ARTICLE IN PRESS

Applied Clay Science xx (2004) xxx – xxx

www.elsevier.com/locate/clay

Copper heterogeneous nucleation on a palygorskitic clay:

an XRD, EXAFS and molecular modeling study
R.A. Alvarez-Puebla a, C. Aisa a, J. Blasco b, J.C. Echeverrı́a a,
B. Mosquera a, J.J. Garrido a,*
a
Departamento de Quı́mica Aplicada, Universidad Pública de Navarra, Campus Arrosadı́a, 31006 Pamplona, Spain
b
ICMA and Departamento de Fı́sica de la Materia Condensada, CSIC and Universidad de Zaragoza, C/Pedro Cerbuna 12,
50009 Zaragoza, Spain

Received 21 June 2002; received in revised form 9 April 2003; accepted 18 September 2003

Abstract

Clay materials play a key role in determining the retention capacity of a soil, and are widely used in waste treatments. One of
the most commonly used is palygorskite. The aim of this research is to determine the chemical species formed by copper when
retained in a clay material, mainly consisting of palygorskite, and find the minimized energy reached by the species adsorbed by
palygorskite. The clay material was put in contact with a copper(II) chloride solution, and after reaching the thermodynamic
equilibrium, the dry residue was analysed by using XRD, X-ray fluorescence (XRF), and extended-X-ray absorption fine-
structure (EXAFS) spectroscopy. Formation of copper hydroxychloride (atacamite, CuCl2.3Cu(OH)2) was studied. Computa-
tional studies, carried out with 890 atoms, showed the formation of an amorphous copper hydroxychloride. However, it seems
probable that the whole precipitate would be firstly amorphous, later becoming crystalline (Ostwald’s rule) in accordance with
XRD and EXAFS data.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Copper; Sorption; Heterogeneous nucleation palygorskite; XRD; EXAFS; Molecular modeling

1. Introduction is rarely found due to isomorphic substitutions in the

Clay materials play a key role in determining the
retention capacity of a soil, and are widely used in
waste treatments. One of the most commonly used is
palygorskite. The ideal mineral formula proposed by
Bradley (1940) for a trioctaedral model is (Si8M-
g5O20(OH)2(OH2)4.4H2O); however, this composition
* Corresponding author. Tel.: +34-948-169601; fax: +34-948-
169606.
E-mail address: j.garrido@unavarra.es (J.J. Garrido).
material.
Formation of transition-metal surface precipitates
during sorption to clay minerals under environmental
conditions may lead to significant long-term stabiliza-
tion of the metal. However, the mechanisms controlling
surface precipitate formation are poorly understood.
Adsorption isotherms reflect the phenomena that take
place in the retention process (Echeverrı́a et al., 1998),
but they do not give information about the species
formed. Applying experimental techniques to the study
of surfaces give us the mineralogical species formed in
the surface (X-ray diffraction); metal distribution on

0169-1317/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2003.09.002

CLAY-00886; No of Pages 8
 ARTICLE IN PRESS
2 R.A. Alvarez-Puebla et al. / Applied Clay Science xx (2004) xxx–xxx

