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Environ. Sci. Technol.

1990, 2 4 , 242-252

(9) Huizenga, D. L. An Examination of Copper Speciation in (12) Kester, D. R. In The Importance of Chemical Speciation
Sea Water. Ph.D. Thesis, University of Rhode Island, i n Environmental Processes; Bernhard, M., Brinkman, F.
Kingston, RI, 1981. E., Sadler,P. J., Eds.; Dahlem Konferenzen: Berlin, 1986;
(10) Muller, F. L. L. A Kinetic Approach to Zinc Speciation in pp 275-299.
Marine and Estuarine Waters. Ph.D. Thesis, University
of Rhode Island, Kingston, RI, 1988.
(11) Cox, J. A,; Sloviawska,K.; Gatchell, D. K. Anal. Chem. 1984, Received for review June 29,1988. Revised manuscript received
56, 650. October 6, 1989. Accepted October 6, 1989.

Kinetics of Trace Metal Complexation: Ligand-Exchange Reactions


Janet G. Herlngt and Franqois M. M. Morel
Ralph M. Parsons Laboratory, Massachusetts Institute of Technology, 48-425, Cambridge, Massachusetts 02 139

In this study, we have investigated rates of complex


Ligand-exchange reactions of copper-nitrilotriacetate dissociation and ligand exchange for copper under envi-
(CuNTA) and copper-humate complexes with a fluores- ronmentally relevant conditions of pH and metal and
cent ligand, calcein, were examined and compared. The ligand concentrations. We have determined the predom-
reverse reactions of copper-calcein with ethylenedi- inant mechanistic pathways for exchange reactions with
aminetetraacetate (EDTA) and NTA were also studied; model ligands under such conditions, focusing on the ef-
the correspondence of equilibrium constants and kinetic
rate constants is discussed. Reactions with model ligands fects of the relative concentrationsof the competing ligands
proceeded both by complete dissociation of the initial and of the metal-to-ligand ratios. We then examined the
complex (disjunctive pathway) and by direct attack of the kinetics of ligand-exchange reactions of humate-bound
incoming ligand on the initial complex (adjunctive path- copper. These reactions can be described in terms of the
way). Reactions of humate-bound copper were also con- mechanisms applicable to the model ligands.
sistent with this mechanistic interpretation. The contri-
butions of the adjunctive and disjunctive pathways de- Background and Theory
pended on the Cu-to-humate loading; both pathways were Studies of the kinetics of ligand-exchange reactions of
important at the Cu-to-DOC loadings typical of natural transition metals (reviewed in ref 4) have shown the re-
waters. A t higher values, disjunctive ligand exchange actions to proceed by direct attack of the incoming ligand
predominated. This pathway could be interpreted in terms on the initial metal complex usually with rate-determining
of dissociation of Cu from a humate-binding site and the dissociation of the intermediate ternary complex thus:
rate constant related to the conditional stability constant
for Cu-humate binding. ML + L fast
LML -+
slow
L ML
The overall rate constants are influenced by steric and
Introduction electrostatic factors and by protonation of the incoming
The speciation of trace metals in natural waters is con- ligand.
trolled by the interaction of the metals with a complex and In contrast, Shuman and co-workers have observed that
varying mixture of inorganic anions, organic ligands, re- ligand-exchange reactions of Cu-DOC complexes involve
ducible or oxidizable dissolved chemical species (e.g., dissociation of the initial copper complexes and have re-
H202),surfaces, and organisms. Filterable concentrations ported rate constants for the dissociation of these com-
of metals may include fine colloidal particles as well as plexes (5-7). Other studies of reactions of humate- or
organic and inorganic metal complexes. fulvate-metal complexes or of reactions of metals with
Both metal speciation and biological availability or humic or fulvic acids have focused on different metals-Fe
toxicity are functions of the tendency of the metal to react, (B-II), A1 (12, 13), Ni (14), and Th (15, 16).
as quantified by the free metal ion activity, under pseu- On the basis of previous work (vide supra), we consider
doequilibrium conditions (1-3). For metals occurring as two mechanistic pathways for the overall ligand-exchange
organic complexes, pseudoequilibrium conditions among reaction: an adjunctive pathway, which proceeds by direct
dissolved species may be maintained only if the rates of attack of the incoming ligand on the initial complex, and
metal complexation reactions are fast compared with rates a disjunctive pathway, which proceeds by dissociation of
of metal uptake. If, however, complex dissociation and the initial complex. [We use this terminology, introduced
ligand-exchange rates are slow compared to biological in Hering and Morel (17), to emphasize that these path-
uptake, the rate of metal incorporation into the biota will ways are stoichiometric mechanisms inferred from rate
be limited by abiotic chemical kinetics (3). laws and do not imply any characterization of the tran-
The apparent rate of other processes, such as precipi- sition state of the substitution reaction: terms and defi-
tation, reduction, or adsorption, will be similarly influenced nitions are given in Table I.] The mechanisms for the
by the rates of metal complexation reactions if (i) the
reacting metal occurs predominantly as an organic complex
and (ii) the process of interest requires removal of the
overall (forward) reaction
-
CuL + D L + CUD
are written below with reaction of the protonated ligands
metal from the initial complex.
included in the overall rate constants, which are thus pH-
dependent. Rate expressions are derived by assuming
+Current address: Institute for Water Resources and Water steady-state concentrations of intermediate species (i.e.,
Pollution Control (EAWAG), CH-8600 Duebendorf, Switzerland. Cu and LCuD) and neglecting back-reaction of the product
242 Environ. Sci. Technol., Vol. 24, No. 2, 1990 0013-936X/90/0924-0242$02.50/0 0 1990 American Chemical Society
Table I. Terms and Definitions
intrinsic rate constants for dissociation of complex CuL or CUD
intrinsic rate constant for acid-catalyzed dissociation of complex CuL or CUDor for dissociation of the
protonated complex CuLH or CuDH
kCuLor kcuD intrinsic rate constant for formation of the complex CuL or CUDby reaction of Cu with D or L
kCuHLor kCuHD intrinsic rate constant for formation of complex CuL or CUD by reaction of Cu with HL or HD (H' is displaced
by the incoming metal)
intrinsic rate constant for direct attack of D or HD on complex CuL to give the product CUD
apparent rate constant (at fixed pH) for dissociation (including acid-catalyzed dissociation) of complex CUDor
CUL
apparent rate constant for reaction of all D species with complex CuL to give the product CUD (rate constant
for adjustive pathway)
apparent rate constant (at fixed pH) for formation of complex CuL or CUD by reaction of Cu with all L or D
species (including protonated ligand species)
ratio of rate constants for reaction of Cu with D, and LE, kCuDz/kCuLz
apparent rate constant (at fixed pH) for dissociation of CuHum
apparent rate constant (at fixed pH) for reaction of Cu with Hum
overall rate constant describing dependence of the rate, usually -d[D]/dt, on reactant concentrations as
specified in the text
component of the overall rate constant attributed to reaction via disjunctive pathway
component of the overall rate constant attributed to reaction via adjunctive pathway
rate constant for reaction of CuHuml with D,
rate constant for reaction of CuHuml with Dz by disjunctive or adjunctive pathway
rate constant for reaction of CuHum2 with D,
equilibrium stability constant for complex HD or HL
conditional stability constant (pH-dependent) for complex CUD
fitting parameter used to account for imperfect mixing in kinetics experiments
total concentration of suecies Y (Y = D, L, Hum, Cu)
Dk or Lz or Hum, concentration of free or-protonated species D, L;or Hum (e.g., LE = HL + L = - CuL)
[HumX] or [CuHumX] concentration of humate binding site X or of Cu bound at humate site X (X = 1, 2 for two binding sites)
[XI0 or [XI, concentration of species X (X = D, L, Hum, CUD,CuL, etc.) at time t = 0 or at some later time, t
S site density of Cu humate binding sites/mg of humic acid

