Soil Chemistry
Estimation of Single-Metal and Competitive
Sorption Isotherms through Maximum
Likelihood and Model Quality Criteria
Emanuela Bianchi Janetti*
Dipartimento di Ingegneria Idraulica,
Ambientale, Infrastrutture Viarie,
Rilevamento (DIIAR)
Politecnico di Milano
Piazza L. Da Vinci, 32
20133 Milano, Italy
Ishai Dror
Dep. of Environmental Sciences and
Energy Research
Weizmann Institute of Science
Rehovot 76100 Israel
Monica Riva
Alberto Guadagnini
Dipartimento di Ingegneria Idraulica,
Ambientale, Infrastrutture Viarie,
Rilevamento (DIIAR)
Politecnico di Milano
Piazza L. Da Vinci, 32
20133 Milano, Italy
Brian Berkowitz
Dep. of Environmental Sciences and
Energy Research
Weizmann Institute of Science
Rehovot 76100 Israel
Soil Science Society of America Journal
Metal sorption of single and binary (competitive) systems for several soils
is analyzed to assess the ability of alternative isotherm models to interpret
experimental observations. The analysis is performed within a Maximum
Likelihood framework and on the basis of model identification (sometimes
termed “quality” or “information”) criteria. These methodologies allow the
assessment of the measurement error variance in the parameter estimation
process and the uncertainty arising from the use of alternative (conceptual-
mathematical) models. We first analyze Cu and Zn sorption in two Israeli
soils, Bet Dagan and Yatir, which are slightly alkaline but with substantially
different sorption capacities and perform an extensive set of batch experi-
ments in single and binary systems. We then analyze the data set published
by Liao and Selim (2009) where Ni and Cd sorption was studied in three dif-
ferent (one neutral and two acidic) soils. Single component data from both
sets of experiments are interpreted on the basis of the Langmuir, Freundlich,
and Redlich–Peterson (RP) models. The family of binary systems results is
analyzed in light of the Sheindorf–Rebhun–Sheintuch (SRS) model, the modi-
fied RP model, and the modified and extended Langmuir models. All of the
considered models are expressed in terms of initial and equilibrium concen-
trations, two variables that are measured independently. Maximum Likelihood
and model identification criteria (such as Bayesian criteria BIC and KIC, and
information theoretic criteria AIC, AICc, and HIC) are employed to (a) esti-
mate model parameters, (b) rank alternative models, and (c) estimate the
relative degree of likelihood of each model by means of a weight, or poste-
rior probability. We show that modeling observation error variance either
as a constant or as a function of concentration does not significantly affect
parameter estimates for a given model. These different representations of
measurement error variance impact the ranking of alternative models based
on posterior probability weights. The weights associated with different
models can be very similar when a uniform measurement error variance is
considered, so that it is difficult to clearly identify a single best model.
Abbreviations: ICP, inductively coupled plasma; ICP-MS, inductively coupled plasma-
mass spectrometry; RP, Redlich–Peterson; SRS, Sheindorf–Rebhun–Sheintuch.
A
common cause of soil and water resources contamination is the subse-
quent release of mixtures of heavy metals to the environment, seriously
threatening the well-being of humans and ecological systems. In this
context, understanding of metal partitioning between solid and aqueous phases is
critical for proper design of control and remediation measures.
It is known that the adsorption properties of a metal in the presence of other
metal(s) are often different from those associated with the adsorption of the indi-
vidual metal (Sheindorf et al., 1981). Sorption and competitive behavior of met-
Soil Sci. Soc. Am. J. 76:1229–1245
doi:10.2136/sssaj2012.0010
Received 6 Jan. 2012.
*Corresponding author (emanuela.bianchi@mail.polimi.it).
© Soil Science Society of America, 5585 Guilford Rd., Madison WI 53711 USA
All rights reserved. No part of this periodical may be reproduced or transmitted in any form or by
any means, electronic or mechanical, including photocopying, recording, or any information storage
and retrieval system, without permission in writing from the publisher. Permission for printing and for
reprinting the material contained herein has been obtained by the publisher.
als is typically studied under laboratory batch conditions, that is,
equilibrium conditions (Liao and Selim, 2009; Saha et al., 2002;
Srivastava et al., 2005). A standard method of interpreting such
experimental observations is based on several types of (equilib-
rium) isotherm models that relate the amount of metal sorbed
to the equilibrium concentration of metal in solution. Therefore
these isotherm models allow mathematical description of single
metal systems (e.g., Freundlich, 1906; Langmuir, 1918; Redlich
and Peterson, 1959) and multi-component systems (e.g., Redlich
and Peterson, 1959; Sheindorf et al., 1981; Bellot and Condoret,
1993; Liao and Selim, 2009 and references therein). An advan-
tage of these models with respect to more complicated mecha-
nistic models (e.g., Barrow, 1983, 1989) is that they provide an
easy and straightforward tool to describe sorption. It has been
shown recently (Barrow, 2008) that the Langmuir model, used
extensively in sorption studies (e.g., Bolster, 2008; Srivastava et
al., 2008; Dişli, 2010; Ofomaja et al., 2010), is in general not ap-
propriate to describe metal sorption in soils.
With a few notable exceptions (Liao and Selim, 2009),
most of the competitive studies available are performed in the
presence of a limited range of concentrations of the competing
ion, while proper modeling and characterization of the system
requires exploration of a wide range of concentrations. In all of
these studies, calibration of model parameters is performed by
minimizing a suitable norm on the basis of standard optimiza-
tion techniques (Doherty, 2002).
While some comparative studies among different mod-
els have been presented (e.g., Roy et al., 1986, Barrow et al.,
2005, Srivastava et al., 2008; Liao and Selim, 2009; Dişli, 2010;
Ofomaja et al., 2010), they typically lack the analysis of issues
related to conceptual model uncertainty that are key elements in
uncertainty assessment of natural systems and in discriminating
among the predictive powers of competing models. In particu-
lar, Liao and Selim (2009) consider the sorption of Ni and Cd
in three different soils (characterization is provided in Table 1),
with the main objective of quantifying the sorption of Cd and
Ni in single and binary Cd–Ni systems for soils having different
properties. For single element systems, Liao and Selim (2009)
considered only the Freundlich model. For binary component
systems, the authors interpreted the results by (a) estimating the
parameters of the Freundlich model, similarly to a single-metal
system, for a range of concentrations of the competing ion, and
(b) considering the competitive SRS model.
Table 1. Characterization of the soils.
Soil Bet Yatir† Olivier‡ Webster‡ Windsor‡
Dagan†
pH 7.0 7.5 5.80 6.92 6.11
CEC, cmolc kg–1 6.0 32.0 8.6 27.0 2.0
Clay, % 16.2 36.9 6 22 3 and properties of the soils. For single- and binary-metal systems,
Silt, % 6.3 14.8 89 39 20
Sand, % 77.5 48.3 5 39 77
Organic carbon, % 1.2 3.7 0.83 4.02 2.03
† Experiments performed in this manuscript.
‡ Experiments performed by Liao and Selim (2009).
1230
A notable weak point of the above-referenced studies is
their reliance on a single conceptual-mathematical model of the
processes driving the system (e.g., Liao and Selim, 2009), or their
consideration of alternative mathematical models and selection
of a best performing model on the basis of criteria such as least-
square regression (e.g., Srivastava et al., 2008). Yet, geochemical
processes and porous media within which they occur are com-
plex, rendering observed state variables amenable to multiple
interpretations and mathematical descriptions, including pa-
rameterizations. Predictions and uncertainty analyses based on a
single hydrogeochemical model can then result in statistical bias
(due to reliance on an inadequate model) and possible underes-
timation of the global system uncertainty (which derives from
undersampling of model space).
These issues can be addressed conveniently within a
Maximum Likelihood framework and employing Model
Quality criteria to consider (i) measurement error variance in
the parameter estimation process and (ii) conceptual model un-
certainty. The benefit of this approach has been illustrated and
demonstrated in the context of groundwater flow problems (e.g.,
Carrera and Neuman, 1986; Ye et al., 2004) where measurement
errors and conceptual model uncertainties can be significant.
While system errors in laboratory batch experiments can be well
controlled, such errors are always present and error variance can
depend on the measured concentration (Tellinghuisen, 2009;
Tellinghuisen and Bolster, 2010). Applications of Maximum
Likelihood and Model Quality criteria to complex competitive
sorption processes are still lacking and can present significant
challenges that are related mainly to the strongly nonlinear be-
havior of the system and parameter identifiability.
In this work, we illustrate the use of Maximum Likelihood
and model identification (quality, information) criteria on a set
of batch experiments involving single and binary (competitive)
systems of Cu and Zn in two Mediterranean soils, for an exten-
sive range of concentrations of the competing ions. We then re-
visit in light of these theoretical frameworks the interpretation
of the single- and binary-component experimental data provided
by Liao and Selim (2009). These experimental data are inter-
preted by means of several equilibrium isotherm models, and the
uncertainty associated with each competing model is quantified.
The variance associated with measurement errors is considered
directly in the model parameter estimation process and has an
impact on the calculation of model identification criteria.
MATERIALS AND METHODS
We performed a set of batch experiments with two
Mediterranean soils, Bet Dagan (pH 7.0, 1.2% organic matter,
16.2% clay content), and Yatir (pH 7.5, 3.7% organic matter,
36.9% clay content). Table 1 reports the complete composition
samples of 1 g of soil were mixed with 40-mL solutions contain-
ing metals at different concentrations. All initial solutions were
obtained by dissolution of a given quantity of copper chloride or
zinc chloride in double deionized (18.2 MΩ) water. Details on
Soil Science Society of America Journal
the initial and equilibrium pH values for the Cu and Zn solu-
tions are reported in the following sections.
The pH was not manipulated or kept constant by adding
a buffer, to allow the soil to react with the metal solutions un-
der “natural” conditions. The capacity of the soil to adsorb these
metals depends on the soil chemical composition and properties.
The same procedure was applied for all experiments, with a fixed
initial pH in each case. The mixtures were shaken continuous-
ly for 48 h and equilibrium isotherms were analyzed for metal
concentration in solution. Preliminary kinetic experiments were
performed to ensure that this time scale was sufficient for equi-
librium to be attained. In the case of Bet Dagan soil, adsorption
increased sharply for the first 15 h, displaying a mild increase be-
tween 15 to 40 h and then attaining a relatively constant value.
Adsorption onto Yatir soil was essentially constant from the be-
ginning of the experiment.
At the end of the equilibration phase, a 10-mL sample of
the solution was extracted from each vial and passed through a
0.22 μm filter. Each experiment was performed in three different
(macroscopically homogeneous) samples, for each of the soils an-
alyzed. The resulting mean and variance of equilibrium concen-
trations represent, respectively, the average behavior of the sys-
tem and its variability. While evaluated only with three samples
for each experimental scenario, these quantities take into account
the intrinsic heterogeneity of the three samples and solutions, to-
gether with random and systematic measurement errors.
Element concentrations were measured by inductively cou-
pled plasma-mass spectrometry (ICP–MS) (PerkinElmer Ellen
9000). The limit of quantification for these measurements is
<1 μg L–1 and filtered samples were diluted to attain concen-
trations ranging between 1 and 1000 μg L–1. All ICP measure-
ments were performed in three replicates for each sample. The
variability of ICP measurements was not taken into account,
being at least one order of magnitude lower than the variability
observed among the three experiment replicates.
We then extended the range of scenarios investigated by
considering the experiments of Liao and Selim (2009), who
studied the sorption of Ni and Cd in single and binary Ni–Cd
systems for one neutral and two acidic soils (see Table 1). The
authors performed each experiment in duplicates; additional
details of the experimental procedure are reported in Liao and
Selim (2009).
Single Component Systems
Seven different initial concentrations, C0, for each met-
al and soil were considered: C0 = 20, 30, 50, 75, 100, 150,
200 mg L–1were applied to Bet Dagan soil, while C0 = 20, 50,
100, 300, 500, 650, 800 mg L–1 were applied to the Yatir soil
samples. These values correspond to C0 = 0.31, 0.47, 0.79, 1.18,
1.57, 2.36, 3.15 mmol L–1for Bet Dagan soil and C0 = 0.31,
0.46, 0.76, 1.15, 1.53, 2.29, 3.06 mmol L–1 for Yatir soil. The av-
erage initial values of pH of the Cu solutions for Bet Dagan and
Yatir soils were 4.7 and 5.7. These resulted in final average pH
values at equilibrium of 4.9 and 5.9 for Bet Dagan and Yatir soils,
www.soils.org/publications/sssaj
respectively. Average initial values of pH of the Zn solutions for
Bet Dagan and Yatir soils were 5.9 and 5.7. These resulted in final
average pH values at equilibrium of 6.4 and 6.7 for Bet Dagan
and Yatir soils, respectively.
Different concentrations were selected for the two soils
tested, recognizing that the Yatir soil is characterized by a higher
sorption capacity than Bet Dagan soil because of its high clay and
organic carbon contents (see Table 1). The experiments on the
two soils were thus comparable in terms of the relative fraction
of metal sorbed onto the two soils, that is, the application of C0
= 200 mg L–1 or C0 = 800 mg L–1, respectively to Bet Dagan
and Yatir soil, resulted in the sorption of approximately 35% of
the initial mass in solution for both soils. Liao and Selim (2009)
also applied a range of six initial Cd or Ni concentrations (C0
= 0.025, 0.050, 0.100, 0.250, 0.500, 0.800 mmol L–1) in their
single metal sorption studies. These values correspond to C0 =
2.8, 5.6, 11.2, 28.1, 56.2, 89.9 mg L–1 for Cd and C0 = 1.5, 2.9,
5.9, 14.7, 29.4, 47.0 mg L–1 for Ni.
Experimental equilibrium data were interpreted according
to the following set of typically adopted isotherm models:
qe  K FC n , Freundlich (1906) [1]
qm K LC
qe  , Langmuir (1918) [2]
1  K LC
K RC . Redlich–Peterson (RP) (1959)
qe = [3]
1+ α RC 
Here, qe (mmol g–1) indicates the amount of metal sorbed
per gram of soil and is evaluated as
qe = ( C 0 −C )V [4]
where C (mmol L–1) is the equilibrium concentration of metal
in solution after equilibration and V (L g–1) is the ratio between
the solution volume and the soil mass.
The Freundlich isotherm in Eq. [1] is based on the assump-
tion that sorption energies are described by an exponential dis-
tribution. It is characterized completely by two parameters,
that is, the Freundlich distribution or partition coefficient,
KF (Ln mmol1–n g –1), and a dimensionless exponent, 0 < n
< 1. An alternative to the format of Eq. [1], which we do not
explore in this paper for ease of illustration of the methodol-
ogy, allows the exponent n to depend on anion concentration
in solution. This model was introduced by Sibbesen (1981) and
was demonstrated to be effective in interpreting single-compo-
nent selenite and phosphate sorption onto a Chilean Andisol
(Barrow et al., 2005).
The Langmuir model in Eq. [2] assumes that adsorption
occurs at a fixed number of well-localized sites, all of which are
associated with uniformly distributed sorption energies. The
model does not allow interaction between adsorbed molecules
and includes two parameters, that is, qm (mmol g–1), represent-
ing the saturation of all sorption sites, and KL (L mmol–1), which
1231
represents adsorption rate. The Redlich–Peterson isotherm, Eq. qmax K EL,iCi
[3], is a combination of Eq. [1] and [2] and is associated with qe,i  N
, Extended Langmuir (Yang, 1987) [9]
three model parameters, that is, KR (L g–1), αR (Lβ mmol–β), 1   K EL,jC j
j 1
and 0 < β < 1. It tends to (a) the Langmuir equation in the limit
ni −1
of low concentrations, or to (b) the Freundlich model in the ⎛ N ⎞
limit of high concentration values. As previously mentioned, it qe,i = K F,iC i ⎜ ∑α ijC j ⎟ , SRS model
has been suggested that the Langmuir model (Barrow, 2008) is ⎝ j=1 ⎠ (Sheindorf et al., 1981) [10]
generally not appropriate to interpret metal sorption in soils.
K R ,i ( C i  i )
We prefer to consider it in our analysis as (i) it has been used qe,i = N