the surface (X-ray fluorescence); as well as the coor- characterized to determine: (i) chemical composition
dination number and distances around the photoad- by atomic absorption spectrophotometry (AAS) after
sorbing atom (extended-X-ray absorption fine-stru- alkaline fusion a 1273 K; (ii) mineralogical composi-
cture, EXAFS). tion (Rigaku D/max B X-ray diffractometer); (iii)
A detailed treatment on EXAFS can be found in cationic exchange capacity (López Ritas and López
the work of Koningsberger and Prins (1988). Many Melida, 1990); (iv) porous texture by N2 (77 K) and
researchers have often applied this technique to study CO2 (273 K) adsorption and mercury porosimetry
the retention and distribution of cations in different (Echeverrı́a et al., 1999); (v) surface topography and
materials. O’Day et al. (1994) identified complexes of microanalysis by scanning electronic microscopy
cobalt strongly bound to kaolinite. Reich et al. (1998) (JEOL JSM 6400 mod. 6210) equipped with an
studied the sorption of uranium(VI) onto silica gel and EDAX system (Link Analytical Pentaler Oxford,
ferrihydrite, Korshin et al. (1998) studied the most EXL-10). Selected physical and chemical character-
stable structures formed during the sorption of copper istics of the clay material are listed in Table 1.
on humic acid. Zhang et al. (2001) studied the The adsorption experiments were performed at 10
adsorption process of barium on montmorillonite. copper initial concentrations in the range 0– 31.5 mM,
Another approach is to apply computational techni- in aqueous solution, and temperature 298.0 F 0.2 K.
ques to perform theoretical studies at nanochemical For each isotherm point, 0.5000 F 0.0003 g of the
level (Schulten and Leinweber, 2000). Molecular me- palygorskitic material were placed in 50 ml polyeth-
chanics (MM) is based on Newtonian mechanics and ylene centrifuge tubes, the corresponding volume of a
has the advantage of being able to work with very large 2000 mg l 1 CuCl2 stock solution (Merck, Darm-
systems and gives the equilibrium geometry with stadt, Germany) to obtain the desired total concentra-
reasonable precision (Kubicki and Apitz, 1999). Mole- tion of Cu and distilled water was added to get a final
cular dynamic (MD) simulations introduce time and volume of 12.5 ml. The equilibrium pH was measured
temperature into the calculations, which allow the sys- after 24 h. Suspensions were centrifuged at 9000  g
tem to sample configurations that energy minimization for 5 min. Sub-samples of the supernatants were
calculations might not be able to sample due to poten- directly injected into a Malvern Zetasizer 3000 instru-
tial energy barriers (Gunstered and Berendsen, 1990). ment (Malvern Instruments, Malvern, UK); the ap-
The aim of this research was to determine the plied voltage was 100 V through 5-cm quartz cell.
chemical species formed by copper when retained by
a clay material mainly constituted by palygorskite, and Table 1
to find the most stable energy reached by the species Selected physical and chemical characteristics of the clay material
adsorbed by palygorskite. The clay material was put in Chemical composition (%) SiO2 57.1
contact with a copper solution, and after the thermo- Al2O3 18.3
Fe2O3 5.8
dynamic equilibrium was reached, the suspension was MgO 5.5
centrifuged. The dry residue was analysed by XRD to K2O 1.0
reveal the presence of new chemical species, by X-ray CaO 0.5
fluorescence (XRF) spectroscopy to check out the hete- Na2O 0.5
rogeneous distribution of the metal on the surface and, TiO2 0.1
H2O 9.9
by EXAFS to corroborate the chemical species formed Total 98.7
by the Cu. Finally, the sorption and precipitation Mineralogical composition (%) Palygorskite 51
processes were simulated using energy minimization Illite 22
and molecular dynamics computational techniques. Quartz 18
Smectite 5
Kaolinite 3
Calcite <1
2. Experimental CEC (meq kg 1 ) 361
BET surface areaa (BET) (m2 g 1
) 122
The selected material, extracted from the Perdi- pH 8.0
a
guera hill (Segovia, Spain) palygorskitic deposit, was Obtained from N2 adsorption at 77 K.
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R.A. Alvarez-Puebla et al. / Applied Clay Science xx (2004) xxx–xxx
Supernatant not used for electrophoretic measurement
was vacuum filtered (Millipore, 0.45 Am) and copper
concentrations in supernatants were analysed by AAS,
Perkin-Elmer mod. 2100 (Perkin-Elmer, Überlingen,
Germany). The amount of Cu retained was obtained
from the difference between the initial and equilibri-
um concentrations.
To make sure the formation of a new phase that
could be detected by EXAFS and XRD, 10.0-g
samples of clay were suspended in 250 ml of 31.5
mM copper chloride solution. Suspensions were
placed in a thermostated water bath, Grant Mod.
SS40-2 at 3 Hz during 24 h, sufficient time to reach
the thermodynamic equilibrium. The amount of Cu
retained was 365 mmol kg 1. The residue was dried
at 378 K to perform the rest of the research.
The samples were air-dried at 333 K before carry-
ing out the X-ray powder diffraction by orientated
aggregated method. The patterns were collected using
a Rigaku D/max-B instrument with a copper rotating
anode and a graphite monochromator to select the Cu
Ka wavelength. The device was working at 40 kV and
100 mA. The measurements were carried out in step-
scanned mode from 2j V 2h V 60 j in steps of 0.031
with a counting rate of 1 s step 1. The phase
identification was performed by matching the exper-
imental powders with the powder diffraction files of
the International Centre for Diffraction Data (Joint
Committee on Powder Diffraction Standards, 1986),
and the data given by Brindley and Brown (1984), and
Wells (1984).
The micrographs of the clay and clay – copper
system were obtained by SEM, in the experimental
conditions described by Humphries (1992). We used a
JEOL JSM 6400 mod. 6210 microscope, equipped
