Environ. $ci. Tochnol.
1995, 29, 446-457
Metal Ion Binding to Hemic
Substances: Application of the
Non-Ideal Competitive Adsorption
Model
MARC F. BENEDETTI,* *it't
CHRIS J. MILNE,6
DAVID G. KINNIBURGH,6
WILLEM H. VAN R I E M S D I J K , * ·+ AND
LUUK K. KOOPAL"
Department of Soil Science and Plant Nutrition and
Department of Physical and Colloid Chemistry,
Wageningen Agricultural University, Dreijenplein 10,
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
6703 HB Wageningen, The Netherlands, and British Geological
Survey, Wallingford, Oxon, 0X10 8BB, U.K.
The application of a new model to describe metal
Downloaded via INRAE on October 2, 2020 at 19:30:49 (UTC).
ion binding by humic acids is discussed. Metal ion
binding is always of a competitive nature since the
proton is always present. Although of great practical
importance, the combination of a chemically hetero-
geneous system with competitive binding poses
difficult problems from both experimental and theoretical
points of view. The new Non-Ideal Competitive
Adsorption model (NICA model) used here is able to
account for the non-ideal binding to heterogeneous
ligands. A good description of the binding of H, Ca, Cd,
and Cu to a purified peat humic acid is achieved
over a wide range of free metal ion concentrations (-2
>
log Me2+ > -14) and pH (2 < pH < 10). The
results show that binding of metal ions to humic acid
is strongly influenced by the intrinsic chemical
heterogeneity of the humic material itself as well as
by ion-specific non-ideality. The results indicate
that copper competes much more efficiently with protons
bound to the phenolic type groups than calcium and
cadmium.
446 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995
Introduction
Humic substances play an important role in the behavior
and fate of metal ions in the natural environment. They
can control metal ion concentrations in soils and natural
waters and can affect the mobility of metals through soils
and aquifers (I, 2). The interaction between metal ions
and soil particles can also be controlled by humic sub-
stances. Humic substances are believed to play a major
role in trace metal availability and toxicity to plants and
living organisms.
Among the humic substances, the humic acids (HA) and
fulvic acids (FA) are polydisperse mixtures of natural organic
polyelectrolytes having different types of functional groups
to which ions can bind. Two major types of functional
groups are of particular importance: carboxylic groups and
phenolic groups {3-7). Amino, sulfhydryl, and quinone
groups can also be present and may have strong interactions
with trace metal ions (1,3,4). However, since their number
is much smaller, their contribution to ion binding is also
generally small, although under certain conditions it can
be substantial.
In natural systems, metal ion binding will be affected by
different processes and humic acid properties. Due to their
diverse functional groups, the humic acids behave as
heterogeneous ligands (1,4-9), and this chemical hetero-
geneity will be reflected in their ion binding properties.
The polyelectrolytic behavior of humic acids will also affect
ion binding due to electrostatic interactions {1,5,6,9-12).
Natural waters contain a variety of ions that will compete
to a greater or a lesser extent for the available binding sites.
Protons are always present in aquatic systems, and they
too will compete with metal ions for binding to humic acids.
The proton concentration determines the degree of ioniza-
tion of the functional groups as well as the charge of the
humic acids. Multivalent ions such as Ca2+, Mg2+, Fe3+,
and Al3+ are known to bind to humic acids (1). In principle,
all these ions will compete for the same sites and hence
influence the binding of each other.
The complexity of such a system is great and has led to
the development of various models {2,10,11,13-15). The
aim of forward modeling is to be able to describe ion binding
at different pH’s and ionic strengths and over a wide range
of concentrations for the different ions. Models of ion
binding by humic substances described in the literature
can be divided into two categories: those assuming a
discrete distribution of ligands and those assuming a
continuous distribution of heterogeneous ligands. The
discrete ligand approach can successfully describe metal
binding in the absence of competing ions (proton excluded)
within the range of the conditions of the calibrating titrations
{13). Although competition among ions can be described
by the discrete approach, because of the variable nature of
the natural ligands discrete models generally require extra
Corresponding authors; e-mail address: Willem van
*
Riemsdijk@BODSCH.BENP.WAU.NL; Fax: 31 83 708 37 66.
f
Department of Soil Science and Plant Nutrition.
* On leave from Géosciences de l'Environnement Ura CNRS 132,
Case 431, Faculté des Sciences de St Jéróme, 13397 Marseille Cedex
20, France.
5 British
Geological Survey.
11
Department of Physical and Colloid Chemistry.
0013-936X/95/0929-0446Í09.00/0 1995 American Chemical Society
ligand sites in order to satisfactorily match the experimental
data (16). Whether this difficulty can be overcome by
models based on a continuous distribution is still a matter
of discussion (15). Dobbs et al. (17) and Susetyo et al. (14)
successfully used a continuous binding site model to predict
