les can be generated through bubble formation and

ng. which forms on the underside of the


12.

filter during vacuum filtration could, therefore,

generate particles which, if they adhere to the filter,

will cause a positive error in the weight of the sus-

pended matter. This source of error is eliminated by the

use of pressure rather than vacuum filtration. Salt not

washed out of the filter can introduce analytical error.

Cranston and Buckley (1972) showed that on the average

Millipore filters (Type HA) retain 1.6 mg sea-salts even

after a rinse with 25 ml distilled water. This source

of error was eliminated by the use of Nuclepore filters,

which do not retain significant amounts of sea-salts

(Cranston and Buckley 1972) .

The measurement is affected by random errors introduced

when weighing the filters and/or measuring the volume of

the filtrate. The weighing error is estimated from

duplicate weighings of a large number of filters. The

average standard deviation of the weight of a filter is

O.025 mg/filter. The standard deviation of the differ-

ence between two filter weights (before and after

filtration) becomes O.025 x 12 = O.035 mg per sample.

This amounts to a 10% error when as little as 0.35 mg

suspended matter is collected from one sample. Typically

this error amounts to less than 2% of the weight of the

suspended matter.
13.

The volume of the filtrate is estimated to to.ll for

volumes greater than 2.0 1 and to to. OIl for 2.0 I and

less. Thus, the volume measur error is a max

of 5%, decreasing to 1% for large volumes (10-1 samples).

Fortunately, the smallest volumes correspond to the

highest concentrations, and vice versa. Therefore, where

the weighing error is large, the volume error is small

and vice-versa. The overall error is estimated conser-

vatively as 10%. The systematic error caused by the

settling of particles during the time it takes to complete

the f tration worth noting. This is not a problem

where the whole sample is filtered, but where only a

portion of the filtered, a positive error is

introduced. In an experiment involving multiple filtra-

t of coastal water samples with concentrations from

0.5 to 2.5 mg/l, the first of two subsequent determina-

tions gave on the average a concentration 5% higher than

mean of the two (B. Sundby, unpublished

data). Assuming a similar s ion for Gulf samples, a

5% overestimate in the concentration values is reasonable.

Initial Sample t

The 1 preparation of s involves the subsampling of

original sample sentat ions and the subsequent

treatment(s) required before the analyses can begin.


14.

Apparatus and Equipment

Grain size separations require 2000, 500, 53 and 37 ~m

sieves, Atterberg cylinders, drying oven and evaporating dishes.

A large capacity centrifuge is highly desirable although not

absolutely necessary for washing samples free of sea salts and

separating clay size fractions. The same centrifuge with smaller

head or a centrifuge of smaller capacity is also needed to separate

the acetic acid soluble fraction.

In this laboratory, a centrifuge with maximum capacity of 6xl

litre (MSE LR-6) was used to make the samples salt free and to

separate the clay size fraction. Accessory slotted cups 18xlOO ml

were utilized to separate the acetic acid soluble fraction.

Sedimentological Analyses

Samples designated for sedimentological analysis are unfrozen

and air dried for 24 hours, after which, sufficient sample material

is obtained for the analyses by splitting and quartering. For all

gravel samples, about 300 pebbles are set aside for petrographic

ana s. Sand and mud samples for grain size analysis are sorted,

it, and dried at 110G C. A representative sample is obtained by

separating the mater 1 >2 rom from the finer material. Material

>2 rom is set aside for petrological analyses. The analyses for

particle size distributions are carried out by the normal combined

sieve-pipette methods after the removal of CaC0 by 4N RCI and


3
organic carbon matter by 10% H20 2. A sodium phosphate solution is

used as the dispersing agent. The size fraction (500-53~) obtained

by dry sieving, is set aside for mineralogical analyses. The heavy


15.

and light minerals are separated by heavy liquids and identified

by various techniques. Since this report is primarily concerned

with the chemical analyses, the reader interested in the details


of the sedimentological analyses should refer to the standard

textbooks on the subject, such as Krumbein and Pettijohn (1938).

Chemical Analyses

The selection of sUbsamples for chemical analyses involves

procedures for subsampling, drying (where required), removal of

soluble sea salts, physical and chemical partition, mixing,

weighing and storage.

Initially, zen samples are allowed to thaw. Representative

samples are obtained using plastic utensils. Extreme care is

taken during this procedure~ as in all cases~ to avoid metallic

contamination by metallic objects~ undecontaminated plastic and

glassware~ and uncovered hands.

Both dry and wet subsamples are required.

At least two separate samples are taken and dried under diff-

erent c These are (1) a suff sample (~ 0.5 gm)

the analyses of mercury which 1 be dried at <60C to avoid

the loss of Hg I and ( 2) a fic amount (1-10 gm) for other

al c 1 s hare dried at 110C.

Samples are placed in or teflon containers and placed in

a ing oven at either 60C (Hg) or 110C to remove water the

24 hours ter are placed in a sicator

until cool, and stored in a tight plastic vials until required

for future use.


16.

Samples in the wet state are used for (a) determination of

H contents, (b) removal of soluble sea salts, and (c) separation


20
of grain size fractions For the latter two requirements, the wet

samples are used because the sediment is much easier to disperse

wet than oven-dried.

Removal of Soluble Sea Salts

Soluble sea salts are removed from samples required for the

major and trace element analyses, particularly the major cations

Na, K, Ca and Mg. This is done to ensure that there is no contam-

ination of sediments by sea water present in them and that there

are no chlorine-induced inferences in the chemical analyses.

About 10-20 g of dry sample is transferred to 1 liter poly-

propylene centrifuge bottles and dispersed by shakhg mechanically

about 30 minutes with 1 litre of H 0 (distilled and deionized


2
water). The suspension is centrifuged at 2000 rpm until clear.

The water is off. This is repeated until supernatant is

chlorine The sediment is transferred in the evaporating

dish and dr drying oven at 11OGC. The dried sample is

in agate mortar, mixed well to avoid selective crush-

ing and an a tight vial until required.

Removal of the Biologically Available


Acetic Acid Soluble Fraction

The sources of heavy metals in the aqueous environment and

the in iments and suspended matter is shown below.


Dissolved
Adsorbed positions
Suspended matter - Organic matter
HEAVY METALS IN THE Iron and manganese oxides
AQUEOUS ENVIRONMENT Lattice positions
Deposited sediment Discrete minerals
Interstitial water
17.

