oLN67037/90/s3.00 + .

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Geochimim et Cosmochimiecr Acta Vol. 54, pp. 1535-1553
Copyright 8 1990 Pcrgamon PICSYpk. Rintcdin U.S.A.

Complex&ion by natural heterogeneous compounds: Site occupation distribution functions,

a normalized description of metal complexation
J. BUFFLE,'**
R. S. ALTMANN,'*~
M. FILELLA,' and A. TESSIER’
‘Dkpartement de Chimie Minkale, Analytique et Appliqute, Universitk. de GenLve,
Sciences II, 30, Quai Ernest Anwmet, 1211 Geneva 4, Switzerland
‘INRS-Eau, Universid du Qu&ec, Complexe Scientifique, CP 7500, Ste Foy, Qu&ec, Canada, GIV 4C7

(Received June 2, 1989; accepted in revisedform March 12, 1990)

Ahatract-This paper presents a new conceptual approach to interpreting titration curves of metal com-
plexation by physically and chemically heterogeneous natural complexants such as humic acids, clays,
complete soils, or sediments. The physico-chemical and analytical difficulties encountered with such
systems are reviewed by comparison with a system containing only a few simple ligands, followed by
discussion of the new approach on the same basis. It is shown that interpretation of heterogeneous
complexant properties necessitates a preliminary transformation of experimental raw data into a function
sufficiently normalized so as to allow comparison of results obtained under different conditions. A nor-
malized function called a Site Occupation Distribution Function (SODF) and its potential usefulness is
described here. The SODF is a readily computable function which relates the complexation buffer intensity
of the system to the differential free energy of the complexation sites present. Its major interest is that it
enables one to obtain both a rigorous mathematical description of the complexant properties (even when
highly heterogeneous) at the macroscopic level and, in certain cases, an estimation of the molecular-scale
behavior of particular site types.
The relationship of the SODF to other distribution functions proposed in the literature is discussed
and applications are exemplified using simulated and real natural systems. In particular, its utility is
discussed in detail for ( 1) discriminating between different site types (major, minor, dominant, back-
ground), (2) evaluating the degree of heterogeneity of an unknown complexant system, (3) estimating
the nature and true thermodvnamic constants of complexes, and (4) yielding a rigorous definition of
“complexation capacity.”

TABLE OF SYMBOLS 19~

CM (mole/l) =
Total metal ion concentration
[M] (mole/l) =
Concentration of free metal ion
[Mlb (mole/l) =
Total concentration of bound metal ion
[Mlb,, (mole/l) =
Concentration of metal ions bound to site
typei
Cs (mole/l) = Total complexing site concentration
Csi (mole/l) = Concentration of site type i
ACs (mole/l) = Concentration of sites with K values in a
given interval A log K
{ S} t (kg/l) = Total mass concentration of complexant
(proportional to the total concentration
of all sites)
jX = Cumulative mole fraction of all site type
i, for which Ki 2 jK, wherejK = any par-
ticular value of K (‘X =c Cs,/ C’s)
X = Cumulative mole fraction of sites having
an equilibrium constant larger than K
AXi = Mole fraction of site type i (=Cs,i/C,)
AX = Analogous to AXi, but for complexants
having continuous behaviour (=ACs/Cs)
0 = Degree of occupation of all site types
(=[M]b/Cs),where[M]bandCsareex-
pressed in the same units. Conceptually,
0 is equivalent to the experimental pa-
rameter [M]b/{S}, where {S}, is ex-
pressed in kg/l
* Corresponding author.
t Present address: 125 me Legendre, 750 17 Paris, France.
1535
= Degree of occupation of site type i
(= [Mlb,i/CS,i)
a = CM/[W
Ki ( l/mole) = Thermodynamic equilibrium constant of
the complexes formed between M and
sites of type i
K* (l/mole) = Differential intensity parameter = weighted
arithmetic mean of thermodynamic equi-
librium constants of all complexes (see
Eqn. 1)
K,,, (l/mole) = Equilibrium constant of Freundlich iso-
therm
/.I(mole/ kg) = Complexation buffer intensity ( = d( CM/
{S)*)ldlog [MI)
o* (mole/kg) = Dependent variable of the SODF
(= -d([M],/{S},)/dlogK*)
I = Slope of a linear DEF or SODF (see Fig.
4) and exponent of Freundlich isotherm
CC(mol/kg) = complexation capacity
I. BACEGROUND
1.1. Introduction
A GREAT AMOUNT OF RESEARCH effort has been devoted
over the last two decades to studying the aqueous solution
chemistry of such environmentally important trace metals
as Cd, Cu, Pb, Zn, and Ni. This interest stems largely from
the known low toxic thresholds exhibited by most aquatic
organisms to these and similar metallic elements that are
introduced into the environment in substantial amounts by
1536 J. Buffle et
anthropogenic activities. More particularly, a large number
of observations and important questions point to the im-
portance of understanding the speciation of trace metals in
natural aquatic environments. Examples include
( 1) the demonstration that, in laboratory experiments, bio-
logical response is often correlated with the free aquo
cation activity (e.g., Cu*+. Cd’+, Pb’+), and not with
total metal concentration;
(2) the need to understand total metal partitioning between
dissolved, colloidal, and particulate phases in order to
predict metal migration through groundwater and pore-
water systems;
(3) questions concerning the relationship between biological
uptake and metal association with other compounds or
phases;
(4) the dynamics of free aquo ion activity response to changes
in total metal loading or pH (i.e., the metal ion buffer
capacity of the system).
The speciation of a given metal is defined as the partitioning
of the total metal present in a particular system among all
possible chemical forms through reactions with all available
complexant sites (Fig. 1). Complexants are considered here
to be all compounds, particulate or dissolved, organic or in-
organic, which can combine with the metal cation ( BUFFLE.
1988). They range from the most simple ligands (e.g., OH -,
DISSOLVED
cobIPLExEs
FIG. 1. Metal complexation by_dissolved _ and particulate complexants in natural systems determines metal ion
buffering response, biological uptake, and transport.
al.
Cl ~, amino acids) through groups of complexants made up
of relatively small-sized compounds having similar properties
and often with several sites per molecule (e.g., fulvic acids,
peptides) to high molecular weight compounds or particles
having large numbers of sites per physical entity (e.g.. humic
substances, polysaccharides, hydrous metal oxide surfaces,
clays). Prediction of the fraction of total metal complexed
with each of the different complexant sites present would
require complete knowledge of all physico-chemical param-
eters controlling metal speciation. Particularly important in
such a description are the complexation equilibrium con-
, 1
status.
At present, most of the equilibrium constants for metal
complexes with natural materials (humics, clays, hydrous
metal oxides, soils and sediments, etc.) are either unknown
or too empirical to be of predictive use. A procedure for
determining sound physico-chemical parameters from raw
experimental titration data is needed, but this poses many
difficulties. Various interpretation models have been proposed
( SPOSITO, 1986; BUFFLE, 1988) which make assumptions
concerning the nature of the reactions involved. Although
such models yield adjustable reaction parameters, the chem-
ical meaning of these parameters seems questionable when
the complexity of natural systems is considered. Indeed, any
CIpriori model which takes this complexity into account must
include so many independent and non-directly measurable
\
 Theory of metal complexation
parameters that no curve fitting procedure would be able to
allow discrimination of the most important ones from those
less significant ( CABANISSet al., 1984).
1.2. Difficulties in Modeling Complex&ion
in Natural Systems
The difficulties associated with representing and inter-
preting complexation reactions in natural systems are a direct
consequence of ( 1) their inherent physico-chemical com-
plexity and (2) the limited information content of measurable
experimental data.
Physico-chemical complexity
All important aquatic environments contain significant
concentrations of macro-molecular, colloidal, or particulate
components which are known to play a major role in trace
cation chemistry (GREENLANDand HAYES, 1978; TESSIER
et al., 1979; SCHINDLER, 1981; LUOMA and BRYAN, 1981;
BALISTRJERI and MURRAY, 1983; SIGG, 1985; etc.). Although
these substances can frequently be differentiated based on
physical, chemical, or operational similarities (e.g., humic
and fulvic substances, proteins, polysaccharides, specific clay,
and hydrous metal oxide fractions) into what can be called
an homologous compound group ( BUFFXE, 1988), each
group will still exhibit
( 1) heterogeneous polyfunctionality resulting from possession
of many complexing sites of different nature;
(2) polyelectrolytic character due to a large number of dis-
sociable functional groups per physical entity;
(3) specific properties linked to geometricalfactors resulting
from conformational changes, reactions on surfaces or
within gels, aggregate formation, etc.
Heterogeneous polyfunctionality results from the inclusion
of many “contaminant” compounds during the natural syn-
thesis of any given homologous compound as well as from
the large number of processes to which they are subjected
(e.g., adsorption, polymerization, crystallization for hydrous
metal oxides; condensation, oxidation, biological transfor-
mation for humics and fulvics) . The final products are mix-
tures of a large number of similar but non-identical com-
pounds, each product’s structural heterogeneity being ex-
pressed, for example, as physical and chemical defects in
inorganic complexants and extremely complex organic mol-
ecules. Further, a given type of macromolecular or particulate
homologous complexant (e.g., an iron hydrous oxide, a clay,
a humic fraction) is unlikely to exist in a “pure” state in a
natural environment, but rather to be found associated with
other complexants. Mineral complexant surfaces will adsorb
both inorganic and organic compounds from solution thereby
covering or modifying their trace cation complexation sites.
The functional groups on organic macromolecules will be
subject to coordination with other cations present which must
be displaced before a given trace metal can be complexed.
Such associations reinforce the need for studying whole sys-
tems and indicate the difficulties involved in recreating the
behavior of natural systems using simple mixtures of synthetic
complexants.
1537
Experimental d#culties
The difficulties involved in measuring classical thermo-
dynamic characteristics of cation complexation in compli-
cated natural complexant systems are daunting. Barring exotic
techniques restricted to observing simple systems containing
unrealistically high cation concentrations vis-a-vis natural
environments, the principal approach available for complex-
ation studies is varying metal to ligand ratio. Laboratory ti-
trations are the most often used, and this paper will be based
on this experimental approach. For instance, for trace cation
complexation, experimental data is often obtained by incre-
mentally increasing total cation concentration, CM, in so-
lutions containing constant complexant mass concentration,
{S } t. Mass-based as opposed to mole-based concentration
must be used for the complexant because it is the only con-
centration parameter unambiguously measureable for most
natural complexants. This constitutes one of the experimental
difficulties. A titration curve is obtained by measuring the
molar concentration (or activity) of the uncomplexed cation,
[M] , for various distinct states of the system expressed by
the ratio, C,/ { S} ,. Such titrations are shown in Fig. 2a for
a simple 3 ligand system and in Fig. 2a’ for a hypothetical
natural complexant having a very large number of site types
(seeSec.III. 1 for details concerning these simulations). These
curves can be transformed into the corresponding working
curves, Fig. 2b, b’, by defining the total complexed metal
concentration as [Mlb = Ct,, - [Ml. However, for reasons
of precision and instrumental limitations, [M] is only mea-
surable over a restricted range, or analytical “window”( BUF-
FLE, 1988; ALTMANNand BUF!=LE,1988) delimited by the
lower and upper attainable values of [ M] , [M] lo, and [M] up,
respectively (e.g., realistically between [M] lo = lo-” and
[Ml,, = IO-* M in Fig. 2). This restriction adds a second
important difficulty for complexation measurements in nat-
ural systems since the beginning and end of the titration can-
not be precisely defined.
Interpretation d@culties
Extraction, from a working curve, of the total concentra-
tions ( CW, G.2, . . . C’s,“)and equilibrium constants ( Kr , K2,
. * . K,,) for each of the sites present in a sample depends on
our ability to distinguish the contributions of each site to the
shape of this curve. This has been discussed in detail in pre-
vious papers (BUFFLEand ALTMANN, 1987; ALTMANNand
BUFFLE, 1988). Without going into detail, the following im-
portant points are worth highlighting:
(1) Only those complexes actually titrated within the “win-
dow” of [M] values may be detected by any interpre-
tation method. This means that only those sites with
-log [M] lo r log K 2 -log [ Mlup can be measured with
accuracy. For the window given in Fig. 2, complexants
can be detected only if they have log K values in the
approximate range 10 > log K > 2.
(2) In order to be distinguished, the “adjacent” K values of
complexant sites must be sufficiently different from one
another. Complexants having log K values separated by
less than approximately one log unit will generally be
difficult to resolve.
1538 J. Buffleet al.

