Environ. Sci. Technol.

2003, 37, 4235-4241

chromium. These sorbents can be biomaterials from agri-

Removal of Hexavalent Chromium culture such as condensed tannin gel (5), grape stalk (6),
with a Lignocellulosic Substrate sphagnum moss peat (7), coconut-shell-based activated
carbon (8); natural material such as sawdust (9); or industrial
Extracted from Wheat Bran waste materials such as red mud (10) and steel wool (11). All
these materials showed interesting capacity for hexavalent
chromium recovery. In our local context, which can be widely
L. DUPONT* AND E. GUILLON
extended, we studied the retention properties of a ligno-
GRECI (Groupe de Recherche En Chimie Inorganique), cellulosic substrate (LCS) toward hexavalent chromium. This
Université de Reims Champagne-Ardenne, BP 1039, material constitutes a byproduct of the industrial process of
F-51687 Reims Cedex 2, France the wheat bran treatment, which leads to the extraction of
cosmetic biomolecules. This process generates the LCS
compound in very high quantities. Nowadays, LCS has no
real potential application, which constitutes a serious
In this paper, a new recovery system of the toxic hexavalent handicap for the profitability of the industrial wheat bran
chromium Cr(VI) is proposed that uses a lignocellulosic treatment. Previous characterizations (12) have revealed that
substrate derived from the industrial treatment process of the lignocellulosic substrate is constituted by lignin and
wheat bran. We studied the adsorption mechanism of Cr- cellulose as its major constituents and a nonnegligible
(VI) onto the lignocellulosic substrate and showed that the proportion (although not quantified) of fatty acid. Lignin
adsorption reaction consumes a large amount of protons and fatty acids bear functional groups such as alcohol, ketone,
goes along the reduction of Cr(VI) into Cr(III). The oxidation and carboxylic groups that can be involved in complexation
of lignin moieties takes place concurrently to the chromium reactions with metallic cations. In a previous work, we
reduction and leads to the formation of hydroxyl and reported the study of the retention properties of this material
toward copper and lead ions (13, 14).
carboxyl functions. The latter contribute to an increase in
This paper examines the adsorption of hexavalent chro-
the number of ion-exchange sites for the reduced mium from aqueous solutions by a LCS in order to understand
chromium. The maximum adsorption capacity for hexavalent the mechanisms that govern hexavalent chromium removal
chromium was found at about 35 mg g-1 in an acidic by natural materials. We report here the influence of the pH
medium. This is comparable to other natural substrates and analytical concentration of hexavalent chromium on
and ordinary adsorbents. the adsorption. Moreover, in addition to the macroscopic
Cr(VI) sorption studies, we used extended X-ray absorption
fine structure (EXAFS) spectroscopy to characterize the
Introduction structure of the sorption complex formed on LCS.
Hexavalent chromium species are strong oxidants that act
as carcinogens, mutagens, and teratogens in biological
Materials and Methods
systems. Hexavalent chromium exists in water as oxyanions Materials. All the reagents used were of the highest
such as chromate (HCrO4-) and dichromate (Cr2O72-). Its available purity (Aldrich and Fluka). Standard solutions of
speciation is dependent on the pH. It causes diseases such hexavalent chromium were prepared using potassium dichro-
as epigastric pain nausea, vomiting, severe diarrhea, and mate (K2Cr2O7).
hemorrhage by ingestion. The maximum allowed contami- Sample Preparation. Agro Industrie Recherche Dével-
nant drinking level for the drinking water is 0.05 mg L-1 (1). oppements (ARD) provided the wheat bran used in this study.
Chromium(VI) is used in various industries including The air-dried, coarsely powdered wheat bran (30 g) was
metallurgy, leather tanning, and electroplating. It is also used subjected to two successive treatments without light protec-
as a control agent for corrosion. Therefore, such ions can be tion: (i) acid hydrolysis by 2 mol L-1 H2SO4 (1:1 w/w dry
a major pollutant of the wastewaters rejected by these matter, at 100 °C for 30 min) to remove starch, proteins, and
industries. Because of this extensive use of chromium, the sugars; and (ii) alkali treatment by 0.5 mol L-1 NaOH (5:1
contamination of groundwaters is unfortunately unavoidable. ratio of bran/sodium hydroxide, stirring for 24 h at room
Among available conventional processes used to remove temperature) to remove the low molecular weight lignin
hexavalent chromium, the most commonly used are reduc- compounds after filtration. The solid was then stirred with
tion and precipitation as chromium hydroxide (2) or ion 0.04 mol L-1 HNO3 during 4 h in order to protonate all acid
exchange (3). However, these methods suffer from some sites and was washed with deionized water until the pH
disadvantages due to their relatively high operational costs. reached a constant value close to neutrality. The protonation
There is therefore a need for the developments of cheaper of all acid sites was checked by potentiometric titrations (13).
alternative technologies that can be used as complement to After these treatments, the material was dried under vacuum,
the usual methods mentioned above. ground to a powder, and sieved at 400 µm.
Adsorption processes were studied and emerged as one IR, 13C-CP/MAS NMR spectroscopies and XPS led us to
of the most promising techniques (4). This process can be identify carboxylic and phenolic moieties as the main
a potential alternative to the usual treatments of waters and functional groups (12, 13). The content of acidic surface sites
wastewaters in order to reduce the metal content to the levels was estimated using ion-exchange reactions and potentio-
established by the legislation. Nevertheless, the sorbent must metric titrations in aqueous and nonaqueous media. We
also be cheap and have a high biodisposibility to render the determined a concentration of 0.6 and 0.4 mmol g-1 for
cleanup process suitable and competitive. Several inexpen- carboxylic and phenolic moieties, respectively.
sive sorbents have been tested in the removal of hexavalent Experimental Procedure of Cr(VI) Removal. The ad-
sorption equilibrium experiments of chromium were con-
* Corresponding author phone: +33 (0) 3 26 91 31 75; fax: +33 ducted to determine the adsorption capacity of Cr(VI) under
(0) 3 26 91 32 43; e-mail: laurent.dupont@univ-reims.fr. a given set of conditions. Chromium sorption experiments
10.1021/es0342345 CCC: $25.00  2003 American Chemical Society VOL. 37, NO. 18, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4235
Published on Web 08/12/2003
FIGURE 1. Effect of time on the adsorption of hexavalent chromium. [LS] ) 8 g L-1; [Cr(VI)] ) 4 × 10-4 mol L-1; (9) sorbed chromium;
(0) soluble trivalent chromium; ([) pH variation.