with an EDAX system (EXL-10) from Link Analyt-
ical Pentaler (Oxford, United Kingdom). The Cu K-
edge XAFS measurements were carried out at the
EXAFS National Service (Zaragoza, Spain). The
source was a rotating anode X-ray generator (Rigaku
RU-300, 18 kW). A bent crystal of Ge (220) was used
as monochromator. The anode, the bent crystal and
the receiving slit were held on a Rowland circle with
R = 320 mm. The device was working at 25 kV and
120 mA using a gold anode. A divergence slit of 11
and a receiving slit of 0.1 mm were used. The energy
resolution was around 3 eV at the Cu K-edge. Incident
and transmitted beams were detected by using an
3
ionisation chamber and a solid-state detector, respec-
tively. Specifications about the measurement geome-
try can be found in the work of Tohji et al. (1983). The
spectra were collected between 8900 and 9500 eV in
steps of 1 eV and a counting rate of 20 s step 1. Three
scans were measured and added for each sample. The
measurements were performed in transmission mode
in pellets composed by 60 – 100 mg of the metal –clay
system and the appropriate amount of boric acid
( f 100 mg) in order to achieve an accurate thickness
and a good noise/signal ratio.
The experimental EXAFS signal was extracted
from the raw spectra following standard methods
(Koningsberger and Prins, 1988). Background remov-
al was performed and the atomic absorption coefficient
was determined by a low order polynomial fit of the
spectra. The EXAFS spectra were analysed by using
the EXCURV package program from SERC Dares-
bury laboratory (Binsted et al., 1991). The Fourier
transform of Cu K-edge, k3c(k), spectra was calculated
using a Gaussian window in the range from 3 to 11
Å 1. The structural parameters for the first and second
coordination shells were obtained by least square
fitting of the Fourier filtered EXAFS signal between
1.2 and 3.3 Å to the EXAFS formula (Sánchez-Sierra
et al., 1995). In order to test backscattering amplitudes
and phase shifts for Cu – O and Cu – Cl contributions
provided by the EXCURV program, CuO and CuCl2
crystals were also measured and analysed under the
same conditions. The agreement between experimental
and theoretical spectra was satisfactory in both cases.
Computational calculations were carried out by
using HyperChem 7 (HyperChem 7, 2002) in a Tosh-
iba Pentium III computer. To simplify the problem,
twelve palygorskite cells (2  2  3) were fixed and
put into contact with 4
Cu2Cl(OH)3 formulas as adsor-
tive. The crystalline structure of palygorskite was
constructed according to Chisholm (1992), and the
charges were placed by using the SE methods
PM3(tm) (Gale, 1997). Two experiments were
designed: four Cu2Cl(OH)3 formulas were placed over
the (001) surface (system I), and over the (100) surface
(system II). In both cases, MM simulations were
carried out with MM+ force field (Hypercube, 1994).
Energy minimizations were performed on initial struc-
tures, then MD simulations were performed at 300 K
for 30 ps with fs time steps. Energy minimizations
were performed on final structures of MD simulations.
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3. Results and discussion
As shown in Table 1, the clay material used in this
research was heterogeneous. The X-ray diffractogram
of the clay material suspended in water (Fig. 1a)
showed that palygorskite was the main component
phase, with appreciable amounts of illite and quartz,
and traces of smectite, kaolinite, and calcite (Table 1).
Sorption isotherm for Cu(II) was Type L-3 (Fig. 2)
according to Giles et al. (1960). This isotherm results
from a high affinity of the adsorbent for the adsorbate
at low concentration, common to processes like ion
exchange and surface complexation that take place on
a two-dimension scale. The isotherm shows a plateau
for equilibrium concentrations in the range 5– 10 mM,
where the amount retained stabilized at approximately
210 mmol of Cu kg 1. For equilibrium concentra-
Fig. 1. X-ray diffractograms: (a) palygorstikic material suspended in
distilled water, and (b) clay – copper system. (A, Atacamite; Al,
Kalium Albite; C, Calcite; I, Illite; K, Kaolinite; M, Montmo-
rillonite; P, Palygorskite; Q, Quartz).
Fig. 2. Adsorption isotherm at 298 K of copper on the palygorskitic
clay.
tions higher than 10 mM, the amount retained in-
creased exponentially. When plotting experimental
data in log ns-log ce scales (Stumm, 1992), the new
retention mechanism can be put down to precipitation
by heterogeneous nucleation in the absence of a free
energy nucleation barrier.
Fig. 3 shows zeta potential (ZP) of palygorskitic
clay as a function of the amount Cu retained in each
point of adsorption isotherm. ZP increased linearly
from 12.5 mV without Cu retention to 2.5 mV for
approximately 210 mmol of Cu kg 1 retained. For
larger amounts, retention of Cu did not modify the
electrokinetic properties of the solid. This section in
which ZP remained constant fitted with the heteroge-
neous nucleation in the isotherm.
Comparison of the X-ray diffractogram of the
clay –copper system (Fig. 1b) with that of the clay
mineral showed the absence of calcite signals, and
the apparition of new signals at 2h values 16.1j (5.49
Å); 17.5j (5.04 Å); 31.5j (2.84 Å); 32.3j (2.77 Å);
32.6j (2.74 Å); 39.7j (2.27 Å); 50.1j (1.82 Å);
53.5j (1.71 Å), which indicated the precipitation of
a new phase. The new peaks in the X-ray patterns
matched with the expected X-ray signals for ataca-
mite (i.e. Cu2Cl(OH)3). The small discrepancies be-
tween the peaks observed in Fig. 1b and the expected
ones for natural atacamite could be put down to the
synthetic nature of the mineral in our compounds
(Wells, 1984).
The SEM-micrographs showed a great variety of
morphologies, typical of a multiphase system. Quan-
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Fig. 3. Zeta potential variation as a function of the amount of Cu

