Hydrometallurgy 71 (2003) 191 – 200

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Gold sorption on chitosan derivatives

Martha Ly Arrascue a, Holger Maldonado Garcia a, Olga Horna a, Eric Guibal b,*
a
Departamento Academico de Quimica, Universidad Peruana Cayetano Heredia, Av. Honorio Delgado,
430 Urbanizacion Ingenieria, Lima 31, Peru
b
Laboratoire Génie de l’Environnement Industriel, Ecole des Mines d’Alès, 6 avenue de Clavières, F-30319 Alès cedex, France

Abstract

Four derivatives of chitosan have been prepared by cross-linking and by grafting of sulfur compounds. Sorption isotherms
were performed at different pHs in order to optimize the pH conditions at fixed chloride concentration. Sorption isotherms were
correlated with gold speciation in solution. Sulfur grafting decreases the influence of the pH on sorption isotherms. Introducing
sulfur chelating moieties gives a dual structure to the polymer: chelating and ion exchange capability. Sorption kinetics was
influenced by the sorbent dosage and the type of sorbent used.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Gold; Chitosan; Sulfur derivatives; Sorption; Isotherms

1. Introduction metals, but solid– liquid separation is sometimes pre-

Precious metals (PMs), including silver, gold and
platinum group metals, are recovered from a wide
variety of sources such as primary sources constituted
by ores, and also secondary sources usually more
complex such as copper nickel sulfide leach residues,
copper and silver anode slimes, as well as recycled
scraps (Brooks, 1991). Besides the traditional precip-
itation processes, hydrometallurgy provides techniques
based on solvent extraction processes (Villaescusa et
al., 1996; Barroso et al., 1996; Sánchez-Loredo and
Grote, 2000) and ion exchange reactions (Warshawsky
et al., 1980; Chanda et al., 1987; Chanda and Rempel,
1990; Gomes et al., 2001). Solvent extraction techni-
ques can be very useful in the recovery of precious
* Corresponding author. Tel.: +33-466-78-5000; fax: +33-466-
78-5034.
E-mail address: Eric.Guibal@ema.fr (E. Guibal).
ferred because the mixing and settling requirements are
usually more easily achieved than with solvent extrac-
tion processes. Moreover, the loss of solvent, which
may be hazardous for the environment and limiting for
the economic balance, is avoided in the case of sorption
processes. However, common strong base anion ex-
change resins do not selectively adsorb negatively
charged PM chlorocomplexes. Base metals (BMs) are
frequently adsorbed simultaneously. For this reason,
chelating resins have been developed, taking advantage
of the intrinsic selectivity provided by the grafted
functional groups (Koster and Schmuckler, 1967;
Grote et al., 1990; Chen et al., 1998; Iglesias et al.,
1999, 2000).
Dubois et al. (1995) have shown that the pyrolysis
and incineration of ion exchange resins (especially
anionic resins) produce hazardous products. The
elimination of exhausted resins at the end of their life
cycle is then an important parameter to be taken into
account in the selection of the sorbent. Moreover,