were performed according to the batch method. The solid EXAFS Spectroscopy. (a) Data Collection. The EXAFS
was equilibrated during at least 3 h in NaNO3 solution (0.1 spectra were collected at the Laboratoire d’Utilisation du
mol L-1) to achieve a complete hydration of the surface Rayonnement Electromagnétique (LURE), Paris-Sud Uni-
groups. The suspensions were then adjusted to the required versity, on the storage ring DCI with an energy of 1.85 GeV
pH and chromium concentration values and magnetically and a mean intensity of 300-200 mA. The measurements
stirred at room temperature for 24 h (except for kinetic were carried out at chromium K-edge (5989 eV) in the
experiments). The LCS particles were separated from the fluorescence mode at the XAS-4 station. The monochromator
solutions by filtration with a 0.2-µm Millipore filter. The used was a Si(111) channel cut, which was detuned to 50%
solution pH was continuously monitored during the experi- of the maximal intensity to remove the higher-order har-
ments. monics. The detectors were low-pressure (≈0.2 atm) air-
The solutions were analyzed for hexavalent and total filled ionization chambers. The spectra were the sum of 10
chromium. Hexavalent chromium (Cr(VI)) was detected by recordings in the 5840-7000 eV range, including the chro-
the diphenyl carbazide method (15): 1,5-diphenyl carbazide mium K-edge (≈5989 eV). The photon energy was calibrated
forms a pink complex in the presence of Cr(VI) ions in acidic from the spectrum of a chromium foil, assigning 5989 eV to
solutions. The concentration of Cr(VI) was calculated from the preedge peak. Spectra were recorded using sampling steps
the absorbance at 542 nm using a UV-visible spectropho- of 2 eV (EXAFS), and an integration time of 2.0 s per point
tometer. Total chromium (Cr(III) and Cr(VI)) was determined was used.
by an inductively coupled plasma spectrometer (ICP-AES, EXAFS Spectra Analysis. The EXAFS data analysis was
Varian Liberty II). The difference in concentration between performed with the “EXAFS pour le Mac” and EXAFS98
total and hexavalent chromium was taken as the concentra- programs (16). This standard EXAFS analysis (17) includes
tion of trivalent chromium. The ICP-AES measurements were merging of scans, linear preedge background removal,
compared to the measurements made with the Cr(VI)- polynomial atomic absorption calculation (of 5th order),
diphenylcarbazide method on Etalon samples. Analytical Lengeler-Eisenberger EXAFS spectra normalization (18), and
measurements made by the two techniques were always reduction from the absorption data µ(E) to the EXAFS
comparable within 5%. spectrum X(k). Radial distribution functions F(R) were
Spectroscopic Characterizations. IR Spectroscopy. In- calculated by Fourier transforms of k3w(k)µ(k) in the range
frared spectra were recorded on KBr pellets on a FTIR of 2-13 Å-1; w(k) is a Kaiser-Bessel apodization window
Spectrometer System from MIDAC Corporation. with a smoothness coefficient τ ) 2.5. Interatomic distances
(R), number of coordinated atoms (N), and Debye-Waller
X-ray Photoelectron Spectroscopy. XPS was used to char-
factor (σ) were evaluated by least-squares fitting Fourier-
acterize the surface chemistry of the LCS. Information was
filtered EXAFS spectra using the standard EXAFS formula
thus obtained on the elemental composition and the
without multiple scattering:
functional groups of the surface to a depth of about 0.1-1