DISCRETESYSTEM CONTINUOUS
SYSTEM

-6
-3og $2 O

-12 -10 -6 -6 -I -2 0
log IMI
Experimental
-..-..-..-..-..-..-..-..-..-..-..-..-... .-..-..-..-..-.._
Theoretical

12 10 6 6 4 2 0 12 10 6 6 4 2 0
log Ki log K

l2 lo a10:K4 * ’
FIG. 2. Comparison of various representations of data for simulated discrete and continuous complexant systems.
Discrete system: three ligands having log K, = 4, 6, and 8; mole fractions, Axi = 0.33 for each. Continuous systems:
simulated by 27 “background” sites spaced at 0.5 log K intervals along a Sips’ SADF (r = 0.5; log Km = 1); three
discrctc “dominant” sites are superimposed on the background at log Ki = 4,6, and 8 with CF = 15, 10 and 20 times
that of the background (CF = concentration ratio of the minor dominant site with respect to the background at a
given log K value). (SeeSec.111.1for more details concerning the continuous system and Table of Symbols for
definitions.)

(3) The minimum detectable concentration of site types
varies across the analytical window and is a function of
K value spacing; as the spacing decreases, the difference
in relative site concentrations should increase; otherwise
the influence of the site having the lower concentration
is “swamped” by that present in a much higher relative
concentration ( ALTMANN and BUFFLE,1988 ) .
(4) The experimental error affects the minimum amplitude
of the structural features in the titration data which can
be detected and, therefore, the sites which can be mea-
sured and characterized.
Given the complexity of natural system briefly described
above, the difficulties likely to be encountered in interpreting
their complexation behaviour using classical, discrete site ap-
proaches should be apparent. These considerations also sug-
gest the utility of differentiating the site types present in com-
plexant systems into those which are amenable to classical
interpretation approaches and those for which another tack
must be taken. The former are the major sites and the latter
the minor sites. This site distinction is discussed in greater
detail in Sec. IV. 1.
1.3. A Proposed Approach
Since interpretation of complexation by natural hetero-
geneous complexants cannot be based on any a priori physic
chemical model (step 2’ in Fig. 3), a deductive approach
must be taken to develop a realistic model based on experi-
mental observations (steps 2a, 2b in Fig. 3). This implies
accumulation of a large number of experimental titration
curves obtained under a wide range of different conditions
 Theory of metal complexation
I
I
Deduction of 6%
dominant factors
affectiq complexation
L
r-----l
Formulate
quantitative
model
(3)
(‘)
FIG.3. Approaches for interpreting simple ligand and heteroge-
neous complexant titration curves.
(pH, T, ionic strength, competing metal, etc.) which are then
normalized (step 2a) and compared (step 2b) to deduce (step
2c) the most important factors (e.g., polyelectrolytic, site na-
ture, polyfunctionality) influencing the metal complexation
reactions. Deductions can then be made by formulating a
quantitative model. This approach is similar to that classically
used in studying “simple” ligands, the difference being that
( 1) the chemical characteristics of simple ligands are generally
known beforehand and (2) the number of possible complex
types is small. Consequently, formulation of a priori hy-
potheses in this’case (step 2’ in Fig. 3) is not particularly
difficult.
For heterogeneous complexants, titration curves are used
to obtain information on a large number of complexes for
complexants having an unknown physico-chemical structure.
Step 2b in Fig. 3 is, therefore, critical and must include the
recording of titration curves over a much larger range of con-
ditions than is needed for interpreting the complexation
characteristics of simple ligands. Furthermore, the all-im-
portant step in the comparative approach for heterogeneous
complexants is the transformation of the experimental data
into some normalized format (function, curve, spectra; i.e.,
step 2a). This step is essential in order to ( 1) allow data inter-
comparison irrespective of the conditions under which they
were obtained and (2) permit formulation of initial “working”
hypotheses regarding the most important factors affecting
complexation (site nature, complexation capacity, secondary
influences). It is essential that this transformation be purely
mathematical and not dependent upon any a priori hypoth-
1539
esis as to the physico-chemical reasons for the shape of the
resulting curve. This paper discusses how such normalized
spectra can be obtained and how they might be employed.
IL THE SITE OCCUPATION DISTRIBUTION FUNCI’ION:
A NORMALIZED REPRESENTATION OF
COMPLEXATION TITRATION DATA
The purpose of any normalized representation of com-
plexation data is to transform conditional experimental data
(only valid under the experimental conditions used) into
representative, non-conditional, physico-chemical parameters
to allow making predictions about the complexant behaviour
under different conditions, or to compare this behaviour to
those of other complexants, in a meaningful fashion. For
heterogeneous complexants, representation of complexation
properties is not based on constants, but rather on the dis-
tribution functions described below: SADF (Site Affinity
Distribution Function), DEF (Differential Equilibrium
Function), SODF ( Site Occupation Distribution Function).
Sec. II. 1. summarizes the relationships between the discrete
values of classical complexation parameters and these con-
tinuous functions. It also discusses the relative degree of con-
ditionality of the latter, i.e., the extent to which they depend
on experimental data. Sets. II.2 to II.4 describe SADF, DEF,
and SODF. The SADF is the only rigorous distribution func-
tion representative of the complexation properties, but its
direct computation leads to severe artifacts. The SODF is
based on the DEF, and it is a mathematically well-defined
surrogate for the SADF.
11.1. Representative Physico-Chemical Parameters
of Simple versus Heterogeneous Complexants
The relevant thermodynamic information of a complexant
system is
( 1) the total concentration of each complexant, Cs,i;
(2) the stoichiometry of each complex species of the metal
being studied, M,
( 3) the free energy of formation or the thermodynamic equi-
librium constant, Ki, for each complex species.
For heterogeneous natural complexant systems, Cs,i and
Ki are, respectively, the total molar concentration of site type
i and its complexation constant with M. These are the pa-
rameters which we are seeking (Fig. 3 ) since they are the
only ones which are non-conditional. The corresponding
measurable parameters which govern the overall behaviour
of M in the system, however, are (Figs. 1 and 3)
( 1) the free metal ion activity, [M] , which is the master vari-
able representing the overall metal adsorption or com-
plexation energy of the system:
(2) the overall metal ion buffering intensity, /3, representing
the capability of the system to fix or release a particular
increment of M. (/3 is defined as @ = d(CM/{ S},)/
dlog [Ml.)
Although [Ml and B are dependent variables, [M] may
also be taken as a master variable (STUMMand MORGAN,
198 1) reflecting global complexation energy (i.e., an intensive
variable), while B can be employed as an indicator of com-
1540 J. Buftle et al.

