Journal of Colloid and Interface Science 286 (2005) 596–601

www.elsevier.com/locate/jcis

Adsorption of several metal ions onto a model soil sample:

Equilibrium and EPR studies
Karine Flogeac, Emmanuel Guillon ∗ , Michel Aplincourt
GRECI (Groupe de Recherche en Chimie Inorganique), Université de Reims Champagne-Ardenne, B.P. 1039, F-51687 Reims cedex 2, France
Received 27 August 2004; accepted 21 January 2005
Available online 9 March 2005

Abstract
Soils play an important role in the control of metallic cations in the environment. Therefore, knowledge of the adsorption properties of soil
is crucial in understanding and solving pollution problems. Adsorption isotherms provide a macroscopic view of the retention phenomena.
The aim of this paper is to study iron, manganese, and chromium adsorption onto a soil sample as a function of the reaction time, pH, and
metal concentration. The adsorption isotherms allow the determination of the affinity order of metals for the surface of the soil sample as
such: Fe3+ > Cr3+ > Mn2+ . The equilibrium data fit well with the Langmuir and Freundlich models and confirm the affinity order of the
soil sample for these metals. These adsorption data are combined with EPR spectroscopy to obtain structural information about the surface
complexes formed. Iron is held in inner-sphere complexes. Manganese is simultaneously held in outer- and inner-sphere complexes. Due to
poor resolution, chromium was not detected by EPR and thus it is impossible to infer coordination sphere and coordination number. Iron and
manganese are in an octahedral environment.
 2005 Elsevier Inc. All rights reserved.

Keywords: Soil; Iron; Manganese; Chromium; Adsorption isotherms; EPR

1. Introduction plays a significant role in the type, strength, and reversibility

Metals, especially transition metals, complexed or not,
present a particular risk because, in contrast to many pol-
lutants (organic compounds), they are stable in the en-
vironment (i.e., no degradation). Consequently, retention
processes at liquid–solid interfaces play a major role in envi-
ronmental studies, especially in the control of metallic cation
transport toward surface and ground waters [1,2]. Therefore,
a complete understanding of the availability of long-term
pollutants depends on our knowledge of the adsorption re-
actions taking place at the soil surfaces.
In natural environments, many sorbent phases are able
to adsorb metal ions such as metal oxides and oxyhydrox-
ides, clay minerals, and organic matter. The sorbent phase
* Corresponding author. Fax: +33(0)3-26-91-32-43.
E-mail address: emmanuel.guillon@univ-reims.fr (E. Guillon).
0021-9797/$ – see front matter  2005 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2005.01.027
of the metal complexes formed and, thus, determines if the
metal ion is immobilized or leached. This is why many stud-
ies established the importance of independent surfaces in the
retention of metals [3–8], such as organic matter (lignocel-
lulosic substrate, humic substances), goethite, gibbsite, and
silica.
The metal ions investigated in this study are iron, man-
ganese, and chromium. In small quantities, iron and man-
ganese are necessary for living organisms. However, in areas
where the level of metals is important because of ore smelt-
ing, land application of biosolids, or other anthropogenic
processes, metals are often a detriment to the environment.
Chromium is a metal used in various industrial processes:
tanneries, cement industries, plating and alloying industries,
and corrosive paints [9]. Chromium, in its trivalent form,
is an essential trace element for plants and animals: it is
involved in glucose metabolism and nucleic acid synthe-
sis [10]. However, chromium(III) has also been shown to
 K. Flogeac et al. / Journal of Colloid and Interface Science 286 (2005) 596–601
be a potential hazard, especially in the aquatic environment.
Indeed, in vitro tests showed that trivalent chromium is a po-
tential toxin because it is a competitive inhibitor of many
cellular processes [11].
The present paper aims at studying the adsorption of
iron, manganese, and chromium onto a soil sample from
the Champagne–Ardenne region (France) as a function of
the reaction time, pH, and metal concentration. This study
is combined with electronic paramagnetic resonance (EPR)
spectroscopy to characterize the geometry of the surface
complexes formed.