extensively in sorption studies (e.g., Bolster, 2008; Srivastava et
al., 2008; Dişli,2010; Ofomaja et al., 2010), and (ii) it is a limit-
ing form of Eq. [3].
When isotherm models are presented in the form of Eq. [1–
3], C and qe are not independent quantities, because qe is evalu-
ated according to Eq. [4]. The problem is then recast in terms of
the independently measured quantities C0 and C upon consider-
ing the isotherm equations coupled with Eq. [4] (Barrow, 2008;
Tellinghuisen and Bolster, 2010)
K FC n
C0 = +C , (Freundlich) [5]
V Langmuir equation. The parameters ηi take into account metal
1 qm K LC
C0 = +C , (Langmuir) [6]
V 1+ K LC
1 K RC
C0 = +C , (RP) [7]
V 1+ α RC β
Optimization routines can then be used to find best esti-
mates of parameters as explained in the following.
Binary Component Systems
Solutions containing initial concentrations of Cu and Zn
were considered according to all combinations of the values
C0,i = 50, 100, 200 mg L–1 (corresponding to C0,Cu = 0.79, 1.57,
3.15 mmol L–1 for Cu and C0,Zn = 0.76, 1.53, 3.06 mmol L–1 for
Zn) for Bet Dagan soil and C0,i = 100, 300, 500 mg L-1 for Yatir
soil (corresponding to C0,Cu = 1.57, 4.72, 7.87 mmol L–1 for Cu
and C0,Zn = 1.53, 4.59, 7.65 mmol L–1 for Zn). The concentration
values adopted for the experiments performed on Yatir soil were
dictated by the large clay content of the soil. The average initial
value of pH of the competitive solutions analyzed for Bet Dagan
soil was 5.2, resulting in a final average pH value of 5.1.The average
initial value of pH of the competitive solutions analyzed for the
Yatir soil was 4.8, resulting in a final average pH value of 5.7.
In their competitive Ni–Cd sorption experiments, Liao and
Selim (2009) added to the system a concentration of the compet-
ing ion of 0.047, 0.235, 0.766 mmol L–1. These concentrations
correspond to C0 = 5.3, 26.4, 86.1 mg L–1 for Cd and C0 = 2.8,
13.8, 45.0 mg L–1 for Ni.
Experimental data were interpreted according to the follow-
ing four isotherm models:
qm ,i K L,i Ci i 
qe,i 
N
( ) , Modified RP
β, j
1+ ∑α R , j C j  j
j =1
(e.g., Srivastava et al., 2008) [11]
Here, qe,i is the amount of metal species i adsorbed per gram
of soil, and is calculated as

qei  C0,i  Ci V  [12]
where Ci is the concentration of metal species i in the equilib-
rium solution.
The parameters qm,i and KL,i appearing in the Modified
Langmuir model are derived from the single component
competition and are calibrated against the binary system ob-
servations. The Extended Langmuir model has the same func-
tional format of its single component counterpart and the
parameters appearing in Eq. [9] are estimated on the basis of
competition experiments. The SRS equation was derived by
assuming that single component behavior is described by the
Freundlich model, Eq. [1]. The parameters KF,i and ni are the
Freundlich constant and exponent of a single component iso-
therm of metal species i, respectively. For simplicity and clarity
of illustration, we consider in this study the parameters αi,j and
αj,i to be symmetrical (i.e., αi,j = 1/αj,i), as originally proposed
by Sheindorf et al. (1981). This implies that different ions com-
pete only for adsorption sites. When other effects, such as elec-
trical effects following ion penetration to soil grain surfaces,
can be considered as relevant, one might fit independently the
two competition parameters (e.g., Barrow et al., 2005). The pa-
rameters αR,i and KR,i appearing in the Modified RP model are
derived from the single component RP equation. The param-
eters i take into account metal competition and are calibrated
against the binary system observations.
As already noted for the single component isotherms, Ci
and qe,i are correlated by virtue of Eq. [12]. This problem is
handled (Barrow et al., 2005) by solving the following system
of equations: sorption equations (in the format of Eq. [8–11],
depending on the model selected) and related to the two ion
species involved in the system, and equations linking sorption to
change in concentration (in the format of Eq. [12]). This leads,
for N = 2, to the following equations, relating the independently
measured quantities C0,i and Ci
qm ,i K L,1 Ci i 
C0,i   Ci
 2  (i = 1,2), Modified