Chemical partition of the elements into the non-detrital

(acid soluble) and detrital contributions allows certain deductions

made as to the site of the elements and the pathways by which

they have entered the sediments. The non-detrital contribution

represents the proportion of the total trace metal concentrat

that has been transported in solution or in colloidal form, and

incorporated into the sediments in a variety of ways such as prec

itation, adsorption onto suspended particulate matter or extraction

living organisms. It is this fraction that is most easily avail-

able to the biota and constitutes the greatest danger to them if

present excessive amounts. In contrast, the heavy metals in

trital fraction are not readily available to the biota as they

are locked up the lattices of their host minerals. The heavy

metals in the trital fraction, however, constitute the long term

supply of these metals to the environment. They may, however, become

ava able to biota some time after deposition as a result of

bioturbation, changes in pH, Eh, etc. For this reason it is impor-

tant to determine the non-detrital and detrital contributions to the

total elemental content when evaluating the levels and behaviour of

bio ica heavy metals in mar environment. The

term are also va in evaluating other material des~~.u~~

r dis sal and deposition the environment such as t derived

from disposal of and mine wastes particularly for those toxic

elements des under the Ocean Dumping Act and the Env 1

Contaminants Act.

Acetic acid is u to remove elements held in carbonates,

easi s of Fe and Mn, loose ion

excHUHYC;; and posit s, and weakly attached to organic matter.


18.

This treatment leaves the lattice structure of silicate minerals

intact and does not attack the resistant iron and manganese oxide

minerals.

Procedure:

In this method exactly 5.0 g of washed sediment is transferred

in a 100 ml teflon evaporating dish and the sample + dish weight is

determined. 50 ml of 25% acetic acid is added followed by stirring.

The evaporating dish is covered and let stand in the fume hood for

24 hours with occasional stirring. After 24 hours, acetic acid is

decanted in a 100 ml centrifuge tube. It is centrifuged until clear

and the supernatant poured in a 200 ml volumetric flask. The sedi-

ment in the teflon dish is washed 3 times with 10 ml of distilled

water each time pouring the washings in the centrifuge tube. It is

recentrifuged and again the supernatant collected in the volumetric

f sk. The sediment in the teflon dish is now free from acetic acid

soluble fraction; however, the sediment in the centrifuge tube should

be washed twice with 20 ml of H2 0 each time stirring the sediment,

centrifug and combining the washings in the volumetric flask. If

the last washing the supernatant does not become clear a few

drops of 25% acetic acid should be added and recentrifuged. The non-

ital fraction is made up to 200 ml with H 0 and stored in a


2
polypropylene bottle for analysis.

Finally, all the sediment will be washed back in the evapor-

ating dish and dried in the oven at 110C. Care must be exercised

that none of the sediment is lost at any time. When dry, the dish

plus sample is weighed and the weight of the acetic acid soluble
19.

fraction is determined by subtraction from the original weight.

The dried detrital fraction is crushed, mixed well and stored in

an air-tight vial until required.

Grain Size Separation

It has been found (Loring and Nota 1973) that the elemental

and mineralogical composition change with sediment grade and grain

size. This occurs because the host minerals of the elements and

the surface area of the particles making up the sediments, change

with grain size. In addition significant regional comparisons of

elemental concentrations can only be made by using texturally

equivalent sediments and/or size fractions. For these reasons it

is often necessary to determine elemental concentrations in

different size fractions of the sediments.

Procedure:

scheme for size separation is shown in Figure 2.

<500]J 500]J sieve


I
500-53]J
l 53]J sieve

53-37]J
l 37]J sieve

<2]J
C <2]J centrif.
I
16-2]J <16]J Atterberg
I Cylinder
I
37-16]J >16]J Atterberg
f Cylinder

Figure 2 : Scheme for grain size separation.


20.

Water soluble salts are removed from 10 - 20g of sample as

described on p. 16. However, the sediment is not dried, but passed

through 500~, 53~ and 37~ sieves in sequence with the aid of H20
and light brushing. The fractions are collected from each sieve

and transferred in pre-weighed teflon evaporating dishes, dried at

110oe, and weighed. The dry > 500~ fraction is passed through a

2 mm sieve to remove rock fragments > 2 mm. The < 37~ fraction is

put back in the centrifuge bottle, made up to 1 litre with 0.16N NH


40H
as dispersive agent, and shaken mechanically for about 30 min.

Alternatively, an ultrasonic probe could be used in place of NH


40H
for dispersing the sample. The < 2~ fraction is separated by

centrifuging. The centrifuging time is calculated from Stoke's Law

(Tanner and Jackson 1947) and the < 2~ material is syphoned off and

s centri bottles. 0.16N NH is again added and the


40H
c fuge bottle is shaken mechanically and centrifuged. The whole

process is repeated until the supernatant syphoned off is clear.

Usually, 4 times is ficient, although this depends on the amount

of c present. The stored < 2~ fraction is centrifuged to remove

water, trans in the pre-weighed dish, dried at 1100e (60 oe Hg)

and we
The 37-2~ fraction is transferred from the bottle into an

cylinder with mark 30 cm from the bottom of syphon tube

made up to mark with 0.16N NH shaken and let stand for the
40H,
i time derived from Table 2.
21.

Table 2

Sampling Times for Size Fractions in a


Beaker or Atterberg Cylinder.

<2 11 <4 11 <8 11 <8 11 <16 11 <32 11

+:
TEMP C 5 em 5 em 10 em 30 em 30 em 30 em

10 5'h 12" l'h 18 111 39'0" l'h 57" 29'15" 7'19"


11 5 3 1 16 37 55 1 54 28 27 7 7
12 4 55 1 14 36 53 1 51 27 41 6 55
13 4 47 1 12 35 54 1 48 26 56 6 44
14 4 40 1 10 34 58 1 45 26 13 6 33
15 4 32~ 1 8 34 4 1 42 25 32 6 23
5
16 4 25~ 1 6~ 33 12 1 39 24 53 6 13
17 4 19 1 5 32 21 1 37 24 15 6 4
5
18 4 12 1 3 31 32 1 34 23 39 5 55
19 4 6 1 1~ 30 45 1 32 23 4 5 46
20 4 0 1 0 30 0 1 30 22 30 5 37~

21 3 54 58~ 29 16 1 28 21 57 5 29
5
22 3 49 57 28 31 1 25 21 24 5 21
23 3 44 55~ 27 46 20 51 5 13
24 3 39 54 27 01 20 18 5 05

+: Column from which particles larger than indicated have


settled down in specified time and temperature
22.