CUD. For each mechanism, contributions of the proton- dissociation of the ternary complex, which is assumed to
ated species to the rate constants can be expressed ex- be at steady state, were not resolved and so are expressed
plicitly if equilibration of protonated species is assumed as a single term (kDZCUL).
to be rapid. Thus, for the disjunctive mechanism These two types of mechanisms can be distinguished
experimentally based on the effect of the free (excess) L
concentration on the overall rate. The apparent rate
constants (that is, for the reaction considered as first order
in both [CuL] and [D,]) for the disjunctive pathway should
be strongly influenced by the relative concentrations of D
and L. For [L] >> [D], competitive behavior is predicted
and the rate should be inversely proportional to [L]. For
[L] << [D], "trapping" behavior is predicted and the rate
should be dependent only on the rate constant for disso-
ciation of the initial metal complex at fixed pH (kquLz)..In
where contrast, the apparent rate constant for the adjunctive
pathway should be unaffected by the concentration of free
kULZ = kCUL + kCULHIH+l (4) L or the L:D ratio.
Experimental Section
Materials. Analytical-grade reagents were used without
further purification, except for NaC1. Solutions of 5 M
NaC1, prepared with analytical-grade salts, were treated
with Chelex 100 to remove trace metals and then diluted
with Milli-Q water. (Chelex 100 resin was cleaned with
[N.B.,, kcuDz is neglected in consideration of the reaction 3 M NH,OH, rinsed extensively, and then reconverted to

-
as written above. It is shown here for future discussion
on the reverse reaction (i.e., CUD + L D + CuL)].
For the adjunctive reaction
the Na form before use to minimize leaching of organic
chelators from the resin.) Humic acid (Aldrich) was ob-
tained as the Na salt and cleaned before use by repreci-
pitation from acid solution (as described in ref 18). The
+
CUL D, ~i LCUD F! L, + CUD (7) fluorescent reagent calcein, 3',6'-dihydroxy 4',5'-bis[N,-
N'-(dicarboxymethyl)aminomethyl]fluoran,(herein refer-
red to as dye or D) was used as received from Sigma.
All kinetics experiments (except for the study of the
where reverse reaction of NTA with CUD) were performed in 0.1
M NaCl and M (PO,), (pH = 7.4 f 0.2) at room
temperature. The experiment on the reverse reaction was
done in 0.1 M NaCl buffered to pH 7.3 with 5 mM HEPES
[N- (2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid].
In this study, the rate constants for the formation and Experiments were routinely conducted using acid-washed
Environ. Sci. Technol., Vol. 24, No. 2 , 1990 243
(dilute HCl) polyethylene and sample handling was done
in a laminar flow hood.
Use of the Fluorescent Reagent. Calcein, the con-
dye speciation. However, the reaction of Cu2D+ L CUD-
formation of Cu2Dwas also considered in calculating initial
+ CuL was neglected in the kinetic analysis as it does not
densation product of fluorescein with aminodiacetate and result in any fluorescence change.
formaldehyde, is fluorescent over the pH range of -3-11. Kinetic rate constants were extracted from the data
The fluorescence is quenched on formation of complexes (observed concentration of free dye over time at varying
with paramagnetic transition metals, in this case Cu(1I) initial reactant concentrations) based on the models for
(ref 19 and references cited therein). The structure, based the ligand-exchange reactions described above. For ki-
on proton NMR and acidity constants for calcein, has been netics experiments performed with the dual-syringe as-
determined by Markuszewski (20). Metal complexation sembly, the imperfect initial mixing affects the initial
with calcein occurs through the aminodiacetate function- concentrations of the reagents. A fitting parameter P,,
alities and the phenolic hydroxy groups of the parent P, = apparent [DIo/undiluted [D], was introduced in the
compound fluorescein. Both 1:l and 2:l metal-calcein data analysis to account for this imperfect mixing (P, =
complexes have been reported. The conditional stability 0.5 corresponds to ideal mixing). The method af extraction
constant for the 1:1 complex at pH = 7 reported by Saari of rate constants is described in detail in Appendix I.
and Seitz (21) is 1012.3.The overall stability constants for Briefly, for the forward reaction of CuNTA with dye with
the 2:l complex range from 1020.8in 50% ethanol (20) to NTA in excess, the reaction was analyzed as first order in
lOZ9.O (22). Our best estimates for conditional stability both [CuNTA] and [D]. For [CuNTA] >> [D], the [CuN-
constants at pH = 7.3, based on fluorescence quenching, TA] was constant over time and a pseudo-first-order rate
are KCuL= 1012.8and pCulL= 1024.5.Equilibrium fluores- constant was obtained from an exponential fit to [D]vs
cence quenching experiments in the presence of NTA also time. For [CuNTA] = [D] (again with NTA in excess),
suggest the formation of a fluorescent ternary complex, the second-order rate constant was obtained explicitly from
the expression

[ -1
calceinNTACu (23).
Fluorescence was measured with a Perkin-Elmer LS-5 b(a - x )
fluorescence spectrophotometer at an excitation wave- u - b In a(b - X ) = kt (10)
length of 492 nm and an emission wavelength of 511 nm.
Fluorescence signals were integrated over 4 s. The where a and b are the initial reactant concentrations and
fluorescencedye concentration relationship was calibrated x is the amount reacted (24). Rate constants thus obtained
for all kinetics experiments in the presence of NTA or for the disjunctive (kCuLzkCuDE/kCuLz) and adjunctive
EDTA. For experiments with humic acid, the dye (kDzCuL)pathways were then used in modeling the forward
fluorescence was calibrated at each humic acid concen- reaction of CuNTA with dye where NTA was not in excess.
tration. The decrease in apparent dye fluorescence at high In this case the data was interpreted such that
concentrations of humic acid is attributed to light ab- -d[D,1
sorption by the humic acid in solution. Fluorescence
quenching arising from dyehumate association is unlikely
rate = -=
dt .
due to the hydrophilic nature of the fluorescent reagent.
Kinetics Experiments. All kinetics experiments (again
excepting the NTA reverse-reaction experiment) were
performed by mixing approximately equal volumes of the
two reagent solutions (one a solution of the initial Cu-
I
-
kCuLrkCuDZ

kcULz[NTA]+ kcuDz[D]
+kDPL
I
-

and the parameter a (the ratio of kCuD~/kCuL~)