plexation capacity (i.e., related to complexant concentration,
an extensive variable). The complexation properties of nat-
ural systems will always be represented by functions of ex-
tensive vs. intensive parameters. But a number of different
functions can be used, two extremes being the rigorously non-
conditional one, Cs,i = f( Ki) on the one hand, and the ex-
perimental data expressed as fl = g( [Ml) on the other. It is
obvious that, for these two examples, the second will be more
conditional, i.e., will depend more on experimental conditions
than the first. In particular, Cs,, and K,, in contrast to fl and
[Ml, are independent of the metal to ligand ratio. The former
will, on the other hand, certainly necessitate mathematical
deconvolution with the accompanying high risk of artifact
generation. In order to be able to make a valid comparison
of experimental results, a normalized representation (Fig. 3 )
should minimize the number of conditionality factors, which
can only be done through comparison of many experimental
results obtained under appropriately varied conditions. The
normalization function proposed below, the Site Occupation
Distribution Function (SODF). has a level of conditionality
somewhere between the log C’s,,vs. log Ki function (called a
Site Affinity Distribution Function; SADF), and the log /l
vs. log [M] function. The SODF is based on the concept of
the SADF and on that of the Differential Equilibrium Func-
tion (DEF). the characteristics of which are shown in Fig. 4
and discussed below.
It is important to point out that DEF and SODF are con-
ditional for one or both of the following reasons in addition
to the “classical” conditionality factors (PH. T. and ionic
strength ) :
( 1) Since the structure, and often composition, of most nat-
ural complexants is unknown, the stoichiometry of the
metal coordinating groups is also unknown. As a con-
sequence a complexing site can only be defined opera-
tionally as consisting of all functional groups involved
in the complexation reaction under the conditions ex-
isting at the titration point of interest ( ALTMANN and
BUFFLE, 1988; BUFFLE, 1988). This definition of “site”
does not make any reference to the chemical nature of
the coordinating group, and the corresponding stoichi-
ometry therefore becomes irrelevant. All metal-site re-
actions are then treated mathematically on a 1 / 1 basis
with no implication being made concerning the actual
nature of the coordinating groups. The coordinating
group nature. as well as the corresponding true stoichi-

.-:

-15 -12 -9 -6 -3 0

-12 9 6 12 9 6 3
?og KS0 log K”
differentiation
I .It_ integration

12 9 6 3 12 9 6 3
log Kp log I!

FIG. 4. (a-c) Steps involved in representing titration data for heterogeneous complexant systems. (d, e) Desired
thermodynamic description of the complexing system in terms of SADF or cumulative SADF ( =CADF). (The con-
tinuous system is the same as in Fig. 2; maximum values of [Ml,/{ S}, and Cs = 1 mole/kg and 1 mole/ 1, respectively.)
 Theory of metal complexation 1541

ometry and all other equilibria between the site and the
other components of the system, will have to be deduced
from the changes observed in the above functions with
experimental conditions (step 2c in Fig. 3).
(2) The above definition of complexing sites means that the
corresponding complexation energy or equilibrium
“constant” will not be thermodynamic parameters but
rather an average of the free energies of all sites, weighted
-:12 -10 -8 -6 -4 -2 0
in a fashion dependent on the way in which they are
1% FI
computed. As has been discussed elsewhere ( ALTMANN
and BUFFLE, 1988; BUFFLE, 1988), the intensive param-
eter of the DEF, log K*, is a rigorous and direct means
of obtaining a mathematically well-defined and physico-
chemically meaningful value (see Sec. 11.3) for such a
complexation free energy.

11.2. Site Affinity Distribution Functions

(SADF and CADF)

A Site Afinity Distribution Function (HUNSTON, 1975;