The syphon tube is then unclamped and the 2-16 ~ fraction collected

in the centrifuge bottle. This is repeated until clear. Water is

centrifuged off the 2-16 fraction. This fraction is then trans-

ferred into a pre-weighed evaporating dish, dried at 110C (60C Hg)

and weighed. The fraction remaining in the Atterberg cylinder is

16-37 ~ tion. It is also transferred in pre-weighed evaporating

dish, dried at 110C (60C Hg) and weighed.

Dried fractions are crushed, mixed and stored in vials.

If centrifuge is not available the < 2 ~ fraction is sepa~ated

the beaker according to the sampling times shown in Table 2.

F Atomic Absorption Analyses

ratus and Equipment

The major item of equipment required is an atomic absorption

It should be equipped with a recorder readout

accessory to obtain a permanent record of elemental

absorbance to al se determination of the absorbances.

acces to correct non -a \..V.Ul.l..'-' is also requ ed

1 Co Ni Pb are to determined.

The : a lance ~~~~u1e of weighing to

the neare f mortar pes , decomposition vessels, water

bath for h the vessels, mechanical shaker, polypropylene

flasks bo s making up to the volume and storing

the es. A source water is a

es 1 to obta metal free water.


23.

For preparation of standards and dilution of large numbers

of samples micropipettes and sampler-diluter are desirable.

In this laboratory Perkin-Elmer 303 and 306 atomic absorption

spectrophotometers equipped with the recorder readout accessory,

deuterium background corrector and lO-mv full scale deflection

recorder are used in all the A.A. analyses.

The decompositions were carried out in all-teflon pressure

vessels designed in this laboratory, Rantala and Loring (1973).

A Kimble Model SDM-60 sampler-diluter was utilized in the dilutions.

Sample Decomposition

Sediments

The sample decomposition is carried out in a sealed all-Teflon

vessel with hydrofluoric acid and aqua regia as shown in Fig. 3.

Fig. ~. Tefl,," .Bomb-Cross-Seclion (nol 10 scale). Dimensions: Height of


body 2%", outside diamete. 2", inside diameter 1", maximum c"pocit)'
21 ml. Thre"ded COVer. Height 1", oUhide di"meter 21h".
24.

Boric acid is used to complex the fluorides which also makes the

solution very stable.

The only variation in decomposing sediment samples for major

or trace elements is the sample size. 0.1 g sample is decomposed

for major elements, but a larger 1.0 g sample is required for trace

elements.

Reagents:

Aqua Regia HN03-HCl (1:3 v/v)

Hydrofluoric Acid ACS reagent

Boric Acid ACS reagent

Decomposition procedure:

A finely ground sample of 0.1 g or 1 g is weighed accurately

in the Teflon vessel and wetted with 1 ml of aqua regia. Six ml

of concentrated HF are added slowly, and the cover is placed on

The vessel is immersed in a water bath (90C - 100C)

for 1 hr. Care should be taken that the vessels remain immersed

during the entire heating period. Following the heating, the

vessels should immediately be removed from the water bath and placed

in cold water. The water level should not reach the threaded cover.

These precautions are necessary to avoid sucking water into the

vessels by the vacuum created during cooling. Alternatively the

vessel may be heated on the hot plate or in the drying oven located

the fume hood. After cooling, the contents are washed into a

100 ml polypropylene volumetric flask containing 5.6 g H that


3B0 3
has been shaken with approximately 20 ml of H The flask is shaken
20.
to complete the dissolution and made up to volume. The solutions

are stored in polypropylene bottles.


25.

Sample solutions thus prepared are extremely stable. In more

concentrated trace element solutions, a gelatinous precipitate of

bOrosilicates will form due to the high concentration of silicon.

This has no adverse effect on trace element determinations and the

removal of the bulk of silicates is desirable.

The organic matter leaves a black residue that settles. Its

element contribution is negligible. If a clear solution is desired

it is necessary to treat the sample solution after decomposition with

perchloric acid. As perchloric acid is hazardous and requires a

special fume hood, it is not recommended.

Suspended Particulate Matter

Suspended matter samples on Nuclepore filters are decomposed

in similar fashion as sediments although it is necessary to use lesser

reagents and of higher purity. Nuclepore filters themselves are not

decomposed.

In decomposing small (.2 - 10 mg) samples of SPM it is neces-

sary to use high purity Ultrex grade HCI, HN0 and HF. The reagent
3
grade acids contain large amounts of silicon and iron. For some

elements, reagent grade acids may be sufficient.

Reagents:

Aqua Regia HN03-HCI Ultrex (1:3 v/v)

Hydrofluoric Acid Ultrex

Boric Acid ACS reagent


26.

Procedure:

Transfer a filter into a Teflon vessel with plastic tweezers

and squash it in the bottom of the vessel. Add 1 ml of aqua regia,

1 ml of HF and place the cover on tightly. Submerge the vessel in


GC
a water bath (90 - 100G C) for 1 hr. Same precautions should be

observed as described for sediment decomposition.

After cooling, the contents are decanted through a polypropylene

funnel into a 25 ml polypropylene volumetric flask containing 0.93 g

H and approximately 5 ml of H The filter remaining in the


3B0 3 20.
Teflon vessel is washed several times with small volumes of H each
20
time collecting the washings in the 25 ml flask. Finally the volu-

metric flask is shaken to complete the dissolution and made up to

25 ml with H The solutions are stored in polypropylene bottles.


20
The blank solution is prepared in the same fashion but omitting the

Standard Preparation

Stock Standards

AI, 1000 pg/ml. Dissolve 1.000 g of Al wire in a minimum amount

of (l+l) HCl, adding a small drop of mercury as a catalyst.

lute to 1 litre with 1% (v/v) HCl. Filter the solution to

remove the mercury.

Ca, 1000 \lg/ml. To 2.497 g of dried CaC0 add 50 ml of deionized


3,
water. Add dropwise a minimum volume of HCl (approx. 10 ml)

to fect complete solution of the caCo Dilute to 1 litre


3.
with H
20.
27.