2. Materials and methods
2.1. Reagents
KNO3 , HNO3 , and KOH were obtained in the purest
commercially available grade (Prolabo for KNO3 , Fluka
for HNO3 and KOH) and used without further purifica-
tion. Ferric nitrate (Fe(NO3 )3 ·9H2 O), manganese nitrate
(Mn(NO3 )2 ·4H2 O), and chromium nitrate (Cr(NO3 )3 ·6H2 O)
were purchased from Fluka.
2.2. Soil sample extraction
The soil sample was extracted from the Champagne–
Ardenne region (France), which is known to be a calcare-
ous region. The sample was dried at 293 K and sieved at
<100 µm. The crude solid was suspended at 293 K for 24 h
in chloroform (10 ml per gram), essentially to extract free
lipids. After filtration, the residue was mixed for 24 h with
a 1 mol L−1 HCl solution (10 ml per gram) to eliminate
carbonates, sulfates, adsorbed metals, and hydroxides. Af-
ter a new filtration and a water wash, necessary to obtain
a neutral pH, an alkali treatment was implemented (NaOH
0.1 mol L−1 , 10 ml per gram) for 6 h to make humic and
fulvic acids soluble. Then, the insoluble solid obtained was
stirred in a nitric acid solution (5 × 10−2 mol L−1 , 10 ml
per gram) to saturate the proton surface sites and vacuum-
dried. These treatments allowed a quasi-insoluble solid ad-
sorbent in the pH range studied (2–10), which is a neces-
sary condition for further metallic cation adsorption experi-
ments. The solid was air-dried and ground to pass a 100-µm
sieve.
The chemical composition and structure of the soil sam-
ple, after treatment, are detailed elsewhere [12]. Briefly, the
site density was estimated by potentiometric titrations to be
equal to 3.2 sites/nm2 , and the specific surface area deter-
mined by the BET method (N2 , 77 K) was 33.5 m2 g−1 . An
X-ray diffraction (XRD) analysis identified the solid as sil-
ica (SiO2 , 60%), illite and smectite (27%), kaolinite (6%),
goethite (α-FeOOH, 5%), and rutile (TiO2 , 2%) for the min-
eral phase. The organic fraction represented 5% of the total
composition of the soil particles.
597
2.3. Adsorption experiments
All experiments were carried out at a fixed ionic strength
of 0.1 mol L−1 KNO3 . Two different types of adsorption ex-
periments were conducted: variable pH and variable metal
concentration. Both studies were conducted using batch ex-
periments at room temperature (293 K).
For the adsorption studies as a function of the pH, the
soil sample (2 g L−1 ) was immersed in 15 ml of background
electrolyte solution and stirred using a magnetic stir bar for
4 h, which corresponds to the hydration time of the solid. Af-
ter this pre-equilibration step, the metallic cation was added
at a concentration of 2 × 10−4 mol L−1 , and the pH was in-
crementally adjusted to a fixed value by dropwise addition
of 0.1 mol L−1 HNO3 or 0.1 mol L−1 KOH. The final vol-
ume was adjusted to 25 ml. The flasks were then shaken
with an automatic shaker at 293 K for the time necessary
to ensure complete adsorption. After filtration through a
0.20-µm polyamide membrane, the supernatants were acidi-
fied and the unsorbed metal ion concentration was measured
by a Varian ICP-AES spectrometer. The amount of metal ad-
sorbed was deduced from the initial concentration.
The adsorption equilibrium was predetermined by kinetic
experiments in which different contact times between the
metal and the solid were applied at a constant pH value. The
experimental pH was taken to be the pH measured after the
reaction time.
The adsorption isotherms as function of metal concen-
tration experiments were carried out in the same way at a
fixed pH value (3.2 for iron, 7.7 for manganese, and 5.0 for
chromium) with a metal concentration ranging from 10 to
1500 µmol L−1 .