[ ]
nm. XPS spectra were recorded on a VSM-hemispheric
Ni
spectrometer with a Mg KR incident X-ray beam. The X-ray
source was run at 100 W, and the spectra were recorded at
ø(k) ) S 20 ∑ R A (k)e
i
2
i
-2 i k2 -2Ri/λ(k)
σ2 e sin(2kRi + Φi(k))
15 kV. The analyzer chamber pressure was in the 1 × 10-7-1 i
× 10-10 Torr range. The powdered samples were mounted
on double-sided carbon tapes. Binding energies were cali- Experimental phase, Φi(k), and amplitude, Ai(k), functions
brated by assuming 284.6 eV for the C-C component of the for Cr-O atomic pairs have been extracted from the model
C1s line. The elemental composition was estimated using the compounds K3[Cr(C2O4)3]‚3H2O, Cr(H2O)63+, and Cr(acac)3.
area of C1s and O1s peaks corrected with their sensitivity factors
given in Scofield table. Analysis of sorbed chromium oxidation Results and Discussion
state was deduced by comparing experimental spectra with Kinetic Studies. The effect of time on adsorption of Cr(VI)
those of trivalent (Cr2O3) and hexavalent (CrO3) chromium was first investigated and is shown in Figure 1, which indicates
references. that the process is rather quick. Nearly 50% of the adsorption

4236 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 18, 2003
FIGURE 2. pH effect on the sorption and reduction of hexavalent chromium. [LS] ) 8 g L-1; [Cr(VI)] ) 4 × 10-4 mol L-1; (9) sorbed chromium;
(0) soluble trivalent chromium.