retained in the adsorption isotherm.

titative microanalysis by XRF at several spots selected

by their different electronic densities revealed that
copper was heterogeneously distributed on the clay
surface (Table 2). The percentages of Cu and Cl
obtained in spot 2 imply the formation of a new
compound of Cu and Cl in an atomic proportion of
2.2:1. Spots 1 and 3 showed a Cu/Cl ratio similar to
that found to spot 2, but they also had percentages of
Si higher than 10%. This could reflect that part of the
area analysed by XRF remained uncovered by the
new phase. Spot 4 did not show the presence of Cu or
Cl, and the percentages of Si, Al, and K represented
approximately 94% of the total, therefore, it must
correspond to an uncovered mineralogical phase.
Fig. 4a shows the Fourier transform of the mea-
sured spectra corresponding to the Cu – clay system.

Table 2
X-ray fluorescence microanalysis from several spots on the clay –
copper system (expressed as atomic percentage) Fig. 4. Radial structure functions from EXAFS analysis: (a) Fourier
transforms of the measured spectra corresponding to the Cu
Element Spot 1 (%) Spot 2 (%) Spot 3 (%) Spot 4 (%)
adsorbed at the palygorskitic material; (b) filtered EXAFS and
Si 18.5 1.3 10.1 45.9 theoretical simulation for the first and second coordination shell;
a a
Al 6.1 29.3 and (c) Fourier transforms of filtered spectrum and theoretical
a a a
Mg 3.4 simulation of the first and second shell of the retained Cu.
a a
K 1.1 19.1
a
Fe 2.8 1.3 3.1
a
Cu 46.8 67.2 57.7
Cl 21.6 31.0 25.7 a
The radial distribution shows a main peak around 1.55
Total 96.9 99.5 98.2 97.4 Å (without energy shift correction) corresponding to
a
Non detected. the first coordination shell. The peak at lower distances
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6 R.A. Alvarez-Puebla et al. / Applied Clay Science xx (2004) xxx–xxx

Table 3 the Fourier transform of these shells; experimental

Structural parameters derived from extended-X-ray absorption fine and calculated spectra closely agreed. The interatom-
structure (EXAFS)
ic distances are shown in Table 3; the first shell is
Shell Coordinationa Atom Rb (Å) [r2] c (Å2)
composed by four oxygen atoms with a relatively
First 4 O 1.951 (2) 0.016 (1) high Debye– Waller factor, which is a common fea-
Second 0.5 O 2.247 (14) 0.009 (4)
ture of two Cu environments in atacamite. The Cu –
0.5 Cl 2.561 (13) 0.011 (5)
1.0 Cl 2.731 (16) 0.026 (1) Cl contribution only appeared in the second coordi-
3.0 Cu 3.037 (3) 0.026 (8) nation shell.
a
Coordination index. When four Cu2Cl(OH)3 formulas were docked
b
Interatomic distance. with (001) plane of palygorskite in system I (Table
c
Debye – Waller Factor (the numbers in brackets correspond to 4), the total energy for the initial system was
the standard deviation of the last digit).