2.4. Adsorption isotherms
The equilibrium data were analyzed in accordance with
the Langmuir and Freundlich sorption isotherms. These
isotherms allow to describe adsorption phenomena of met-
als from aqueous solution onto soil sample.
The Langmuir isotherm is expressed by
Ce Ce 1
= max + max with Cs = Kd Ce , (1)
Cs Cs Cs b
where Kd is the distribution coefficient that characterizes
the affinity of the metal for the sorbent, Csmax is the maxi-
mum adsorption capacity of the solid corresponding to com-
plete monolayer coverage, Ce is the measured concentra-
tion (µmol L−1 ) of metal in solution when the equilibrium
is reached, Cs is the measured adsorption per unit weight
of solid (µmol g−1 ), and b represents the Langmuir bond-
ing term (L µmol−1 ) related to the adsorption energy. The
Freundlich isotherm, which assumes that different sites with
several adsorption energies are involved, is expressed by
log Cs = log KF + n log Ce , (2)
598 K. Flogeac et al. / Journal of Colloid and Interface Science 286 (2005) 596–601
where KF is the Freundlich distribution coefficient related to
the total adsorption capacity of the solid, and n is a nonlinear
constant.
2.5. EPR experiments
The solid state EPR spectra were obtained with a Bruker
ELEXYS 500 spectrometer operating at an X-band fre-
quency with a 100-kHz modulation frequency. The spectra
were recorded in the following conditions: microwave power
1 mW for chromium and 15 mW for iron and manganese;
modulation amplitude 0.4 mT. The spectra were carried out
at 10, 77, and 298 K for the iron, chromium, and manganese
complexes, respectively. The soil sample was also recorded,
for comparison, at each temperature. Simulations of the EPR
spectrum were performed using WINSYMPHONIA Bruker
software package.
3. Results and discussion
3.1. Adsorption experiments
Kinetic experiments were first carried out to determine
the equilibrium time of the complexation reaction between
iron, manganese or chromium, and the soil sample. The ki-
netic of each metal adsorption was studied by varying the
contact time from 5 min to 48 h. The adsorption equilibrium
was reached in 10 h for iron and manganese and in 24 h for
chromium. These results agree with several previous studies
on metal adsorption [13–15]. Several mechanisms have been
postulated to explain this slow uptake [13,15]. The most
likely is that in the first hours of the adsorption process, an
equilibrium is reached between the adsorbed metal amount
and the metal cation amount in solution (fast process). Then,
formation of polynuclear complexes, diffusion into the soil
sample, and surface precipitation could occur. In order to
obtain a complete adsorption of the metals, and for practical
reasons, the experiments were carried out with an equilib-
rium time equal to one night for iron and manganese, and
24 h for chromium.
The effect of the solution pH on the adsorption of met-
als is reported in Fig. 1. Adsorption of metals is strongly
dependent on the pH, increasing when the pH of the solu-
tion increases. The adsorption edge is different from each
metal. Indeed, the adsorption begins around pH 2.0 for iron,
2.5 for chromium, and 6.0 for manganese. The adsorption of
the metallic cations by the soil sample occurs in a relatively
narrow pH range (around 2 pH units). The affinity of each
metal ion is reflected in the percentage adsorption obtained
at a fixed pH. Thus, in all the pH range, the order of affinity
was Fe3+ > Cr3+ > Mn2+ . More generally, with increasing
pH, the adsorption edges were reached for Fe3+ , Cr3+ , and
Mn2+ in this sequence. These results were compared with
the precipitation of metals to ensure that no hydrolysis and
Fig. 1. Chromium, manganese, and iron adsorption on the soil sample
(2 g L−1 ) as a function of pH at 293 K in KNO3 0.1 mol L−1 medium,
with [Mn+ ] = 2 × 10−4 mol L−1 . Points on the continuous lines represent
the metal cation precipitation curves (without solids).