FIGURE 3. Cr(VI) adsorption isotherms on LCS at two HNO3 concentrations. [LS] ) 4 g L-1; (9) CHNO3 ) 8 × 10-3 mol L-1 (pH 2.1); (2) CHNO3
) 8 × 10-4 mol L-1 (pH 3.1); ([) without HNO3.

capacity was reached within 4 h. The initial rapid adsorption the reduction process of hexavalent to trivalent chromium,
gives way to a very slow rate of approach to the equilibrium, which requires a large amount of proton. At pH below 4, the
and saturation is reached only after 24 h. Beyond 15 h, the concentration of soluble trivalent chromium increases when
concentration of trivalent chromium increases in the solution, pH decreases, which can be attributed to an increasing
which indicates that the removal of hexavalent chromium competition between protons and trivalent chromium toward
proceeds according to a redox process. The pH variations surface sites.
reported in Figure 1 also show that the adsorption reaction Influence of Analytical Chromium Concentration. Figure
of hexavalent chromium consumes protons. 3 shows typical adsorption isotherms for the chromium LCS
pH Dependence of Chromium Removal. The pH of the system. It is generally observed that the adsorption density,
aqueous solutions is an important controlling parameter in which corresponds to the concentration of chromium
the heavy metal adsorption processes. Its role on the removal removed (10-3 mol g-1) increases when the pH of the solution
of hexavalent chromium was studied by varying the initial decreases. Isotherm data have been used to calculate the
concentration of nitric acid in the suspension. Figure 2 maximal sorption capacity of the lignocellulosic substrate
demonstrates that the conversion of Cr(VI) mainly depends by substituting the required equilibrium concentration in
on the proton concentration. The higher the proton con- the Langmuir equation. The Langmuir isotherm is expressed
centration, the higher the efficiency of the Cr(VI) conversion. by
Such a dependence was already observed with anionic
materials (5,7) as well as on the amphoteric substrate (19), Ce Ce 1
) max + max with Cs ) KdCe
such as ferrous oxide. It has been explained both by a surface- Cs C C b
s s
exchange reaction between chromate and hydroxyl ions,
which favors chromate adsorption in acidic media, and by where Kd is the distribution coefficient that characterizes the

VOL. 37, NO. 18, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4237
FIGURE 4. IR spectra of untreated LCS (a) and LCS contacted 24 h with acidic containing Cr(VI) solution (b). The arrows indicate the main
modifications induced by the adsorption of hexavalent chromium.