[CuNTA][D,]

(11)
was ob-
ligand complex and the other of the incoming ligand), using tained.
a dual-syringe assembly to deliver the mixed reagent so- For the reverse reaction of CUD with excess ligand
reading was obtained at -20 s and thereafter at 10-s
intervals. Fluorescence was measured over 10-30 min.
-
lutions into a fluorescence cuvette. The first fluorescence (either NTA or EDTA), the data were analyzed as pseudo
first order in [CUD]. Rate constants for the adjunctive
(kLzCUD)and disjunctive (kCUDE,for [L] >> [D]) pathways
The extent of reaction occurring over this time varied were calculated from the dependence of the pseudo-
considerably depending on the reaction conditions. For first-order rate constant on the concentration of the in-
the NTA reverse reaction (performed in duplicate), the coming ligand L.
reaction was initiated by spiking a solution of the dye
preequilibrated with Cu in 100-mL volumetric flasks with Results
a small aliquot of 0.01 M NTA to give a total NTA con- Mechanisms and Rates for Ligand-Exchange Re-
centration of 10 pM. The solutions were mixed and ali- actions with Model Ligands. Ligand-exchangereactions
quots removed for fluorescence measurements. The first
fluorescence measurement was obtained at -4 min. Each
flask was sampled at -10-min intervals for the first hour
-
between the fluorescent dye and synthetic ligands were
studied for the forward reaction, CuL + D L + CUD,
with L = NTA. Ligand exchange WRS inhibited in the
and the reaction was followed to equilibrium (-4 h). presence of an excess concentration of the outgoing ligand,
Data Treatment and Modeling. In all kinetics ex- free NTA, as shown in Figure 1. For experiments with
periments, measured fluorescence was related to free dye a sufficient excess of NTA (free NTAdye > 5), rate con-
concentration by calibration curves obtained immediately stants for the disjunctive pathway (NTA-dependent) and
following the kinetics experiments. Only the free or pro- adjunctive pathway (NTA-independent) were extracted
tonated dye species were considered to contribute to ob- from a plot of overall second-order rate constant (i.e., rate
served fluorescence. The quenching of fluorescence in the = -d[D]/dt = kOved[CuNTA][D])as a function of l/[free
forward reaction was attributed solely to the formation of NTA] as shown in Figure 2. The nonzero intercept in-
a 1:1 CUDspecies. Thus, from the total concentrations of dicates that at high free NTA concentrations the dominant
reagents, the (assumed) stoichiometry of the complexes, pathway for ligand exchange does not involve complete
and the observed fluorescence, the concentrations of free dissociation of the CuNTA complex. From Figure 2, the
D and CUDover time could be calculated. For the reverse following rate constants are obtained an NTA-dependent
reaction (ie., reaction of NTA or EDTA with CUDspecies), rate constant of (1.31 f 0.07) X s-l and an NTA-in-

244 Environ. Sci. Technol., Vol. 24, No. 2, 1990


10

-r,
v

w
n
Y
0
4 -- 0.0 1 .o 2.0 3.0 4.0 0

EDTA (M) x 1 0 6

tion, CUD -tEDTA


= k,#[CuD])
-. +
Figure 3. Overall (pseudo-first-order) rate constant for reverse reac-
D CuEDTA, (Le., k- for rate = -d[CuD]/dt
vs [EDTA]. The slope corresponds to the EDTAde-
pendent rate constant for the adjunctke pathway and the intercept to
the EDTA-independent rate constant for the disjunctive pathway under
"trapping" conditions of excess incoming ligand.

pendence on ligand concentration arises from treatment


0 100 200 300 400 500 of the reverse reaction as pseudo first order in the con-
centration of the initial complex rather than as first order
time (s) in both concentrations of the initial complex and of the
incoming ligand.) On the basis of the value of the dis-
CuNTA D + -.
Figure 1. Dye concentration, [DE], over time for forward reaction,
+
NTA CUD, at varying NTA concentrations for D, =
10 nM, C h = 50 nM, NTA, = 60 nM (0, A),80 nM (O), 120 nM (V),
junctive rate constant obtained from the EDTA experi-
ments, this pathway can be neglected for the reaction of
or 200 nM (0). CUDwith a very large excess of NTA. In this case, only
the adjunctive pathway was considered to contribute to
25 , I the observed rate constant of 25 f 2 M-' s-l.
Interpretation of Rate Constants for Reactions of
Model Ligands. The various ligand-dependent and lig-
--
and-independent rate constants obtained for the forward
reaction, CuL + D CUD + L (L = NTA), and the reverse
reaction, CUD + L CuL + D (L = NTA, EDTA), can
be related to the rate constants for the adjunctive and
disjunctive pathways (as summarized in Table 11).
Thus, for the forward reaction in the presence of excess
L, the NTA-dependent rate constant for the disjunctive
pathway corresponds to the term kCuLzkCuDz/ kCuLZ. Since
the inverse of the ratio kCuL /kcuLz equals the conditional
0
0.0 5.0 10.0 15.0
stability constant for CuN?FA (Kf$"TA = 1010.6, pH = 7.3,
p = 0.1; ref 25), the intrinsic rate constant kcuDzcan be
1/NTA ( M - ~ ) x ~ O - ~ calculated. Thus

CuNTA -t D
k,,[CuNTA][D])
NTA-
Figure 2. Overall (second-order) rate constants for forward reaction,
+
CUD, (Le., k,, for rate = -d[D]/dt =
vs l/[NTA]. The slope corresponds to the NTA-
dependent rate constant for the disjunctive pathway and the intercept
to the NTA-independent rate constant for the adjunctive pathway. For ligand-exchange experiments under conditions for
which the free NTA was not in excess of the dye, the value
dependent rate constant of (4.8 f 1.0) X lo3M-' s-'. For of a (i.e., the ratio of kCuDz/kCuLZ) was obtained from the
these conditions (i.e., excess free NTA), the contributions NTA-dependent (disjunctive) rate constant (defined in eq
of the two pathways are equal at a free N T A concentration 11). Due to the difficulties with imperfect mixing (and the
of -270 nM.
-
The reverse reaction, CUD + L D + CuL, was studied
in the presence of excess concentrations of the incoming
necessity for the additional mixing parameter Pm),the
value of a is not well constrained by the experimental data.
The experimental results are consistent with a value of this
ligand, for L = NTA with a very large excess of NTA and ratio of 0.6 f 0.3 (shown for a sample data set in Figure
for L = EDTA over a range of EDTA concentrations. For 4).
the reaction of CUDwith EDTA (EDTA in excess), con- Based on this value for a, the rate constants kCuLZand
tributions of disjunctive and adjunctive pathways to the kCuLE can be estimated. Thus
overall rate could be assessed by plotting an overall
pseudo-first-order rate constant (i.e., for rate = d[D]/dt
= koverall[CUD])against EDTA concentration (Figure 3).
In this case, the EDTA-independent rate constant of (4
f 2) X 10" s-l is due to the contribution of the disjunctive
pathway (under "trapping" conditions) and the EDTA-
dependent rate constant of 33 f 4 M-' s-' to the contri-
bution of the adjunctive pathway. (Note that this de-
Environ. Sci. Technol., Vol. 24, No. 2, 1990 245
Table 11. Summary of Rate Constants for Ligand-Exchange Reactions
kap
disjunctive mechanism: CuL -.!% Cu
w + LE Cu + DZ km
CUD