Fe, 1000~g/ml. Dissolve 1.000 g of iron wire in 50 ml of (1+1)

HN0 dilute to 1 litre with H


3. 20.
K, 1000 ~g/ml. Dissolve 1.907 g of KCl, in 1 litre of H~O.
~

Mg, 1000 ~g/ml. Dissolve 1.000 g of magnesium ribbon in a minimum

volume of (1+1) HCl. Dilute to 1 litre with 1% (v/v) HCl.

Mn, 1000 ~g/ml. Dissolve 1.000 g of manganese metal in a minimum

volume of (1+1) HN0 Dilute to 1 litre with 1% (v/v) HCl.


3.
Na, 1000 ~g/ml. Dissolve 2.542 g of NaCl in 1 litre of deionized

water.

Si, 1000 ~g/ml. Decompose 1.070g of Si0 in Teflon vessel according


2
to procedure for major and trace elements. Dilute to 500 ml

and store in polypropylene bottle.

Ti, 1000 ~g/ml. Decompose 0.834 g of Ti0 in Teflon vessel


2
according to procedure for major and trace elements. Dilute

to 500 ml and store in polypropylene bottle.

Ba, 1000 ~g/ml. Dissolve 1.779 g of barium chloride, BaC1 2.2H


20
in 1 litre of H
20.
Be, 1000 ~g/ml. Dissolve 1.000 g of beryllium metal in a minimum

volume of (1+1) HCl. Dilute to 1 litre with 1% (v/v) HCl.

Note: In preparing Be standards it is advisable to use

commercially available stock standard solutions since beryllium

dust is potentially toxic.

Co, 1000 ~g/ml. Dissolve 1.000 g of cobalt metal in a minimum

volume of (1+1) HCl. Dilute to 1 litre with 1% (v/v) HCl.

Cr, 1000 ~g/ml. Dissolve 3.735 g of potassium chromate K '


2cr0 4
in 1 litre of H20. If the determination is carried out in a

air-acetylene flame it is necessary to reduce cr 6+ to cr 3+

(Rantala and Loring 1975). Although sensitivity is reduced


28.

in a nitrous oxide-acetylene flame it is less prone to

interferences and is recommended for marine sediments.


Cu, 1000 llg/ml. Dissolve 1.000 g of copper metal in a minimum

volume of (1+1) HN0 Dilute to 1 litre with 1% (v/v) HN0


3. 3
Li, 1000 llg/ml. Dissolve 5.324 g of Li in a minimum volume
2C0 3
of (1+1) HC1. Dilute to 1 litre with H
20.
Ni, 1000 llg/ml. Dissolve 1.000 g of nickel metal in a minimum

volume of (1+1) HN0 Dilute to 1 litre with 1% (v/v) HN0


3 3
Pb, 1000 llg/ml. Dissolve 1.598 g of lead nitrate, Pb (N0 in
3)2
1 litre of 1% (v/v) HN0
3.
Rb, 1000 llg/ml. Dissolve 1.415 g of RbCl in 1 litre of H
20.
Sr, 1000 llg/ml. Dissolve 2.415 g of Sr(N0 in 1 litre of 1%
3)2
(v/v) HN0 3

V, 1000 llg/ml. s 1.000 g of vanadium metal in a minimum

volume of HN0 and dilute to 1 litre with 1% (v/v) HN0


3 3.
Zn, 1000 llg/ml. Dissolve 1.000 g of Zn metal in a minimum volume

of (1+1) I and dilute to 1 tre with 1% (v/v) HCl.

Standards: Sed s

Al, Ca, Fe I !S.,


a combined stock standard solution from 1000 ppm

solut s by tak 30 ml of , and 10 ml of Ca, Fe, K, Mg, Na

and 5 ml of Mn solutions and dilute to 100 ml with H


20.
lute C Ulll.U i.UC:Ll sta 25, 5 0, 75, 100, 200 and 400

times for working ~~.u~~rds. All the working standards to have

concentration of 1500 ppm K as KCl except standards for K that

are in 1500 ppm Na as NaCl. Working standards thus obtained have

the 1 concentrations of metals:


29.

llg/ml

Ca, Fe, K, Na, Mg .25 .50 1.00 1.50 2.00 4.00

Al
'7 c:;
I .,J
1
.J..
J:;
..J V
n ':l
..JeVV
nn 4.50 6.00 12.00

Mn .125 .25 .50 .75 1.00 2.00

Ba standard

Dilute 1000 ppm stock solution to obtain working standards

of 0.1 - 2.0 ppm Ba. Working standards to be made up in the

decomposition blank matrix. Add solid KCl to each standard so

that the final concentration is 1500 ppm K.

Si standard

Dilute 1000 ppm stock solution to obtain working standards

of 200 - 400 ppm Si. Working standards to be made up in the

decomposition blank matrix.

Sr standard

Dilute 1000 ppm stock solution to obtain working standards

of 0.1 - 1.0 ppm Sr. Add KCl to each standard so that the final

concentration is 1500 ppm K.

Dilute 1000 ppm stock solution to obtain working standards of

2~10 ppm Ti. Add KCl to each standard so that the final

concentration is 1500 ppm K.

Co, Cu, Li, Ni, Pb, Zn standards

Prepare a combined stock standard solution from 1000 ppm

solutions by taking 5 ml of each Co, Cu, Li, Ni, Pb and Zn and

dilute to 100 ml to obtain the combined standard of 50 ppm for each

element. the combined standard to obtain working standards

of G. l - 2.0 ppm. Working standards to be made up in the decompo-

si blank matrix.
30.

Be standard

Dilute 1000 ppm stock solution to obtain working standards

of 5 - 30 ppb Be. Working standards to be made up in the decom-

position blank matrix.

Cr standard

Dilute 1000 ppm stock solution to obtain working standards of


0.1 - 1.5 ppm Cr. Working standards to be made up in the decom-

position blank matrix.

Rb standard

Dilute 1000 ppm stock solution to obtain working standards

of 0.2 - 3.0 ppm Rb. Working standards to be made up in the

decomposition blank matrix matching K concentration of the standards

to the samples.