the effect of protons and Al on Eu binding to humics. Up
until recently, the main restriction with models based on
a continuous distribution is that it is assumed that the
different metal ions experience the same chemical het-
erogeneity (15, 18). When single metal ion adsorption
experiments are carried out using the same humic acid, it
is found however that the different metal ions do not
experience the same apparent heterogeneity. Competitive
adsorption cannot then be adequately described by the
"classical” (18) multicomponent models. Therefore, to
address this problem, Koopal et al. (19) developed a new
non-ideal competitive adsorption (NICA) model in which FIGURE 1. Calibration curve for Cu ISE produced by titrating Cu-
heterogeneity and component-specific non-ideality are (N03)2 with ethylenediamine. Free Cu activities were calculated
considered explicitly. explicitly for each point using a speciation model, the measured pH,
The NICA model is based on a continuous distribution and the total concentrations of the components. Two limits are
shown.
of heterogeneous ligands in which the overall non-ideality
is divided into an intrinsic heterogeneity contribution (a
Cadmium and Calcium. Data for Cd and Ca binding
property of the humic substance) and ion-specific non- to PPHA are taken from Milne et al. (22). Metal ion
ideality contributions. In the NICA model, the polyelec- concentrations were measured potentiometrically using Cd
trolytic nature of ion adsorption to humic substances is or Ca ion-selective electrodes (ISE) to give ion binding
accounted for in a generic way by the non-ideality
isotherms at pH 4, 6, and 8 for Cd and at pH 6, 8, and 10
parameters. In literature, several attempts have been made for Ca. All experiments were performed in a 0.1 KN03
to model the electrostatic interactions more specifically.
For example, Tipping and Hurley (15) use an empirical background electrolyte.
Copper. Copper concentrations in solution were mea-
equation to relate charge and potential. Marinsky et al. sured potentiometrically using a sulfide-based solid-state
(10, 20, 21) employ a Dorman potential term, and De Wit ion-selective electrode (Orion 9429). This technique has
et al. (5, 6, 9), Bartschat et al. (12) and Milne et al. (22)
been used before for measuring Cu binding to humic
compute the electrostatic potential with the Poisson- materials with considerable success (24, 25). It was
Boltzmann equation, assuming a given geometry (e.g., demonstrated using ethylenediamine (en) titrations that
sphere or cylinder) for the shape of the FA or HA particles. linear response of Cu ISEs can be obtained for Cu activities
It is also possible to extend the NICA model to take into
as low as pCu 19 (26). Other authors have calibrated using
account specifically the ionic strength effects on both proton
standard solutions at higher Cu activities and have assumed
and trace metal binding, and we will return to this aspect
an extension of the calibration using linear (24) or poly-
in a future paper. The binding will be studied predomi- nomial extrapolation (25). Here the electrode performance
nantly at a single ionic strength of 0.1 M. We assume that was verified by titrating aqueous (en) (0.1 M) into Cu(N03)2
at constant ionic strength electrostatic interactions are of
(0.01 M). The total concentrations of the component
similar magnitude for the various divalent ions under
species and the measured pH were then fed into the
investigation. ECOSAT speciation model (27) to calculate the concentra-
The aim of this paper is to test the NICA model for a
tion and activity of free Cu2+ at each point in the titration.
wide range of competitive conditions using a single humic
acid sample. The sample used is a purified peat humic
Stability constants for complexes were taken from refs 28
and 29:
acid (PPHA) for which the proton-charging behavior has
previously been analyzed using an electrostatic diffuse
double layer model (7). Ca and Cd (22) binding data are Cu(en) ^ Cu2+ + en log K =
10.48
also available for the PPHA material, and new experimental
data for Cu binding are presented here. Hence, the model Cu(en)2 2=1 Cu2+ + 2en log K = 19.55
can be tested with H, Cd, Cu,and Ca data for the same
humic acid. In the following, we will first briefly describe H2(en) ^ H + H(en) log K = 6.848
the experimental procedures adopted and then describe
the model and its use for modeling proton and trace metal The calculated free Cu activities were plotted against the
binding. observed ISE emf readings to give a calibration curve (Figure
1) which was linear over the whole range of the calibration
Experimental Section titration from pCu 2 to pCu 12. For experimental data points
All experiments were performed on purified peat humic between pCu 12 and pCu 14, we assume that the linear
acid (PPHA), the purification and properties of which have response continues; we saw no evidence to the contrary
been described by Milne et al. (7). The initial concentration during the experiments. The fitted slope of the calibration
of the humic acid suspension was 5.28 mg of PPHA/g of (30.9 mV) is larger than might have been expected from
suspension. Potentiometric experiments were carried out Nemstian theory, but it was consistent and reproducible
using a fully automated titration system, which is described both in calibrations and during experiments with humic
in detail elsewhere (23). acid.

VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 447

 During the calibration titration, up to 20 min was allowed
for each dose to equilibrate before a reading was taken.
The full titration procedure therefore took approximately
16 h, which was too time consuming to allow satisfactory
routine calibration of individual experiments. Routine
calibration therefore used only unbuffered solutions ( 2
to 1CT6 M Cu(N03)2 in 0.1 M KN03) and took up to 2 h. Full
calibrations were repeated at intervals to verify that the ISE
performance continued to be linear. We saw no evidence
that the performance of the Cu ISE was disturbed by the
presence of the humic acid (24). This conclusion is also
supported by other authors (30), who using electron
microprobe analysis were unable to detect adsorption of
fulvic acid on the surface of the electrode.
pH stat experiments were carried out at pH 4, 6, and 8.
A solution of PPHA in 0.1 KN03 was titrated to the stat pH
(0.004 pH) and then maintained for up to 12 h to stabilize
the PPHA before Cu(N03)2 was added to the solution in
progressively larger doses. The additions were done in two
ranges, high Cu (0.1 M Cu(N03)2 in H20) and low Cu (10-3
in 0.1 KN03). The concentration of free Cu was measured
after the stat pH had been maintained for 15 min, and the
Cu electrode deviation was less than 0.2 mV min-1. This
generally meant that there was a total time of 25-35 min
between successive Cu doses. The total concentration of
Cu species in solution was then calculated, and the amount
of bound Cu2+ was estimated by difference. The H+/Me2+
exchange ratio was corrected for the hydrolysis of the
unbound Cu in solution. The binding data have been
corrected for Cu hydrolysis products using thermodynamic
data of Baes and Mesmer (31). In solution, CuOH+ (log
Kcuoh* = -8) is the major hydrolysis species; higher
complexes have only trace importance. The dominant
hydrolysis feature is the precipitation of Cu(OH)2 (log Ksp
=
8.64), which precludes ISE measurements at log[Cu2+] >
-3.3 for pH 6 and log[Cu2+] > -7.3 for pH 8.
Model Description
The proton or metal ion binding to each site type S at the
ligand is assumed to follow the reaction:
S + M^SM
This reaction implies monodendate binding to all of the
sites. The total adsorption 0<>t of a component i is then
described by the following integral equation:
„= /
Alog K,
,/log Kt) d(log Kt)
where /(log K,) is the distribution function of the affinity
constant, 0¿,¡ is the local adsorption isotherm, i.e., the
binding to a group of identical sites (32), and Alog K¡ is the
range of log K¡ to be considered. This equation can be
solved analytically for certain distribution functions in
combination with certain local isotherms. For a multi-
component system, Koopal et al. (19) have derived the
following nonideal competitive adsorption expression for
0¡,t by using the extended Henderson-Hasselbalch as the
non-ideal local isotherm in combination with a Langmuir-
Freundlich (LF) type affinity distribution function (quasi-
Gaussian) by Sips (33):
448 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995
Qmax
i +
/c/r
where Qt_, is the total amount of component i bound to the
humic acid, and Qmax is the total site density. K¡ is a median
affinity constant for component i, and c¡ can be either the
concentration or the activity of i. The parameter n¡ accounts
for the “non-ideal” behavior ( ^ 1, non-ideal; n = 1, ideal)
of component i. For ion adsorption, n¡ takes values of 0 <
n¡ < 1. The value of p (0 < p < 1) determines the width
of the distribution due to the intrinsic chemical hetero-
geneity of the sorbent and is the same for all components.
The value of p cannot be obtained from monocomponent
binding data since in this case only the combined effect
can be deduced. Therefore, a multicomponent set of
binding data are needed to derive the value p for a given
sorbent.
The more classical (ideal behavior) multicomponent
Langmuir-Freundlich eq (18) follows from eq 3 if all n¡ are
set equal to 1:
< * >'
kc
Qi,
=
Qmax--(4)
YjCfi
i
1 +
(¿>/
Equation 4 gives very poor results for the description of
pH-dependent metal ion binding to humic materials if non-
ideality effects due to lateral electrostatic interactions or
due to component-specific heterogeneity are not accounted
for as has been shown for Cd binding to soil water-derived
fulvic acid (data set of Saar and Weber (25)) by Koopal et
al. (19). Moreover, pH-dependent copper binding cannot
be described in a satisfactory way using this approach. The
NICA approach has been shown to be able to give excellent
results for pH-dependent cadmium binding to fulvic acid
when electrostatic interactions are not accounted for
explicitly (19).
Experimental evidence indicates that there are two major
(1) types of site in the affinity distribution for the binding of
protons and/or metal ions to humic substances (4-7),
usually considered to be due to carboxylic type groups and
phenolic type groups, respectively. We can now extend
the NICA model to reflect this by introducing a bimodal
affinity distribution which transforms eq 3 to
(2)
(Kitlcri
u!
Qi,t Qmax,l ^
Xc^ic,.)""'11 + {£(^)nu}pi
Qmax,2--(5)
1 +
where the subscripts 1 and 2 relate to the first and second
peak of the affinity distribution.
Figure 2 illustrates schematically the general procedure
which is used to derive the various parameter values of the
NICA model for a multicomponent set of ion binding data.
 STEP 1 INPUT
Parameter Optimisation
output
STEP 2 Input
parameter Optimisation
Output
SUBSEQUENT Input
METALS
Parameter Optimisation
Output
FIGURE 2. General scheme of the fitting procedure used during modeling with the nonideal competitive adsorption model (NICA).
First, monocomponent binding data are used in order to
derive a value of m, describing the combined effect for one
component (m,· = n¡p). For this purpose, the proton binding
as a function of pH in indifferent electrolyte is used. The
salt level is chosen to be the same as what is used for the
study of the metal ion binding. A relatively high salt level
may be chosen to suppress the effects due to electrostatic
interaction. In the first step, the value of the average proton
affinity constants, the total number of sites, and the value
of m.H for both peaks can be established. In the second
step, the value of p can be derived using data from a metal
binding experiment in which metal binding is studied as
a function of the metal concentration at different pH’s.
This enables p to be calculated from both the metal and
the proton data and at the same time K¡ and n, can be
derived for the metal. The value of is given by mu I p.
For subsequent metal ions, only K¡ and n¡ have to be derived
since p is already known. Therefore, each new metal ion
species requires only two new parameters for each affinity
distribution. For the extended NICA (eq 5), the same
procedure applies, but now the constants for both groups
of sites should be determined.
To summarize, for the extended NICA model, six
parameters are derived from the proton data. These consist
of two median affinity constants, two site densities, and
two mH values corresponding to the widths of the two
apparent affinity distributions. Then for the first metal, i,
six additional parameters have to be derived: again two
median affinity constants for metal i, plus two p values and
two n, values. Finally, each additional metal requires four
further parameters: two median affinity constants and two
values for n¡. The total number of parameters needed to
describe the interaction of the proton and one metal with
humic, 12; is moderately high but is within the range used
by other authors, e.g., 10 parameters (34) or 13 parameters
(15), and reflects the complex heterogeneous nature of
humic materials. However, if within the range of the
experimental conditions only one group of sites (e.g., the
carboxylic) is needed to account for the observed experi-