adjunctive mechanism: CuL + D p CUD + LE


kDE"
E

(a) Rate Constants for Forward Reaction


description of rate constant
or parameter obtained (value) interpretation value
NTA-dependent (1.31X 9-l) kCuLzkCuD"kCuL= kcuDz= 5.2 X 10 M-'K1
(for kCuLx/kCuLZ = KFz)
cy (0.6) kCuDzlkCuLL kCuLr= 9 X lo7 M-I s-l
kCuLr= 2 X IOw3s-l
NTA-independent kDzCUL 4.8 x 103 M-1 s-l
(b) Rate Constants for Reverse Reaction
description of rate constant
or parameter obtained (value) interpretation value
EDTA-independent
EDTA-dependent
(assumed) NTA-dependent
tp
kLrCUD
4 x 10-5 8-1
33 M-I s-l
25 M-' 8-l
(c) Values of Equilibrium Stability Constants Obtained from Kinetic Rate Constants
n d - kCuDZ/kCaZ
p ocfi = lo".'
p o n d - [kDLCUL/kLzCUD]
Kcond- 1012.9
CUL -
for L = NTA, Kr$ = 1010.6

45
~

i m I 1

20 : : : : : : : ; : : : ; ; : : o i 1
0 2 4 6 8 10 12
0 100 200 300 400

time (s) ]'H[ x106

Fhure 4. Dye concentration, [Dz], over time for forward reaction of


CuNTA with DE (for D, = 40 nM, C h = 50 nM, NTA, = 60 nM). Model
fit to data for (-) a = 0.7, P, = 0.49; (---) a = 1.1, P, = 0.47; (..a)
Maguire (26). For the reaction Cu i- NTAz
+
(kCuNTAkaWAKMA /(1 + +
-
Flgure 5. Effect of pH on formation of CuNTA based on work of
CuNTA, kCuNTAz =
KWA[H+]). Thus, the intrinsic rate
a = 0.3, P, = 0.52. constants kCuMA and can be obtained from a plot of kCUNTAr
(1 + KHNTAIH+l) vs [H'!.
An independent estimate of kCuLZmay be obtained from
the work of Maguire (26) in which the effect of pH on the For the reverse reaction under "trapping" conditions (i.e.,
rate of CuNTA formation was studied. For the reactions excess EDTA), the EDTA-independent rate constant

and
Cu + NTA - kamA
CuNTA
(disjunctive pathway) corresponds to the rate constant for
dissociation of the CUD complex, kcaD,, and the EDTA-
dependent rate constant to the rate constant for adjunctive
exchange, kL The consistency of the kinetic data may

Cu + HNTA -
kc"-A
CuNTA + H+
be assessed %y comparison of kinetic and equilibrium
constants. The ratio of disjunctive rate constants, k C u D ~
(obtained from the forward reaction of CuNTA) and Kcaz
the overall rate constant for reaction of Cu with both NTA (from the reverse reaction of CUD with EDTA), is the
species is conditional stability constant for CUD;then
- -
kCuDz
- kea = 5*2 lo7 - 1012.1i0.2
kCuDz 4 x 10-5
Values for the rate constants kcumA (7.1 X 109 M-l s-l) and This value for KF$ is somewhat less than the best esti-
kCuHmA (1.0 X lo5 M-' s-l ) were obtained from a plot of mate from equilibrium studies (KFS = 1012.8).Some of
kCuNTAz(l KHNTA[H+]) VS [H+] as shown in Figure 5. the discrepancy between estimates for K F S may be due
The predicted value for kCuNTAzat pH = 7.3 of 2.0 X lo7 to the involvement of minor species (see Discussion).
M-' s-l is in reasonable agreement with our value for kCuLz The value of KFt,"Ddcan also be obtained from the ratio
of 9 x 107 M-' s-l. of the adjunctive rate constants for forward and reverse
246 Environ. Sci. Technol., Vol. 24, No. 2, 1990
25 'I

-0.25

0 -0.50
0 100 200 300 400 0 100 200 500

time (a)
time (a)

-.- ,

20 -1.5
0 100 200 300 400 0 100 200 300

time (a)
+ - time (a)

-
Figure 6. Dye concentration [DE], over tlme for CuHum D Hum
+ CUD for Cu, 50 nM and 4 = 20 nM (a) or 50 nM (b). Total humic Flgure 7. Logarithmic transform of the free dye over time (normalized
acid: 1.1 mg/L (0),5.4 mg/L (A),and 10.8 mg/L (0). to apparent [D],) for CuHum D + +
Hum CUD for Cu, = 50 nM,
4 = 20 nM, (a) Hum, = 5.4 mg/L (A),and 10.8 mg/L (0) and (b)
reactions with L = NTA. The ratio of kD cuL,the NTA- Hum, = 1.1 mg/L. Wlh [CuHum] > [D], the reaction is pseudo first
independent rate constant for the forward reaction, and order in [D].
kLpD, the rate constant for the reverse reaction with a
Table 111. Summary of Overall Rate Constants for
large excess of NTA, corresponds to the ratio of the con-
ditional stability constants for CUD and CuNTA. Thus Ligand-Exchange Reactions with Humate-Bound Cu, CUT=
50 nM (i.e., kovedlfor Rate = -d[D]/dt =
k,ve,ll[CuHuml[DI)
overall (second-order)
DT,nM HumT, mg/L rate constant, M-'s-l
Then for K?;iTA = 1010.69 KMnd
CUD = 1012.9*0.1in good agree-
ment with the value from equilibrium studies of 20 10.8 6.6 X lo3
50 10.8 7.4 x 103
Ligand-Exchange Reactions of Humate-Bound 20 5.4 1.1 x 104
Copper. The reaction of the dye with Cu-humate com-
-
50 5.4 1.0 x 104
plexes was studied at several humic acid concentrations. 20 1.1 (early) 9 x lo6
For the forward reaction CuHum + D Hum + CUD,a (late) 6.0 X lo4
decrease in the ligand-exchange rate was observed with
increasing humic acid concentrations (Figure 6). For the for 1.1mg/L are omitted from Figure Ba, which shows the
ligand-exchangereaction with 5.4 or 10.8 mg/L humic acid, second-order rate constant vs the reciprocal of the humic
each reaction could be described with a single rate constant acid concentration (in mg/L). Again by analogy with the
89 shown in Figure 7a. However, for lower concentrations model system, we expect that the disjunctive and ad-
of humic acid (1.1mg/L), two rate constants were required junctive rate constants may be obtained from the observed
(Figure 7b). Values obtained for the rate constants are dependence of the overall rate constant (for rate = -d-
summarized in Table 111. As discussed for the model [D]/dt = k,~d[CuHum][D]) on the free humate concen-
system, the contributions of the disjunctive and adjunctive tration, that is
mechanisms may be estimated from the dependence of the
overall (second-order)rate constants on the free humic acid
concentration (i.e., [HumT] - [CuHum]). For 5.4 and 10.8
mg/L humic acid, the humic acid Cu-binding sites appear From Figure 8a,
to be sufficiently in excess of CUT (50 nM) that [free
humic] = [total humic]. However, for 1.1 mg/L humic kdis = (3.95 f 0.63) X lo4 mgmol-l
acid, the necessity for two kinetic rate constants suggests and
that the Cu concentration is not negligible compared to
the concentration of strong binding sites. Thus, the data
Environ. Sci. Technol., Voi. 24, No. 2, 1990 247
-" h I