For the most accurate Rb determination, the K concentration

of the sample should be determined first and the K concentration

of the sample matched to the standards. For fast, but less accurate

results, several standard curves with varying K concentrations can

drawn by using just one standard each case as Rb absorption

was found to be linear at least to 3 ppm. Rb concentration of the

~a!ll~I~e is read from the standard curve having K concentration

closest to that of the sample.

V standard

ute 1000 ppm stock solution to obtain working standards of

0.3 5.0 ppm V. Working standards to be made up in the decompo-

sition blank with 100 ppm Al and 500 ppm K.


31.

Working Standards: Suspended Particulate Matter

To avoid contamination and to simplify standardization,

international rock standards are used as working standards. Large

numbers of such rock standards are available from various sources

Flanagan (1974). In this method, U.S.G.S. rock standards AGV-l,

BCR-l, G-2 and GSP-l and Canadian Certified Reference rock standards

MRG-l and SY-2 are used. The concentrations of the elements

analyzed are given in Table 3.

TABLE 3

Elements in Standard Rocks (%) Cu and Zn (ppm)

1
AGV-1 BCR-l 1 G-2 1
GSP-l 1 MRG-1 2 SY-2 2

Al 9.13 7.20 8.15 8.07 4.50 6.43


Ca 3.50 4.95 1. 39 1.44 10.5 5.74
Fe 4.73 9.37 1.85 3.03 12.5 4.43
K 2.40 1.41 3.74 4.59 0.15 3.75
Mg 0.92 2.09 0.46 0.58 8.13 1.60
flm 0.075 0.14 0.026 0.033 0.13 0.25
Na 3.16 2.43 3.02 2.08 0.53 3.24
27.6 25.5 32.3 31. 5 18.3 28.1
Cu 60 18 12 33 135 7
Zn 84 120 85 98 185 250

IFlanagan (1973)
2Abbey et aL (19'75)
32.

Four rock standards giving the expected range for each element

were chosen as working standards. Approximately 10 mg of each rock

standard is accurately weighed on Nuclepore filter, decomposed and

diluted to 25 mI. This gives standard solutions for Si, Mn, Cu and

Zn. When these solutions are further diluted 10 times in the

appropriate matrix, working standards are obtained for AI, Ca, Fe,

K, Mg and Na.

Concentration source rock of each working standard prepared

in this manner are shown on Table 4 assuming exactly 10 mg of each

rock is weighed.

TABLE 4

Elements in working solutions from standard rocks (ppm)

2500x dilution

Si Mn Cu Zn

MRG-1 73 G-2 0~10 G-2 0.005 G-2 0.034

102 AGV-l 0.30 GSP-l 0.013 BCR-l 0.048

SY-2 112 0.56 AGV-l 0.024 MRG-l 0.074

G-2 129 1.00 MRG-l 0.054 SY-2 0.100

25000x dilution

4
Ca Fe K Mg Na

MRG-l 1.80 G-2 0.56 G-2 0.74 MRG-l 0.06 G-2 0.18 MRG-l 0.21

SY-2 2.57 AGV-l 1.40 SY-2 1.77 BCR-l 0.56 AGV-l 0.37 GSP-l 0.83

G-2 3.26 BCR-l 1 98 BCR-l 3.75 AGV-l 0.96 SY-2 0.64 BCR-l 0.97

AGV-l 3.65 2.30 MRG-l 5.00 GSP-l 1.84 BCR-l 0.84 SY-2 1.30
33.

Additional standards may be prepared when small samples are

analyzed for silicon, although the silicon working curve is linear

in the concentration range expected.

Determination of Major and Trace Elements in Sediments


and Suspended Particulate Matter

Table 5 shows the analytical scheme for the major and trace

elements in sediments.

Table 5
Sample Preparation Diagram for Silicate Rock Analyses

+lOOOX dilution +Mn, Si


O.l-g sample + Teflon +Ba, Sr, Ti
+lOOOX dilution in 1500 ppm K
Vessel Decomposition
+20000X dilution in 1500 ppm K +Al, Ca, Fe, Mg, Na
+20000X dilution in 1500 ppm Na +K

I-g sample + Teflon +Be, Co, Cr, Cu, Li


Vessel Decomposition Zn
+ 100X dilution Ni, Pb, Rb, V,

For the major and some minor elements, a 0.1- g sample is

decomposed with HF and aqua regia in a Teflon vessel and initially

diluted to 100 mI. From this solution Mn and Siare determined

directly.

Solid KCl is added to separate aliquots to give a potassium

concentration of 1500 ppm, and these are analyzed for Ba, Sr and Ti.
34.

For the determinations of AI, Ca, Fe, Mg, and Na, a further

20X dilution is made to give the desired dilution factor of 2 x 10 4

for these elements in the KCl (1500 ppm K) matrix. A similar

dilution is also made for the determination of K by substituting

NaCl as the diluent.

For trace element determinations, a separate 1- g sample is

decomposed in the Teflon vessel and diluted to 100 mI. From this

solution Be, Co, Cr, Cu, Li, Ni, Pb, Rb, V, and Zn are determined

directly.

In the suspended matter analyses: Si, Mn, Cu and Zn are

determined directly from the decomposition solution. For the

determination of AI, Ca, Fe and Mg, the solution is diluted 10

t in a KCl solution (1500 ppm K). Similar dilutions are made

K and Na in NaCl and KCl solutions (150 ppm-Na or K) respec-

tively. This is necessary, if reagent grade KCl and NaCl are

used, since they have respectively significant amounts of Na and

K as impurit s. Alternatively, ultrex grade KCl and NaCl or

alkali metal with fewer impurities could be used to suppress

the ization.

S L-UHU,Q.L c t atomic absorption analyses (Perkin-

Elmer 306) are g Table 6.


- 35 -

Table 6

Standard Conditions for Atomic Absorption Analysis

Perkin-Elmer 306

Reducing Red
Element Wavelength Setting Slit Setting Oxidant 'Flame Filter

Al 309* UV 4 N 0 .;
2
Ca 211 Vis 4 N 0
2
Fe 248* UV 3 Air

K 383 Vis 4 Air

Mg 285 UV 4 N 0
2
Mn 279* UV 3 Air

Na 295 Vis 4 Air

Si 252* UV 3 N 0 .;
2
Ti 365* UV 3 N 0 .;
2
Ba 277 Vis 2 N 0 .;
2
Be 235 UV 4 N 0 .;
2
Co 241* UV 3 Air

Cr 358* UV 4 N2 0

Cu 325 UV 4 Air

Li 335 Vis 4 Air .;


Ni 232* UV 3 Air

Pb 283 UV 4 Air

Rb 390 Vis 5 Air .;


Sr 230 Vis 3 N 0
2
I
V 318 UV 4 N 0 .;
2
Zn 214 UV 4 Air

*Exercise care when setting wavelength as other less sensitive lines


are nearby.
36.