Fig. 2. Chromium, manganese, and iron adsorption isotherms on the soil
sample (2 g L−1 ) at 293 K.
only surface complexation occurred. The fact that the ad-
sorption edge systematically occurred at a pH value lower
than that of the metal cation precipitation, confirms the sur-
face complexation and rules out the metal hydroxide surface
precipitation. Consequently, in order to avoid metal hydroly-
sis processes at the surface, pH values equal to 3.2, 5.0, and
7.7 were chosen for isotherm experiments as a function of
the metal concentration for iron, chromium, and manganese,
respectively.
The adsorption isotherms of metal ions onto soil sam-
ples are reported in Fig. 2. These isotherms can be subdi-
vided in three parts. In the low-concentration part, the metal
introduced is quantitatively adsorbed. In the intermediate
part, there is a plateau or a pseudo-plateau, which prob-
ably corresponds to the saturation of the surface or to a
co-precipitation phenomenon (i.e., sorption and precipita-
tion simultaneously). In the larger concentration part, the
amount of metal adsorbed increases again with the concen-
tration of the metal ion introduced, corresponding to a sur-
face precipitation. Equilibrium adsorption experiments were
performed to provide the maximum metal adsorption capaci-
ties of the soil sample and the presence of a plateau indicates
that this maximum adsorption capacity has been reached.
This capacity can be estimated at 8 mg g−1 (155 µmol g−1 )
for chromium, 4 mg g−1 (70 µmol g−1 ) for manganese, and
 K. Flogeac et al. / Journal of Colloid and Interface Science 286 (2005) 596–601
(a)
(b)
Fig. 3. Langmuir adsorption (a) and Freundlich adsorption (b) isotherms for
Cr3+ adsorption on soil sample (2 g L−1 ) at 293 K.
Table 1
Langmuir and Freundlich parameters for chromium, manganese, and iron
adsorption onto soil sample (2 g L−1 ) at 293 K
Langmuir Freundlich
Csmax (µmol/g) b (L/µmol) r2 KF (g/L) n
Chromium 151.0 8.4 × 10−3 0.967 3.05
Manganese 77.5 8.8 × 10−3 0.993 1.15
Iron 104.0 15.0 × 10−3 0.840 6.03
5.5 mg g−1 (100 µmol g−1 ) for iron. These values indicate
that the soil sample presents a significant affinity for metals.
Adsorption isotherms could be mathematically represented
by the Langmuir and Freundlich adsorption isotherms. As
an example, the Langmuir and the Freundlich adsorption
isotherms of chromium are represented in Fig. 3. The Lang-
muir isotherm parameters were deducted for each metal by
performing a linear regression and are reported in Table 1.
The good agreement (r 2 ) with the experimental data sug-
gests that the metal ions sorbed form a monolayer cov-
erage on the adsorbent surface. The sites involved in the
metal sorption are probably the acid moieties from the or-
ganic matter coated onto the mineral phases [12]. In the
case of iron(III), the lower r 2 value may be due to weak
co-precipitation of iron hydroxide. The Freundlich isotherm
parameters are also added for comparison. Generally, to a
lesser extent, the equilibrium data were also well described
by the Freundlich model, probably due to the real hetero-
geneous nature of the soil sample surface sites. However,
adsorption data for each metal ion better fit the Langmuir
model, since the Langmuir isotherms present better cor-
relation coefficient values than the Freundlich model. The
599
Csmax values obtained by the Freundlich isotherms are in
accordance with the experimental data. These values indi-
cate that metal ions are significantly uptaken by the soil
sample in these conditions. Therefore, it implicates low mo-
bility of metal ions in natural environment. As expected
with the experimental isotherms, the greatest equilibrium
fixation capacity Csmax was obtained for Cr3+ ions, that is,
151 µmol g−1 , which decreased to 104 µmol g−1 for Fe3+
and 77.5 µmol g−1 for Mn2+ . This affinity sequence is dif-
ferent from the one deduced for the pH influence. The in-
version of chromium and iron values is probably due to the
co-precipitation phenomenon, which cannot be unambigu-
ously distinguished from the sorption one [14]. It has been
shown, in the case of chromium, the formation of polynu-
clear species since low pH values, which can be sorbed at
the same time than the chromium(III) ion. The values of the
Langmuir bonding term b give an idea of the adsorption in-
tensity. Indeed, the energy of a metallic cation adsorption on
a solid surface increases with b. These values are close to
the ones obtained for the adsorption of metal cations onto
biosorbent [16]. The Freundlich adsorption intensity con-
stants n are similar to constants previously reported [17].