?
v
r--

nW
Y

0 lo!
0.00 0.05 0.10 0.15 0.20 0 4 : : : : : : : : : ; : : : : ; : : : : I
0 100 200 300 400
1/ free humic (L/mg) time (s)

-
Flgure 9. Model fit for reaction of dye with two Cu-humate species
(solid lines) and data for ligand-exchangereactlon of dye with Culhumic
acid ( C y 50 nM, Hum, = 1.1 mg/L) and D, = 20 nM (0)or 50 (A)
nM.

the change in Cu-humate concentration is significant


compared to the change in the dye concentration. Instead,
for these conditions, we compared the observed reaction
rates predicted based on the rate constants obtained in
other ligand-exchange experiments with humic acids using
the following model. (A complete description of the model
is given in the Appendix TI.) In this model, the dye reacts
with Cu bound at two humate sites (Le., with CuHuml,
the slow-reacting species, and CuHum2, the fast-reacting
o0.00 c : : : 0.50
: : : : : : 1.oo
I : : : : I species). The initial concentrations of these Cu-humate
1.50 species (for c u T = 50 nM, HUmT = 1.1mg/L) were ob-
tained from the experiments with 20 nM dye. The reaction
1/ free humic (L/mg)
of the dye with CuHuml is described with two rate con-
Figure 8. Plot of overall (secondorder) rate constant (Le., kml for stants, for ligand exchange via disjunctive and adjunctive
+ D -
rate = -d[D]/dt = k-[CuHum]
+
[D]) vs l/[free humic] for CuHum
Hum CUD, where kmM = k,/[free humic] k,. +(a)
Experimental results for 5.4 and 10.8 mg/L of humic acid ( w d ~the
pathways, obtained from Figure 8a. The reaction of the
dye with CuHum2 is described with a single rate constant.
The value for this rate constant was optimized from the
assumptkm that [free hwnic] = [total humic]). (b)ExperkTlentalvalues
for 5.4 and 10.8 mg/L (0)and extrapolated value for 1.1 mg/L Hum, model fit for the experiment with 20 nM dye, 1.1mg/L
(A)used in calculations for Figure 9. humic acid. Then for
These results indicate the contribution of the disjunctive
pathway (predominant at low [free humate]) and the ad-
D, + CuHum2
kH1
- km
CUD + Hum2

junctive pathway (predominant at high [free humate]) to DZ + CuHuml- CUD + Huml


the observed reaction. Under these reaction conditions,
the contributions of the two pathways are equal at a free
humate concentration of -13 mg/L, that is, at a Cu-to-
where kH1 = - "'
[Huml]
+k 3
humate ratio of -4 kmol of Cu/g of humate.
For the experiments with 1.1 mg/L humic acid, the
apparent change in the rate constants over the course of
the reaction indicated that the amount of Cu bound was
not negligible compared to the concentration of strong
Cu-binding sites. If, for the reaction with 20 nM dye, it
kH2[CuHum2][D,] + (&+ kfJj)[CuHuml][D,]