mental binding curves, the basic NICA (eq 3) can be used
and only six parameters will be needed to model the binding
of a proton plus one metal. The pH-dependent cadmium
Charge vs. pH data
NICA:eq6
Qmax,Kn andmH
1 set of metal binding
experimental data at different
pH
NICA: eq3or5
Ki, «/ and p (p same for all
other elements)
1 other set of metal binding
experimental data at different
pH
NICA: eq3orS
k, and «,·
binding to fulvic acid as measured by Saar and Weber (25)
can be described perfectly in this way (19).
Results
Experimental Data. Proton. The proton data are discussed
extensively elsewhere (7), but since the proton charging
curve is used to derive the proton parameters the major
results are summarized here. Surface charge versus pH
curves for the PPHA measured at different ionic strength
could be modeled reasonably well with the master curve
(surface charge versus surface pH) approach (7, 9). Het-
erogeneity analysis (35,36) of the data suggested an affinity
distribution with two peaks. Since the proton binding curve
to PPHA at 0.1 KNO3 is used to obtain the proton
parameters (Ku mu, and Qmax) for each of the two peaks
,
of the affinity distribution, the experimental binding curve
and the derived affinity distribution are shown in Figure 3,
panels a and b, respectively.
Metals. The symbols in Figure 4 present the Cd binding
data, log[Cdads]> as a function of free cadmium concentra-
tion, log [Cd2+], for pH 4,6, and 8. The binding is strongly
pH-dependent as previously seen by Saar and Weber (25)
for fulvic acids. Cadmium binding increases with increasing
pH, although the separation between the pH 4 and 6 and
the pH 6 and 8 curves in the log-log plot is not the same.
In Figure 5, the measured Ca binding is given for pH 6,
8, and 10, by the symbols, as before; results are plotted as
log[Caadsl versus log[Ca2+]. As for Cd, the binding is strongly
pH-dependent with more Ca bound to the humic acid at
higher pH. ·
The Cu binding data (log[Cuadsl versus log[Cu2+]) are
shown by the symbols plotted in Figure 6. Results show
similar features to the other two metals, but Cu is clearly
more strongly bound than Ca or Cd. The extent of binding
is comparable to that found for Cu binding to Suwannee
River fulvic acid and natural DOC (34, 37).
A comparison between the binding on PPHA of Cu, Cd,
and Ca at pH 6 and in a 0.1 KN03 background electrolyte
is given in Figure 7. The effect of pH on the binding (Figures
4—6) is larger for Cu than for Cd, and for Cd it is larger than
for Ca. It should be noted that the slope of the different
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 449
 Delta Charge in mol/kg
FIGURE 3. (A) Charge (<0) as a function of pH curves in a 0.1 N
1:1electrolyte. (B) Proton affinity distribution obtained from 0 versus
pH curve for the purified peat humic acid (PPHA) at 0.1 M ionic
strength (data from Milne et al„ ref 22).
binding curves at low adsorption values is not the same for
all three metals.
Exchange Ratio. Since pH was maintained constant
during the metal binding experiments, it is possible to
estimate a H+/Me2+ molar exchange ratio from the amount
of base required to pH stat the system after each addition
of metal. The observed exchange ratios are given by the
symbols in Figure 8 for Cu, Cd, and Ca at pH 6 and 8. Cd
and Ca have an observed exchange ratio less than 1,
log{[Cd ads]/mol kg-lj
-10 -8 -6
log{[Cd2+]/mol l-1}
FIGURE 4. Cadmium binding to the PPHA as a function of !og[Cd2+] at pH 4,6, and 8 showing the comparison between experimental data
and the NICA model description.
450 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995
decreasing from 0.9 to 0.3 with increasing free metal
concentration. A similar trend is also found for Cu, but the
observed exchange ratio is always greater than 1, ranging
from 1.8 to 1.3. For all three metals, pH has little effect on
the observed exchange ratio.
Modeling. Modeling the Proton Binding. In the first
step of the determination of the model parameters, the
surface charge pH data at 0.1M ionic strength are required.
However, direct measurement provides data for Q (relative
surface charge) versus pH. AQ was converted to Q by
assuming an initial charge, Q0, (based on experimental
determinations) of 0.35 equiv kg™1 (see discussion of Q0 in
Milne etal. (7)). The thus obtained data are shown in Figure
3A, and these data are fitted with the extended NICA (eq
5) model, which simplifies to eq 6 if the proton is the only
cation present in the system:
{k1[H\}mi {k2[H\}m2
Q ~
+
QmaXi11 + {K.LHir Qmax'21 + {k2mm2
(6)
Fitted parameters values are given in Table 1; fitted
results are shown in Figure 3A as the drawn curve. The
first peak (log , = 4.60 L mol™1, mi = 0.44, and Qmax,i =
2.48 mol kg'1) can be assigned to carboxylic moieties while
the second peak (log Kn,2 = 9.34 L mol™1, m2 = 0.39, and
Qmax,2
=
1.93 mol kg'1) can be assigned to more “weakly
acid” groups such as phenols, alcohols, and enols (4). In
this monocomponent case, the m parameter reflects the
apparent heterogeneity of the humic acid, which combines
the effects of intrinsic heterogeneity together with those
due to non-ideality experienced by the proton. This ion-
specific non-ideality includes the electrostatic interactions
at a given ionic strength. The moderately small values of
both mi and m2 indicate that the humic acid exhibits a
strongly heterogeneous and/or non-ideal behavior with-
respect to protons. From the values of Qmax, it is apparent
that the carboxylic type of sites are more numerous than
the weak, phenolic type sites. This supports the general
observation that carboxylic type groups are more abundant
than the weak acid groups (38).
The proton-derived values for the various parameters
given in Table 1 are also assumed to apply in the presence
Data
o
NICA
-4 -2
 log{[Ca ads]/mol kg-1}
2+
log{[Ca
FIGURE 5. Calcium binding to the PPHA as a function of log[Ca2+] at pH 6,8, and
and the NICA model description.
log{[Cu ads]/mol kg-1}
FIGURE 6. Copper binding to the PPHA as a function of log[Cu2+] at pH 4, 6, and 8 showing the comparison between experimental data
and the NICA model description.
of metal. The competitive nature of the NICA model
requires the assumption that Qmax,H Qmax,metal· Further-
=
more, mi and m2 will be used to derive pi and p2 in the
multicomponent case (Figure 2).
Modeling Ca, Cd, and Cu Data. Metal ions bound in the
diffuse double layer could produce differences between
model results and the experimental data. However, it is
possible with a Donnan model {10,20,21) to estimate the
composition of the diffuse layer and to correct for elec-
trostatic effects. These matters will be discussed in a
separate article (39), but an important conclusion from these
calculations is that non-specific binding is always lower
than 1-10% for all metals (high values occurring for high
metal concentrations). A similar result has been found by
Tipping and Hurley (15) Therefore, we have decided to
.
neglect diffusely bound metal.
We have already emphasized the large number of
parameters needed in the NICA model during step 2 of the
]/mol 1_1}
10 showing the comparison between experimental data
fitting procedure (Figure 2). Initial estimates of the six
parameters are needed before automatic optimization can
proceed. Although in numerical fitting procedure a “blind
guess” could be made for the initial values for each
parameter, we prefer to derive initial estimates of the metal
parameters graphically from the adsorption curves. In this
way, failure of convergence in the fitting routine is
minimized.
For the graphical analysis, the second peak in eq 5 is
neglected. This simplification is the more reasonable the
lower the pH. At constant low pH and low free metal ion
concentration, it is assumed that the proton term in eq 3
is constant and always much larger than the metal term,
i.e.
KHcH « constant (7a)
and
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 451
 log{ [Metal ads]/mol kg-1}