1   K L, j C j  j 
, Modified Langmuir
(Bellot and Condoret, 1993) [8]
1  
V
 j 1
K L, j C j  j  

Langmuir [13]
j 1

1232 Soil Science Society of America Journal

 qmax K EL,iCi Here, the two parameters  02 and θ are obtained by a least
C0,i   Ci (i = 1,2), Extended square fitting procedure of the logarithmically transformed ex-
 2  2 2
V 1   K EL,jC j  Langmuir [14] perimental estimates of  i , ˆ i , derived on the basis of m exper-
 j 1  imental replicates. This transformation renders unnecessary the
ni −1 estimation of the variance function through an iterative adjust-
C ⎛ 2 ⎞
C 0,i = K F,i i ⎜ ∑α ijC j ⎟ +C i (i = 1,2), SRS [15] ment of the fitting weights (Tellinghuisen, 2009). Calibrations
V ⎝ j=1 ⎠ performed on the basis of Eq. [19] consider each component
of the measured concentrations vector C* in Eq. [17] to [19]
K R ,i ( C i  i )
C 0,i = +C i as the average among the m replicates performed for each ex-
⎛ 2 ⎞ (i = 1,2). Modified RP
( )
β, j
V ⎜ 1+ ∑α R , j C j  j ⎟ perimental condition (m = 3 in our set of experiments) and are
⎝ j=1 ⎠ [16]
termed weighted calibrations in the following. Considering that
m is typically low, the width of the confidence interval associ-
with i = 1 for Cu or Ni and i = 2 for Zn or Cd. ated with the estimate of  i 2 can be large. Note that a significant
The best parameter estimates are determined for each model reduction in the confidence interval associated with ˆ i 2 would
by means of a Maximum Likelihood optimization procedure, as require changing the order of magnitude of m (e.g., Ballio and
detailed in the following section. Guadagnini, 2004 and references therein). Such extensive ex-
perimental analyses are not typically available for practical and
Model Calibration economic reasons.
Let NP be the number of unknown model parameters Another possible approach is to consider the error variance
and NC be the number of equilibrium concentration measure- as a constant, that is, independent of concentration measure-
ments. We introduce the vector of unknown model parameters, ments. This methodology is used mainly when paucity of data
p 
p1 , p 2 ,..., p N P  , the vector of concentration measure- does not allow to reliably estimating a variance function. In this
ments, C  C 1 ,C 2 ,...,C N* C  , the vector of model predictions,
*  * *
case the covariance matrix BC can be expressed as a product be-
Cˆ  Cˆ ,Cˆ ,...,Cˆ  , and the covariance matrix of the concentration tween a constant term, σ2, representing the (uniform) measure-
 1 2 NC 
measurement errors, BC. As commonly assumed (e.g., Carrera ment error variance and the identity matrix I. Minimization
and Neuman, 1986), we consider errors between C i* to be uncor- of NLL in Eq. [17] is then equivalent to minimizing the least
related. This renders BC diagonal with the nonzero terms equal square criterion
to the observation error variance,  i 2 (with i = 1, …, NC). NC 2
The Maximum Likelihood (ML) estimate, p̂, of p is ob- J 1   Ci*  Cˆ i
  . [21]
i 1
tained by minimizing the negative log likelihood criterion (e.g.,
Carrera and Neuman, 1986) After calibration, the ML estimate of σ2 is given by
NC
Ji J 1,min ,
NLL = ∑ + ln|B C |+ N C ln(2π) [17] 2  [22]
i i2 NC
with respect to p. In Eq. [17], Ji is defined as the squared differ- J1,min being the minimum of J1.With reference to our experi-
ence between measured and predicted concentration ments and consistently with what indicated above, when per-
2 forming minimization according to the above criteria, compo-
J i  C i*  Cˆi
 . [18]
nents of the measurement vector C* are calculated as the average
Minimizing NLL (for fixed NC) is equivalent to the mini- among the m replicates performed for each experimental condi-
mization of the weighted least square criterion tion. We will refer to the above minimization of the least square
2 criterion as unweighted calibration in the following.
 Cˆ i 
J 
*
C
NC i
[19]
i 1  i2 Model Identification Criteria
Minimization of Eq. [19] is performed using the iterative When a set of NM available alternative interpretive models
Levenberg–Marquardt algorithm implemented in the public do- is available, one can use various criteria to (a) rank these models,
main code PEST (Doherty, 2002). The observation error variance, and/or (b) weigh predictions generated by multiple models (e.g.,
 i 2, is in general unknown and is usually considered as a constant Neuman, 2003; Neuman and Wierenga, 2003; Ye et al., 2004,
(i.e., independent of Ci; e.g., Liao and Selim, 2009). Tellinghuisen 2008; Neuman et al., 2011). These criteria include
(2009) and Tellinghuisen and Bolster (2010) proposed the adop- AIC = NLL  2 N P , [23]
tion of an estimated variance function that links the error variance
to the measured concentration. Following Tellinghuisen (2009), 2 N P  N P  1 ,
AICc = NLL  2 N P  [24]
we consider here a power variance function
NC  N P  2
 i 2   02Ci2 [20] BIC = NLL  N P ln  N C  , [25]

www.soils.org/publications/sssaj 1233
 N 
KIC = NLL  N P ln  C   ln Q . [26]
 2 
These allow discrimination among different competing
models on the basis of their quality of fit to observations, number
of parameters, and quality of the available data and parameter
estimates. Here, Q is the Cramer–Rao lower-bound approxima-
tion for the covariance matrix of the parameter estimates, AIC is
due to Akaike (1974), AICc to Hurvich and Tsai (1989), BIC to
Schwartz (1978), and KIC to Kashyap (1982). All of these iden-
tification criteria support the principle of parsimony, in the sense
that when everything else is equal, one should prefer adoption of
the model with the smallest number of parameters.
KIC balances parsimony with the expected information
content by means of |Q| and favors the model that is least prob-
able (in an average sense) of being incorrect (Ye et al., 2008). On
the other hand, Tsai and Li (2008, 2010) and Li and Tsai (2009)
suggest that KIC can potentially favor models with large param-
eter estimation uncertainty following unreliable estimation of
Q, potentially leading to controversial results. An extensive dis-
cussion of these model selection criteria is presented in Ye et al.
(2008, 2010 and references therein).
The posterior probability associated with model Mk (k =
1,..., NM) is then calculated as (Ye et al., 2008)
2 with the soils. This is consistent with the observation that the two
Fig. 1. Experimental variance,  i , and corresponding estimated
variance function for (a) our experiments on Bet Dagan and Yatir
soils; and (b) the experiments of Liao and Selim (2009) on Windsor,
Olivier, and Webster soils.
1234
 1 
 IC k  p M k 
exp 
 2 

p Mk C* NM  1 
[27]
 IC i  p M i 
 exp 
i 1  2 
Here, ΔICk = ICk − ICmin, ICk being any of the considered mod-
el information criteria Eq. [23] to Eq. [26] and ICmin = min {ICk} its
minimum over all considered models; p(Mk) is the prior probability
associated with each model. In the following, because no prior infor-
mation is available, we set p(Mk) = 1/NM (i.e., an equal prior probabil-
ity is assigned to each model). Adopting model identification criteria
and posterior model probabilities Eq. [27] can lead to ranking a set of
candidate models in terms of their associated posterior probabilities
and allows discrimination among models in a relative sense.
The traditional approach has been to calibrate a model against
observed state variables by means of a suitable inverse methodolo-
gy. In addition to estimating model parameters, the key advantage
of the theoretical framework we adopt here is to allow (i) ranking
of models according to their individual skill to predict observed
system states, and (ii) assigning posterior probability weights to
each tested model, thus quantifying prediction uncertainty.
RESULTS AND DISCUSSION
Variance Function
Because of the different laboratory conditions, we consider
separately the set of experiments performed in this work and the
experiments performed by Liao and Selim (2009). Figure 1 re-
ports the experimental estimates of measurement error variance
(symbols) together with the estimated variance functions (solid
curves) for Bet Dagan and Yatir soils (Fig. 1a) and Windsor
(mixed, mesic Typic Udipsamments), Olivier (fine-silty, mixed,
active, thermic Aquic Fraglossudalfs), and Webster (fine-loamy,
mixed, superactive, mesic Typic Endoaquolls) soils (Fig. 1b). The
corresponding R2 regression values are reported for complete-
ness. Even though a general trend for  i 2 is detectable, the deter-
mination of the variance functions is affected by some ambiguity,
as also reflected by the relatively low R2 values.
Single Metal Systems
Figure 2 reports the dependence of the experimental equi-
librium concentrations on the initial concentrations for Bet
Dagan soil. The corresponding model predictions obtained
through the weighted and unweighted calibration procedures
are also reported. The main differences between the results based
on these approaches (weighted/unweighted calibration) can be
observed for the smallest initial concentrations. The correspond-
ing results obtained for Yatir soil are reported in Fig. 3.
We observed a similar behavior in the adsorption of Cu and
Zn for both soils. The equilibrium concentration of Cu and Zn
for a given initial ion concentration are comparable in our ex-
periments indicating that Cu and Zn ions have similar affinities
cations have the same valences (+2) and similar hydrated radii
(2.07 Å and 2.17 Å, respectively for Cu and Zn). The estimated
Soil Science Society of America Journal
Fig. 2. Experimental equilibrium concentration data and calibrated models for single component adsorption on Bet Dagan soil: (a) Cu, weighted
calibration; (b) Cu, unweighted calibration; (c) Zn, weighted calibration; (d) Zn, unweighted calibration. Error bars of ± 2σi are reported.