is assumed that the observed rate constant for the later (14)
part of the reaction conforms to the equation determined where
for the reaction at higher humic acid concentrations, Le., [Huml] (mg/L) =
kwerall= 3300 + 39500(1/[free humic]), then the concen-
tration of free humic at 1.1mg/L total humic acid and 50 [CuHuml] (mol/L)
(15)
nM CuT can be calculated. As shown in Figure 8b, for HumT (mg/L) - site density (mol/mg)
koverdl= 60 000, the calculated free humic concentration
is 0.7 mg/L. Thus, by difference, the Cu-bound humic The site density mol/mg) was obtained from the 20
concentration is 0.4 mg/L. The amount of Cu bound at nM DT, 1.1mg/L HumT experiment as described above.
this site is -42 nM (since some of the total 50 nM of Cu The model fit to the data is shown for experiments with
is bound at the faster reacting site; see Appendix 11). Thus, 1.1mg/L HumT, 50 nM CUT,and both 20 and 50 nM DT
the site density is in Figure 9. (Note that there are no adjustable parameters
in the fit to the 50 nM dye experiment.) The deviation
42 nM c u 10-7 mol Cu-binding site of the model fit from the data at longer times may indicate
0.4 mg/L mg humic acid that the system is approaching equilibrium. The general
agreement of the model with the data demonstrates the
For the experiment with 50 nM dye and 1.1 mg/L humic consistency of ligand-exchange experiments with 1.1,5.4,
acid, rate constants could not be obtained directly because and 10.8 mg/L HumT.
248 Environ. Sci. Technol., Vol. 24. No. 2, 1990
Table IV. Cu-to-DOC Loadings in Natural Waters commercial (soil-derived)and aquatic humic materials (I@,
there are significant structural differences between the
water type Mmol of Cu/g of C ref commercial and natural materials (34). In addition, the
oceanic (Sal 36.1) 3.8 27 normalization to DOC for natural waters may overestimate
coastal (Sal 32) 4.7-9.7' the proportion of the DOC involved in metal binding.
7.0b 28 Comparisons of whole waters with isolated fulvic acids
coastal (Sal 26.8-36.4) 1.9-5.6' suggest that approximately 50% of the DOC is important
3.Ib 27 in metal binding (35),though the lower apparent metal
estuarine (Sal 5.4) 6.5 29 binding for whole waters might also result from higher
estuarine (Sal 10.9) 14 29
estuarine (Sal 13.9) 13 29 ambient metal concentrations (36). Nonetheless, the
tidal pond (Sal 23-28) 3.7-12.1' comparison in Table IV suggests that both of these types
7.36 28 of mechanisms may be important under natural conditions.
four lakes (pH 5.5-6.5) 6-26' In contrast, only a disjunctive pathway for ligand exchange
16b 30 was observed in the experiments of Shuman et al. (6), as
ten lakes (pH 4.6-6.3) 1.1-32'
9.2b 31 would be expected for their much higher Cu-to-DOC
two ponds 27,61 32 loadings (340 pmol of Cu/g of DOC).
two rivers (pH 5.8) 5.7 31 The rate constant for ligand-exchange reactions by the
stream 60 32 disjunctive pathway of Cu-humate complexes with the
lake sediment pore waters 5.26 33 fluorescent dye provides information on Cu-humate
'Range.
Discussion
bAverage.
-
binding. By analogy with the model system, for the lig-
and-exchange reaction, CuHum + D Hum + CUD,by
a disjunctive mechanism
Cu + Humz
kCYHumZ
The results obtained in model systems (with well-defined CuHum
ligands) demonstrate that the kinetics of ligand-exchange ka''-Z
reactions are consistent with a relatively simple interpre-
tation. In this interpretation, ligand-exchange reactions
at high concentrations of the out-going ligand are domi- the observed humic-dependent rate constant is
nated by direct attack of the incoming ligand on the initial
metal-ligand complex (adjunctive pathway). This result kCuHum&!uDr
is consistent with previous observations. However at low kdb = = (3.95 f 0.63) X lo4 mgmol-' s-l
kCuHUmz
concentrations of the outgoing ligand (in this case NTA),
a disjunctive pathway becomes important. Based on this From the model study, kcuD~= (5.2 f 0.3) X lo7 M-ls-l,
model, kinetic constants can be derived from the data. The then
agreement of the rate constant for the formation of CuN-
TA (at pH = 7.3) derived from ligand-exchange experi- --
kCuHumz
- 3'95 'lo4 = (7.6 f 1.3) X mg/L
ments with the value predicted from the work of Maguire /tCpmz 5.2 x 107
(26)as well as the coherence of kinetic rate constants and
equilibrium stability constants supports our interpretation or kCuHumZ/kCaumr = (1.3 f 0.2) X lo3L/mg. This ratio
of the ligand-exchange kinetic data. is related to a more conventionally expressed conditional
Although this mechanistic model for ligand-exchange stability constant for CuHum by the Cu-binding site
reactions is reasonably consistent with kinetic and equi- density (in mol/mg of humic acid). Thus
librium observations, it is nonetheless an oversimplification kCuHumr/kCuHumZ = 1O3.l2=
of the actual system. Equilibrium experiments show that KeAum[L/mol] site density [mol/mg] (18)
some minor species, particularly the dinuclear species
Cu2D,are not negligible. The presence of a stable ternary For the calculated site density of mol/mg, the
complex, NTACuD, is also suggested by equilibrium ex- corresponding stability constant for Cu binding at this site
periments (23). However, with only the available infor- (KcuHuml) is 10lO.l. Although equilibrium Cu-humate in-
mation on the concentration of reacting species, a more teractions (determined by complexometric titrations) have
detailed mechanism cannot be defined. also been described in terms of Cu binding a t discrete
Based on results from the model system, ligand-ex- humate-binding sites, comparison of model parameters
change reactions of the fluorescent reagent with Cu-hu- obtained from kinetic and equilibrium studies would be
mate may be interpreted by using the same models. These misleading. It has clearly been shown that the discrete
results suggest both disjunctive and adjunctive pathways ligand model (derived from equilibrium studies) does not
for the ligand-exchange reactions. The contributions of uniquely describe complexometric titration data and thus
the two mechanisms to the overall reaction are approxi-
mately equal at a free humic acid concentration of 13
f 4 mg/L with 50 nM CuT or at a Cu-to-humate loading
- physical-chemical significance cannot necessarily be at-
tributed to model parameters, i.e., stability constants and
concentrations of binding sites (37-39). It remains to be
of -4 pmol of Cu/g of humic acid (or -8 pmol of Cu/g seen whether alternative models for metal-humate inter-
of humic C). actions are also consistent with kinetic data.
To assess the contributions of these pathways in natural The results of ligand-exchange experiments with humic
waters, this value for Cu-to-humate loading may be com- acids demonstrate the crucial role of metal-to-humate
pared with CuT/DOC ratios measured in the environment loading in kinetics experiments. Only at low Cu-to-humate
(Table IV). The Cu-to-humate carbon loading for which loadings (approximately environmental values) can the
the disjunctive and adjunctive mechanisms are equally contribution of the adjunctive mechanism be discerned.
important in ligand-exchange reactions falls within the At higher Cu-to-humate loadings, more than one rate
range of Cu-to-DOC loadings in natural waters. This constant is required to describe the exchange reaction.
comparison must be regarded with some caution. Although Several rate constants were also required to model the
similar metal-humate interactions have been observed for reactions of CuDOC with 4 42-pyridy1azo)resorcinol(PAR)
Environ. Sci. Technol., Vol. 24, No. 2, 1990 249
at 340 pmol of Cu/g of DOC (6),of Ni-fulvate with PAR the rate constants for the disjunctive (kCazkCuDz/kCuLZ)
at 120-1100 pmol of Ni/g of fulvic acid (14), and of Th- and adjunctive (kD?&) mechanisms obtained (as described
humate with arsenazo(II1) at 50 pmol of Th/mequiv of above) from experiments with NTA in excess. For each
humic acid or 250 pmol of Th/g of humic acid, assuming data set, the fit was optimized with two fitting parameters,
5 mequiv/g of humic acid (16). a (the ratio of kCuDZ/kCuL)and P,, by comparing the
For ligand-exchange reactions at low Cu-to-humate
ratios, the requirement for only a single rate constant for
the disjunctive mechanism does not necessarily indicate
-
observed [D] over time with the predicted values based
on the following model. For CuNTA + D NTA + CUD,
involvement of only one type of humate binding site. The
apparent saturation of the site(s) by Cu at 1.1 mg/L dt
humic acid puts an upper bound on the site density and
thus a lower bound on the Cu-humic stability constant.
However, the involvement of stronger sites at corre-
spondingly lower site densities cannot be excluded.
Conclusion
kcuL.[NTA] + kcUDz[D]
+ kDECUL
1 [CuNTA][D,] (3)

Let [D], = y; then the amount reacted is [D], - y and from


stoichiometry
The ligand-exchange reactions of Cu-humate species [CUNTA], = [CUNTA], - [D], + y
with the fluorescent reagent can be interpreted on the basis
of the model used for the reaction of this reagent with [NTAI, = AI, + [Dl0 - Y
CuNTA. Experiments with well-defined ligands demon-
strate that the concentration range and relative concen- then
trations of the reactants chosen for study determines
whether the contributions of different mechanisms can be
discerned. Ligand-exchange reactions of Cu complexes
with well-defined ligands and with humic acid proceed by
mechanisms involving dissociation of the initial Cu com-
plex (disjunctive pathway) and direct attack of the in-
coming ligand on the initial complex (adjunctive pathway). J
Both pathways are likely to be important at Cu-to-humate
loadings occurring in natural waters. The rate constants or
observed for the disjunctive reaction of Cu-humate species
may be further interpreted to provide information on
equilibrium stability constants for Cu-humate interactions.
Appendix I