In natural environment, systems are more complicated
because several other parameters govern the adsorption phe-
nomena, and the natural solids are much more complex sys-
tems. But our experiments give some useful pieces of infor-
mation on the retention properties of a model soil sample.
This can be the starting point for the study of a natural sam-
ple without pretreatment.
r2
After the macroscopic studies of metal adsorption onto
0.67 0.966 the soil sample, we carried out molecular-scale studies of
0.46 0.943 surface complexes using EPR spectroscopy, to obtain infor-
0.51 0.779
mation on the geometry of the surface complexes formed.
3.2. EPR experiments
Before recording the spectra of the metal–soil sample
systems, we have recorded the spectrum of the soil sample
alone [12] in order to compare it to the former ones. Fig. 4a
represents the spectrum of the soil sample at 10 K. Briefly,
this spectrum is dominated by high-spin Fe3+ contributions
(d 5 , S = 5/2). We can distinguish at least two types of iron
signal [18,19]. The first one corresponds to some rhombic
iron(III) with an isotropic signal at g = 4.3, originating from
the middle Kramers doublet, and a very weak feature at
g = 9 due to the highest Kramers doublet (Fig. 4b). The
second one corresponds to some nearly tetrahedral or octa-
hedral iron(III) sites giving a resonance at g = 2.1 (Fig. 4c).
The first type of iron ions probably originates from trivalent
iron in the illite/smectite or kaolinite fraction [20], and the
second type originates from the goethite fraction [21]. This
broad signal, at g = 2.1, is difficult to attribute because it
also resembles dipolar couplings. Moreover, another signal
appears around g = 2 (Figs. 4d and 4e). This signal seems
to correspond to a vanadyl porphyrin [22] with an axial g
tensor from S = 1/2 with an hyperfine coupling to an ax-
600 K. Flogeac et al. / Journal of Colloid and Interface Science 286 (2005) 596–601
Fig. 4. EPR spectra at 10 K of soil sample (a), rhombic iron contribution (b),
nearly octahedral iron contribution (c), and vanadyl contribution (d) with an
enlargement of the 350-mT region (e).
Fig. 5. EPR spectrum of iron–soil system at 10 K.
ial A tensor. We can then determine g coupled with a A ,
and g⊥ coupled to A⊥ , arising from a S = 1/2 coupled to a
I = 7/2 nucleus. The Hamiltonian parameters obtained were
g = 1.95, g⊥ = 1.96, A = 16.3 mT, and A⊥ = 5.0 mT.
Superimposed to this spectrum we can observe a narrow
signal at g = 2, which corresponds to an organic free rad-
ical [23] originating from the organic fraction (Fig. 4e).
The metal–soil sample systems for EPR analysis were ob-
tained by stirring a weighted amount (50 mg) of soil sample
with metal solution (2 × 10−4 mol L−1 ) at pH 3.2, 5.0, and
7.7 for iron(III), chromium(III), and manganese(II), respec-
tively.
The EPR spectrum of the Fe-soil system (Fig. 5), recorded
at 10 K, was obtained after subtraction of the soil sample
spectrum recorded at the same temperature. It consists of a
strong band at g = 4.157 (157.0 mT) and a weak signal at
g = 9.586 (64.0 mT). These peaks are characteristics of an
Fe3+ ion in a high-spin state in a tetrahedral or octahedral
site. The symmetry is given by D and E terms, which corre-
spond to the tetragonal and rhombic distortion, respectively.