0304-386X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0304-386X(03)00156-7
192 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200
these expensive materials are not economically com-
petitive for the treatment of low-concentration solu-
tions. Therefore, many studies have been focused on
the development of alternative sorbents produced
from renewable and low-cost resources, and more
specifically materials of biological origin. Biohydro-
metallurgy has been extensively developed during the
last 40 years in order to recover metals from lower-
grade marginal ores using bioleaching processes, and
also for the competitive recovery of metal ions from
dilute solutions using biosorption processes. Many
biosorbents from bacteria, fungi and algae have been
investigated for the sorption of toxic or valuable
metals (Volesky and Holan, 1995). More recently,
interest has been focused on the use of materials of
biological origin extracted from agriculture wastes or
seafood by-products (Hsien and Rorrer, 1997; Guibal
et al., 1999; Wan Ngah and Liang, 1999, Remoudaki
et al., 1999). Some of these materials exhibit very
high sorption capacities, which make the use of these
products competitive despite their higher cost, com-
pared with traditional biosorbents, especially in the
case of strategic and precious metals (Baba et al.,
1998; Inoue et al., 1999; Guibal et al., 1999; Ruiz et
al., 2000). Chitosan has proven to be very efficient for
the recovery of several toxic and strategic metals such
as mercury, uranium, molybdenum, vanadium, plati-
num and palladium, exhibiting sorption capacities as
high as 2 – 7 mmol (metal) g 1 (sorbent) (Inoue,
1998; Guibal et al., 1999; Guzman et al., 2002).
Chitosan is produced by the alkaline deacetylation
of chitin, the most abundant biopolymer in nature
after cellulose. It is extracted from shrimp and crab
shells. The biopolymer is characterized by its high
percentage of nitrogen, present in the form of amine
groups that are responsible for metal ion binding
through chelation mechanisms. However, due to its
pKa that ranges between 6.2 and 7 (depending on the
degree of deacetylation of chitosan), it is protonated
in acidic solutions (Sorlier et al., 2001). Thus, it is
also possible to sorb metal ions through anion ex-
change mechanisms. Glutaraldehyde has been fre-
quently used to cross-link chitosan and to stabilize
it in acidic solutions (Hsien and Rorrer, 1997; Guibal
et al., 1998). The reaction occurs through a Schiff’s
base reaction between aldehyde groups of the cross-
linker (glutaraldehyde) and some amine groups of
chitosan. The chemical modification of the biopoly-
mer may be used to increase the sorption efficiency
and also to improve sorption selectivity and decrease
the sensitivity of sorption to environmental condi-
tions (Guibal et al., 2000a). In the present work,
rubeanic acid was grafted on chitosan through reac-
tion with glutaraldehyde as the linker/spacer. This
compound bears two CMS groups (instead of a single
CMS in the case of thiourea, which was previously
investigated). Sulfur compounds are very efficient at
chelating metals and especially precious metals,
according to Hard and Soft acid theory used by
Pearson for the prediction of complexation reactions
(Chanda and Rempel, 1990).
2. Materials and methods
2.1. Sorbents
Chitosan was supplied by Aber Tech (France) as a
flaked material, which was first crushed and sieved in
several size fractions, the 125 –250-Am fraction was
selected for experiments. Chitosan was characterized
by the degree of acetylation (DA) of 13% (using FT-
IR techniques) and a molecular weight of 125,000
(using light scattering facilities coupled with a dif-
fractometer) (Guibal et al., 1998).
Chitosan cross-linking with glutaraldehyde was
performed by mixing for 16 h a known amount of
chitosan with an equimolar quantity of glutaraldehyde
(50% v/v) in a large volume of demineralized water to
obtain fluid slurry. The equimolar quantity of glutar-
aldehyde was calculated taking into account the
deacetylation degree of chitosan (equimolarity is
based on the number of free amine groups of the
biopolymer). After cross-linking treatment the solid
was separated and washed several times with water to
remove unreacted glutaraldehyde, and the solid was
then dried at 50 jC for 16 h. Glutaraldehyde cross-
linked chitosan (GCC) was formed. Alternatively, the
cross-linking of the biopolymer was performed using
hexamethylene diisocyanate to produce the so-called