+ -
Extraction of Rate Constants from Kinetic Data.
A. Forward Reaction, CuL D L + CUD. 1. Ex-
cess L. (a) For [CuNTA] >> [D], a pseudo-first-order rate
and

constant, k (s-l), (for rate = -d[D]/dt = k[D]) was obtained


from an exponential fit to the concentration of free dye
over time. The extrapolated value of [D], was used to
calculate the mixing parameter P,, P, = [apparent
[D],/(undiluted [D])] where the apparent [D], is obtained
by extrapolation of the observed [D] vs t to t = 0 and the
undiluted [D] is the known dye concentration before The mixing parameter P, affects the initial values of all
mixing. Then the second-order rate constant, k (M-l s-l), concentrations such that
(for rate = -d[D]/dt = k[CuNTA][D]) was calculated such apparent [D], = undiluted [D](P,)
that
apparent [NTA], = undiluted [NTA](l - P,)
pseudo-first-order k (s-l)
second-order k (M-l s-l) = apparent [Cu], = undiluted [Cu](l - P,)
[CuNTA]
(1) Because there are two fitting parameters in this model, a
where the concentration of CuNTA is corrected for the
mixing inefficiency [where apparent [CuNTA] = (1- P,)
-
and P,, there is a large uncertainty in the value of a.
B. Reverse Reaction, CUD+ L D CuL. For the +
reaction of CUD with excess ligand (either NTA or EDTA),
undiluted [CuNTA]].
(b) For [CuNTA] = [D], the second-order rate constant
was obtained explicitly by plotting [CUD]. Thus, for CUD + L -
the data were analyzed as a pseudo-first-order reaction in
D + CuL (excess L), the
pseudo-first-order rate constant for the indirect pathway
is

vs time, where x is the amount reacted (24). The mixing


parameter P, in this case was also obtained from the ratio and the pseudo-first-order rate constant for the direct
of the apparent initial dye concentration (again extrapo-
lated from a simple exponential fit) to the expected initial pathway is
concentration.
2. [L] = [D]. For the reaction of CuNTA with dye
(NTA not in excess), the data were modeled by applying for
250 Environ. Sci. Technol., Vol. 24, No. 2, 1990
The site density, S is calculated as described in the text
under Results.
For experiments with EDTA, a value for P, based on the Literature Cited
apparent concentration of [D], was applied BS a correction Sunda, W. G.; Guillard, R. R. J. Mar. Res. 1976,34,511-29.
to all concentrations. In these cases the effect of the Anderson, D. M.; Morel, F. M. M. Limnol. Oceanogr. 1978,
formation of Cu2Don the expected [D], was also included
in the calculation. However, the reaction of Cu2D + L
CUD + CuL is neglected in the kinetic analysis as it does
- 23, 283-95.
Anderson, M. A.; Morel, F. M. M. Limnol. Oceanogr. 1982,
27, 789-813.
Margerum, D. W.; Cayley, G. R.; Weatherburn, D. C.; Pa-
not result in any fluorescence change. genkopf, G. K. In Coordination Chemistry;Wll,A., Ed.;
ACS Monograph 174; American Chemical Society: Wash-
Appendix 11 ington, DC, 1978; Vol. 2, pp 1-220.
Shuman,M. S.; Michael, L. C. Enuiron. Sci. Technol. 1978,
Model Used for Reaction of Dye with Cu-Humic 22,1069-72.
Acid (50 nM CuT, 1.1 mg/L Humic Acid). Dye reacts Shuman, M. S.; Collins, B. J.; Fitzgerald, P. J.; Olson, D.
with Cu bound at two humate sites (Le., CuHuml, slow- L. In Aquatic and Terrestrial Humic Materials Christ-
reacting species, and CuHum2, fast-reacting species). mann, R. F., Gjessing, E. T., Eds., 1983, Ann Arbor, MI:

D, + CuHum2 -kw
CUD + Hum2
Ann Arbor Science.
Olson, D. L.; Shuman, M. S. Anal. Chem. 1983,55,1103-7.

D, + CuHuml -kH1
CUD + Huml
Langford, C. H.; Khan, T. R. Can. J. Chem. 1975, 53,
2979-84.
Langford, C. H.; Kay, R.; Quance, G. W.; Khan, T. R. Anal.
Lett. 1977, 10, 1249-60.
where Langford, C. H.; Wong, S. M.; Underdown, A. L. Can. J.
Chem. 1981,59, 181-6.
Waite, T. D.; Morel, F. M. M. Anal. Chim. Acta 1984,162,
263-74.
Mak, M. K. S.; Langford, C. H. Can. J . Chem. 1982, 60,
Then species concentrations over time are predicted from 2023-8.
Plankey, B. J.; Patterson, H. H.; Cronan, C. S. Enuiron. Sci.
Technol. 1986, 20, 160-5.
Lavigne, J. A.; Langford, C. H.; Mak, M. K. S. Anal. Chem.
__ 1987,59, 2616-20.

[ + ,,]~cuHumll,]~D1']At
Choppin, G. R.; Nash, K. L. J. Znorg. Nucl. Chem. 1981,
43,357-9.
Cacheris, W. P.; Choppin, G. R. Radiochim. Acta 1987,42,
185-90.
Hering, J. G.; Morel, F. M. M. Enuiron. Sci. Technol. 1988,
,
[ C ~ H u m 2 ] , +=~ ,[CuHum2] - [kH2[CuHum2],[D]
,]At 22, 1469-78.
Hering, J. G.; Morel, F. M. M. Enuiron. Sci. Technol. 1988,
=
[cUHUml]t+~, 22, 1234-7.

[CuHuml], - [[& ]
[Huml] + kfd [CuHuml],[D], At ] Pribil, R. Applied Complexometry; Pergammon Press:
Oxford, UK, 1982.
Markuszewski, R. Ph.D. Thesis, Iowa State University,
Ames, IO, 1976.
and Saari, L. A.; Seitz, W. R. Anal. Chem. 1984, 56, 810-3.
Miyahara, T. Bunseki Kagaku 1977, 26, 615-20; Chem.
Abstr. 1978,88, 28490a.
Hering, J. G. Ph.D. Thesis, Massachusetts Institute of
Technology-Woods Hole Oceanographic Institution Joint
The input parameters to this model are as follows: kgi = Program in Oceanography. Cambridge, MA, 1988.
39500 mg-mol-' s-l; kyd = 3300 M-' s-l; kH2 = 9 X los M-' Moore, J. W.; Pearson, R. G. Kinetics and Mechanism,3rd
ed.; Wiley-Interscience: New York, 1981.
s-l; HumT = 1.1 mg/L; [D], = 20 or 50 nM; [CuHumlIo Martell, A. E.; Smith, R. M. Critical Stability Constants;
= 42 nM; [CuHum2Io = 8 nM; S = lo-' mol/mg; At = 10 Plenum Press: New York, 1974; Vol. 1.
S. Maguire, J. Can. J. Chem. 1974, 52, 4106-8.
The rate constants kyd and k$ are obtained from Sunda, W. G.; Ferguson, R. L. In Trace Metals In Sea
analysis of ligand-exchange experiments conducted with Water;Wong, C. S., Boyle, E., Bruland, K. W., Burton, J.
high humic acid concentrations, as shown in Figure 8a. D., Goldberg, E. D., Eds.; Plenum Press: New York, 1983;
The rate constant kH2is optimized from the model fit for pp 871-91.
the experiment with 20 nM dye, 50 nM CU,, and 1.1mg/L Anderson, D. M.; Lively, J. S.; Vaccaro, R. F. J. Mar. Res.
Hump 1984,42, 677-95.
Newell, A. D.; Sanders, J. G. Enuiron. Sci. Technol. 1986,
The initial concentrations of CuHuml and CuHum2 and 20, 817-21.
the site density S are calculated as follows: For the ex- Hutchinson, N. J.; Sprague,
~. J. B. Enuiron. Toxicol. Chem.
periment with 20 nM dye, 50 nM CUT,and 1.1 mg/L, In 1987, 6 , 755-65.
[D] is plotted vs time (shown in Figure 6b). The extrap- Giesy, J. P.; Briese, L. A.; Leversee, G. J. Enuiron. Geol.
olation of the line fit t o these data (for t I130 s) to zero 1978,2, 257-68.
time gives the concentration of dye reacting with CuHuml Giesy, J. P. Enuiron. Toxicol. Chem. 1983, 6, 203-24.
(the slow-reactingCu-humate species). The remainder of Piemontessi, D.; Baccini, P. Enuiron. Technol. Lett. 1986,
the dye is taken to have reacted with CuHum2. Thus 7, 577-92.
Malcolm, R. L.; MacCarthy, P. Enuiron. Sci. Technol. 1986,
DT - extrapolated value of [DIo = [CuHumB], 20, 904-11.
McKnight, D. M.; Feder, G. L.; Thurman, M.; Wershaw,
CUT- [CuHumZ], = [CuHuml], R. L.; Westall, J. C. Sci. Total Enuiron. 1983, 28, 65-76.
Environ. Sci. Technol., Vol. 24, No. 2, 1990 211
Environ. Sci. Technol. 1990, 24, 252-257