FIGURE 7. Comparison of the relative strengths of Ca, Cd, and Cu binding to PPHA at pH 6.

in pH be derived from eq and gives:

(kHcH)na» dfor (7b) can 11

Then the right-most term in eq 3 is equal to a constant, Alog c =

(%/«,·) (12)
and eq 3 reduces to a Freundlich isotherm:
When n, is estimated graphically as previously described,
Qu
=
QmMcr (8) it is relatively easy to derive an estimated value for nH from
the metal log-log plots at two different pH values. Once
or « is estimated, an estimated value for p can be derived
from mH = nKp· Estimates of p, n¡, and nH were made in
log Qit =
log Qmax| + n¡ log (c,) (9) this way for both the Cd and Cu binding data (Figures 4 and
6).
where the product Qmax is a constant that is dependent
Another limiting equation for the shift of the curve of
on the pH. In a log-log plot such as Figure 4, the limiting
a Freundlich plot as a function of pH at constant (low)
slope of the isotherm at constant pH corresponds to n¡, amount of metal bound and intermediate pH values has
which is the parameter describing the non-ideal behavior been derived by Van Riemsdijk (40) and can provide
of the humic material with respect to the bound metal. The estimates of h and p under the conditions that (KiC¡)n<«
limiting slope of the isotherm thus provides the n¡ value. (AhCh)"h and (AThCh)"11 « 1), eq 3 reduces to
Note that this analysis also exposes the weakness of the
classical multicomponent equation since the limiting slope
of the eq 4 isotherm is always 1 regardless of the nature of Qu
=
QmJkfinklicHr,p-11 (13)

the element under investigation, and yet it is clear from A pH-induced shift of the metal binding curves, expressed
our experimental results for Cd and Cu (Figures 4 and 6) as log-log plot now gives
that this is not often the case. Hence, as was previously
shown by Koopal et al. (19) with literature data from Saar nH(p 1)
-

and Weber (25), eq 4 cannot adequately describe the Alog c =- ni

(14)

experimental data.
Equation 3 can also be reduced to another simplified
form. This time the proton term is no longer assumed to
be constant, but it is still assumed to be much larger than
the metal term at low metal concentrations and also Kn Ch
is assumed to be larger than 1 i.e., eq 7b still applies. This
leads to
The interesting aspect of eq 14 is that it illustrates that the
pH effect on the metal ion binding may be dependent on
the intrinsic heterogeneity (p) and on the non-ideality factor
for the proton (nH) and the metal ion (n¡). From measure-
ments of metal ion binding measured for different (con-
stant) pH values, an estimate can be obtained of the term
tzh(p
—

1) from the Freundlich plot once n¡ has been

jkfr (10)
estimated from the limiting slope. The individual values
Qi,t Qn of p and nH can be estimated from eq 14 if the proton
(* %)" binding behavior of the heterogeneous substrate has been
and analyzed separately. Such an analysis gives the product of
p and nH (see eq 6, which is equal to mu). The results of
the initial estimates using the limiting equations and the
log Qi t =
log r + n¡ log(cf) + —

pH
where v is a new constant equal to Qmax , ^ . The
shift of the logarithm of the free metal ion concentration
for a given value of bound metal as a function of a change
(11)
graphical procedure outlined above are given in Table 2.
Initial values for p are calculated from p=ma/nn using the
fitted mu and estimated nH.
Since a bimodal affinity distribution was introduced in
the NICA model, initial estimates of the parameters for the