cross-linked chitosan (CHMDI). The polymer was
mixed with methanol to remove residual water
through several methanol baths and then it was con-
tacted for 16 h with hexamethylene diisocyanate (in
methanol) based on the equimolarity between amine
groups and cross-linker agent.
 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200
For the preparation of the sulfur derivative of
chitosan (RADC), the detailed procedure was previ-
ously described in the case of thiourea grafting
(Guibal et al., 2000a). In the present work, rubeanic
acid (dithioxamide) was substituted to thiourea.
Rubeanic acid was pre-reacted with glutaraldehyde
for 16 h and then the mixture was contacted with
chitosan for 16 h. The product was then rinsed with
demineralized water and finally dried at 50 jC for 16
h. Previous experiments on palladium sorption using
RADC have shown a partial release of rubeanic acid
during metal ion sorption (Guibal et al., 2002). To
increase the stability of the sorbent and to reduce
possible losses of reagents, RADC was submitted to a
complementary cross-linking using hexamethylene
diisocyanate following the experimental procedure
described above and RADC-HMDI sorbent was
obtained. Table 1 presents the elementary composition
of GCC and RADC and more specifically the per-
centage of nitrogen and sulfur (in the case of RADC).
2.2. Sorption experiments
Gold solutions were prepared by dilution from
standard solution (HAuCl4, in 1 M HCl) purchased
from Fluka. The pH of the solutions was controlled
and adjusted with either nitric acid (5 M), hydro-
chloric acid (4 M) or sodium hydroxide (5 M)
solutions.
The investigation of the influence of pH was
performed at pH 1, 2, 3 and 4 by mixing 8 mg of
sorbent with 150 mL of a gold solution. After 5 days
of contact, the solution was filtered on a filter mem-
brane (pore size 1.2 Am) and analyzed for gold
concentration using an inductively coupled plasma
atomic emission spectrometer JY 2000 (Jobin Yvon,
Longjumeau, France). The sorption capacity (mg Au
Table 1
Elementary analysis of the sorbents (%, weight; and into brackets
mmol element g 1 sorbent)
C H N O S is weakly sensitive to the pH, as shown by complex-
GCC 50.4 7.3 5.1 [4.25] 37.1 –
RADC 34.7 7.0 6.3 [5.25] 44.4 2.6 [0.81]
Analytical results from the Service Central d’Analyses of the Centre
National de la Recherche Scientifique (SCA-CNRS Vernaison,
Solaize).
193
g 1 sorbent) was obtained by a mass balance between
liquid and solid phases.
Sorption isotherms were determined by mixing
(reciprocal shaker) fixed volumes of gold solutions
(at a defined metal concentration) with varying
amounts of sorbent. Isotherms were plotted at pH
1.6, 3.2, 5, 6 and 8 in order to verify the influence of
gold speciation on sorption performances. Sorption
kinetics experiments were performed by mixing a
known amount of sorbent with 1 L of solution at a
concentration of 25 mg Au L 1 in an agitated vessel
(jar test). Samples were regularly withdrawn and
analyzed for gold content.
3. Results and discussion
3.1. Influence of pH on gold sorption
Fig. 1 shows the influence of pH on gold sorption
using four different derivatives of chitosan: GCC,
CHMDI, RADC and RADC-HMDI. The influence
of the pH is given as a function of the relative residual
concentration (Ceq/Co) and sorption capacity ( q, mg
Au g 1). The optimum pH appeared to be around pH
2– 3, depending on the sorbent. Sorption efficiency
(and sorption capacity) strongly increased from pH 1
to pH 2. A maximum was reached at pH 2 for GCC,
RADC and RADC-HMDI, while with CHMDI, sorp-
tion slightly increased at pH 3. Above pH 2 (pH 3 for
CHMDI), sorption capacity decreased again, but it
appears that the decrease was significantly less im-
portant for sulfur derivatives than for sorbents that
were only cross-linked, at pH 4, the sorption capacity
decreased by less than 10% with sulfur derivatives,
while for GCC and CHMDI, the decrease exceeded
30%. It appears that the grafting of sulfur compounds
allowed the influence of the pH to be decreased due to
the partial change in the sorption mechanism instead
of a pure ion exchange mechanism with cross-linked
material; sulfur derivatives are also able to chelate
gold ions. Metal ion chelation with sulfur compounds
ation constants for silver and mercury with thiourea
(Ringbom, 1967).
Chelating resins are characterized by their intrinsic
complexation constants, which, according to the
Gibbs – Donnan model, are related to the complexa-
194 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200