SHUMANet al., 1983; FISH et al., 1986; TURNER et al., 1986)
describes the distribution of site number as a function of site
complexation energy with the metal of interest. Site number
is usually expressed in either concentration units, C& (or
ACs) or mole fraction, AXi = Cs,ilCs (or AX = AC’s/Cs).
The corresponding complexation energy is represented either
by AGP (or AG) or an equilibrium constant, log Ki (or log
K) (see Figs. 2d,d’, and 4d). For the mixture of a few simple
ligands, the SADF is a discrete spectrum (log Axi = f(log
Ki); Fig. 2d), whereas for heterogeneous natural systems (Figs.
2d’ and 4d), the concentration, ACs, of each site type be-
comes so small and the number of site types so large that
ACs (or AX) tends toward 0 as does the A log K interval
defining each site type, both becoming effectively continuous
variables. The SADF becomes then a continuous function
expressed as log ( dCs/d log K) =f( log K) (or log (dx/d log
K) = f( log K)) , where dCs is the concentration of sites having
K values within the interval d log K. The complexing prop-
erties of a heterogeneous system therefore may be represented
either as a mixture of a very large number of discrete sites,
or by continuous functions. The two symbolisms will be used
in parallel hereafter to facilitate understanding of the concepts.
This formulation also shows that a continuous SADF
should preferably be considered as a probability density
function expressing the probability of finding sites having log
K values within a particular interval d log K ( BUFFLE and
ALTMANN, 1987). Integration of the area under this curve,
between two log K values gives the number of sites which
possess log K values in this interval. This provides an alter-
native, equally useful, means of representing the complexa-
tion properties: the Cumulative form of the SADF (denoted
CADF), shown in Fig. 2c for the simple ligand mixture and
in Figs. 2c’ and 4e for continuous distributions. As explained
in detail in ALTMANN and BUFFLE ( 1988), a Cumulative
SADF is obtained by computing for each particular value of
K, j K, the corresponding cumulative mole fraction, J X, de-
fined as the sum of the Axi’s (or the integral of dx/d log K
= f(log K)) for all sites for which K ;1. j K. This is repeated
for all values of K, the corresponding plot log x = f( log K)
being the CADF. The CADF can also be expressed as a plot
12 10 8 6 4 2 0
log K* or log K
FIG. 5. Comparison of SODF and SADF for simulated heteroge-
neous complexant systems. Systems calculated as described in fig.
2 except P = 0.2, 0.5, and 0.8. (a) Working curves. (b-d) SODF
(solid lines) and SADF (dotted lines + points).
of log Gc”rn= f( log K), where C’,,, is the cumulative site
concentration, obtained by integrating ACs (or more rigor-
ously the function d&/d log K = f(log K)), as explained
above for the parameter X.
The continuous SADF function provides the same type of
description as does a list of the C’s,iand log Ki values for the
discrete system. Successful thermodynamic interpretation of
a given titration working curve therefore ideally involves
finding the underlying SADF. Unfortunately, mathematical
extraction of affinity distribution functions From titration data
containing normal amounts of experimental error is subject
both to severe mathematical artifacts ( THAKUR et al., 1980)
and to conceptual limitations ( ALMNN and BUFFLE,1988).
In most cases, the affinity distributions obtained are therefore
incorrect and the use of such surrogate functions as the SODF
is therefore preferable. Despite this practical limitation, the
concept that there is always an SADF underlying all titration
data still serves as an extremely useful reference for all that
follows.
1541 J. Buffle et al.
It must be noted that CADF and SADF are complementary
functions. The DEF and SODF functions described below
are surrogates for the CADF and SADF, respectively. Most
of the concepts presented in Sec. II are illustrated in Figs. 4
and 5 which show the above four functions calculated from
a simulated titration data set. The ligand mixture used (see
legend of Fig. 2a’-d’ and Sec. III. 1) was chosen ( 1) to simulate
characteristics of real natural materials and (2) to exhibit
several inflections or peaks. Although this is not frequently
the case with natural systems, this situation was deliberately
chosen to exemplify the properties of these functions and
their potential for finding the properties of unknown systems.
11.3. Differential Equilibrium Function (DEF)
The problems associated with interpreting actual titration
data for highly polyfunctional natural complexant substances
are partially addressed in the description of the D@rentiaI
Equilibrium Function, DEF, log ( [M] b/ { S} t) = f( log K* )
(Fig. 4b) originally defined by GAMBLE ( 1970). The deri-
vation of and supporting reasoning for this function have
been discussed in many publications (GAMBLE and
SCHNITZER,1973; GAMBLEet al., 1980; Bu~E, 1984, 1988;
SPOSITO, 1986) and will not be repeated here. The most im-
portant qualities and characteristics, taken from the above
works and from ALTMANNand BUFFLE( 1988), are the fol-
lowing:
(1) The DEF is based on the D@erential Intensity Parameter,
K*. This variable has been recently shown (ALTMANN
and BuF~%E, 1988 ) to be a weighted arithmetic mean of
the conditional equilibrium constants, Ki, for all sites i
present in a given system:
i Ki*Bi*( 1 - Bi)*AX,
K* = ‘=I
(1)
i$ Bi. ( 1 - Si) * AX~
where Bi is the fractional degree of occupation by M of site
type i. K* varies continuously with changes in the state of a
system, most frequently because of changes in the normal&d
total complexed metal concentration, log ( [Ml,,/ { S} t) as
shown in Fig. 4b. The value of K* at any given point in a
titration can be seen to depend on (Eqn. 1)
(i) the complexing site composition (i.e., the form of the
SADF) through the Ki, AXi terms. Sites having larger
K values or present in larger proportions have a stronger
influence than weaker complexing sites or those present
in lower concentrations;
(ii) the degree of occupation of each site type i, i.e., the
factors 0i* ( 1 - 0i) in Eqn. ( 1). These terms vary con-
tinuously during a titration, each one having a max-
imum value at and being symmetrical about the point
log [M] = -log Ki and falling off steeply for log [Ml
greater or less than -log Ki. This means that those
sites being actively titrated at a given point in a titmtion
(e.g., with 0.05 5 0i I 0.95) will have a greater weight
than those which are already near saturation (i.e.,
having Ki $ 1/[M] and t$ -, 1) or which are nearly
uncomplexed (i.e., having K, < 1/[M] and Hi+ 0).
It may be shown (BUF’FLE et al., 1990) that this
weighting factor causes K* to be controlled mainly
by the small fraction of sites which are near half-sat-
uration at a given titration point. Nevertheless, because
it always incorporates some influence from all sites
present, the K* value calculated at any given point in
a titration obviously cannot be associated with only
a single site’s K< value.
(2) A significant advantage of K* is its direct and simple
computation from a continuous function fit of experi-
mental data without requiring knowledge of the total
molar site concentration, Cs. Indeed, K* can be written
( BUFFLE, 1984)
l __(a- l)dln{S),
K.=_$ dln (Y
(2)
M , + lN _ ,: din (Cd{SjJ 1
L- ‘-- -’ dln (Y J
where (Y= CM/[M] and { S} f can be expressed in any
units having a fixed relationship to total site concentra-
tion (e.g., grams of complexant per 1, surface area per
1). This property is important, since Cs is rarely mea-
surable for natural complexants (Sec. V). The K* func-
tion, despite its limitations, represents the best rigorous,
normalized, pseudothermodynamic parameter directly
calculable from experimental data obtained on highly
polyfunctional systems. As such it is also the best sur-
rogate for identifying sites in terms of their complexation
intensity for a particular cation.
(3) Finally, the extensive parameter of the DEF, [Ml,,/ {S} r,
is analogous, although not equal, to that of the CADF,
CScum.Indeed, during the course of a titration, the stron-
gest binding sites are those first occupied by M so one
can consider, as a first approximation, that [ Mlb is an
experimental integration of the strongest sites analogous
to the mathematical integration necessary to get C,,,
(Sec. 11.2). The close relationships between C&, and
[M]b/{S},, on the one hand, and K* and K, on the
other hand, therefore suggest, as mentioned in Sec. 11.2,
thatDEF(log([M]b/{S},)=f(logK*))mayserveas
an analogue of CADF (log C,,, = f(log K)) (Fig.
4b, e).
11.4. The Site Occupation Distribution Function (SODF)
Any method of representing and interpreting titration data
of natural system cation complexation must be judged by its
capacity in answering the environmental questions raised in
the first part of this paper. These concerns can be grouped
depending on whether they deal with system behaviour at
the microscopic or macroscopic level. The former category
of questions concerns true reaction stoichiometry and free
energy while the latter, as mentioned previously, includes the
overall cation buffer capacity of the system and its Bee metal
ion activity. What we would like to point out is that a well-
conceived normalized representation of the complexation
properties of a system (even if tied to specified conditions)
provides a powerful means of addmssing both types of con-
 Theory of metal complexation
terns. First, it can be expected to allow prediction of the
partitioning and buffering behaviour in a particular environ-
ment; in addition, observation of changes in the form of the
normalized representation can be correlated with variations
in experimental conditions (e.g., pH, competing metal con-
centrations, ionic strength), providing valuable insight when
searching for and testing hypotheses concerning the nature
of complexation reactions. Given the above-mentioned dif-
ficulty of extracting the true SADF from experimental data,
we propose here a function based on K*, therefore directly
calculable from titration data, which mimics the form of the
SADF. This function is called the Site Occupation Distri-
bution Function, SODF.
As for all complexation representation functions, the Site
Occupation Distribution Function (SODF) expresses a con-
centration (extensive variable) as a function of an identi@ing
intensity parameter. The intensity variable employed is
log K* for the reasons presented in the foregoing sections.
The concentration parameter, since it must also be directly
calculable from titration data, is taken as the differential
change in total complexed metal concentration (normalized
in terms of total complexant quantity, { S} ,) associated with
a differential change in log K*. The dependent variable of
an SODF is then defined as
w,, = _ dt[Mlb/{S>t)
(3)
dlogK* ’
In the following we shall represent the SODF as
log w* = f( log K* ).
The usefulwss of an !3ODF at the microscopic level derives
from the mathematical analogy existing between the depen-
dent variable of the SODF, w*, and that of the SADF. The
latter is rigourously defined as dCs/d log K (Sec. 11.2) which
clearly shows the analogy with o* (Eqn. 3). It has been shown
(Sec. 11.2) that the dependent variable of SADF represents
the concentration of sites having log K values in a particular
d log K interval. Similarly, o* is the concentration of metal
actually complexed to produce a small change, d log K*, in
the system. The important point is that, since K* is closely
related to K, it may be expected that SODF (log w* = f( log
K*)) may be used as a good estimate of SADF (log (dCs/d
log K) = f(log K)) (Fig. 4c, d). Indeed, as we shall see in
the next section, the SODF calculated from titration data
closely reflects the shape of the underlying SADF.
The usefulness of an SODF at the macroscopic level derives
from the analogy between w* and the overall metal buffer
intensity of the system, j3, defined as
B = dtCd{st)) (4)
d log [MI
(by analogy with the acid-base buffer intensity, &, = -dCH/
d( pH) where dCH is the change in total acid concentration).
Furthermore, under conditions where [M] < CM and there-
fore CM - [M]b, it can be shown (see Appendix A) that
K* = 1 - w’/(cM/{s)t)l
(5)
[Ml *M’/(Gd~s),)l
where 8’ = 812.303. It can be demonstrated that for highly
1543
polyfunctional complexants giving titration responses char-
acteristic of natural complexants, B’/( CM/ { S} ,) is usually
close to 0.5 (BUFFLE et al., 1990) in which case log K* is
approximately equal to -log [M] at any point in the titration.
Under these conditions there is clearly a close analogy be-
tween
d(CMI{S}t) t=8) and _ d([Mlb/{S)t) (_*)
a’log[Ml d log K*
or between the functions
p =f(log [MI) and w* = g(log K*).
This parallel is important given the central roles played by j3
and [M] in defining the behaviour of A4 in any system
(Fig. 1).
III. CALCULATION OF SODF FROM SIMULATED
AND REAL SYSTEMS
The utility of Site Occupation Distribution Functions will
be exemplified in this section using both simulated and real
data sets. The simulated data is used to demonstrate ( 1) the
similarity existing between the SODF and the actual SADF
for a range of complexant systems and (2) that SODF struc-
ture (i.e., peaks) may greatly aid in elucidating the nature of
the sites.
Examples in this section are restricted to conditions most
often encountered in natural waters, i.e., 0 5 0.1, where 0
= [M]b/CS is the degree of site saturation. As explained in
Sec. IV (Fig. 8)) under these conditions complexant properties
are dominated by those of the minor sites. These sites can
be divided into ( 1) a large number of background site types,
whose concentration increases in a continuous manner in-
versely to their log K value, and (2) a few dominant sites,
whose concentrations are significantly larger than those of
the background sites having similar K values. The former are
responsible for the globally linear shape of the DEF and SODF
of most natural complexants ( SFQSITO,1980; ALTMANNand
BUFFLE, 1988) (Fig. 7). The latter are responsible for the
small deviations from linearity sometimes observed on these
curves (Fig. 4b, c).
111.1. Simulated Data
III. 1.1. Simulating background and dominant sites
The behaviour of the background minor sites is simulated
by considering that it is well represented, over a wide range
of log K, by a linear DEF, i.e.,
log ([M]b/(S}t) = r-log K; - r-log K* (6)
where I’ and Kz are constants. For conditions realistic for
trace metal complexation, the slope, r, generally falls near
the middle of the range 0.2 5 r 5 0.8. Conversion of DEF
showing this logarithmically linear behaviour into the cor-
responding SODF also results in a linear function
logo* = log[-d([M]b/{S},)/dlogK*]
= log [2.303’r’[M]b/{S}t] (h)
I544 J. Buflle et al.