452 " ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995
Exchange Ratio (H/Cu)
Exchange Ratio (H/Cd)
Exchange Ratio (H/Ca)
FIGURE 8. Measured and calculated proton metal exchange ratio
for three metals (Ca, Cu, and Cd) as a function of log free metal
concentration for pH 6 and 8.
second peak are also needed. We assumed, with the
exception of the median binding constants, that these values
were the same as those for the corresponding parameters
of the first peak. This assumption was supported by the
small difference between mi and m2 found during the fitting
of the proton data (T able 1). Initial estimates of the median
binding constants for the metals were taken from literature
data (15). The final values of the model parameters were
derived with the non-linear least squares program FIT
developed by Kinniburgh (41).
It is also possible to derive the values of pi and p2
common to all metals by fitting all of the metal data
simultaneously. However, we decided to derive these values
by fitting the Cu and the Cd data independently. This
provides a simple sensitivity analysis of the model. After
p was derived for the first metal, pairs of k¡, n¡ values were
derived for each of the subsequent metals. The results for
the three metals (Cu, Cd, and Ca) are given in Table 3,
Sections A (using Cu to determine p) and B (using Cd to
determine p).
Comparing Tables 3 and 2, it follows that eq 14 gives an
excellent estimate of nH,i and thus also of pi, whereas
estimates based on eq 12 are much less accurate. It also
follows from Table 3 that the results obtained for the
parameters that pertain to the first peak are quite insensitive
for the choice of the metal used for the determination of
Pi. For the determination of p2, a large uncertainty is
observed when the cadmium data are used. This is easily
understood, since, as we will see later, the second peak
contributes relatively little to the total cadmium binding
for this data set. For a reliable estimate of the parameters
for the second peak, the use of the copper data instead of
the cadmium is therefore to be preferred. Therefore the
set of parameters based on Cu (Table 3, Section A) were
used in order to calculate the model curves shown in Figures
4-6 for Cd, Ca, and Cu, respectively.
The description of the Cu data is very good (Figure 6)
over a wide range of free metal concentrations (10 pCu2+
units) and over a range of 4 pH units. The parameters
derived from the modeling show a strong non-ideal behavior
for Cu with respect to the carboxylic site (nCu,i = 0.52). An
even stronger Cu-specific non-ideality is found for the
second type of site since «cu.2 = 0.30. The phenolic sites
have a higher affinity for Cu than the carboxylic site since
log K2 > log k\. Both p values are small (pi = 0.47 and p2
=
0.68), pointing toward a strong intrinsic heterogeneity
for the peat humic acid (PPHA); since p\ < p2, our results
suggest that the carboxylic sites display a greater hetero-
geneity than the phenolic sites.
Good agreement between model predictions and the
measurements is also found for Cd over a wide range of
free metal ion concentrations (2 < pCd2+ < 10) and pH (4
pH < 8). The main difference in median affinity constants
between cadmium and copper is that the median affinity
constant for the second peak is much smaller for cadmium
than for copper, whereas for the carboxylic peak a much
smaller difference is observed. The non-ideality for cad-
mium is smaller than for copper since nca is closer to one
than «cu·
The agreement between model description and the
measurements for Ca is somewhat less good as found for
Cd or Cu, but was nevertheless satisfactory. The calcium
median affinity constants are smaller than those derived
for the other trace metals, which is in agreement with
literature data, which shows smaller calcium stability
constant values for the carboxylic and phenolic acid
complexes of various organic molecules compared with
the other metals (28, 29). For calcium log ^ is slightly
smaller than log K2.
The parameters «h,i and nHl2> which account for the
non-ideal behavior of the proton toward the humic acid or
for a specific chemical heterogeneity of the humic toward
the proton are also given in Table 3. They are quite different
for both types of sites. The carboxylic sites show very little
non-ideal behavior for protons since « , is almost 1, while
for the phenolic sites uh,2 0.57 indicates a strong non-
=
ideal behavior for the protons.
Proton/Metal Molar Exchange Ratio. Once all the
parameters are known for both the metals and the protons,
it is possible to calculate the proton metal exchange ratio
with the NICA model and compare the results with
experimentally measured data. The results (Figure 8)
indicate that the model predicts exchange ratios in the range
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 453
TABLE 1

Parameters Derived from Proton Charging Data at Ionic Strength of 0.1 KN03 Using NICA Eq 6
log Ah,i m\ Qmax.i log Ah,2 rn2 Omax,2

4.601 ± 0.002 0.440 ± 0.001 2.48 ± 0.01 9.34 ± 0.01 0.39 ± 0.01 1.93 ±0.02

TABLE 2 modeled for the exchange ratio is 1. Therefore, no

agreement was achieved between model and experimental
Average Graphical Estimates of Non-Ideality data sets for the H+/Me2+ exchange ratio for Cu. The
Parameters and p Parameter of NICA eq 3 exchange ratio was recalculated assuming that Cu(OH)+
(Procedures Outlined in Text) was the bound species, but although higher values were

metal «h,i (eq 14)

obtained for the exchange ratio, they were still smaller than
o/,i «H,1 (eq 12) p (eq 12) p (eq 14)
the experimental values. Thus, this hypothesis cannot be
Cu 0.41 0.67 0.95 0.66 0.46 used to fully account for the Cu data set. Adding a different
Cd 0.75 0.75 0.95 0.58 0.46
stoichiometry for the metal binding might explain the higher
experimental values of the proton/metal exchange ratio.
For example, a bidendate metal ion adsorption on salicylic
TABLE 3
acid- and phthalic acid-like surface groups play a role in
Parameters Derived for NICA To Model Metal and metal binding (1,42,43). The importance of such bidendate
Proton Binding to PPHA at 0.1 M KN03a binding is still a matter of discussion (44), but clearly its
incorporation into the model would require a series of new
Section A: Metal / Parameters (p¡ and p¡ adjustable parameters. Such an extension of the model is
Estimated from Cu Isotherms at pH 4,6, and 8)
first possible and under investigation (45). Another explanation
for the high exchange ratio could be that extra protons are
peak n/,1 , Pi log An
released due to electrostatic effects. Both release of protons
Cu 0.52 ± 0.01 0.93 ± 0.01 0.47 ± 0.01 3.41 ± 0.04 and binding of metal ions will lead to a decrease of the
Cd 0.78 ± 0.01 0.93 0.47 2.95 ± 0.02
Ca 0.79 ± 0.02 0.93 0.47 1.83 ±0.05 negative charge on the organic matter. This lower charge
will induce a release of bound protons due to weaker
second
electrostatic interactions.
peak flu Thu Pi log A«

Cu 0.30 ± 0.02 0.57 ± 0.02 0.68 ± 0.02 8.17 ±0.19 Discussion

Cd 0.47 ± 0.04 0.57 0.68 3.81 ±0.25
Ca 0.51 ± 0.05 0.57 0.68 2.13 ±0.2 Distribution of Bound Metal over Two Sites. It is
instructive to examine the contribution of each class of
Section B: Metal / Parameters (pi and p¡
Estimated from Cd Isotherms at pH 4,6, and 8) sites to the overall binding. In order to visualize the amount
first of metal ion bound to each type of site, we simulate data
peak /ij,i , Pi log A/,i sets with the parameters of the carboxylic site given in Table
Cu 0.45 ± 0.01 0.892 0.493 3.35 ± 0.04 3, Section A. In this case, eq 5 reduces to eq 4 since we do
Cd 0.75 ± 0.01 0.892 ± 0.006 0.493 ± 0.005 2.89 ± 0.02 not take into account the contribution of the phenolic type
Ca 0.79 ± 0.02 0.892 0.493 1.90 ± 0.05 of sites. In Figure 9, the results of the simulation are given
second as the percent of total metal bound to the carboxylic type
peak flii flH2 Pi log Am of sites at pH 6 and 8 for Cd, Ca, and Cu. For both pH
Cu 0.3 ± 0.2 0.86 0.45 9.0 ± 0.2 values, Ca binding is dominated by carboxylic sites across
Cd 0.5 ± 0.3 0.86 ± 0.2 0.45 ± 0.3 4.9 ± 0.9 the range of concentrations which are important for natural
Ca 0.5 ± 0.2 0.86 0.45 1.9 ±0.2 systems (pCa2+ < 5). Cadmium is also bound mainly to
Cu was used first to derive p and r?H for both first and second peaks carboxylic sites at high Cd concentrations (pCd2+ < 6), but
8