1
Fig. 1. Influence of pH on Au(III) sorption efficiency (relative residual metal concentration: Ceq/Co; left) and sorption capacity ( q, mg Au g ;
.
right) on GCC (5), CHMDI (n), RADC (o) and RADC-HMDI ( ) (Co(Au): 25 mg Au L 1; sorbent dosage, SD: 50 – 55 mg L 1).

tion constants in solutions with ligands having a
similar structure to that of active groups in the resin
(Pesavento and Biesuz, 1998). It is also interesting to
note that sorption capacity was significantly higher
with sulfur derivatives at pH 1 than with CHMDI. In
very acidic solutions, the competition between the
counter anions (chloride ions) of the acid and gold
species strongly reduced sorption capacity, while with
the chelating groups grafted on chitosan, the compet-
itor effect was less significant. This was not true when
chitosan is cross-linked with glutaraldehyde: In this
case, sorption efficiencies were comparable at pH 1
and pH 2 with the levels reached with sulfur deriva-
tives of chitosan. This is consistent with previous
results on platinum sorption using thiourea derivative
of chitosan (Guibal et al., 2000a). Sorption perfor-
mance at equilibrium was comparable for RADC and
RADC-HMDI: Complementary experiments on the
influence of pH on sorption isotherms were carried
out with GCC and RADC.
3.2. Influence of pH on gold sorption isotherms
Sorption isotherms were obtained at different pH
conditions for both GCC (Fig. 2) and RADC (Fig. 3).
The pH was controlled using nitric acid and sodium
hydroxide, and the chloride concentration was main-
tained at 25 mM. These figures confirm the trends
observed above. Sorption capacities were comparable
at pH 1.6, while above this value, RADC maintained
sorption capacities at a high level (between 400 and
600 mg Au g 1), while with GCC, increasing the pH
progressively decreased maximum sorption capacity.
These values were considerably higher than the sorp-
tion levels cited by Byerley et al. (1989) (200 mg Au
g 1) using un-cross-linked chitosan with a greater DA.
With RADC, the optimum pH was 3.2 as shown by
both the maximum sorption capacity and the initial
slope of the curve (which is indicative of the favor-
ability of the sorption isotherm): At pH 1.6, the
maximum sorption capacity was comparable to that

Fig. 2. Influence of pH on gold sorption isotherm on GCC. Fig. 3. Influence of pH on gold sorption isotherm on RADC.
 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200 195