exponent of the Freundlich model, n, for Cu (n = 0.26 or 0.23, re- unweighted calibrations in Bet Dagan soil and n = 0.29 or 0.30 for
spectively for weighted and unweighted calibrations in Bet Dagan the Yatir soil). The maximum sorption capacities, qm, calculated
soil and n = 0.18 or 0.27 for Yatir soil) is always smaller than that of according to the Langmuir model, are 2.80 or 3.49 (for weighted
Zn for both soils (n = 0.39 or 0.36, respectively for weighted and and unweighted calibrations, respectively) and 3.68 or 4.31 (for

Fig. 3. Experimental equilibrium concentration data and calibrated models for single component adsorption on Yatir soil: (a) Cu, weighted
calibration; (b) Cu, unweighted calibration; (c) Zn, weighted calibration; (d) Zn, unweighted calibration. Error bars of ±2σi are reported.

www.soils.org/publications/sssaj 1235
Fig. 4. Comparison between parameters values obtained when single component systems isotherm equations are interpreted by weighted and
unweighted calibration. Symbols indicate different interpretive models: (open diamond) Freundlich model, (open circle) Langmuir model, and
(open triangle) RP model. Different colors indicate different metals and soils; (a) Cu: solid and empty symbols indicate Bet Dagan and Yatir soils,
respectively; (b) Zn: solid and empty symbols indicate Bet Dagan and Yatir soils, respectively; (c) Cd: black symbols indicate Windsor soil, empty
symbols represent Olivier soil and gray symbols indicate Webster soil; (d) Ni: black symbols indicate Windsor soil, empty symbols represent
Olivier soil and gray symbols indicate Webster soil.

weighted and unweighted calibrations, respectively) g kg–1 for Cu
and Zn ions, respectively, in Bet Dagan soil. Yatir soil is associated
with qm = 11.14 or 15.59 and 11.69 or 15.48 g kg–1, respectively,
for Cu and Zn ions and for weighted or unweighted calibration.
The maximum sorption capacity of Yatir soil is about three to four
times larger than that of the Bet Dagan soil sample, consistently
with the different CEC of the two soils (see Table 1).
The scatter plots in Fig. 4a and 4b compare parameter es-
timates obtained by unweighted calibrations and those related
to weighted calibrations for Cu and Zn, respectively. The com-
Table 2. Single-component posterior model weights (%) and corresponding model ranks (in parentheses) for Bet Dagan and Yatir soils.
panion information related to the experiments of Liao and Selim
(2009) and related to sorption of Cd and Ni on Windsor soil is
reported in Fig. 4c and 4d (see also below for additional comments).
The complete list of the parameter estimates is provided in Table
A1 of the Appendix together with the square root of the estimation
error variance (RSD). Our results show that the largest differences be-
tween parameter estimates can be observed for KL (Langmuir model).
We further note that these estimates are associated with large relative
uncertainty, as evidenced by the relatively large RSD.

Model identification Cu Zn
Soil
criterion Freundlich [5] Langmuir [6] RP† [7] Freundlich [5] Langmuir [6] RP [7] †
Bet Dagan‡ AICc 94.41(1) 0.05(3) 5.55(2) 94.20(1) 1.55(3) 4.25(2)
KIC 88.51(1) 3.69(3) 7.80(2) 26.29(2) 2.95(3) 70.76(1)
Yatir‡ AICc 90.51(1) 0.00 9.49(2) 85.92(1) 0.00 14.08(2)
KIC 1.13(2) 0.00 98.87(1) 8.39(2) 0.00 91.62(1)
Bet Dagan§ AICc 24.49(2) 0.00(3) 75.51(1) 54.47(1) 41.16(2) 4.37(3)
KIC 1.06(2) 0.00(3) 98.94(1) 11.96(3) 12.96(2) 75.08(1)
Yatir§ AICc 98.94(1) 0.01(3) 1.05(2) 97.44(1) 0.26(3) 2.30(2)
KIC 3.93(2) 0.00(3) 96.06(1) 1.93(2) 0.01(3) 98.06(1)
† Redlich–Peterson model.
‡ Weighted calibration.
§ Unweighted calibration.

1236 Soil Science Society of America Journal

 Posterior model weights and corresponding model ranks
resulting from AICc and KIC are presented in Table 2. Posterior
model weights associated with AIC and BIC provide information
which is qualitatively similar to that embedded in AICc, due to
their structure. The complete set of results obtained in terms of
model quality criteria is reported in Tables A2 and A3 (Appendix).
Our results support the findings of Barrow (2008) that the
Langmuir model does not provide an appropriate interpretation
of these processes, the only exception being the results of the
unweighted calibration for Zn sorption on Bet Dagan soil. The
Freundlich and RP models provide the best overall interpreta-
tions of the system behavior. This is likely linked to the fact that
the amount of metal sorbed does not display a clear tendency to
attain a saturation limit for the range of concentrations tested.
Considering the results associated with the weighted
calibration, both model discrimination criteria AICc and KIC
indicate a clear preference for the Freundlich model to interpret
Cu sorption on Bet Dagan soil. The response of the Bet Dagan
soil to Zn as well that of the Yatir soil to both Cu and Zn is best
described by the Freundlich or the RP model according to AICc
or KIC, respectively.
With reference to the unweighted calibrations, the re-
sults obtained for the Yatir soil practically coincide with those
stemming from considering the effect of a variance function.
Considering the Bet Dagan soil, both model discrimination cri-
teria tend to prefer the RP model to interpret Cu sorption (albeit
AICc renders a non-negligible weight also for the Freundlich
model), while they provide contrasting results for Zn sorption,
with relatively large weights for all models tested.
Fig. 5. Experimental equilibrium concentration data and calibrated models for single component adsorption of Cd and Ni onto Windsor soil: (a)
weighted calibration; (b) unweighted calibration. The width of error bars of ±2σ are of the same size of the symbols.
www.soils.org/publications/sssaj
While the relative merits of KIC and AICc within the con-
text of applications to natural systems are still studied and de-
bated extensively (e.g., Foglia et al., 2007; Ye et al., 2008; Tsai
and Li, 2008, 2010; Li and Tsai, 2009; Riva et al., 2011), our
results suggest that in the case of an unweighted calibration it is
not possible to select one model to interpret the observed data
at the expense of the others. On the other hand, we observe that
adopting a weighted calibration for our experiments leads to a
clear identification of a best performing model.
We then applied the methodological framework above illus-
trated to analyze the single metal systems presented by Liao and
Selim (2009). Figure 5 depicts equilibrium concentration experi-
mental data and the calibrated model predictions for Windsor
soil, relative to weighted and unweighted calibration for sorption
of Cd (Fig. 5a and 5b) and Ni (Fig. 5c and 5d). Results obtained
for Olivier and Webster soils provided information which is
qualitatively similar to that encapsulated in Fig. 5 (not shown). A
complete list of the parameters estimated is provided in Table A1
(Appendix), together with the associated relative standard devia-
tions. Table 3 reports the model posterior probability weights
and associated ranks calculated on the basis of AICc and KIC
for both weighted and unweighted calibrations. Tables A2 and
A3 completes the picture by including the complete set of results
associated with Eq. [23] to Eq. [26]. Similar to what observed for
our experiments, using the approach of weighted calibration the
Freundlich and RP models provide the best overall interpreta-
tions of the system behavior. The Freundlich or RP models can
be preferred to depict Cd sorption depending on the soil, while
1237
Table 3. Single-component posterior model weights (%) and corresponding model ranks (in parentheses) for Windsor, Olivier, and
Webster soils.
Cd Ni
Soil Model identification criterion
Freundlich [5] Langmuir [6] RP† [7] Freundlich [5] Langmuir [6] RP [7] †
Windsor‡ AICc 74.93(1) 0.00 25.07(2) 99.98(1) 0.02(2) 0.00
KIC 4.70(2) 0.00 95.30(1) 98.75(1) 1.25(2) 0.00
Olivier‡ AICc 2.90(2) 0.00 97.10(1) 100.00(1) 0.00 0.00
KIC 0.05(2) 0.00 99.95(1) 100.00(1) 0.00 0.00
Webster‡ AICc 100.00(1) 0.00 0.00 100.00(1) 0.00 0.00
KIC 100.00(1) 0.00 0.00 100.00(1) 0.00 0.00
Windsor§ AICc 98.45(1) 0.71(3) 0.84(2) 0.51(3) 2.24(2) 97.25(1)
KIC 65.58(1) 0.47(3) 33.95(2) 0.22(3) 58.12(1) 41.66(2)
Olivier§ AICc 97.34(1) 2.61(2) 0.05(3) 100.00(1) 0.00 0.00
KIC 94.52(1) 2.53(3) 2.95(2) 99.99(1) 0.01 0.00
Webster§ AICc 82.39(1) 17.40(2) 0.21(3) 1.00(2) 98.34(1) 0.66(3)
KIC 73.12(1) 15.44(2) 11.44(3) 0.72(3) 70.50(1) 28.78(2)
† Redlich–Peterson model.
‡ Weighted calibration.
§ Unweighted calibration.

the Freundlich model is always preferred to describe Ni sorption
for all the soils tested.
It is interesting to observe that the unweighted calibration
procedure considers the Langmuir model to be associated with a
relatively large probability (larger than 50%) to be able to char-
acterize Ni sorption onto both Windsor and Webster soils and
a non-negligible probability (larger than 15%) to interpret Cd
sorption on Webster soil. Note that this is consistent with the
observation that in this case the largest measured concentrations,
which are close to saturation, have the largest impact on the cali-
bration results.