Fig. 6. EPR spectrum of manganese–soil system at 298 K.
The value of the ratio E/D (D and E are the zero-field
splitting parameters) was found to be 1/3, in accordance
with rhombic symmetry. The spectrum feature is typical of a
FeO4 or FeO6 chromophore. Iron(III) in surface complexes
is held in inner-sphere complexes. A wide signal is also
observed around g = 2 (337.0 mT). It corresponds to iron
hydroxide formed by co-precipitation of metal onto the soil
sample surface [24]. Finally, a narrow band was observed
at g = 2.0045 (335.0 mT); it is assigned to semiquinonic
species from organic fraction of the soil sample. The pres-
ence of this radical signal, after subtraction of the soil sample
spectrum, indicates an increase of the semiquinonic species.
This increase is due to redox processes and electron trans-
fers between the organic radical and the metal center on the
soil sample surface [4]. The phenolic moieties are the main
functions involved in these redox processes [4] and such re-
dox phenomenon may be explained by the fact that iron is
probably adsorbed on the organic matter fraction of the soil
sample.
The EPR spectrum of the Mn–soil system, recorded at
room temperature, is represented in Fig. 6. It was also ob-
tained after subtraction of the soil sample spectrum at the
same temperature. It presents the six-line pattern, character-
istic of a manganese(II) ion with g = 1.979 (350.0 mT). This
spectrum is in accordance with a MnO6 chromophore and
an octahedral environment around the metal cation. In ad-
dition, it is similar to that of the Mn(H2 O)2+ 6 compound.
This shows that the manganese(II) ion is predominantly
bound to the surface acid sites by van der Waals interactions;
i.e., the complex is an outer-sphere complex. The hyper-
fine coupling constant of manganese(II) is equal to 8.2 mT.
This value is particularly high compared to Mn(H2 O)2+ 6
one (2.2 mT). This relatively high value is due to an in-
teraction of Mn(H2 O)2+ 6 ions with the soil sample surface
(outer-sphere complexes) and can also be explained by the
formation of hydroxo species such as Mn(OH)+ that can
bind to the surface sites. So these two species are proba-
bly sorbed on the surface. Moreover, a more precise analysis
of the spectrum shows the presence of several superimposed
hyperfine signals, which indicates the existence of several
sites of complexation for manganese onto the soil sample
surface. Hence, we cannot exclude the formation of some
inner-sphere manganese surface complexes.
 K. Flogeac et al. / Journal of Colloid and Interface Science 286 (2005) 596–601
In the case of chromium(III), the contributions of chrom-
ium could unfortunately not be extracted from the spectrum
of the Cr–soil system because of the poor resolution of this
spectrum.
These data clearly show a significant retention (adsorbed
amount) of iron, chromium, and manganese by the soil sam-
ple surface at different pH values on a case by case basis.
This implies that metal cations are immobilized in soils
and/or are relatively slowly leached towards aquifers. Our
results give a starting point for the comprehension of the
bioavailability of metallic cations in soils and can be used
in geochemical models. However, to fully understand these
processes, further studies examining the influence of pH,
time, and concentration directly onto natural soil samples
need to be assessed.
4. Conclusion
This work allows a better understanding of the role of dif-
ferent physicochemical parameters in metal retention, such
as reaction time, pH, or metal concentration. Indeed, we
showed that the metal adsorption is relatively rapid (less than
24 h). The maximum adsorption is reached around pH 4 for
iron, 5 for chromium, and 8 for manganese. The maximum
amount of metals bound to soil sample was found to be equal
to 77.5 µmol g−1 for manganese, 104 µmol g−1 for iron, and
151 µmol g−1 for chromium. Thus, the sorption experiments
indicated that the soil sample has a great affinity for iron,
manganese, and chromium cations.
We also characterized the surface complexes using EPR
spectroscopy. This study showed that iron forms relatively
stable complexes through inner-sphere complexes while
manganese ions are involved in less stable complexes (mixed
outer- and inner-sphere complexes).