to lignin components: guaiacyl (1030, 1160, 1230, and 1270

TABLE 1. Isotherm Parameters for Hexavalent Chromium cm-1) and syringyl units (1110 and 1320 cm-1). The bands
Sorbed onto LCS at 1460 and 1510 cm-1 were attributed to methoxy deforma-
CHNO3 C max (mmol g-1) b (g L-1) r2 tion and to vibration of aromatic skeleton, respectively (21).
s
The bands at 900, 1060, and 1380 cm-1 were characteristics
8× 10-3 0.72 6.7 0.99 of carbohydrate units (22). The band at 1740 cm-1 was
8 × 10-4 0.19 3.2 0.97 attributed to the stretching vibration of free carbonyl from
0.16 2.6 0.99
carboxylic groups, whereas the shoulder at 1710 cm-1 suggests
the possibility of intermolecular associations of carboxylic
affinity of the metal for the sorbent, C max is the maximum functions (23). The relatively large bands at 1637 cm-1 can
s
adsorption capacity of the solid, Ce is the concentration in be confidently attributed to the stretching vibration of
the equilibrium solution, Cs is the measured sorption per carboxylate anion.
unit weight of solid, and b represents the Langmuir bonding The adsorption of Cr(VI) induces some substantial
term related to the energy of adsorption. Table 1 summarizes modifications of the IR spectrum. The suppression of the
the Langmuir parameters of hexavalent chromium adsorption peaks located at 1460, 1510, and 1710 cm-1 and the decrease
for different nitric acid concentrations. The retention capacity of the ratio of the COOH and COO- groups intensities can
(about 0.72 mmol g-1, i.e., 35 mg g-1) of LCS toward hexavalent be observed. This decrease was already observed in the case
chromium in acidic medium compares well with those of copper ions, and the coordination of the latter with
reported onto various natural substrates, which range from carboxylate moieties was underlined by XAS spectroscopy
15 to 60 mg of Cr/g, and commonly used adsorbent such as (24). Our results obtained by IR spectroscopy suggest that
activated carbon and resin (about 50 mg of Cr/g of dry resin) hexavalent chromium induces an oxidation of only lignin
(20).The very low cost of lignocellulosic materials is a real components and that the retention of Cr ions occurs through
advantage that renders it a suitable alternative for the cleanup a complexation reaction involving carboxylate moieties
of industrial effluents. (lignin and fatty acids). Moreover, the bands at 900, 1060,
The retention capacity of hexavalent chromium in acidic and 1380 cm-1 that are characteristic of carbohydrate units
media is unexpectedly high if we compare this result with remain unaltered by the adsorption of hexavalent chromium.
those obtained previously in the case of copper and lead Fatty acids are characterized in the IR spectrum (not schown
ions on the same materials (14). This is a strong piece of here) by two aliphatic vibrations at 2920 and 2850 cm-1. These
evidence in supporting that the adsorption of hexavalent two bands are not affected by the sorption of hexavalent
chromium yields to the creation of new ion-exchange sites chromium.
through a redox process. X-ray Photoelectron Spectroscopy. The XPS survey spec-
Adsorption isotherms have been monitored onto pure trum of LCS consists of two major elements: carbon and
cellulose and pure lignin under similar conditions of pH and oxygen. The presence of sorbed chromium has been detected
analytical chromium concentrations. No significant sorption on LCS after chromium sorption, and the Cr2p peaks have
has been observed onto cellulose even in acidic medium. been analyzed. It consists of two contributions corresponding
For lignin, an extensive conversion of hexavalent Cr was respectively to 2p1/2 and 2p3/2 energy levels. Quantification
observed although not quantified because of the high of chromium sorbed was possible only with the sample
solubility of this substrate in our conditions. These observa- containing a high level of sorbed metal, and the error was
tions clearly demonstrate that the adsorption reaction of estimated within 10%. The C1s peak has been deconvoluted
hexavalent chromium onto lignocellulosic substrate involves considering three components and a constant half-width
lignin moieties. peak at 2.0 eV. Due to similarities of the O1s chemical shifts,
Infrared Spectroscopy. Figure 4 shows the infrared spectra which brought up difficulties in estimating their relative
of the virgin lignocellulosic substrate and the lignocellulosic intensities, the discussion in this section will focus on the
particles contacted with the acidic Cr(VI) solutions. The most relative intensities of C1s peak components as well as on the
prominent peaks in the untreated material were attributed O/C ratio (Table 2).

4238 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 37, NO. 18, 2003
FIGURE 5. XPS spectra of LCS: (a) Cr2p signals of Cr-LCS system (-), CrIII2O3 ([), CrVIO3 (]); (b) C1s signal of untreated LCS; (c) C1s signal
of LCS contacted 24 h with acidic-containing Cr(VI) solution. The continuous line represents the superimposition of experimental and fitted
curve.