Fig. 6. Experimental equilibrium concentration data and calibrated models for competitive adsorption of Cu and Zn on Bet Dagan soil: (a)
Cu equilibrium concentration for initial concentration of Zn = 100 mg L–1, weighted calibration; (b) Cu equilibrium concentration for initial
concentration Zn = 100 mg L–1, unweighted calibration; (c) Zn equilibrium concentration for initial concentration of Cu = 100 mg L–1, weighted
calibration; (d) Zn equilibrium concentration for initial concentration of Cu = 100 mg L–1, unweighted calibration. Error bars of ± 2σ are reported.

1238 Soil Science Society of America Journal

Fig. 7. Experimental equilibrium concentration data and calibrated models for competitive adsorption of Cu and Zn on Yatir soil: (a) Cu equilibrium
concentration for initial concentration of Zn = 300 mg L–1, weighted calibration; (b) Cu equilibrium concentration for initial concentration Zn =
300 mg L–1, unweighted calibration; (c) Zn equilibrium concentration for initial concentration of Cu = 300 mg L–1, weighted calibration; (d) Zn
equilibrium concentration for initial concentration of Cu = 300 mg L–1, unweighted calibration. Error bars of ± 2σ are reported.

Binary Systems
Figures 6a and 6b depict equilibrium experimental concen-
trations of Cu on Bet Dagan soil for a selected initial concentra-
tion of Zn ions and model predictions obtained through weight-
ed and unweighted calibrations. Figures 6c and 6d report the
corresponding depiction for Zn equilibrium concentrations for
a given initial concentrations of Cu. Corresponding experiments
performed on Yatir soil samples are shown in Fig. 7. Results relat-
ed to different values of initial ion concentrations display a very
similar behavior (not shown).
With reference to Bet Dagan samples, while the two cations
analyzed display almost the same affinity to the soil when consid-
ered separately, in a competitive system they are associated with
different dynamics. It is noted that equilibrium concentration of
Cu onto Bet Dagan soil is increased by about 10% on average
in the competitive systems in comparison with the behavior of
a single element system for the same initial concentration ad-
opted (considering an average condition over the different initial
concentrations of Zn applied during the competitive sorption
experiments, i.e., 50, 100, 200 mg L–1). This increase in Cu equi-
librium concentration causes a corresponding decrease in the
amount of metal sorbed (see Eq. [4]). The presence of competing
Cu ions significantly affects Zn sorption, increasing Zn equilib-
rium concentration by about 30% on average over the various
initial concentrations of Cu applied to the system. Consistently
with this observation, the estimated value of the SRS coefficient
αij (subscript i and j indicating Cu and Zn, respectively) is small-
er than unity, indicating that the presence of Zn ions has only a
marginal effect on the sorption of Cu.
Figure 8a compares estimated parameter values obtained
through unweighted and weighted calibrations for Bet Dagan and
Yatir soil. A complete list of parameter estimate is reported in Table
A4 (Appendix) together with the associated standard deviations.
Posterior model weights and corresponding model ranks
are presented in Table 4. AICc and KIC clearly identify the
modified RP as the best model to interpret Bet Dagan experi-
ments for both the weighted and unweighted calibrations. This
is consistent with the preference toward the RP model displayed
in most of the single component systems.
With reference to the Yatir soil experiments, we observed
that the sorptive behavior of Cu is only slightly influenced by the
presence of Zn. We calculate an average increase of about 20%
in the presence of the different applied Zn initial concentration
when compared to the single metal experiments. On the other
hand, Zn equilibrium concentration increases by 60% on aver-
age in the presence of the applied initial Cu concentrations. This
suggests that Zn sorption tends to be inhibited by the presence of
Cu, consistently with the estimated value of the SRS coefficient
αij (subscript i and j indicating Cu and Zn, respectively) that is
significantly smaller than unity. All model information criteria and
posterior model weights (see Table 4) are in agreement favoring
the Extended Langmuir as the best performing model within the
weighted calibrations. With reference to the unweighted calibra-
tions, the Modified Langmuir model is associated with the highest

www.soils.org/publications/sssaj 1239
 Table 5. Binary-component posterior model weights (%) and
corresponding model ranks (in parentheses) for Windsor,
Olivier, and Webster soils.

Model Modified Extended

SRS† Modified RP
Soil identification Langmuir Langmuir
[15] [16] †
criterion [13] [14]
AICc 0.00 100.00(1) 0.00 0.00
Windsor‡
KIC 0.00 100.00(1) 0.00 0.00
AICc 0.00 100.00(1) 0.00 0.00
Olivier‡
KIC 0.00 100.00(1) 0.00 0.00
AICc 0.00 100.00(1) 0.00 0.00
Webster‡
KIC 0.00 100.00(1) 0.00 0.00
AICc 0.00 24.03(2) 75.97(1) 0.00
Windsor§
KIC 0.00 4.30(2) 95.70(1) 0.00
AICc 0.00 60.51(1) 39.49(2) 0.00
Olivier§
KIC 0.00 17.33(2) 82.67(1) 0.00
AICc 0.00 100.00(1) 0.00 0.00
Webster§
KIC 0.00 99.98(1) 0.02(2) 0.00
† SRS, Sheindorf–Rebhun–Sheintuch model; RP, Redlich–Peterson model.
‡ Weighted calibration.
§ Unweighted calibration.

related to competitive sorption onto Windsor soil for a given val-

ue of the initial concentration of the competing ion.
The corresponding posterior model weights are listed in
Table 5. An unweighted calibration assigns high posterior prob-
Fig. 8. Comparison between parameters obtained by weighted and abilities to both the Extended Langmuir and SRS models, de-
unweighted calibration of competitive isotherm models. (open pending on the soil and on the model discrimination criterion
diamond) Extended Langmuir model, (open square) modified
Langmuir model, (open circle) SRS model and (open triangle) adopted. Considering dependence of measurement error
modified RP model. (a) Full symbols indicate Bet Dagan soil, empty variance on concentration leads to assigning a 100% probability
symbols represent Yatir soil; (b) black symbols indicate Windsor soil, to the Extended Langmuir model for all soils tested.
empty symbols represent Olivier soil and gray symbols are related to
Webster soil.
These results are consistent with those related to our ex-
periments, in that disregarding the measurement error variance
posterior probability (63%), followed by the Modified RP (22%) associated with different replicates results in a set of generally
and Extended Langmuir (15%) models. The complete list of mod- non-negligible weights associated with different conceptual
el information criteria and posterior model weights for competi- models of the system behavior. For example, posterior model
tive models is reported in Table A5 (Appendix). weights calculated on the basis of AICc for Windsor soil identify
The binary metal systems presented by Liao and Selim the SRS as the best model (with 76% posterior probability) and
(2009) were then analyzed. Figure 9 depicts an example of results assign a 24% probability weight to the extended Langmuir mod-
el. In these cases a multi-model and/or Maximum Likelihood
Bayesian Model Averaging approach (e.g., Hoeting et al., 1999;
Table 4. Binary-component posterior model weights (%) and Ye et al., 2008; Winter and Nychka, 2010) should be preferred.
corresponding model ranks (in parentheses) for Bet Dagan
and Yatir soils.
CONCLUSIONS
Model Modified Extended
SRS Modified RP Natural systems are complex and the uncertainty associ-
Soil identification Langmuir Langmuir
[15] † [16] † ated with our process understanding affects their conceptual-
criterion [13] [14]
mathematical description. Therefore, an appropriate tool to
Bet AICc 0.00 0.00 0.00 100.00(1)
Dagan‡ KIC 0.00 0.00 0.00 100.00(1)
quantify such uncertainty is the adoption of a multi-model
AICc 0.00 99.57(1) 0.43(2) 0.00 analysis based on model selection criteria. We provide an ex-
Yatir‡ ample of application of the methodology to the analysis of
KIC 0.00 99.37(1) 0.63(2) 0.00
Bet AICc 0.00 0.60(2) 0.00 99.40(1) complex single and competitive sorption processes onto differ-
Dagan§ KIC 0.00 0.63(2) 0.00 99.37(1) ent natural soils in the presence of different competing metal
AICc 62.58(1) 15.23(3) 0.00 22.19(2) ions. We present two exhaustive sets of batch experiments, one
Yatir§
KIC 62.05(1) 15.95(3) 0.00 22.00(2) of which taken from the literature, related to single and binary
† SRS, Sheindorf–Rebhun–Sheintuch model; RP, Redlich–Peterson model. metal systems. Calibration of model parameters is performed
‡ Weighted calibration.
following two approaches: (a) a weighted calibration, where the
§ Unweighted calibration.