obtained at pH 3.2, but the slope of the curve was less cates that the electrostatic balance is not the only
steep. Above pH 3.2, both maximum sorption capac- parameter to take into account for the interpretation
ity and favorability decreased, but below pH 6, of experimental results.
maximum sorption capacity was decreased by less Table 1 can be used to calculate the number of
than 30%. At pH 8, sorption capacity was decreased millimoles of N and S per gram of sorbent, and as a
to 10– 20 mg Au g 1. The sorbent is not charged at consequence, the molar distribution of active sorption
this pH, anion exchange cannot take place and the sites per gram of sorbent. For amine functions on
chelating effect was diminished. In the case of GCC, GCC, the molar concentration of nitrogen should be
the sorbent is significantly more sensitive to pH: corrected by the degree of deacetylation, and the
Increasing the pH from 1.6 to 5 halved the maximum UNH2 molar concentration was 3.7 mmol g 1. In
sorption capacity. The curve in Fig. 2 for GCC the case of RADC, taking into account nitrogen and
sorption at pH 8 was not shown because sorption sulfur, and also the fraction of amine groups that are
capacity was close to zero. involved in the linkage of rubeanic acid, the density of
The pKa of chitosan depends on the degree of coordination and ion exchange sites was 4.7 mmol
deacetylation, as well as the degree of neutralization g 1. The density of sorption sites allowed the calcu-
of amino groups. A recent work from Sorlier et al. lation of the molar ratio between gold and functional
(2001) has shown that the intrinsic pKa decreases groups (Table 2). Though the molar ratio decreased
with the degree of acetylation from 6.44 (DA = 0) to above pH 3.2 in the case of RADC, the values
7.1 (DA = 0.89). For the chitosan used in this study remained in the same order of magnitude (from 0.53
(DA = 0.13), the intrinsic pKa is 6.5. The cross-link- to 0.68). On the other hand, in the case of GCC, a
ing treatment was able to slightly change the pKa of strong decrease of the molar ratio was observed with
the polymer; however, for pH 1.6, 3.2 and 5, amine increasing pH (from 0.78 to 0.20). This change in the
groups are predominantly protonated and then avail- molar ratio between adsorbed gold and functional
able for anion sorption, though the protonation de- groups clearly demonstrates the difference in the
gree decreases with increasing pH (Table 2). At pH 6, sorption mechanism for the two sorbents. In the case
the percentage of protonated amine groups decreases of GCC, which is suspected to sorb gold by electro-
to 76%, while at pH 8, the polymer is almost static attraction, the change in the ionic balance was
completely un-protonated and then unable to sorb not sufficient to explain such differences in the
metal anions. The balance between protonated amine sorption performance. The speciation of gold may
sites and anionic gold species is thus only favorable be an alternative explanation depending on the pH,
in acidic solutions (below pH 4 –5). Table 2 also at constant chloride concentration; some of the pre-
presents the maximum sorption capacities for GCC dominating species (cationic or non ionic forms) are
and RADC for the different experimental pH con- less adsorbable than anionic species.
ditions. The change in the pH cannot be correlated to Metal speciation changes with the total metal
the decrease in sorption capacity for GCC; it indi- concentration and the pH (Baes and Mesmer, 1976).
Previous investigations have shown that the metal
speciation and the presence of co-ions can strongly
Table 2
Influence of pH on amine protonation (GCC), maximum sorption
affect sorption properties (Remoudaki et al., 1999;
capacities for GCC and RADC and molar ratio gold/functional Guibal et al., 2000b, Ruiz et al., 2000; Guzman et al.,
groups (Au/FG) 2002). In the case of molybdate, Guibal et al. (2000b)
pH Amine GCC RADC have shown that the shape of sorption isotherms can
protonation qmax Molar qmax Molar be correlated to the presence/predominance of poly-
(%) (mmol ratio (mmol ratio nuclear molybdate species. They demonstrated that
Au g 1) Au/FG Au g 1) Au/FG the sorption capacity remains low when the experi-
1.6 100 2.9 0.78 3.0 0.64 mental conditions on pH and metal concentration lead
3.2 100 2.15 0.58 3.2 0.68 to the predominance of mononuclear species, while
5 97 1.3 0.35 2.6 0.55 sorption became favorable when the concentration (at
6 76 0.75 0.20 2.5 0.53
the selected pH) reached a value corresponding to the
196 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200
appearance of polynuclear species. Similar correla-
tions between high level of sorption for palladium on
GCC and experimental conditions (pH and chloride
concentration) were cited by Ruiz et al. (2000); the
predominance of chloro-palladate anionic species was
correlated to sorption capacity.
Baes and Mesmer (1976) highlighted the discrep-
ancies between the values of formation constants
observed for gold and those calculated from thermo-
dynamic databases. The coexistence of hydroxide,
chloride and hydroxide – chloride complexes makes
gold speciation very complex. At low chloride con-
centrations (below 10 6 M), they found that gold is
present in the solution in hydroxide forms: Au(OH)2+
(pH below 1), Au(OH)3 (between pH 1 and pH 12)
and Au(OH)4 (pH above 12). For high chloride
concentrations (above 0.01 M), AuCl4 predominates