Interferences

Matrix interferences on major and minor elements are reduced

by dilution to bring the concentration to the linear portion of the

absorbance curve. Ionization is controlled by additions of 1500

ppm K or Na to standards and samples. Chemical suppression by

elements such as silicon and aluminum on calcium and magnesium

absorption is avoided by the use of a nitrous oxide-acetylene flame.

This eliminates the need for lanthanum which is essential in an

air-acetylene flame. No interferences were observed for Mn and Si

in a fluoboric-boric acid matrix.

Ionization in Ba and Sr determinations is controlled by adding

1500 ppm K to samples and standards. Standards for Rb and V

require spec 1 attention as scussed under standard preparation.

Molecular absorption is corrected by the Deuterium Background

Corrector in Co, Ni, and Pb determinations. No interferences were

observed for Be, Cu, Li, and Zn in a fluoboric-boric acid matrix.

Rela Accuracy and Precision

Table 7 ind tes the relative accuracy of the major and minor

element data for W-l and G-2 by the comparison of our values to

those compiled by Flanagan (1973). The precision is expressed as

a coefficient variation. To obtain these data, 6 separate portions

of W-l and G-2 were analyzed.


37.

TABLE 7
Elements in U.S.G.S. Standard Rocks:
Coeff.
A B Yar.(%)
AI W-l 7.94 7.68 1.5
G-2 8.15 8.11 '1..7
Co W~l 7.83 7.83 0.7
G-2 1.39 1.40 1.9
Fe W-l 7.76 7.96 0.4
G-2 1.85 1.90 5.0
K W-l 0.53 0.56 4.1
G-2 3.74 3.62 1.2
Mg W-j 3.99 3.86 0.1
G-2 0.46 0.44 4.1
Mn W-l 0.132 0.127 1.1
G-2 0.026 0.025 4.4
No W-l 1.59 1.60 1.2
G-2 3.02 0.8
Si W-l 24.6 24.6 2.6
G-2 32.3 31.5 0.8
TI W-l 0.64 0.67 1.5
G-2 0.30 0.31 2.6
A Flanagan
B Rantala and Loring, (1975 )

8 s the relative accuracy of the trace element

seven U S.G.S. rocks by comparison of our

s to se compiled (1973). The precision is expres

as a coefficient of var ion (Table 9). These data are based on

3 of
38.

TABLE a
Trace Elements in U.5.G.S. Stt:mdcnd Rocks (ppm)
AGV-l BCR-l W-l 075-1 G-2 GSP-l PCC-l
Bo (0) 1208 675 160 2.4 1870 1300 1.2
(b) 1140 630 156 <5 1970 1230 <5
Be (0) 3 1.7 0.8 2.0 1.5
(b) 2.0 2.1 0.9 <0.5 2.9 1.7 <0.5
Co (0) 14 38 41 133 5.5 0 112
(b) 18 36 41 128 7 9 109
Cr (a) 12 18 114 7 12
(b) 9 11 no not enelyzed 7 12 not analyzed
CI.I (0) 60 18 110 7 12 33 11
(b) 59 15 122 7 12 31 11
u (a) 12 13 14 2 37 32 2
(b) 12 14 14 2.7 34 30 1.7
Ni (0) 18.5 16 76 22.59 5 12.5 2339
(b) 12 <12 66 2420 <12 <12 2420
Pb (a) 35 18 8 14 31 51 13
40 16 <1:2 13 34 59 <12
Rb (a) 67 47 21 168 254
(b) 67 49 21 not analyzed 166 248 notol'lclyzed
Sf 657 330 190 0.35 479 233 0.41
(b) 698 363 194 <2 457 245 <2
V (a) 125 399 264 10 35 53 30
128 446 285 <15 42 62 23
Zn (a) 84 120 86 45 85 98 36
90 129 86 32 87 105 28
a (1973)
b Ranta and , (1975)

TABLE 9
Precision of Variation} for the
Determination of Trace Elements in
U.S.G.S. Standard Rocks (%)
W-l DrS-} G-2 GSPl PCC-T
3.2 1.1 1.4
Be 2.8 4.0 1.7 1.9
Co 14 2.4 0.9 7.9 12 0.9
Cr 5.6 0.5 6.1 1.9
Cu 4.2 3.7 4.2 4.3 4.9 5.6
u 2.6 2.2 6.4 0.8 1.5 10
Ni 4.5
Pb 4.3 15 11 8.6
Rb 2.3 1.2 4.1 2.1 0.5
Sr 2.2 2.9 5.1 1.6 3.5
V 1.2 2.4 0.7 6.0 4.3 7.5
Zn 1.3 1.6 0.7 1.5 4.1 1.0 1.8
39.

For suspended matter samples the relative accuracy is comparable

to that obtained for standard rocks.


rro estimate the precision 3 seawater samples from the same

Nisken bottle were filtered. Each filter (mean SPM wt 1.99 mg)

was then analyzed for Fe and Mn as these showed most variability

in the SPM samples. It was found that the coefficient of variation

.div.
mean
x 100) was 2.4% for Fe and 4.4% for Mn.
40.

Flameless Atomic Absorption Analysis for Hg

The method used is modified from Hatch and Ott (1968).

It consists of oxidizing the sediment sample (10 - 100 mg dry

weight) by digesting with a mixture of concentrated nitric and

sulphuric acids at 60C for 1 hour and reducing to the

elemental state with stannous chloride. The mercury vapor is

then passed through a quartz adsorption cell of an atomic

absorption spectrophotometer where its concentration is

measured and recorded by means of a strip chart recorder.

Apparatus

Atomic Absorption Spectrophotometer

Mercury Hollow Cathode Lamp

Recorder 10 mV full deflection

Absorption cell. Constructed from borosilicate glass

tubing, 25-wm o.d. x 15 em with quartz windows (25 mm x

2 mm ckness). Gas inlet and outlet ports attached

2 em from each end.