1240 Soil Science Society of America Journal

Fig. 9. Experimental equilibrium concentration data and calibrated models for competitive adsorption of Cd and Ni on Windsor soil: (a) Cd equilibrium
concentration for initial concentration of Ni = 0.24 mmol L–1, weighted calibration; (b) Cd equilibrium concentration for initial concentration Ni =
0.24 mmol L–1, unweighted calibration; (c) Ni equilibrium concentration for initial concentration of Cd = 0.24 mmol L–1, weighted calibration; (d) Ni
equilibrium concentration for initial concentration of Cd = 0.24 mmol L–1, unweighted calibration. Error bars of ±2σ are of the same size of the symbols.

variance estimation error depends on the concentration, and
(b) an unweighted calibration, where the variance estimation
error is considered to be constant (and generally unknown).
In addition to calibrating model parameters, our analysis al-
lows (a) ranking of models according to their individual skill
to predict observed system states, and (b) assigning posterior
probability weights to each tested model, thus quantifying pre-
diction uncertainty.
Even as these two procedures render similar estimated parame-
ters, the results associated with model discrimination criteria depend
on whether a weighted or unweighted calibration is performed.
In the single component systems analyzed, a weighted cali-
bration leads to ranking the Freundlich or RP model as first or
second best model, while the posterior probability associated with
the Langmuir model is always close to zero. This result supports
the finding of Barrow (2008) who shows that the Langmuir model
is not justified on theoretical bases to describe sorption of ions on
soils. We also note that in several cases the probability weights as-
sociated with Freundlich and RP models cannot be considered
as negligible. In these cases, a single interpretive model might
not succeed in providing a complete uncertainty quantification,
so that a multi-model analysis should be preferred. Unweighted
calibrations result in non-negligible probability weights associated
with the Langmuir model for some combinations of soil and ions
(Zn ions on Bet Dagan soil, Cd and Ni ions on Webster soil, Ni
ions on Windsor soil). As there are no sound theoretical bases for
this model (Barrow, 2008), this result indicates that a weighted
calibration should be preferred for this kind of analysis.
In the binary component systems, a weighted calibration
identifies the Extended Langmuir (for all soils tested with the
exception of Bet Dagan) or the Modified RP model (for the Bet
Dagan soil) as the best performing model with posterior prob-
ability weight close or equal to 100%. Following an unweighted
calibration, selection of one model excluding the contribution of
all others is in general ambiguous for three out of five soils ana-
lyzed. The Modified Langmuir (62%), Modified RP (22%), and
Extended Langmuir (15%) have non-negligible weights for Yatir
soil. The Extended Langmuir model and the SRS model are the
two most highly ranked models for Windsor and Olivier soils.
ACKNOWLEDGMENTS
We are grateful to H.M. Selim and L. Liao for sharing with us their
valuable dataset. The financial support of the European Commission
(Contract no. PITN-GA-2008-212298), the Politecnico di Milano
(Project GEMINO, Progetti di ricerca 5 per mille junior), and the
Sussman Family Center for the Study of the Environmental Sciences
is gratefully acknowledged.

www.soils.org/publications/sssaj 1241
APPENDIX
Table A1. Parameter estimates and associated relative standard deviation (RSD) for single-component isotherms.
Bet Dagan (Cu) Yatir (Cu) Windsor (Cd) Olivier (Cd) Webster (Cd)
Model Parameter
Value RSD Value RSD Value RSD Value RSD Value RSD
KF 0.99 0.04 4.22 0.11 5.95 0.13 23.33 0.06 21.54 0.26
Freundlich† [5]
n 0.26 0.05 0.18 0.12 0.69 0.05 0.61 0.03 0.55 0.16
KL 0.28 0.41 0.40 0.89 5.86 0.34 26.39 0.55 33.81 0.21
Langmuir† [6]
qm 2.86 0.09 11.14 0.09 3.95 0.23 8.12 0.18 8.21 0.12
KR 3.89 0.14 18.97 2.10 29.48 0.12 356.38 0.19 248.72 0.09
RP† [7] α 3.28 0.16 4.03 2.39 5.21 0.24 21.47 0.09 19.71 0.72
β 0.79 0.01 0.84 0.07 0.65 0.23 0.59 0.19 0.80 0.37
KF 1.10 0.04 2.61 0.12 5.61 0.02 19.27 0.04 19.42 0.05
Freundlich‡ [5]
n 0.23 0.04 0.27 0.08 0.66 0.03 0.55 0.03 0.51 0.04
KL 0.09 0.30 0.01 0.49 2.31 0.25 127.08 0.29 14.63 0.15
Langmuir‡ [6]
qm 3.49 0.05 15.59 0.09 6.42 0.14 9.81 0.20 10.46 0.06
KR 3.20 0.47 6.82 4.63 43.12 0.59 0.89 0.27 157.25 0.32
RP‡§ [7] α 2.63 0.52 2.50 4.87 6.91 0.63 10.70 0.16 13.44 0.28
β 0.79 0.01 0.74 0.06 0.44 0.22 10.99 0.07 0.94 0.29
Bet Dagan (Zn) Yatir (Zn) Windsor (Ni) Olivier (Ni) Webster (Ni)
Value RSD Value RSD Value RSD Value RSD Value RSD
KF 0.58 0.13 2.28 0.11 2.97 0.08 14.78 0.04 39.24 0.23
Freundlich† [5]
n 0.39 0.09 0.29 0.08 0.58 0.03 0.60 0.01 0.57 0.11
KL 0.07 0.35 0.08 0.53 12.76 0.31 18.85 0.41 25.75 1.66
Langmuir† [6]
qm 3.68 0.12 11.69 0.11 1.66 0.22 6.38 0.24 16.97 1.93
KR 0.83 1.31 5.65 1.36 36.95 0.78 99.18 0.18 578.33 0.11
RP† [7] α 0.94 1.91 2.08 1.61 13.37 0.96 11.11 1.13 48.31 0.95
β 0.70 0.20 0.74 0.07 0.56 0.14 0.87 0.64 0.89 0.34
KF 0.66 0.17 2.08 0.21 2.49 0.06 12.91 0.02 23.02 0.14
Freundlich‡ [5]
n 0.36 0.11 0.30 0.12 0.48 0.11 0.55 0.02 0.42 0.11
KL 0.04 0.22 0.01 0.48 5.97 0.13 7.62 0.23 459.30 0.21
Langmuir‡ [6]
qm 4.31 0.06 15.48 0.10 2.30 0.04 8.82 0.11 49.14 0.19
KR 0.77 1.95 4.32 5.46 17.10 0.24 75.15 0.47 1.00 0.06
RP† [7] α 0.85 2.59 1.91 5.97 7.14 0.22 7.20 0.33 49.96 0.07
β 0.70 0.18 0.71 0.12 0.87 0.14 0.85 0.40 9.29 0.02
† Weighted calibration.
‡ Unweighted calibration.
§ Redlich–Peterson model.

Table A2. Model information criteria for single-component isotherms.

Model NLL and model information criteria
Model identification Bet Dagan Yatir Windsor Olivier Webster Bet Dagan Yatir Windsor Olivier Webster
criterion Cu Cu Cd Cd Cd Zn Zn Ni Ni Ni
Freundlich† [5] NLL 10.19 27.66 –58.91 –40.33 234.89 16.26 26.82 –48.14 –64.30 175.35
AIC 14.19 31.66 –54.91 –36.33 238.89 20.26 30.82 –44.14 –60.30 179.35
AICC 17.19 34.66 –50.91 –32.33 242.89 23.26 33.82 –40.14 –56.30 183.35
BIC 14.08 31.55 –55.33 –36.74 238.48 20.15 30.71 –44.55 –60.71 178.93
KIC 27.99 39.84 –44.31 –30.47 239.83 31.53 40.55 –35.98 –51.97 179.79
Langmuir† [6] NLL 25.47 89.26 –49.04 399.82 298.39 24.47 83.83 –58.62 555.01 2020.65
AIC 29.47 93.26 –45.04 403.82 302.39 28.47 87.83 –54.62 559.01 2024.65
AICC 32.47 96.26 –41.04 407.82 306.39 31.47 90.83 –50.62 563.01 2028.65
BIC 29.36 93.15 –45.45 403.41 301.98 28.36 87.72 –55.04 558.60 2024.23
KIC 34.35 92.53 –42.94 395.96 296.61 35.91 91.21 –50.00 552.41 2014.19
RP†‡ [7] NLL 8.86 25.17 –59.39 –57.35 375.89 15.45 23.43 –61.08 1117.41 895.65
AIC 14.86 31.17 –53.39 –51.35 381.89 21.45 29.43 –55.08 1123.41 901.65
AICC 22.86 39.17 –41.39 –39.35 393.89 29.45 37.43 –43.08 1135.41 913.65
BIC 14.70 31.00 –54.01 –51.97 381.27 21.29 29.27 –55.71 1122.79 901.02
KIC 32.85 30.89 –52.72 –56.05 371.53 29.55 35.76 –51.69 1112.11 887.05
Freundlich§ [5] NLL 6.55 33.78 –28.19 –64.30 –62.46 26.24 41.00 –66.29 –70.37 –66.17
AIC 10.55 37.78 –24.19 –60.30 –58.46 30.24 45.00 –62.29 –66.37 –62.17
AICC 13.55 40.78 –20.19 –56.30 –54.46 33.24 48.00 –58.29 –62.37 –58.17
BIC 10.44 37.67 –24.61 –60.72 –58.88 30.13 44.89 –62.71 –66.79 –62.59
KIC 27.47 50.05 –18.51 –51.55 –50.30 42.14 55.50 –52.77 –53.86 –56.54
Langmuir§ [6] NLL 29.22 53.01 14.30 –57.06 –59.35 26.80 52.84 –4.46 –50.49 –75.35
AIC 33.22 57.01 18.30 –53.06 –55.35 30.80 56.84 –0.46 –46.49 –71.35
AICC 36.22 60.01 22.30 –49.06 –51.35 33.80 59.84 3.54 –42.49 –67.35
BIC 33.11 56.90 17.88 –53.48 –55.77 30.69 56.73 –0.88 –46.91 –71.77
KIC 42.28 65.21 16.12 –53.15 –55.50 41.98 65.30 –2.53 –47.03 –70.49
RP§[7] NLL –2.71 35.86 –36.00 –59.16 –60.54 24.28 41.49 –59.35 –52.97 –75.35
AIC 3.29 41.86 –30.00 –53.16 –54.54 30.28 47.49 –53.35 –46.97 –69.35
AICC 11.29 49.86 –18.00 –41.16 –42.54 38.28 55.49 –41.35 –34.97 –57.35
BIC 3.13 41.70 –30.63 –53.79 –55.17 30.12 47.33 –53.97 –47.59 –69.98
KIC 18.39 43.66 –30.92 –56.33 –59.36 38.47 47.64 –58.32 –50.88 –74.06
† Weighted calibration.
‡ Redlich–Peterson model.
§ Unweighted calibration.

1242 Soil Science Society of America Journal

Table A3. Posterior model weights for single-component isotherms.