Cabaniss, S. E.; Shuman, M. S. Geochim. Cosmochim. Acta (39) Cabaniss, S. E.; Shuman, M. S. Geochim. Cosmochim. Acta
1988,52, 195-200. 1988,52, 185-93.
Dzombak, D. A.; Fish, W.; Morel, F. M. M. Environ. Sci.
Technol. 1986,20, 669-75. Received for review June 9, 1989. Accepted October 5, 1989.
Turner, D. R.; Varney, M. S.; Whitfield, M.; Mantoura, R. Financial support from the National Science Foundation (Grant
F. C.; Riley, J. P. Geochim. Cosmochim. Acta 1986, 50, OCE 8317532) and the Office of Naval Research (Contract
289-97. N-00014-80-C-0273) is gratefully acknowledged.

A Conceptual Model of Organic Chemical Volatilization at Waterfalls


Michael McLachlan, Donald Mackay, and Philip H. Jones
Institute for Environmental Studies, University of Toronto, Toronto, Ontario, Canada M5S 1A4

of the oxygen deficit above the falls to that below the falls,
A conceptual model of volatilization of organic chemicals namely
at waterfalls is presented. It is suggested that the extent
of volatilization may be controlled by diffusion limitations r = (C, - Ci) / (C, - C,) (1)
(as is the case with oxygen and chemicals with large air-
water partition coefficients), by the flow rate of air into where C is oxygen concentration, subscripts referring to
the plunge pool (for chemicals with low ail-water partition saturation s, upstream or inflow i, and downstream or
coefficients), or both. The model is applied to 11 organic outflow 0. A value of unity for r implies no transfer; a value
contaminants present in the water of Niagara Falls. The of infinity implies attainment of equilibrium.
results suggest that volatilization is significant for chlo- The following correlations have been proposed for r as
roform, chlorinated benzenes, and PCBs, but negligible for a function of fall height (h) and other parameters de-
2,3,7,8-TCDD,r-HCH, and PAHs. The model can gen- scribing water quality (a), weir structure (b),temperature
erate only order of magnitude estimates. Model validation (T,C), flow rate per unit crest length (qw), and depth of
is required for more exact predictions. plunge pool (d):
r = 1 + 0.38abh(l - O.llh)(l + 0.046(T + 273)) (12)
Introduction (2)
The exchange of gases and vapors between air and water
plays an important role in the fate of many organic con- r25 = (25 C) (13) (3)
taminants in the environment (1-3). It has been estab-
lished that dams and weirs significantly enhance river rI5 = 2.05h0.434 (15 C) (Jarvis in ref 13) (4)
reaeration, i.e., the diffusion of oxygen from air into water r20= 1 + 0.21h (20 C) (Holler in ref 13) (5)
( 4 ) . It is expected that volatilization, the diffusion of
compounds from water to air, is also enhanced by these In (rz0)= 5.92h0.816qW4.363d0.310
(14) (6)
hydraulic disturbances. It is thus possible that waterfalls
significantly affect the fate of many organic compounds These correlations were developed from measurements
in rivers and act as point sources of atmospheric con- on laboratory-scale structures or small weirs or falls with
taminants. In the course of a study of organic chemical a maximum height of 3 m. As is shown in Figure 1, they
fate in the Niagara River (5)a conceptual model of mass are in fair agreement in the 1-3-m height range, but for
transfer at Niagara Falls was assembled to evaluate this greater heights the correlations diverge and become un-
possibility. In this paper we present this model, discuss reliable. Measurements at the 21 m high Great Falls, NJ,
the factors that may influence the rate of volatilization, in which r ranged from 4 to infinity (i.e., 80-100% ap-
and suggest that the process is fundamentally different in proach to equilibrium), give an indication of the mass-
nature from volatilization at water surfaces. transfer efficiency of higher waterfalls (15).
Another approach for predicting reaeration at higher
Background waterfalls is the use of semiempirical dimensionless
Early efforts to describe diffusive mass transfer between equations based on the theory of solid jets. Two such
air and water in the environment focused on reaeration equations using the Reynolds number ( R )and the Froude
in rivers. From mass balances for dissolved oxygen and number (F)have been developed from laboratory-scale and
later for various tracers a number of predictive equations small-weir reaeration measurements.
have been developed for oxygen diffusion into rivers as a
function of river depth, gradient, and flow velocity (6). r15 = 1 + 0.627 X 10-4Rj0~53F~787
(4) (7)
These equations have been extended to describe the vol- where
atilization of organic chemicals from rivers (2, 7, 8).
Whitmans two resistance diffusion concept has gained Rj = q j / ~ Fj = (gh3/2qj2).25
widespread acceptance as the appropriate model for mass
transfer across the air-water interface (9-1 1 ) by quantif- r15 =1 + fw,(0.1F1.2)for R > 5 X lo5 (16) (8)
ying liquid film and gas film resistances in series at
the air-water interface. The values of the mass-transfer where
coefficients for the two films are a function of the air and R = qw/U F = (8gh3/qw2)o.25
water turbulence, temperature, and molecular diffusivities.
Considerable research has also been directed toward Here qw is flow rate per unit crest length, qJ is the flow
quantifying reaeration at waterfalls and dams usually in rate per unit wetted jet perimeter (m2/s),g is the gravi-
the form of correlations for the deficit ratio (r), the ratio tational constant, and u is the kinematic viscosity of water.
252 Environ. Sci. Technol., Vol. 24, No. 2, 1990 0013-936X/90/0924-0252$02.50/0 0 1990 American Chemical Society