( f 0.8 Å) corresponds to spurious effects arising from

the process of the EXAFS signal extraction. The broad
peak located at around 2.8 Å is ascribed to the second
coordination shell and indicates the presence of differ-
ent contributions to this coordination shell. The lack of
structures beyond 4.5 Å suggests a small particle size
or a poor crystallisation of the Cu particles. The first
coordination shell was analysed by Fourier filtering of
the spectra between 1.1 and 2 Å. Any attempt to
include a Cu – Cl contribution in the first shell resulted
in very poor fits. The best solution for this shell gave a
coordination of four oxygen around the Cu atom at
1.95 Å.
To test the presence of atacamite, the first and
second shells were analysed by Fourier filtering of
the spectrum between 1.1 and 3.3 Å. The coordina-
tion numbers were fixed to the expected ones from an
atacamite phase (Wells, 1984; Parise and Hyde,
1986). The extracted k3c(k) signal, together with
the best-fit, are displayed in Fig. 4b. Fig. 4c shows

Table 4
1
Components of the total energy (kJ mol ) for systems I and II
System I System II
Initial Final Initial Final
a
EB 16,684.83 0.02 16,684.92 0.04
EAb 2658.13 0.04 2658.10 0.05
EDc 50.82 19.23 49.83 24.08
EVWd 1024.83 347.27 1063.59 478.58
ETe 20,418.61 327.98 20,456.43 454.41
a
Bond energy. Fig. 5. Twelve palygorskitc unit cells facing four Cu2Cl(OH)3
b
Angle energy. formulas after molecular dynamics and geometry optimization: (a)
c
Dihedral energy. system I, over plane (001) and (b) system II, over plane (100).
d
van der Waals energy. (Atom colours: copper blue, chlorine cyan, magnesium green,
e
Total energy. silicon black, oxygen red and hydrogen white).
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20418.61 kJ mol 1 with a converging gradient of
1279.04 kJ nm 1 mol 1. Geometrical optimization
resulted in the structure showed in Fig. 5a, with
energy of 327.98 kJ mol 1 and a converging
gradient of 0.18 kJ nm 1 mol 1. The 4Cu2Cl(OH)3
distributed on the external surface of palygorskite,
fixing close to siloxanic cavities. System II that
included 4Cu2Cl(OH)3 over (100) plane evolved
from 20,456.43 kJ mol 1 for the initial state to
454.41 kJ mol 1 for the final state, with converg-
ing gradients of 5617.49 and 0.20 kJ nm 1 mol 1,
respectively. Even though none of the systems could
be considered as a crystalline structure (Fig. 5), it
seems probable that the whole precipitate would be
amorphous first, later becoming crystalline (Ost-
wald’s rule) in accordance with XRD and EXAFS
data.
The stability of system II is larger than that of
system I, 454.4 and 328.0 kJ mol 1, respective-
ly. As shown in Table 4, the increment in this stability
is due to a decrease in the van der Waals energetic
term. This fact can be read as an increase in the
stability due to the penetration of some adsorbate
atoms inside the channels, since this phenomenon
only occurs in system II. However, the Cu2Cl(OH)3
has such a high affinity for penetrating the channels
that block them (Fig. 5b), also the high adsorbate –
adsorbate and adsorbent – adsorbate interaction limits
the diffusion of ions across the surface to more stable
sites (i.e. channels).
To summarize, the molecular modeling in the two
experiments confirms a preferential adsorption in the
channels (Table 4, Fig. 5b), in agreement with
Janeba et al. (1998). When channels are occupied
or the molecule size is too large and too stable to
break up, sorption takes place on the external surface
(Fig. 5a) (Pruissen et al., 2000). It was also found
that affinity to the retention in the edges was higher
(Fig. 5a), in line with findings by Zhang and Bailey
(1998).
4. Conclusions
The X-ray diffractogram of the clay material sus-
pended in water showed that palygorskite was the
main component, with appreciable amounts of illite
and quartz. The diffractogram corresponding to the
7
copper – clay system reflected the apparition of new
signals characteristic of atacamite. Quantitative micro-
analysis by X-ray fluorescence at several spots select-
ed for their different electronic densities revealed the
heterogeneous distribution of Cu on the clay surfaces.
When Cu and Cl were detected, they appeared in a Cu/
Cl ratio of 2.2:1. EXAFS analysis supported the
presence of atacamite. Finally, molecular modeling
with 890 atoms lead to the formation of an amorphous
copper hydroxychloride instead of an ordered structure
of atacamite. However, it seems likely that the whole
precipitate would eventually become crystalline (Ost-
wald’s rule), as XRD and EXAFS data would suggest.
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