Posterior model weights, %

Model
Model identification Bet Dagan Yatir Windsor Olivier Webster Bet Dagan Yatir Windsor Olivier Webster
criterion
Cu Cu Cd Cd Cd Zn Zn Ni Ni Ni

–––––––––––––––––––––––––––––––––––– % –––––––––––––––––––––––––––––––––––––
Freundlich† [5] AIC 58.26 43.91 67.86 0.05 100.00 63.88 33.37 0.23 100.00 100.00

AICC 94.41 90.51 98.45 2.90 100.00 94.20 85.92 0.51 100.00 100.00

BIC 57.61 43.24 65.58 0.05 100.00 63.27 32.77 0.22 100.00 100.00

KIC 88.51 1.13 1.46 0.00 100.00 26.29 8.39 0.03 100.00 100.00
Langmuir† [6] AIC 0.03 0.00 0.49 0.00 0.00 1.05 0.00 44.20 0.00 0.00

AICC 0.05 0.00 0.71 0.00 0.00 1.55 0.00 97.25 0.00 0.00

BIC 0.03 0.00 0.47 0.00 0.00 1.04 0.00 41.66 0.00 0.00

KIC 3.69 0.00 0.73 0.00 0.00 2.95 0.00 30.06 0.00 0.00
RP†‡ [7] AIC 41.71 56.09 31.65 99.95 0.00 35.07 66.63 55.57 0.00 0.00

AICC 5.55 9.49 0.84 97.10 0.00 4.25 14.08 2.24 0.00 0.00

BIC 42.37 56.76 33.95 99.95 0.00 35.69 67.23 58.12 0.00 0.00

KIC 7.80 98.87 97.81 100.00 0.00 70.76 91.62 69.91 0.00 0.00
Freundlich§ [5] AIC 2.59 88.53 5.19 94.80 73.96 36.58 77.49 98.87 99.99 0.74

AICC 24.49 98.94 74.93 97.34 82.39 54.47 97.44 99.98 100.00 1.00

BIC 2.53 88.25 4.70 94.52 73.12 36.22 77.01 98.75 99.99 0.72

KIC 1.06 3.93 0.20 7.07 0.94 11.96 1.93 5.87 79.46 0.01
Langmuir§ [6] AIC 0.00 0.01 0.00 2.54 15.62 27.64 0.21 0.00 0.00 72.57

AICC 0.00 0.01 0.00 2.61 17.40 41.16 0.26 0.00 0.00 98.34

BIC 0.00 0.01 0.00 2.53 15.44 27.37 0.21 0.00 0.00 70.50

KIC 0.00 0.00 0.00 15.80 12.57 12.96 0.01 0.00 2.62 14.42
RP§ [7] AIC 97.41 11.46 94.81 2.66 10.43 35.79 22.31 1.13 0.01 26.70

AICC 75.51 1.05 25.07 0.05 0.21 4.37 2.30 0.02 0.00 0.66

BIC 97.47 11.74 95.30 2.95 11.44 36.41 22.78 1.25 0.01 28.78
KIC 98.94 96.06 99.80 77.14 86.50 75.08 98.06 94.13 17.92 85.57
† Weighted calibration.
‡ Redlich–Peterson model.
§ Unweighted calibration.

Table A4 Estimated parameters of binary-component isotherm models and associated

relative standard deviation (RSD).
Bet Dagan Yatir Windsor Olivier Webster
Model Parameter
Value RSD Value RSD Value RSD Value RSD Value RSD

Modified Langmuir† ηi 0.30 0.73 0.48 1.53 1.24 0.11 0.78 0.16 0.44 0.12
[13] ηj 0.49 0.77 1.00 0.48 0.62 0.09 0.64 0.17 1.58 0.10
Ki 0.05 0.50 0.32 0.64 3.32 0.13 8.37 0.13 44.04 0.13
Extended Langmuir†
Kj 0.02 0.50 0.02 0.61 5.67 0.13 14.60 0.14 12.21 0.12
[14]
qm 5.36 0.13 12.45 0.07 4.27 0.07 11.75 0.06 13.58 0.05

SRS†‡ [15] αij 0.18 0.27 0.03 0.37 1.20 0.21 1.55 0.19 0.24 0.18
ηi 0.33 0.17 0.19 0.30 0.85 0.08 0.14 0.10 0.35 0.13
Modified RP† [16]
ηj 0.18 0.18 0.68 0.45 0.36 0.06 0.02 0.10 0.58 0.13

Modified Langmuir§ ηi 0.15 2.06 0.50 0.18 1.75 0.09 0.90 0.10 0.75 0.29
[13] ηj 0.18 2.04 2.03 0.18 0.84 0.05 0.67 0.12 0.62 0.23
Ki 0.04 0.57 0.03 0.43 1.08 0.12 1.64 0.14 10.76 0.14
Extended Langmuir§
Kj 0.02 0.54 0.01 0.38 2.96 0.14 3.69 0.15 3.25 0.13
[14]
qm 5.36 0.12 15.75 0.07 5.33 0.06 20.32 0.08 20.50 0.07

SRS§ [15] αij 0.40 0.31 0.12 0.20 1.25 0.13 2.06 0.13 0.27 0.16
ηi 0.37 0.16 0.35 0.13 0.75 0.08 0.85 0.08 0.69 0.27
Modified RP§ [16]
ηj 0.20 0.14 0.94 0.15 0.85 0.04 0.36 0.06 0.60 0.20
† Weighted calibration.
‡ Sheindorf–Rebhun–Sheintuch model.
§ Unweighted calibration.

www.soils.org/publications/sssaj 1243
Table A5. Model information criteria and posterior model weights for binary-component isotherms.
NLL and model information criteria Posterior model weights, %
Model
Model identification Bet Dagan Yatir Windsor Olivier Webster Bet Dagan Yatir Windsor Olivier Webster
criterion
Cu–Zn Cu–Zn Cd–Ni Cd–Ni Cd–Ni Cu–Zn Cu–Zn Cd–Ni Cd–Ni Cd–Ni

NLL 246.34 543.58 1822.18 7227.43 12,526.30

AIC 250.34 547.58 1826.18 7233.43 12,530.30 0.00 0.00 0.00 0.00 0.00
Modified
Langmuir† AICC 250.34 547.58 1826.18 7233.43 12,530.30 0.00 0.00 0.00 0.00 0.00
[13]
BIC 252.12 549.36 1830.08 7239.40 12,534.20 0.00 0.00 0.00 0.00 0.00

KIC 258.41 551.25 1836.44 7235.21 12,540.30 0.00 0.00 0.00 0.00 0.00

NLL 113.06 331.58 633.18 9142.43 7,933.25

AIC 119.06 337.58 639.18 9144.43 7,939.25 0.00 99.74 100.00 100.00 100.00
Extended
Langmuir† AICC 120.06 338.58 639.18 9144.43 7,939.25 0.00 99.57 100.00 100.00 100.00
[14]
BIC 121.73 340.25 645.03 9146.42 7,945.22 0.00 99.37 100.00 100.00 100.00

KIC 138.21 349.49 647.22 9147.09 7,937.98 0.00 98.47 100.00 100.00 100.00

NLL 122.85 347.48 1290.18 13136.40 12,236.30

AIC 124.85 349.48 1292.18 13140.40 12,238.30 0.00 0.26 0.00 0.00 0.00

SRS†‡ [15] AICC 124.85 349.48 1292.18 13140.40 12,238.30 0.00 0.43 0.00 0.00 0.00

BIC 125.74 350.37 1294.13 13144.40 12,240.20 0.00 0.63 0.00 0.00 0.00

KIC 130.02 357.82 1295.02 13161.80 12,244.70 0.00 1.53 0.00 0.00 0.00

NLL 90.23 426.28 824.18 7227.43 16,006.30

AIC 94.23 430.28 828.18 7233.43 16,010.30 100.00 1.53 0.00 0.00 0.00
Modified RP†
AICC 94.23 430.28 828.18 7233.43 16,010.30 100.00 0.00 0.00 0.00 0.00
[16]
BIC 96.01 432.06 832.08 7239.40 16,014.20 100.00 0.00 0.00 0.00 0.00

KIC 105.90 437.53 841.54 7235.21 16,022.10 100.00 0.00 0.00 0.00 0.00

NLL 130.03 144.53 –290.84 –238.14 –194.50

AIC 134.03 148.53 –286.84 –234.14 –190.50 0.00 56.96 0.00 0.00 0.00
Modified
Langmuir§ AICC 134.03 148.53 –286.84 –234.14 –190.50 0.00 62.58 0.00 0.00 0.00
[13]
BIC 135.81 150.31 –282.94 –230.16 –186.52 0.00 62.05 0.00 0.00 0.00

KIC 141.13 154.51 –276.29 –223.72 –182.69 0.02 92.41 0.00 0.00 0.00

NLL 115.70 144.35 –331.40 –334.97 –349.35

AIC 121.70 150.35 –325.40 –328.97 –343.35 0.98 22.85 24.03 60.51 100.00
Extended
Langmuir§ AICC 122.70 151.35 –325.40 –328.97 –343.35 0.60 15.23 24.03 60.51 100.00
[14]
BIC 124.37 153.03 –319.54 –323.01 –337.38 0.63 15.95 4.30 17.33 99.98

KIC 141.96 172.76 –312.02 –319.51 –338.35 0.02 0.01 0.25 5.18 100.00

NLL 132.02 3964.84 –329.70 –330.12 –323.81

AIC 134.02 3966.84 –327.70 –328.12 –321.81 0.00 0.00 75.97 39.49 0.00

SRS§ [15] AICC 134.02 3966.84 –327.70 –328.12 –321.81 0.00 0.00 75.97 39.49 0.00

BIC 134.91 3967.73 –325.75 –326.13 –319.82 0.00 0.00 95.70 82.67 0.02

KIC 137.33 3973.42 –323.98 –325.33 –315.37 0.16 0.00 99.75 94.82 0.00

NLL 108.47 146.60 –293.58 824.18 –202.85

AIC 112.47 150.60 –289.58 828.18 –198.85 99.02 20.20 0.00 0.00 0.00
Modified RP§
AICC 112.47 150.60 –289.58 828.18 –198.85 99.40 22.19 0.00 0.00 0.00
[16]
BIC 114.25 152.38 –285.68 832.08 –194.88 99.37 22.00 0.00 0.00 0.00

KIC 124.44 159.51 –276.87 841.54 –190.43 99.80 7.58 0.00 0.00 0.00

† Weighted calibration.
‡ Sheindorf–Rebhun–Sheintuch model.
§ Unweighted calibration.