Variac, 0 to 120 volts for controlling pump speed

Pump with pe staltic pumping head, such as Cole-Parmer

Masterflex pump model 7017

Water bath

Aerator; Perkin Elmer

BOD bottles

Tygon tubing

Sulphuric ac desiccator. Made by snipping diffuser from

a Perkin Elmer Aerator so that it extends about halfway


41.

into a standard BOD bottle. The bottle is lIed

within 1 cm of the aerator th conc. sulphuric

acid (Kothandaraman and Dallmeyer 1976).

The mercury tern is aS~~"~J~'~~ by attaching tygon tubing

as follows: aerator + ac desiccator + absorption

cell + pumphead + aerator. When aerator is attached to the

reaction vessel (BOD a c system is obtained. After

removing the aerator from re vessel mercury remaining

in the system is vented out means of an exhaust fan.

Reagents

Ni c d conc low Hg

Sulphuric Ac conc. low Hg

Stannous de 10% 6N acid

Sample P

Oven dry the sediment at 60C. the lumps and grind

1 to ze the s Wei accurately 100 mg of

s (less if the > 1 Hg) and transfer

to BOD Add 1 ml conc. HN03 fol by 20 ml conc.

H2S04> Do not s Place the BOD bottle in the water bath

and digest 1 hour at 60C. Remove from water bath and add

water up to the of the etched label on BOD bottle and

place in the freezer until cold.

Note: Be adding ac to any s the blank solution

must be zed r to assure that the reagent

blank is not excess h Another blank should

be the
42.

Standard Preparation

Hg, 1000 ~g/ml. Dissolve 0.1354 g of mercury (II) chloride

in 100 ml of IN sulphuric acid. From this solution prepare

1 ~g/ml solution in 5% HN0 3 and 0.01% K2Cr207(Feldman 1974).

The 1 ~g/ml solution prepared this way is stable several months.

Prepare the working standards for each batch of samples by

dispensing .01 - .10 ml of 1 ~g/ml Hg solution from microburette

into BOD bottles. Add the same volumes of reagents as to the

samples. Digestion of standards is not necessary although it

may be safer to carry them through the same procedure as samples.

Procedure

Prior to analyses find the aeration rate that gives the

best absorption by turning the variac while aerating 0.1 ~g Hg

standard. This setting does not need to be adjusted again

although a new portion of tubing needs to be placed in the pump

head when lower absorption readings are observed for standards.

Pipette 10 ml of Stannous Chloride solution with fast

delivering pipette into cold sample solution in the BOD bottle.

Attach the aerator immediately and observe sample peak on the

recorder. When reaches a plateau detach the aerator and

rinse it with H20. After the peak falls back to the baseline

continue wi next sample. Standards should be run at even

intervals between the samples.

The calibration curve is constructed by plotting peak

height vs ~g Hg and the amount of mercury in the unknown is

read from that curve. The ~g Hg found from this curve is

converted to ppm in sediment by dividing ~gs by the sample


43.

weight in grams.

Relative Accuracy and P sian

Replicate analyses (12) of a sample with an average of 180

ppb gave a standard devi on of 23 ppb (coefficient of variation

of 12.8%). At a level of 410 ppb the standard deviation of

replicate analyses (6) was 30 ppb cae t of variation of

7.3%. At a level of 9.5 ppm, the standard deviation of

replicate analysis (12) was 0.95 (cae cient of variation of

10%). Accuracy of the sis was established by the use of

the rock standards G-1 and W-l for which we obtained values

10% of the value reported for se standards.


44.

Other Chemical Determinations

Determination of Readily Oxidizable Organic Matter

Organic carbon matter is determined to assess the role

played by the organic fraction of sediments in the transport,

deposition and retention of trace elements. The readily

oxidizable organic carbon content of the sediment sample is

determined by the Walkey-Black method (1947), that we adopted and

modified from Jackson (1958, p. 219-22.1). This method differentiates

humus matter from extraneous sources of organic carbon such as

graphite and charcoal. It utilizes exothermic heating and

oxidation with potassium dichromate and concentrated H 2S04 of

a -80 mesh portion of the sample, and the titration of excess

dichromate with 0.5 N ferrous ammonium sulphate solution to a

sharp, 1 drop end point.

The oxidation of Cl can be prevented by the use of Ag2S04

the digestion mixture.

Apparatus and Chemi s

2-50 ml burets with 0.1 ml graduations

Magnetic s rrer

500 ml Erlenmeyer flasks

Reagents

85% H3P04

Solid NaP

Concentrated H2S04 with Ag2S04: Dissolve 2.5g Aq2S04 in

1 liter of H2S04
45.

s 49.04 g of

water lute to 1 1

0.5 N Ferrous sol on

6H20 800 ml of water 20 ml concentrated

Dd phe ny Larru.rie cator: ssolve 0.5 g of

re 20 ml of water and 100 ml

of concent

Procedure

A 0.5 g sieved (0.2 mm non ferrous sieve) sediment

s is a 00 ml r ask. Exac 10 ml of

1 N K2 207 i buret) by gen

of flask for This should be done

care to ure of the reagents th the

Le avoi splo.'O>uJ.. l1 '::i the sides of

the f ask out f contact The mixture is

allowedto s for 0 z blank wi

30 s the s to 200 ml volume

lIed water and 0

Lam...I..lJ.<::: are to sample flask

is back trated

The color 11

brown, to green upon

ferrous sol color 1 con

to a bl sh-black-grey at s po

fe
46.

giving a one-drop end point.

Calculation of Results

% organic matter (readily oxidizable)

= 10(1-~) x F
S
S = standardization blank titration, ml ferrous solution

T = sample titration, ml ferrous solution

F = factor derived as follows:

= (l.ON) x 12 x 1.72 x 100


4000 Sample weight

= 1.03 when sample weight is exactly 0.50000 gm.


12 = meq. wt. carbon
4000

1.72 = for organic matter from carbon

In the back titration, the ferrous solution reduces the

dichromate that has not been used up in the oxidation process.

Therefore, if it takes less than 4 mls of the ferrous

solution to reach an end point, then more than 8 ml of the

available 10 ml of the dichromate has been consumed in the

oxidation. If this is the case, then it is necessary to repeat

the determination using less sediment.