or. with Eqn. (6). MINEQL). In Figs. 2, 4-6, 8, and 9, this simulated titration
curve is used, in turn. to compute the corresponding DEF
logw* =log(2.303.T.(K;)“)- r.logK*. (7b) and SODF from Eqns. ( 2 ) and ( 3 ), to allow comparison of
It has been discussed elsewhere (ALTMANN and BUFFLE, these functions with the underlying CADF (Eqn. Bl 1 ) and
1988) that this type of behaviour implies that the corre- SADF ( Eqn. 9 ).
sponding SADF. i.e.. the function p(log K) = L/X/~ log K
(Sec. Il.?), follows a Sips distribution (SIPS, 1950).$ The III. 1.2. Comparison cfsimulated SADFs and SODFs
complete Sips distribution is a complicated mathematical
function which corresponds to the generalized Freundlich Figure 5a shows the working curves for three complexing
isotherm systems having different values for the parameter, r, deter-
e= (G*[W)’ mining the spread ofthe Sips contribution to the SADF. The
corresponding SODFs are shown on Fig. 5b, c, d ( solid lines)
1 + (K,,*[Ml)’
and can be compared with the SADF distributions (dotted
where K,,, and r are empirical parameters. The shape of the lines) used to generate the titration data. The total concen-
complete Sips distribution is similar to that of a gaussian trations of three sites (with log K, values of 4, 6. and 8) were
distribution, K,,, being the value of K at the distribution max- increased to simulate three dominant sites (see legend of Fig.
imum ( ALTMANN and BUFFLE, 1988). However, under the 5). Also shown is a hypothetical analytical window serving
restricting condition 0 5 0.1, valid for the background minor to indicate that only a portion ofthe complete system response
sites, Eqn. (8a) simplifies into the classical Freundlich iso- will be observable for any given measurement technique.
therm The principal point to be noted in Fig. 5b, c. d is that the
shape of the SODF emulates closely that of the SADF. In
0 = (K,,,.[nci])“. (8b) particular
The corresponding part of the Sips distribution is given ( 1) the slopes, I’. of both functions are the same;
mathematically by the simple expression (Appendix B) ( 2 ) the peaks allowing detection of the dominant sites are
clear;
log @(log K))= log =logO-I’.logK (9) (3) the values of log K* of the dominant site maxima are
close to the corresponding “true” values (the chosen log
where 0 is a constant related to Kt and r (Appendix B). K,‘s ) . Furthermore the distances between these maxima
From Eqn. (9), any value of AX corresponding to a par-
ticular A log K interval (e.g., between log K, and log Kb)is
easily computed, by using the chosen values of K,*and r,
and the expression

Ax =
s l0g.q’

,ogK p(log K) * d log k’.

Y
(10)

In this way, the whole of the background sites is simulated

by a large number of ( AX,, log K,)couples, where log K,is
the centre of the A log K interval corresponding to AX,. The pH=7 .--- -
curve log (AX,/ A log K) = f(log K,)is close to the true Sips 1-12 -10 -8 -6 -4 -2 0
distribution provided A log K 5 0.1.
log MI
The additional contributions of the dominant minor sites
are mimicked by superimposing classical discrete sites, with
particular values of AX, and log K,.over the SADF of back-
ground sites computed as explained above. In practice, the
values of AX,, computed by the Sips distribution and cor-
responding to the chosen K, values of the dominant sites,
were multiplied by a concentration factor CF (e.g., see legend
of Fig. 2).
pH=5 ___
The resulting ensemble of couples (AX,, log K,)can then
be treated as a mixture of classical complexants to find the pH=7 -- --
curve 0 = f( log [MI) (e.g., using a computer program like 12 10 6 6 4 2 0
log K*
* Note: It should be stressed that the Sips equation is chosen only FIG. 6. Variation in SODF with pH for simulated heterogeneous
because it allows ready comparison of the behaviour of a simple complexant incorporating dominant sites with and without acid-base
ligand (Le.. r = 1) with that of complexants having wider distributions properties. System: Sips’ SADF ( r = 0.5, log K,,, = 1) with 2 dominant
in log K (i.e., 0 < r < I ). We certainly do not wish to imply that sites of CF = 20. log KM = 9 and 10; the log KM = 10 site has an
fitting of data with the Sips isotherm or any other mathematical acidityconstantoflogKH=5.(K~=[MS]/[M].[S];KH=[HS]/
model necessarily vindicates any particular conceptualization con- [H] . [S]; S = site) (a) Working curves for pH = 3, 5, 7. (b) SODF
cerning the actual chemistry of the system. for pH = 3, 5, 7.
 Theory of metal complexation 1545

examples corresponding to important aquatic compounds.

Since all measurements were made under the same experi-
mental conditions, the differences observed between the
SODF for the various substances may be attributed to vari-
ations in the nature of the complexing sites, i.e., in the struc-
ture of their thermodynamic SADF. Note that well-defined
maximum are rare. This is a result of the significant peak
broadening due to polyelectrolytic, polyfunctional, and con-
formational effects, the relative contributions of which can
only be determined by the approach represented in Fig. 3.

-a-
IO 9 a 7 6 5 4 3
IV. PRACTICAL UTILITY OF DEF AND SODF
The DEF and SODF functions were derived to aid in mak-
ing rigorous interpretations of the complexation behaviour
Jog IK’ / I .mole-jl

FIG. 7. SODF functions describing Cu2+complexation by several

natural heterogeneous complexants at pH = 6. ( 1) Humic acid, (2)
Onmi Soil, ( 3) Hanford Soil, (4) Montmorillonite. (SeeALTMANN (4
and BUFFLE, 1988 for the corresponding working curves).

dominant

(in log K* units) equals those between the corresponding

log Ki. c_minor-++-maj

The interest in the SODF lies in this mimicry of the shape I 9 8 7 6 51 4 3 2 1 0 -1

log K
of the SADF since the SADF’s form reflects the relativether-
modynamic structure of a complexant site system. The actual (b)
values of an SADF, i.e., its correct positioning along the AX /
A log K and the log K axes, represent the true structure. The
shape of the SODF is useful in and of itself since any changes
in shape with experimental conditions (pH, ionic strength,
etc.) can aid in qualitatively deducing the complexant nature.
The SODF, therefore, can be used for representing complex-
ants based on their relative thermodynamic structure and 10 9 8 7 6 $ 4 3 2 1 0 -1
should permit comparison and interpretation of systems on log K’
this basis. It will be. seen in Sec. IV, that for major and minor
dominant sites, an SODF is also useful for finding the cor-
responding true log Ki values.
The fact that variations in the shape of an SODF with
changes in titration conditions (e.g., pH, ionic strength) can
aid in determining the nature of complexation reactions (e.g.,
proton competition, charge effects) is exemplified in Fig. 6a,
b for an heterogeneous complexant having the same Sips
background site distribution as in Figs. 2, 4 (i.e., r = 0,5,
log K,,, = 1) , but with two dominant sites having concentra-
tions 20 times that of the corresponding Sips’ site. The site
having a peak at log K* = 9 has no acid-base properties and .,,., (d)
a metal complexation constant, log KM = 9 (log KM = log
([M.S]/[M]-IS]). The second site has a log KM = 10 but
also acid-base characteristics (log KH = log ( [ HS] / [ H] * [S] )
= 9). Figure 6a shows the metal titration working curves for
this complexant at pH = 3, 5, and 7. The corresponding ‘5 -4
SODF are shown in Fig. 6b. The shifting of the right-hand $ -5
109876543210-l
peak as a function of pH, i.e., A log K* = f( ApH ) , indicates
log K or log P
the acid-base character of this site and the proton exchange
stoichiometry. FIG. 8. Conceptual distinction of major and minor site types for
heterogeneous systems, (a) Sips SADF (I = 0.5, log K,,, = 2 witb
dominant sites added at log K = 6, 1.5, and 9 and CF of 5, 20, and
111.2. Natural Complexant SODF 50, respectively). (b, c) Linear and log DEFs for above system. (d)
SODF (solid line) and SADF (dotted line) for above system. To
Although the purpose of this paper is not to study the allow direct comparison of o* and AX/A log K, the maximum values
SODF of natural complexants in detail, Fig. 7 gives a few [MJb/{S},havebeentakenasl,asthoseofXandO.
1546 J.Huffleet al.