1244 Soil Science Society of America Journal

REFERENCES
Akaike, H. 1974. A new look at statistical model identification. IEEE T. Automat.
Contr. AC 19:716–723. doi:10.1109/TAC.1974.1100705
Ballio, F., and A. Guadagnini. 2004. Convergence assessment of numerical
Monte Carlo simulations in groundwater hydrology. Water Resour. Res.
40:W04603 10.1029/2003WR002876. doi:10.1029/2003WR002876
Barrow, N.J. 1983. A mechanistic model for describing the sorption and desorption of
phosphate. J. Soil Sci. 34:733–750. doi:10.1111/j.1365-2389.1983.tb01068.x
Barrow, N.J. 1989. Testing a mechanistic model. IX. Competition between anions
for sorption by soil. J. Soil Sci. 40:415–425. doi:10.1111/j.1365-2389.1989.
tb01284.x
Barrow, N.J. 2008. The description of sorption curves. Eur. J. Soil Sci. 59:900–
910. doi:10.1111/j.1365-2389.2008.01041.x
Barrow, N.J., P. Cartes, and M.L. Mora. 2005. Modification to the Freundlich
equation to describe anion sorption over a large range and to describe
competition between pairs of ions. Eur. J. Soil Sci. 56:601–606.
doi:10.1111/j.1365-2389.2005.00700.x
Bellot, J.C., and J.S. Condoret. 1993. Modelling of liquid chromatography
equilibrium. Process Biochem. 28:365–376. doi:10.1016/0032-
9592(93)80023-A
Bolster, C.H. 2008. Revisiting a statistical shortcoming when fitting the
Langmuir model to sorption data. J. Environ. Qual. 37:1986–1992.
doi:10.2134/jeq2007.0461
Carrera, J., and S.P. Neuman. 1986. Estimation of aquifer parameters under
transient and steady state conditions: 1. Maximum likelihood method
incorporating prior information. Water Resour. Res. 22(2):199–210.
doi:10.1029/WR022i002p00199
Dişli, E. 2010. Batch and column experiments to support heavy metals (Cu, Zn,
and Mn) transport modeling in alluvial sediments between the Mogan
Lake and the Evmir Lake, Gölbasi, Ankara. Ground Water Monit. Rem.
30(3):125–139. doi:10.1111/j.1745-6592.2010.01302.x
Doherty, J. 2002. PEST: Model independent parameter estimation, user manual.
4th ed. Watermark Numer. Computing, Corinda, Queensland.
Foglia, L., S.W. Mehl, M.C. Hill, P. Perona, and P. Burlando. 2007. Testing
alternative ground water models using cross-validation and other methods.
Ground Water 45(5):627–641. doi:10.1111/j.1745-6584.2007.00341.x
Freundlich, H.M.F. 1906. Over the sorption in solution. J. Phys. Chem. 57:385–470.
Hoeting, J.A., D. Madigan, A.E. Raftery, and C.T. Volinsky. 1999. Bayesian
model averaging: A tutorial. Stat. Sci. 14(4):382–417. doi:10.1214/
ss/1009212519
Hurvich, C.M., and C.L. Tsai. 1989. Regression and time series model selection in
small sample. Biometrika 76(2):297–307. doi:10.1093/biomet/76.2.297
Kashyap, R.L. 1982. Optimal choice of AR and MA parts in autoregressive
moving average models. IEEE T. Pattern. Anal. 4(2):99–104. doi:10.1109/
TPAMI.1982.4767213
Langmuir, I. 1918. The sorption of gases on plane surfaces of glass, mica and
platinum. J. Am. Chem. Soc. 40:1361–1403. doi:10.1021/ja02242a004
Li, X., and F.T.C. Tsai. 2009. Bayesian model averaging for groundwater
head prediction and uncertainty analysis using multimodel and
multimethod. Water Resour. Res. 45:W09403 10.1029/2008WR007488.
doi:10.1029/2008WR007488
Liao, L., and H.M. Selim. 2009. Competitive sorption of nickel and cadmium in
different soils. Soil Sci. 174:549–555. doi:10.1097/SS.0b013e3181bbbd27
Neuman, S.P. 2003. Maximum likelihood Bayesian averaging of alternative
conceptual-mathematical models. Stoch. Env. Res. Risk A. 17(5):291–305.
doi: 10 D 1007/s00477-003-0151-7.
Neuman, S.P., and P.J. Wierenga. 2003. A comprehensive strategy of
hydrogeologic modeling and uncertainty analysis for nuclear facilities
and sites. NUREG/CR-6805. U.S. Nuclear Regulatory Commission,
Washington, DC.
www.soils.org/publications/sssaj
Neuman, S.P., L. Xue, M. Ye, and D. Lu. 2011. Bayesian analysis of data-worth
considering model and parameter uncertainty. Adv. Water Resour.
10.1016/j.advwatres.2011.02.007.
Ofomaja, A.E., E.I. Unuabonah, and N.A. Olada. 2010. Competitive modeling
for the biosorptive removal of copper and lead ions from aqueous solution
by Mansonia wood sawdust. Bioresour. Technol. 101:3844–3852.
doi:10.1016/j.biortech.2009.10.064
Redlich, O., and D.L. Peterson. 1959. A useful sorption isotherm. J. Phys. Chem.
63:1024. doi:10.1021/j150576a611
Riva, M., M. Panzeri, A. Guadagnini, and S.P. Neuman. 2011. Role of model
selection criteria in geostatistical inverse estimation of statistical
data- and model- parameters. Water Resour. Res. 47:W07502.
doi:10.1029/2011WR010480
Roy, W.R., J.J. Hassett, and R.A. Griffin. 1986. Competitive interactions of
phosphate and molybdate on arsenate adsorption. Soil Sci. 142:203–210.
doi:10.1097/00010694-198610000-00003
Saha, U.K., S. Taniguchi, and K. Sakurai. 2002. Simultaneous
adsorption of cadmium, zinc, and lead on hydroxyaluminum- and
hydroxyaluminosilicate-montmorillonite complexes. Soil Sci. Soc. Am. J.
66:117–128. doi:10.2136/sssaj2002.0117
Schwarz, G. 1978. Estimating the dimension of a model. Ann. Stat. 6(2):461–464.
Sheindorf, C., M. Rebhun, and M. Sheintuch. 1981. A Freundlich-type
multicomponent isotherm. J. Colloid Interface Sci. 79:136–141.
doi:10.1016/0021-9797(81)90056-4
Sibbesen, E. 1981. Some new equations to describe phosphate sorption by soils. J.
Soil Sci. 32:67–74. doi:10.1111/j.1365-2389.1981.tb01686.x
Srivastava, P., B. Singh, and M. Angove. 2005. Competitive adsorption behavior
of heavy metals on kaolinite. J. Colloid Interface Sci. 290:28–38.
doi:10.1016/j.jcis.2005.04.036
Srivastava, V.C., I.D. Mall, and I.M. Mishra. 2008. Antagonistic competitive
equilibrium modeling for the sorption of ternary metal ion mixtures from
aqueous solution onto Bagasse fly ash. Ind. Eng. Chem. Res. 47:3129–
3137. doi:10.1021/ie0709842
Tellinghuisen, J. 2009. Variance function estimation by replicate analysis and
generalized least squares: A Monte Carlo comparison. Chemom. Intell.
Lab. Syst. 99:138–149. doi:10.1016/j.chemolab.2009.09.001
Tellinghuisen, J., and C.H. Bolster. 2010. Least-squares analysis of phosphorus
soil sorption data with weighting from variance function estimation:
A statistical case for the Freundlich isotherm. Environ. Sci. Technol.
44:5029–5034. doi:10.1021/es100535b
Tsai, F.T.C., and X. Li. 2008. Inverse groundwater modeling for hydraulic
conductivity estimation using Bayesian model averaging and variance
window. Water Resour. Res. 44:W09434 10.1029/2007WR006576.
doi:10.1029/2007WR006576
Tsai, F.T.C., and X. Li. 2010. Reply to comment by Ming Ye et al. on ‘‘Inverse
groundwater modeling for hydraulic conductivity estimation using
Bayesian model averaging and variance window’’. Water Resour. Res.
46:W02802. doi:10.1029/2009WR008591
Winter, C.L., and D. Nychka. 2010. Forecasting skill of model averages. Stochastic
Environ. Res. Risk Assess. 24:633–638. doi:10.1007/s00477-009-0350-y
Yang, R.T. 1987. Gas separation by sorption processes. Butterworths, Boston, MA.
Ye, M., D. Lu, P.D. Meyer, and S.P. Neuman. 2010. Comment on “Inverse
groundwater modeling for hydraulic conductivity estimation using
Bayesian model averaging and variance window” by Frank T.-C. Tsai and
Xiaobao Li. Water Resour. Res. 46:W02801.
Ye, M., P.D. Meyer, and S.P. Neuman. 2008. On model selection criteria in multimodel
analysis. Water Resour. Res. 44:W03428. doi:10.1029/2008WR006803
Ye, M., S.P. Neuman, and P.D. Meyer. 2004. Maximum likelihood Bayesian
averaging of spatial variability models in unsaturated fractured tuff. Water
Resour. Res. 40(5):W05113. doi: 10 1029/2003WR002557.
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