(see text for details), see Section A. Next, Cd was used first to derive
the weak acid groups contribute significantly to the binding
p and nH for both first and second peaks, see Section B. The residual
root mean square error (RMSE) defined as at higher pCd values. The importance of the binding to the
nd phenolic sites at high pH and low Cd concentrations (pCd2+
-

X)2
> 10) is
clearly demonstrated; less than 50% of the bound
£<X, Cd is associated with the carboxylic sites under these
RMSE = —-

nd -

q conditions. The contribution of the phenolic sites to Cu

where x, is the measured value of observation /', x, is the fitted value, binding is substantial over the whole pH and Cu concen-
and qis the number of parameters, and nd is the number of observations. tration range although the carboxylic sites are more
RMSE has been calculated for Cu, Cd, and Ca. The values obtained
were respectively 0.045, 0.087, and 0.06 both for the fitting based on important at high concentrations of Cu (pCu2+ < 6) and
Cu (Section A) and Cd (Section B). Uncertainties are dependent on the low pH. Again, the contribution of the phenolic sites
values and the uncertainties of the parameters given in Table 1 which becomes increasingly important with increasing pH. At
are used during the numerical optimization. Slightly different values
for parameters listed in Table 1 may induce different values for the pH 6 and pCu2+ > 10, 70% of the bound Cu is associated
uncertainties associated to the various parameters listed in this table. with the phenolic sites while at pH 8 and pCu2+ = 14 this
increases to 95%. This finding suggests that the copper ion
of those measured for Cd and Ca. However, in the case of binding to humic substances in most natural surface waters
Cu which has an observed exchange ratio of 1.3—1.8, the is dominated by the binding to the weak acid sites since
model cannot possibly predict the measured experimental the pH is typically around 8 and the free copper ion
values since the 1:1 stoichiometry used to describe metal concentration can be as low as 10""15 mol L™1 (46). That the
binding (eq 1) means that the maximum value that can be phenolic sites become more significant in the metal ion