chromium sorbed onto LCS, they were normalized. The XPS

TABLE 2. XPS Data for Untreated LCS and Contacted 24 h spectrum (Figure 5a) of Cr-treated LCS reveals an extensive
with Acidic-Containing Cr(VI) Solution at Two Concentrations reduction of hexavalent chromium sorbed onto LCS to its
LS-Cr(VI) LS-Cr(VI) trivalent form. Indeed, the two contributions of Cr2p peaks
LS (6 mmol L-1) (10 mmol L-1) of chromium sorbed are at 576.3 and 587 eV. These values
BE elemental area elemental area elemental area compare well with the binding energy of Cr(III) in Cr2O3 at
peak (eV) composition (%) composition (%) composition (%) 576.3 and 586.2 eV but are significantly distinct from the
C1 284.6 71.8 65.6 58.5
binding energy of Cr(VI) in CrO3 that are at 579.3 and 588.3
C2 (1s) 286.4 0.76 21.7 0.70 27.2 0.66 32.3 eV. The slight difference between the Cr 2p1/2 peaks (586.2
C3 288.2 6.4 7.2 9.1 and 587 eV) is attributed to different chemical environements.
O (1s) 531.0 0.24 0.29 0.33 Indeed, in Cr2O3, the chromium atoms are bound to oxygen
Cr (2p) 580.1 0.30 0.40 atoms by a double bond, whereas in Cr-LCS it is likely that
589.5 chromium is bound to oxygen with a single bond (25). Only
O/C 0.32 0.42 0.50
small shoulders, which appear on both Cr2p peaks at 580.8
and 584 eV seem to indicate that it can subsist some trace
The three components of the C1s peak (Figure 5b,c) can of hexavalent chromium and that reduction is not still
be assigned to three different classes of carbon atoms present complete. The presence of trivalent chromium onto ligno-
in cellulose and lignin: the C1 peak corresponds to a carbon cellulosic substrate was also checked by ESR.
atom bound to an hydrogen atom or to another carbon atom, Analysis of Surface Functional Modifications by XPS.
C-H or C-C bonds; the C2 peak corresponds to a carbon Table 2 shows the chemical modifications of LCS induced
atom singly bound to an oxygen atom, C-O; and the C3 peak by the conversion of hexavalent chromium. The increase of
corresponds to a carbon atom doubly bound to an oxygen the O/C ratio is attributed to the conversion of C1 into C2 and
atom, CdO, or to two oxygen atoms, O-C-O (13). Com- C3 carbon types. In agreement with IR analysis, this can be
parison of XPS spectra with those of pure lignin and pure explained by the oxidation of lignin aromatic carbons. Indeed,
cellulose coupled with pyrolysis studies (12) have previously oxidized functions, especially alcoholic and carboxylic sites,
shown that the relatively high content of C1 carbon type can have been generated. This interpretation is supported by the
be confidently attributed to the presence of fatty acid, studies of Pizzi (26) and Ostmeyer and Elder (27), which
although no quantification was possible. propose that the preservation of wood components by
Analysis of Chromium Reduction by XPS. To facilitate chromate copper arsenate treatments involves the formation
the XPS spectra intensity comparison of Cr2p peaks of of chromate ester moieties. Chromate ester moieties would

VOL. 37, NO. 18, 2003 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 4239
 were obtained. The chromium ion is surrounded by six oxygen
atoms (N ) 6.05) at an average Cr-O bond distance of r )
2.04 ( 0.02 Å, with a relative Debye-Waller factor σ equal
to 0.024 Å. These data seem to indicate a coordination
through carboxylate functional groups of LS and thus that
chromium ions are held in inner-sphere complexes. Indeed,
these results are in good agreement with those obtained for
chromium complexes through X-ray crystallography with
carboxylic ligands (30, 31) in which Cr-O (COOH) distances
were equal to 1.99 and 2.00 Å. On the other hand, Cr-O
bond distances, which involve phenolic moieties were equal
to 1.91-1.95 Å (30, 32), are less probable. Previous results
obtained by IR and XPS spectroscopies are confirmed by
XAS studies about involvement of carboxylic moieties in
chromium complexation.
These studies show that the lignocellulosic substrate is
an efficient adsorbent for chromium(VI) removal from
aqueous solutions, owing to its very low cost and its relatively
interesting sorption capacity. The process, which is a function
of the pH and the concentration of the analytical hexavalent
chromium, is enhanced by redox processes. Sorption capacity
of the lignocellulosic substrate could be related to the
abundance of lignin and fatty acid moieties, which allow the
reduction of hexavalent chromium into trivalent one as well
as the fixation of Cr(III) on carboxylic moieties. Further
experiments are in progress in order to validate the efficiency
of this material in the cleanup of real industrial effluents.
These results may be of value in developing sound reme-
diation strategies for water contaminated with toxic first-
FIGURE 6. (a) First-shell fit of the EXAFS function of Cr(III)-LCS row transition metals.
system. Experimental first-shell filtered data in the 1.01-2.11-Å
range (dotted line), and best fit (solid curve) modeled as Cr-O Acknowledgments
contributions. Experimental phase and amplitude functions were
We are grateful to J. Lambert from LCPE, Université de Nancy
extracted from the EXAFS spectrum of the Cr(H2O)63+ reference
compound. (b) Radial structure function (RSF) of the first shell and I, for the XPS measurements and B. Richalot for her technical
its numerical simulation. RSF is not phase-shift corrected. assistance.

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