of natural heterogeneous complexants. The theoretical rea- 0

sons for employing functions based on K* as the normalized 0.2

-2
complexation intensity parameter. as opposed to other pos-
i 0.5
sible parameters (e.g., [MI) has been given above. This section -4
2
presents the practical uses of these titration data represen-
-6 0.8
tations.
h%N,
-~ -a
10 9 a 7 6
IV.1. Discrimination of Site Types
log K’
The SODF can aid in subdividing the sites present in a
given complexing system into various categories according
to their location within the SODF or their effect on this func-
tion. The first partitioning is into what we shall term major
and minor sites while the second discriminates between the
dominant and background minor sites (Fig. 8 ).
Major site types are those present in large proportions in
a given complexant system, perhaps accounting for -90%
of the total sites present, and which are, consequently, few
in number. Major sites can be considered to be chemically
homogeneous, including only one rype of functional group;
because of this characteristic, their overall measurable net
free energy change, AGO (or more commonly, log K), for
formation of complexes with a particular metal cation will
be distributed over a relatively narrow range. Having a single
chemical structure, the variation in AGO will be subject only
to variations in physical factors. Typical physical influences
on net AGO include those due to changes in particle net charge
density or in macromolecule conformation (e.g., hydration o 12 3 4 5 6
induced changes in the swelling ofgels. coiling and extension logK,- logK,
of macromolecules). In most cases such effects produce net
AGo variations not exceeding the equivalent of l-2 log K FIG. 9. Relationship between log K* and actual log K, log K,, ,
units ( TANFORD. 196 1). Examples of major sites include the for a single discrete dominant minor site superimposed on SADFs
for Sips distribution functions having I’ = 0.2, 0.5, and 0.8 and
carboxylate and phenolate functional groups of humic and log Km value of 2. (a) SODF variation as a function of r, for a minor,
fulvic compounds, the carboxylate groups of polysaccharides dominant discrete site with log K,,, = 8 and CF = 20. (b) Peak shift
and proteins, and the =Fe - OH surface groups of iron ox- as function of r for three concentration factors CF; log K,, = 8. (c)
yhydroxides. Effect of location of dominant site log K,,, relative to log K,,, on the
shift of log K* at the peak maximum, CF = 20.
Minor sites are those present in trace amounts (corre-
sponding approximately to 0 < 0. I. Fig. 8b ), but whose
chemical diversity may be very large. Since this diversity de-
pends not only on chemical composition but also on physical minor sites are of considerable importance in controlling trace
structure, it is often effectively infinite (e.g.. humic com- metal complexation.
pounds). This however is not required by the definition of The form of the SODF function in the minor site region
minor sites (e.g., natural metal oxides may include only a can be employed to distinguish two categories of sites (Fig.
limited number of minor site types). Examples of minor sites 8). These are the dominant minor sites which show peaks
are the N and S complexing functional groups of fulvic/ in the SODF and the background minor sites which include
humic compounds, the -SH groups of proteins, or the all sites other than the dominants and which produce the
=Mn -OH groups of an iron oxyhydroxide containing Mn roughly linear continuum. To be “visible” in an SODF,
impurities. The exact chemical nature ofthe functional groups dominant sites must present many of the characteristics of
making up the minor sites is most often unknown and highly major sites. In particular, they must be chemically homo-
variable as a result of the diverse formation processes men- geneous (i.e., having a narrow AGO distribution) and be pres-
tioned previously. This forces us to treat all of these sites as ent at a relatively elevated concentration vis-&vis the un-
a whole which, owing to its chemical heterogeneity, may ex- derlying background site continuum. It is this clear grouping
hibit a broader distribution in the AGO for cation complex- of sites around a particular identifying log K value which
ation [e.g., at least several log K units (Fig. Sa)] than that of defines a dominant site.
a typical major site. This distribution broadening may even Discrimination between major, dominant, and background
be accentuated by the physical contributions mentioned sites is important because different interpretation modes
above for the major sites. The fact that for fl I 0.1 (Fig. 7 ), should be used in each case. In particular, it is often possible
natural complexants exhibit log K* variations over many to interpret the complexation properties of samples containing
orders of magnitude suggests, as stated previously, that the only one or two major site types, using an appropriate classical
 Theory of metal complexation
discrete model based on a priori physico-chemical assump-
tions (step 2’ in Fig. 3). Good examples of this approach
include the interpretation of metal complexation by the car-
boxylate and phenolate groups of fulvic compounds (MAR-
INSKYet al., 1980, 1982) or by the =Me-OH groups of
silicon, iron, and aluminum oxyhydroxides ( SCHINDLERet
al., 1976; SCHINDLER,198 1; DAVISand LECKIE, 1978; HOHL
and STUMM, 1976; STUMM et al., 1980) synthesized under
laboratory conditions (thereby minimizing the contribution
of chemical impurities and physical non-homogeneities).
Obviously, use of such models is not possible for the back-
ground continuum in the minor sites due to their low con-
centrations and close log K spacing.
IV.2. Findllg the Nature and Thermodynamic K Values
of Dominant Minor Sites
Classical interpretations of titration curves do not allow
the thermodynamic K values of minor sites to be obtained,
even if they are dominant, owing to a lack of significant in-
flections in titration curves (Fig. 8b). Observation of peaks
on an SODF (Fig. 8d), on the other hand, enables estimation
of the nature and log K values of the corresponding dominant
sites as indicated below.
It should first be noted that the position of the peak of a
dominant site along the log K* axis depends only slightly on
the value of I, i.e., the characteristic of the background sites
located in the same log K* range (Fig. 9a, b). Secondly, in
all cases, the log K* value is very near that of the thermo-
dynamic K, K,,, of the dominant site (Fig. 9b), in the “nor-
mal” range of I’ (0.2-0.8). Finally, the difference between
log K* and log K,,, is nearly independent of the position of
log K* with respect to the K value of the major sites, K,
(Fig. 9c). These characteristics show that normalization of
an experimental titration curve into an SODF allows a good
estimation of Km, from the value of log K* at the peak max-
imum (by using the curves in Fig. 9b, c to make the necessary
corrections based on the value of l? given by the slope of the
background sites below the peak).
The Ktllleobtained as described above is obviously subject
to the same conditionalities as the SODF. By varying the
experimental conditions to generate various SODF functions
followed by plotting the corresponding log K,,,,, as a function
of the varying parameter should allow one to obtain a non-
conditional constant in the classical way. This may aid in
deducing the nature of the site based upon its value and its
change with pH or other parameters.
IV.3. Finding the Parameters of Background Minor Sites
The sites comprising the background minor site continuum
generally observed for natural complexants are especially
important since they ( 1) represent most of the minor sites
and (2) serve to maintain the metal buffering action over
many orders of magnitude of log [M] ( BUFFLEet al., 1990).
This section describes a succinct overall representation of the
complexant properties in the range dominated by the back-
ground site characteristics (Sec. IV.3.1). It also shows how
the true theromodynamic representation of these sites ( SADF,
1547
CADF) can be estimated (Sec. IV.3.2) and incorporated into
equilibrium calculation models (Sec. IV.3.1.).
IV.3.1. Usefulness of linear representations:Incorporation
in predictive models based on Langmuir isotherms
Before discussing how the SADF and CADF of background
sites can be estimated from their complexation properties
represented by linear DEF (Eqn. 6), the advantages of this
linear representation must be discussed and compared to the
global parameters given by classical interpretations based on
the empirical fitting of data by combinations of Langmuir-
type isotherms. Such empirical parameters have been widely
used, the most popular ones being sets of a few ( 1 to 3)
coupled values for the global site concentration and equilib-
rium “constants” for “pseudo-sites” as determined, for in-
stance, by a Scatchard plot (FISH et al., 1986). The use of
such parameters should be avoided for two reasons:
( 1) It has been shown ( BUFFLE, 1984) that these global pa-
rameters have no physico-chemical meaning and that
the corresponding “pseudo-sites” have no relationship
to real sites. The use of these empirical parameters pre-
sented in the same form as the theoretical ones both in
the symbols used and in their mathematical application,
can only confuse those workers entering the field and as
yet unaware of its difficulties.
(2) Such a representation of complexation properties cor-
responds to a summation of 1 to 3 Langmuir-type iso-
therms. Since it is known that each isotherm can rep
resent complexation properties over a maximum of 2
decades of [M] at least 3 sets of couples (i.e., 6 param-
eters) are necessary to cover the large complexation range
exhibited by natural heterogeneous complexants (e.g.,
lo-’ < [M] < low3 M, i.e., 6 orders of magnitude of
[MI).
On the other hand, the metal binding qualities of a com-
plexant displaying a roughly linear DEF function (Eqn. 6)
can be summarized equally well using only the two param-
eters necessary to fit this DEF with a straight line. Such a
fitting yields the slope, I, and the intercept on the log K*
axis, log K,* , corresponding to log ([Ml b/ { $} 1) = 0 (Fig.
11) . These two parameters provide an operational yet ratio-
nally normalized, twodimensional summary of the metal
binding behaviour of heterogeneous complexants over the
entire range of log [M] for which linear behaviour is observed.
In addition, log Kz and r are of direct practical utility. Kz
may be used to compare the complexing strength of different
complexants at equivalent values of [Mlb/ { S}, or of the
same complexant under different conditions. I can be shown
(BUFFLE et al. 1990) to be simply related to w* (Eqn. 3):
w*
(lla)
r = [WLJ{~jt
and for minor sites, to the buffering intensity of the com-