Standard

- Weigh out exactly 0.01 gm dextrose and treat in the

same manner as soil sample

- The result is calculated as follows:


47.

meg. per 100 gm:::::: 10(1-T x 100

There , meq. per 1 gm : : :

:::::: X

Then x meq per gram x 12 ::: C

(x 100 :::: %)

The theore 1 value is 39 99% C from the

a1 f o rmu I

Precision

ana s (10) of a sample with an average of 0.36%

ic matt.er a sL.C1.11uo.rd n of 0.04% (coefficient

f var t 11% At 1 3.17% matter the

was .05% (coeff of variation of 1.6%).

Carbonate ten an of mar sed

s been to an tor of provenance

ispe 1 i 1 f of St. Lawrence.

(Lor and 963, Nota Lor 1969, 1973)

Method

The e trea HCl. The s we

to the escape of a expe led evo CO 2,

add excess to a certain volume CO is


2
evolved, Ie an equal volume of a is lied. As CO2

and a low the Lussac Law, and are

stead of volumes, pressure have no influence


48.

on the analysis, assuming that these quantities do not change

between the two weighings.

Reagents

HCl 4N: dilute 330 ml concentrated HCl to 1 litre with H20.

CaC0 reagent grade, oven dried and stored in the desiccator.


3

Procedure

Transfer 2-10 g of oven dry ground

sediment into a 250 ml conical

flask. Place tube D (see figure),

filled with 5 ml 4 N HCl, in the

flask. Close the flask then with a

rubber stopper, containing tube B,

filled with CaC1 2. Determine the

total weight. Thereafter tube C,

also filled with CaC1 2, is mounted

on top of tube B with the aid of a

piece of plastic tubing. Then the

flask is tilted, so that the HCl is

poured out of Eube D over the

In the following two hours, the flask is carefully swirled

a s. Then remove tube C and weigh. Loss in weight: P g.

At the same a similar determination is carried out with 200 mg

CaC0 3" Loss in weight: Q g.

Calculation
P/Q x 0,200 x 100
% CaC0
3 = weight abs. dry soil
Note: Tubes filled with CaC1 2 should be stored in desiccator and

caC1 replaced if observed to turn hard.


2
Precision

te ses 6 of a sample an average of 6.84%

gave a of .18% (coeff ient

tion of 2.6%)

Soluble Iron ( "

One lements ana on AAS is iron This is

the element In to s, analyses are also done

on extracts marine " iron the of

"free" iron s treatment dissolves iron associated with

and 11 VA.LU,C::S as

hemat sorbed positions

(Lor 1966) The extrac

a hydrosu

(di i te) i trate system seems to be the most effec

Mehra and kson 1 5

amoun sso ln 15 s falls f

rease to 1 to solubility product rela-

t of i to ho pH at

irnum leve becasue 4 moles OH are us up in reac

Na 1, effect ly serves as

fer.

Centr uge

100 ml centri tubes

water bath th therrnomete

50 ml fla
50.

Reagents

Sodium citrate. 0.3M

Dissolve 88 gms Na3C6HSo7.2H20 in H20 and dilute to

1 litre

Sodium bicarbonate. 1M

Dissolve 16.8 gms NaHC0 in H20 and dilute to 200 ml


3
Sodium chloride, saturated solution

Dissolve 360 gms NaCl in hot water, stirring constantly,

and dilute to 1 litre

Sodium dithionite, solid form

Procedure

Weigh out exactly 1.0 gm dry sediment and place in a 100 ml

centrifuge tube.

Add 40 ml of the sodium citrate and 5 ml NaHC0


3.
Place the tube in a water bath at 85C.

Allow to warm up about 20 minutes.

Then add 1 gm sodium dithionite and mix well.

Leave the water bath for 15 minutes, swirling occasionally,

add 10 ml saturated NaCl, mix and warm.

Remove and centrifuge.

Decant the clear liquid into a 200 ml volumetric flask.

Wash the residue twice with 25 ml portions of the saturated

NaCl, centrifuging, decanting, and transferring the

liquid to the flask each time Repeat the treatment

with Na citrate, NaHC0 and Na dithionite and proceed


3,
as before.
5

Then dilute the contents of f to volume th

The can now be ana a ,-u,m..!..\..- ab so r o t "free ll

r di necessary to Fe

1 r range. HlClllJ.'..jCl.llC se can a be

on these ex1:rac '-..L'U,"""

of Ferrous (FeO)

Ferrous is on a separate portion of sediment

e by th 0.5 N cer , after dige of

the H 04 and HF.

ac (us air free d water)

ac %)

Satura ac lut

O~J:nenan Ferrous S .LHU.LI..-ator

Ceri . 5N
52.

Calculation

Fe = No. of ml of titre x normality x 55.85*


Weight of sample

* Atomic weight of iron

Relative Accuracy and Precision

Replicate analyses (8) of standard rock W-l with an average

of 6.83% Fe gave a standard deviation of 0.02% (coefficient of

variation 0.29%). The average value obtained was within 1% of the


+2
value of 6.78% Fe reported for W-l (Flanagan, 1973).

Field Determination of Oxygen Activity in Sediments

In 1964, a technique for the field measurements of the oxygen

activity in mar sediments was adopted from the rapid soil

aeration test used by soil chemists. The basis of this test is

that the ferric/ferrous ratio of the sediments is directly related

to the intensity of the oxygen supply in the sediments. The

lowing procedure has been taken from the method given by

M.L. Jackson (1960).

sediment tests ic and rrous iron should be made

20 or 30 seconds of obtaining the sample because the aeration

and attendant chemical reactions take very rapidly. Two tests

are made on each sample: one from the surface layer and one from the

interior. For each individual test, two pinches of sediment are

placed on opposite ends of the diameter of a filter paper (see

diagram, Fig. 4). Two drops of HCl are added to each of the sediments
5

A B

1
are

4)
1'e

folded over and squeezed

paper One KeNS

paper

to the wet area

oxygen supp

eN) treated area LliUL~cttes ferrous

f The the

to the a

1 and repea test.


54.

A negative ferric iron test soon becomes a positive one and shows

the rapidity of oxidation once the sediment is exposed.


55.

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56.

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7.

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