454 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995


se
log[Me2+lmol
FIGURE 9. Contribution of the carboxylic sites to the total binding
of Cd, Ca, and Cu to the PPHA at pH 6 and 8. Calculated from the
NICA modal by setting the contribution of the phenolic sites to zero
(i.e., Qm,xi = 0) and using the parameter values of the carboxylic
sites given in Table 3, Section A. The x-axis range, different for each
metal ion, corresponds to the range of the experiments.
binding at high pH is an expected result and is in accord
with observations in literature {34, 47). The more striking
result of the model is that the phenolic sites still dominate
at lower pH values provided that the free metal ion
concentration is low. The advantage of the bimodal NICA
approach is that it is capable of describing the metal ion
binding over a very wide range of conditions for all cations
tested. The model can be simplified considerably, without
much loss of accuracy, if one is only interested in metal ion
binding over a limited range of conditions. For metal ion
binding at constant pH, the model can even be simplified
to the two parameters of classical Freundlich equation (eq
8). For conditions where either the phenolic or the
carboxylic sites dominate the binding, the pH-dependent
binding can be described with a monomodal NICA model.
Comparison with a Different Approach and Unique-
ness of the Parameters Sets. In a recent paper, Milne et
al. {22) followed a different approach to model cadmium
and calcium binding to PPHA. Two different models were
tested. The physically most realistic option was the bimodal
competitive LF model in combination with a cylindrical
double-layer model to account for electrostatic interaction.
The binding of both cadmium and calcium could be
described reasonably well assuming that they bind to the
carboxylic type groups. The results were not as good as
TABLE 4
pffi and p#T2 Values Derived with the NICA Model
for Different Metals; Comparison with Recent
Literature Values
Tipping and Hurley (IS) Milne et al. (22) this work
pKMHA pKMHB P*i pti P*i P
Ca 1.97-3.39 6.03-8.76 0.74 0.51 2.77 7.21
Cu 0.36-1.09 3.03-5.69 1.19 1.17
Cd 1.41-1.61 5.24-5.83 2.26 3.10 1.65 5.53
with the NICA model. However, the results with the LF
model were obtained by introducing only one metal ion-
specific parameter, in addition to parameters that are
required for the description of the proton binding. If one
assumes only binding to the carboxylic type groups in the
NICA model, a description of similar quality is obtained as
in the approach of Milne et al. {22). The difference between
the two approaches is less than it seems. The non-ideality
was accounted for by the use of the cylindrical double-
layer model, leading also to an electrostatic correction that
is essentially the same for Cd and Ca since both are bivalent
ions. Also in the NICA model, the non-ideality term for Cd
and Ca are quite similar (ncd = 0.78, «ca 0.79). The value
=
of the heterogeneity parameter p in the NICA approach is
comparable to the value of the heterogeneity parameter in
the LF approach. An advantage of the NICA approach is
that the correction for non-ideality is mathematically much
simpler than the use of the cylindrical (or spherical) double-
layer model. The NICA model shows its particular strength
mainly in the description of the copper binding data. These
data could not be described satisfactorily with the com-
petitive LF model. The NICA approach shows that the non-
ideality parameter n¡ for copper differs significantly from
the same parameters for cadmium and calcium. The
electrostatic correction that was applied by Milne et al. {22)
cannot account for a difference in non-ideality for different
bivalent ions. The reason for the difference in the non-
ideality parameter may be that the affinity distribution as
used for protons does not fully correspond with the affinity
distribution for the copper binding sites. The NICA model
can account for such a difference.
Comparison of the median affinity constants derived
from our model with values achieved by other workers is
encouraging. Tipping and Hurley {15) calculated constants
for the equilibrium expression: I^H + Mz+ *= RiM<z'1J +
H+. When our data is expressed in the same way (Table
4), the results indicate that the constants are in the same
range as those of the Tipping and Hurley {15) study. It
should be remembered, however, that the electrostatic
interactions are accounted for differently in the two models.
Tipping and Hurley {15) correct explicitly for the electro-
statics, while in our model the electrostatic interactions
affect both n, and K¡. If we were to apply a correction factor,
the constants would have smaller values and should result
in a better agreement between the two studies for both the
first and second peaks.
Predictive Capability of the Model. The NICA model
has demonstrated that it can successfully describe experi-
mental metal binding data at different pH values and for
a wide range of free metal concentrations. It is of interest
to know whether it is possible to accurately predict an
unknown adsorption experiment at a different pH. Such
a predictive ability would be of great help for future
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 455
experimental work or for sound risk assessment in the
natural environment. To test the predictive ability, two
different approaches were applied: interpolation and
extrapolation.
In order to test the ability of the NICA model to
interpolate values, two extreme pH experiments were used
in order to derive a new set of parameters for the prediction.
The parameter values derived for Cu, Cd, and Ca (not
shown) were similar those given in Table 3, Section A and
accordingly the interpolated results are in good agreement
with experimental data.
Next, the ability of the NICA model to extrapolate is
tested by using the two lowest pH experiments (for
example: 4 and 6 for Cu and Cd) or the two highest pH
experiments to derive new parameters values. Some
discrepancy is observed between the presently derived
parameters and those listed in Table 3, Section A. For
example, Cd parameters for the phenolic type of site are
always smaller (rcca,2 = 0.23) and the errors associated with
the parameters are also much higher (<0.1—0.2). Conse-
quently, the agreement between the extrapolated simulation
and the experimental data was not as good as was achieved
using interpolation. For example, the Cu binding is
overestimated by a factor of 1.7.
Thus, if an order of magnitude estimate of the binding
is needed, then either extrapolation or interpolation using
the NICA model will give reasonable results. Using data
from only two experiments, one at low pH and one at high
pH (in order to take into account the binding due to both
classes of sites (carboxylic and phenolic)), the NICA model
is able to make useful predictions of the binding under a
wide range of intermediate conditions.
Xue and Sigg (46) have suggested that the very low
concentration of free Cu2+ ions observed in Lake Greiffen
is due to the high concentration of strong organic ligands.
However, the measured copper speciation in Lake Greiffen
is in accord with the copper binding to PPHA. Assuming
that the DOC in Lake Greiffen would exhibit a copper
binding behavior that is similar to the behavior of PPHA,
the free copper ion concentration that would be expected
can be estimated from our data. Assuming that practically
all the copper in the lake water is bound to DOC, knowing
that the pH is around 8, DOC is 3.5 mg L_1, and total
dissolved copper is 10 nmol L-1 (46), a free copper
concentration can be derived from Figure 5 of around 10™15
mol L-1. This estimation is in excellent agreement with
the value found experimentally by Xue and Sigg (46). The
chemical composition of Lake Greiffen is quite different
from the conditions for which the data of Figure 6 have
been obtained. Notably, the salt level in the lake is much
lower, and calcium ions are present. The lower salt level
would promote copper binding, whereas the presence of
calcium would decrease the copper binding. Although our
estimate of the speciation of Lake Greiffen can be considered
a rather rough first-order approach, its result is still quite
encouraging. The results suggest that humic and or fulvic
acids in lake waters are very important in determining the
bioavailability of ions like copper in these systems.
With the parameter values obtained in this study, the
competition between more than one divalent cation for
binding to PPHA can be predicted with the NICA model.
A start has been made to collect experimental results for
such systems. Initial experimental results are in reasonable
agreement with model predictions.
466 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 2, 1995
Conclusion
The non-ideal competitive adsorption (NICA) model pre-
sented here is able to describe the binding of a variety of
ions (H, Ca, Cu, Cd) on a purified peat humic acid. The
models fits the data reasonably well over a wide range of
free metal ion concentrations ranging from pMe2+ = 14 up
to pMe2+ = 2. This is achieved over a wide pH range (4 pH
<
10), which covers the range found in most natural
environments. The results indicate that the binding of the
metals to humic acid is strongly influenced by both the
chemical heterogeneity of the humic material and ion-
specific non-ideality effects. For monocomponent adsorp-
tion, this implies that the apparent heterogeneity is different
for each metal. The model best describes the binding by
assuming the presence of two major classes of metal
complexing sites, which are assumed to correspond with
carboxylic and phenolic type surface groups. The bimodal
NICA model can be simplified to a monomodal model if
one is interested in the modeling of pH-dependent metal
ion binding over a narrow range of conditions. For
conditions of constant pH and low metal ion concentration,
the NICA model can be simplified to the classical two-
parameter Freundlich isotherm. It is therefore in accord
with an extensive literature for trace metal sorption by soils
and sediments which has frequently demonstrated the
applicability of the Freundlich isotherm under these
conditions. The model results indicate that the phenolic
type sites contribute significantly to the binding behavior
at very low concentrations of free metal ions even at
relatively low pH. The results obtained for copper binding
can explain why the free copper concentration in surface
waters is 7 orders of magnitude lower than the total
dissolved copper concentration.
Acknowledgments
This work was partly funded by the European Union STEP-
CT90-0031. C.J.M. andD.G.K. contribute with the approval
of the Director of the British Geological Survey (NERC).
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Received for review May 12, 1994. Revised manuscript re-
ceived October 20, 1994. Accepted October 25, 1994.®
ES940290H
® Abstract published in Advance ACS Abstracts, December 1,1994.
VOL. 29, NO. 2, 1995 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 457