plexant @(Eqn. 4):
B
( 1lb)
r = CM,/{S>, .
1548 J. Buffle et al.
In contrast to the empirical parameters obtained by the
above mentioned classical approaches, 1 has, therefore, the
advantage of being linked to a well-defined property of the
system. In addition, K: and T allow realistic predictions of
complexation behaviour to be made outside the tested ex-
perimental range. This is an additional advantage over the
global empirical parameters discussed above, which have a
poor predictive capacity because they cannot adequately
simulate the fact that complexation properties of natural sys-
tems are buffered over wide ranges of log K values.
An often-mentioned limitation of representing complexant
properties by distribution functions is that they cannot be
readily incorporated into classical computer programs for
the calculation of a species distribution at equilibrium because
these programs require site concentration/equilibrium con-
stant couples as input data. This limitation however is not
applicable to linear DEF since the mathematical expressions
of the corresponding CADF and SADF are known (Sec.
IV.3.2: Appendix B). In particular, numerical values of the
function p( log K) = dx/d log K representing the SADF are
easily computed (Sec. IV.3.2) from the values of Kz and T
obtained from the DEF. As explained in Sec. III. 1, the p( log
K) function can then be split into small discrete A log K
intervals which enable one to compute the corresponding
mole fraction of sites AX (Eqn. 10). The (AX, log K) couples
can then be fed into classical predictive computer models,
like MINEQL, for computing species distribution.
IV.3.2. Finding CADF and SADFfrom linear DEF
For the linear DEF profiles often observed for background
sites, [Mlb/ { S}, is related to K* by Eqn. (6):
log ([M]J{S)J = I’slog K; - Telog K*. (6)
Furthermore, it has been shown that, for [M] 4 [M] b, K*
can be expressed by Eqn. (5). By taking into account the
definition of 0 (Eqn. 4) and the fact that, for linear DEF, I?
=@/(2.303~C~/{S},)(BUm~etal.. 1990),Eqn.(5)can
be rewritten as
i-r
K*=[M].r. ( 12)
Combining Eqns. (6) and ( 12) yields
(13)
with 0 < r < 1. Equation ( 13) is the description of the
Freundlich isotherm (Eqn. fib) where 0 ( = [M]L,/CS) is re-
placed by [Mlb/ { S} t. Equations (8b) and ( 13) are related
by the proportionality constant {S} JCs, which depends only
on the units chosen for ( S} t (e.g., g/l). Consequently, the
parameter K,,, in Eqn. (8b) is related to Kt and I’ by
K = fc*r {SJt “I-
m
l-rcs. ( 1 (14)
The SADF (p( log K) = d x / d log K) corresponding to the
isotherm represented by Eqn. ( 13) is the probability distri-
bution function for finding sites with any particular value K
of the equilibrium constant, and such that the overall be-
haviour of the system follows Eqn. ( 13). A mathematical
expression for the corresponding p( log K) function has been
derived by SIPS ( 1950) and discussed by SPOSITO ( 1980 ).
Simpler derivations of this SADF and the corresponding
CADF are given in Appendix B.
In particular the CADF is expressed by
i0gx = i0g(o/2.303.r) - r.i0gK (15)
which shows that CADF and DEF (Eqn. 6) are parallel
straight lines, thus justifying, as previously mentioned, the
fact that the DEF is a good analogue for the CADF. The
vertical difference between the two lines is obtained by sub-
tracting Eqn. (6) from Eqn. ( 15), for log K = log K*. By
making use of Eqns. ( 14) and (BS), one gets
The interesting feature of Eqn. ( 16) is that it depends only
on l’ and, in particular, is not dependent on K. This implies
that it is independent not only of the nature of the chemical
system, but also of the units used for the distributions, pro-
viding, of course, that the DEF and CADF are expressed in
the same units. Indeed, in this case {S}, = Cs and the last
term of the right-hand side of Eqn. ( 16) is zero.
Another important feature of the function represented by
Eqn. ( 16) is that it is only slightly dependant on I’, as is
shown in Fig. 10. Thanks to this characteristic, it is easy to
estimate the theoretically meaningful CADF corresponding
to the experimentally obtained linear DEF: the two distri-
butions are parallel lines separated by the value given in Fig.
10. This value is most often close to -0.17 since, in the vast
majority of cases, 0.2 < T < 0.8. Note that in practice Cs is
generally not measurable. In this case, only the CADF ex-
pressed by the cumulative concentration of sites per mass of
complexant (x * C’s/ { S} *) can be obtained from Eqn. ( 16 ).
V. RELATlON BETWEEN DEF AND SODF, AND
GLOBAL COMPLEXANT PROPERTIES
It has been shown in the previous sections that DEF and
SODF are good estimates of the rigorous thermodynamic
functions (CADF and SADF) representing the complexing
properties of natural systems, and that they may aid in finding
the characteristics of both dominant and background sites.
They are more informative and preferable, for predictive
purposes, than the global empirical parameters classically
used. However, since these latter are widely used, their re-
lationships to DEF and SQDF are worth addressing. The two
types of global parameters used most frequently for charac-
terizing natural complexants are ( 1) some sort of average
complexation “constant” (or distribution coefficient) and (2)
a single complexation capacity. Such single global average
values are most often meaningless since the K* of the SODF
for the above mentioned complexants extends over several
decades ( BUFIXE, 1988). A need exists, however, for a suc-
cinct means of classifying such complexants; we propose re-
 Theory of metal complexation
-0.2
a3
ha -0.15
2 sites. It effectively means that we cannot measure the
I CC, for natural complexants.
x
3 -0.:
-0.05
0.0
0.0 0.2 0.4 0.6 0.a 1.0
r
FIG. 10. Variation with r in the difference between the ordinate
values of linear DEF (expressed by log 0) , and of the corresponding
linear CADF (log x), at K = K*. (See Sec. IV.3.2. and Eqn. 16 for
details). Note that, for comparison with Eqn. ( 16), the ordinate is
equal to log x - (log [MlbI{S)t - log{S)JCd.
placement of these global, mathematically ill-defined param-
eters, by more meaningful ones based on K*.
V.l. Complexation Capacity
In the following discussion we are excluding site concen-
tration estimates made from acid-base titrations, functional
group analyses, tritium exchange, etc. We consider only CC
values measured by titrating the complexant by the metal of
interest and defined as the total metal bound per unit mass
of complexant as measured under some set of selected ex-
perimental conditions. The purpose of measuring CCs is to
allow inter-comparison of complexants based on their total
complexing site concentrations. As discussed below (Fig.
11b), this comparison has significance only if one of the fol-
lowing two criteria is met:
(1) that the conditions used for determining the CC assure
measurement of the true total complexant site concen-
tration, CC, or
(2) that the reported CC is coupled with a particular value
of an intensity parameter, which may be any of the three
already mentioned above (i.e., K, K*, or [MI) and serves
to specify the cutoff point for the sites included in the
CC value (see below, Fig. 11b) .
Obviously, titration of the complexant by the metal of in-
terest can be done only up to some maximum value of [ M] ,
[M],, (Fig. 1la). This value is generally limited by the oc-
currence of undesirable secondary reactions such as metal
precipitation, complexant coagulation, etc. This being the
case, the following points can be made:
( 1) Since we are limited in the safely usable value of [M],,r ,
we obviously cannot measure the true total complexation
capacity, CC, = [Ml,,,,& { S} t (Fig. 1la), of heteroge-
neous complexants. This is because these complexants
have a wide range of log K and consequently their DEF
1549
curves tend only gradually towards the limiting value of
[ I%&,,~/ { S} f (Fig. 1 la). For most trace metals the up
per cutoff in [Mlup is in the range 10-4-10-3 A4 which
means that all sites having log K < 3 are not saturated.
These sites may include a large portion of the major
(2) One could simply employ [ Mlup as the intensity param-
eter of reference for the measured value of CC, CCM.
CCM is then defined as the value of [Mlb/ { S}, corre-
sponding to this reference value (Fig. 1la). This is an
acceptable approach both from a practical standpoint
and in terms of providing a valid normalization of [ M],,-
based CC values. Conceptually, however, it is often pre-
ferred that CC values be referenced to an intensity pa-
rameter more closely related to a normalized complex-
ation energy of the sites.
(3) A preferable alternative for this reference complexation
intensity parameter would be to employ K* and use the
concept of the SODF for defining a K$,-based CC, CC*.
Considering the definition of w* given in Eqn. (3) and
the schematic representation of Fig. 11b, CC* can be
defined by
m
CC* = . a*- dlogK*. (17)
s b&Cl,.
This integration is done automatically in the calculation
of the DEF curve from the titration working curve as
shown in Fig. 4a, b. Any log K* on a DEF curve (log
([M]J { S} ,) vs. log K*; Fig. 1 lc) therefore could be
taken as a specification for a particular value of CC*.
The advantages of using CC * rest in ( 1) its direct cal-
culation from titration data, (2) its use of a normalized
binding intensity parameter, K*, as a reference, and (3)
the fact that the choice of the value of K$n to be used
for CC* can be made based on the shape of the SODF
curve. This latter point is important since SODF enables
us to discriminate between different types of complexing
sites of the system (Sec. IV. 1).
V.2. Buffer Intensity
The nearly linear behaviour in the minor site-dominated
SODF and DEF curves of most natural heterogeneous com-
plexants reflects a particular metal ion buffering action which
plays an important role in the biogeochemistry of natural
media, as well as on the signal of certain analytical methods
such as voltammetry (FILELLA et al., 1990). As mentioned
above, the slope I of the DEF is related to the buffer intensity
/3 by I = p/( CM/ { S}t). A constant value of I’ therefore
implies that for natural complexants, fl = constant CM; i.e.,
the buffering action gradually increases with CM, over several
order of magnitude. This behaviour is in stark contrast with
that exhibited by systems where only one or two simple li-
gands account for the majority of the total metal complex-
ation capacity. Here, as illustrated in Fig. 2a, the slope and
therefore the buffer intensity vary dramatically. By contrast,
natural complexants show smooth, constant slopes, thanks
to the cooperative action of the background sites having
closely spaced K values. This means that there is always a
suite of sites actively complexing the metal, some beginning
1550 J. Buffle et al.