Acknowledgments
We are grateful to the Région Champagne–Ardenne for a
grant to K.F. We also thank Y.M. Frapart (Université René
Descartes, Paris V, UMR 8601, France) for the EPR experi-
ments.
601
References
[1] D.L. Sparks, Environmental Soil Chemistry, Academic Press, London,
1995.
[2] M.F. Hochella, in: M.F. Hochella Jr., A.F. White (Eds.), Mineral–
Water Interface Geochemistry, vol. 23, Mineralogical Society of
America, Washington, DC, 1990, pp. 87–132.
[3] D.R. Roberts, R.G. Ford, D.L. Sparks, J. Colloid Interface Sci. 263
(2003) 364.
[4] P. Merdy, E. Guillon, M. Aplincourt, New J. Chem. 26 (2002)
1638.
[5] E. Guillon, P. Merdy, M. Aplincourt, Chem. Eur. J. 9 (2003) 4479.
[6] K. Xia, A. Mehadi, R.W. Taylor, W.F. Bleam, J. Colloid Interface Sci.
185 (1997) 252.
[7] G.S. Pokrovski, J. Schott, F. Farges, J.L. Hazemann, Geochim. Cos-
mochim. Acta 67 (2003) 3559.
[8] S.E. Fendorf, G.M. Lamble, M.G. Stapleton, M.J. Kelley, D.L. Sparks,
Environ. Sci. Technol. 28 (1994) 284.
[9] R.L. Ramos, A.J. Martinez, R.M.G. Coronado, Water Sci. Technol. 30
(1994) 191.
[10] F.C. Richard, A.C.M. Bourg, Water Res. 25 (1991) 807.
[11] A.R. Walsh, J. O’Halloran, A.M. Gower, Ecotoxicol. Environ. Safety
27 (1994) 168.
[12] K. Flogeac, E. Guillon, M. Aplincourt, E. Marceau, L. Stievano,
P. Beaunier, Y.M. Frapart, Agronomy (2005), in press.
[13] A. Kokorevics, J. Gravitis, E. Chirkova, O. Bikovens, N. Druz, Cell.
Chem. Technol. 33 (1999) 251.
[14] K. Flogeac, E. Guillon, E. Marceau, M. Aplincourt, New J. Chem. 27
(2003) 714.
[15] K. Csoban, M. Parkanyi-Berka, P. Joo, P. Behra, Colloids Surf. A 141
(1998) 347.
[16] Z. Reddad, C. Gerente, Y. Andres, P. Le Cloirec, Environ. Sci. Tech-
nol. 36 (2002) 2067.
[17] J.C. Echeverría, M.T. Morera, C. Mazkiarán, J.J. Garrido, Environ.
Pollut. 101 (1998) 275.
[18] D. Goldfarb, M. Bernardo, K.G. Strohmaier, D.E.W. Vaughan,
H. Thomann, J. Am. Chem. Soc. 116 (1994) 6344.
[19] R.S.T. Manhaes, L.T. Auler, M.S. Sthel, J. Alexandre, M.S.O. Mas-
sunaga, J.G. Carrio, D.R. Dos Santos, E.C. Da Silva, A. Garcia-
Quiroz, H. Vargas, Appl. Clay Sci. 21 (2002) 303.
[20] A.U. Gehring, R. Karthein, Clay Miner. 25 (1990) 303.
[21] A.U. Gehring, A.M. Hofmeister, Clay Miner. 42 (1994) 409.
[22] G.W. Hodgson, B. Hitchon, K. Taguchi, B.L. Baker, E. Peake, Geo-
chim. Cosmochim. Acta 32 (1968) 737.
[23] P. Merdy, E. Guillon, J. Dumonceau, M. Aplincourt, Anal. Chim. Acta
459 (2002) 133.
[24] N. Senesi, G. Sposito, J.P. Martin, Sci. Total Environ. 62 (1987)
241.