FIG. 11. Comparison of different definitions of complex&on capacities: CC, (true total completing site concentration),
CC& (the complexing site ~oncen~~on corresponding to a particular value of [Ml, [Ml,; Fig. 1la) and CC* (the
complexing site concentration obtained for a particuhrr log K* value, log K& ; Fig. 11b). (a) Comparison of CC, and
CCM in a working curve. (b) Comparison of CC* with CC,. (c) Significance of CC,, CC,, Kz and r in a DEF.

to be occupied, some near their half&ration point, and some
close. to saturation. The composite behaviour yields both the
slope smoothness and the average value of I’ close to 0.5 as
it is described in detail in BUFFLE et al. ( 1990). As a con-
sequence of this property, the complexant is able to “absorb”
the metal over a large concentration range (several orders of
m~itude) with only a gradual increase in the biologicahy
critical free metal ion concentration (i.e., no sharp concen-
tration jumps are observed). This property of the background
sites is important ecologically since it helps living organisms
to adapt to chemical changes in their environment.
V-3. Heterogeneity Limits
The simulation used to compute the DEF and SODF
curves in this paper (in particular, Fii. 4b) assumes that there
 Theory of metal complexation 1551

large _

log K*

i
c :8 -’
-3 -2

SO
,E1EI_
P
-5 -4
z

F -7 -6
-a -9 -10 -11 1 0 -1 -2 -3 -4 -5

logK*
FIG. 12. General shapes of log ( [Mlb/ { S},) = f(log K* ) curves. (a) Schematic curves for various degrees of
heterogeneity. Since each analytical method has a limited analytical “window,” only a portion of the overall curve will
be “seen.” (b) Cd adsorption on amorphous Fe oxyhydroxide (BENJAMIN and LECKIE,1981). (c) Cd, Cu, and Zn
adsorption on goethite in seawater medium ( BALESTRIERI
and MURRAY,1983)

is no upper limit in the log K* values for sites present in a
system. For real chemical systems, however, even extremely
heterogeneous ones, there must exist some site with the max-
imum log K* value. If this is so then the leftmost portion of
the DEF curve must tend towards a vertical line (i.e., constant
K* ) , One can, therefore, expect the shape of DEF curves for
heterogeneous complexants to be as schematically shown in
Fig. 12a. Three regions of these idealized curves can be iden-
tified as
( 1) one which is asymptotically horizontal ([Ml,,/ { S} r +
Cc) corresponding to the region where complexation is
controlled by major sites (minor sites being fully satu-
rated);
(2) one which is asymptotically vertical corresponding to
the state where even the strongest sites are largely free;
(3) an intermediate zone where the minor sites are partially
occupied by the metal and the major ones are almost
entirely free. For highly heterogeneous complexants this
zone tends to be roughly linear with a slope in the vicinity
of 0.5 ( BUF~E et al., 1990).
For most natural systems only one or two of the above
DEF zones may be observed because the analytical window
(Figs. 2, 12) is not sufficiently wide to allow determination
of the entire curve. This representation is of course largely
conceptual, but one may note that curves having similar
shapes (Fig. 12b, c) have been observed in a few cases for
metal complexation with metal ozides (BENJAMIN and
LECKIE, 198 1; BALISTRIERIand MURRAY, 1983 ) .
VI. CONCLUSION
This paper shows that DEF and SODF have useful poten-
tialities for representing complexation characteristics of nat-
1552 J. Buffle et al.
Ural systems, as well as for predictive purposes. They are
more informative and closer to the rigorous thermodynamic
description than the classically used global parameters. In
particular, as opposed to the latter, they are free of any a
priori assumptions, making them particularly useful for ob-
jective comparison of complexation behaviours of different
systems.
The main limitation to this approach is the same as for
computation of any type of site affinity spectrum: it is linked
to the propagation of errors during the mathematical decon-
volution of the raw data into the DEF and SODF. Indeed,
although K* is obtained by applying a simple equation (Eqn.
2) free of any a priori assumption, its computation neces-
sitates derivation of the curve In (C,/ { S} t) = f(ln (Y). As
a result of this step, the error in the DEF, and particularly
the SODF, may become large due to the errors in the exper-
imental measurements. Curve fitting techniques may be em-
ployed to overcome this problem, but classical procedures
frequently introduce artifactual oscillations or production of
apparent jumps or peaks which are transferred to and am-
plified in the DEF and SODF. The criticalness of the data
fitting step cannot be overemphasized since any subsequent
physico-chemical interpretation is entirely dependent upon
it. This, however, is a purely mathematical problem, different
from the conceptual ones discussed here. A curve fitting pro-
cedure addressing the above questions has been developed
for computing DEF and SODF and will be described else-
where.
Acknowledgments-This work was supported by the Swiss National
Foundation (Projects Nos. 2.07 l-O.86 and 2000.5.5 12).
Editorial handling: J. I. Drever
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 Theory of metal complexation 1553

THAKURA. K., MUNSONP. J., HUNSTOND. L., and RODBARDD. 11- B’l(chllI~~t)l
( 1980) Characterization of @and-binding systems by continuous (AZ)
K* = [Jw~w’I(chd~~~,) - [WCMI
affinity distributions of arbitrary shape. Anal. Biochem. 103,240-
254. where /3’ = ,8/2.303. For most natural systems, /3’/( C,/{ S},) is
TURNER D. R., VARNEY M. S., WHITFIELD M., MANTOURA close to 0.5 ( BUFFLEet al., 1990), so that under conditions of strong
R. F. C., and RILEY J. P. ( 1986) Electrochemical studies of copper complexation, where [M] 6 CH, Eqn. (A3) simplifies to Eqn. (5).
and lead complexation by fulvic acid. I. Potentiometric measure-
ments and a critical comparison of metal binding models. Geochim. APPENDIX B
Cosmochim. Acta SO.289-297.
An SADF ( = d x / d log K) is the probability, p( log K) , of finding
sites with any particular value, K, of the equilibrium constant.
GLOSSARY p( log K) also expresses the mole fraction, dx, of the sites whose K
valuesare within the interval d log K. The relation between 0 ( = [A&,/
Cs) and p( log K) is given by ( ALTMANNand BUFFLE, 1988)
COMPLEXANT: Any compound, organic or inorganic, dissolved,
colloidal, or particulate, containing one to several complexing sites.
HETEROGENEOUS COMPOUND: A compound presenting
physical and/or chemical heterogeneity (note: our use of “hetero-
B=
s m K.[M]
-.z, I + K.[M]
.p(logK).dlogK (Bl)

s-
which may also be written
geneous” is broader than in normal usage, i.e., systems containing
more than one distinct phase. Here an heterogeneous compound K.[M]
may be truly dissolved if it includes only chemical heterogeneity, 8= .p’(K).dK W)
-m I + K.[M]
e.g., fulvic compounds).
where
MAJOR SITES: One (or possibly a few) group(s) of sites which is/
are chemically homogeneous and which account for the large majority p’(K) = p(log K)/2.303. K. (B3)
of the sites of the complexant of interest.
Furthermore, mathematical tables (SPIEGEL, 1968 ) give
MINOR SITES All sites other than the major site type(s). For
heterogeneous complexants, this group accounts for most of the
chemical heterogeneity. sm
Xm/andx=
-m 1 + x”Ja”
m~ x”Ja” X(m-n). &
s-- 1 + x”/a”
*. a(m+l-n)
Background minor sites: The whole of the minor sites which, taken
together, produce a gradual change in the complexation parameter = sin [(m + 1)*/n]
(M)
(K, [M] ) without any predominant single site type.
whichisvalidforO<(m+ l)<n.Byreplacingn= l,x=K,and
Dominant minor site(s): A minor site present in a concentration [M] = I /a, in Eqn. (B4), and comparing the resulting right- and
much greater than neighboring sites, which dominates the com- left-hand sides of this equation with the right-hand sides of Bqns.
plexation properties of the system over a given restricted range of (8b) and ( B2), respectively, one obtains
log K(or log [Ml).
m=-F (B5)
SADF: Site Affinity Distribution Function (see Sec. II.2 and Figs. 2,
4). and
CADF: Cumulative Site Affinity Distribution Function (see Sec. II.2
and Figs. 2, 4). p’(K)=bsin[(l -r).*].(K,)r.K-(“r). (B6)

DEF: Differential Equilibrium Function (see Sec. II.3 and Fig. 4). Combining Bqns. (B6) and (B3) gives the SADF
SODF: Site Occupation Distribution Function (see Sec. II.4 and Fig. dx
4). -=p(logK)=O.K-r
dlogK
= 0.exp( -2.303. Felog K) (B7)
APPENDIX A
with
For systems where the complexant is titrated by M, i.e., the com-
plexant concentration is constant, d In {S},/d In (Y= 0, d lnCk( = d 8 = 2.303 - sin [ ( I - r). ST]
(Kn)“. (J38)
In C,/ { S},, and Eqn. (2) can be transformed into k

1 The CADF is a plot of the cumulative mole fraction, ix

KG-2 = C AX,-(summation on all sites for which log K B log ‘K), as a
(AI)
Ckl[l +(a-l)-dlnCH/dlncu]’ function of log jK. It is therefore obtained by integrating Bqn. (B7)
with respect to log K, from log K = co to log K = 1ogjK:
By taking into account the definition of OL
(=C,/[m), the derivative
in the denominator can be expressed in the form
ix= m p( log K) +d log K;
(B9)
dlnCD( 1 I og]K
-=
dln 01 1 -dln[M]/dlnC, i.e.,

1 ‘x = & (‘K)-r (BlO)

(A2)
= 1 -dln[~U]/dln(C~/{S}~)’
or, for any value of j,
Combining Eqns. (Al ) and (A2) and taking into account that
(din [Mlldln (CM/{S)~) = 2.303~(Cd{SIt)/8) (Eqn. 4)gives log x = log (O/2.303. P) - I’. log K. (Bll)