in acidic solutions, while in alkaline solutions, both
Au(OH)4 and Au(OH)3, Au(OH)3Cl coexist and/or
predominate depending on the value of the constants
used for the calculation of predominance diagrams. In
the near neutral region, the existence of AuOHCl3
(pH 3.5– 6.5) and Au(OH)2Cl2 (pH 4.5 – 8) is debat-
able. In the case of intermediate chloride concentra-
tions (between 0.01 and 10 6 M), many species may
co-exist depending on the pH: In acidic solutions
(below pH 5), AuCl4 , Au(OH)Cl3 , Au(OH)2Cl2 ,
Au(OH)3, AuCl3, AuOHCl2 and Au(OH)2Cl may be
present in the solution. Under selected experimental
conditions corresponding to 25 mM chloride concen-
tration, and with pH 1.6, 3.2, 5, 6 and 8, AuCl4 ,
AuOHCl 3 , Au(OH) 2 Cl 2 and Au(OH) 3 Cl (or
Au(OH)3) predominate, respectively.
The grafting of sulfur compounds brings new
functionalities to the sorbent that make it less sensitive
to the speciation of the metal. Indeed, as stated in the
previous section, the chelating sites on the sulfur
derivative (UCMS and UNH2) are very reactive (as
reactive are thiourea and rubeanic acid) for gold. A
similar result was obtained with platinum sorption on
a thiourea derivative of chitosan; in sulfuric acid,
platinum sorption capacity was strongly decreased
while adding chloride in order to enhance the forma-
tion of adsorbable platinum species increased sorption
capacity (Guibal et al., 2000a). This favorable effect
was especially effective with GCC, while with the
sulfur derivative of chitosan, sorption capacities were
significantly higher and the favorable effect of the
presence of chloride anions was less significant (in
percentage).
3.3. Influence of chitosan modification on sorption
isotherms at pH 2
Fig. 4 shows gold sorption isotherms obtained at
pH 2 with each sorbent: GCC, CHMDI, RADC and
RADC-HMDI. This figure shows that sorption capac-
ities were comparable for GCC, RADC and RADC-
HMDI at pH 2, while the sorption isotherm obtained
with CHMDI was completely different. At equilibri-
um, the grafting of sulfur derivatives on chitosan did
not increase sorption capacity. The plateau that
appeared at low residual concentration (about 4– 5
mg L 1) indicates that the sorption isotherm can be
described by a Langmuir equation. The sharp increase
in sorption capacity at low residual concentration
confirmed that gold sorption is very favorable. While
at low gold concentration, sorption capacity was very
low, when the residual concentration exceeded 10 mg
L 1, the sorption capacity sharply increased to reach
a level comparable (slightly higher) to those reached
with the other derivatives of chitosan. The sorption
isotherms were determined in triplicate, and this
unexpected trend was consistently obtained. No ex-
planation was found for this phenomenon.
3.4. Gold sorption kinetics
Sorption kinetics are reported in Figs. 5 – 7 for
selected sorbents and experimental conditions (sor-
Fig. 4. Comparison of gold sorption isotherms at pH 2 on GCC (5),
CHMDI (n), RADC (o) and RADC-HMDI ( ). .
 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200
bent dosage, pH and type of acid used for pH control).
It appears that sorption is a fast phenomenon in
comparison to the sorption of other metal anions on
similar sorbents (GCC). While 12 h or 1 day of
contact was generally sufficient to reach equilibrium
with RADC or GCC, respectively, 3 days was neces-
sary for molybdate and vanadate to reach the same
level of sorption (Guibal et al., 1998).
Fig. 5 shows the sorption kinetics obtained at pH 2
using nitric acid for pH control. There is no chloride
additional and the speciation is less favorable to the
formation of adsorbable gold species. Sorption was
more efficient and faster for HMDI-treated sorbents:
Equilibrium was almost achieved after 24 h of con-
tact, while in the case of non-treated sorbents, up to 5
days of contact was necessary to reach equilibrium
(especially in the case of RADC). Sulfur grafting did
not significantly affect sorption kinetics under select-
ed experimental conditions: Initial sorption was slight-
ly faster with sulfur derivative (non-treated with
HMDI) than for the reference material (glutaraldehyde
cross-linked chitosan), while for HMDI-treated mate-
rials, reference material was faster than the sulfur
derivative. It appeared that the treatment of the sorb-
ents with HMDI enhanced uptake kinetics; this may
be due to an improvement of diffusion properties. The
enhancement of sorption rates after reaction with
hexamethylene diisocyanate may be related to the
expanding effect of this cross-linking agent. Uragami
et al. (1995) have shown that using long-chain alde-
hydes for the cross-linking of chitosan membranes
Fig. 5. Gold sorption kinetics at pH 2 (controlled with nitric acid) on GCC (5), CHMDI (n), RADC (o) and RADC-HMDI ( ) (Co(Au): 25
mg Au L 1; sorbent dosage, SD: 50 mg L 1).
197
results in largest polymer ‘‘pores’’ and enhanced
diffusion properties (for permeation applications). It
may also induce a change in the crystallinity of the
sample and then a greater accessibility to inner sorp-
tion sites as pointed out by Kurita et al. (1988).
Fig. 6 shows the sorption kinetics at pH 2 using
hydrochloric acid for pH control under comparable
experimental conditions to those used in Fig. 5 (same
initial gold concentration and sorbent dosage), but
with a higher chloride concentration. Obviously, using
HCl for pH control improved sorption kinetics: A few
hours of contact was necessary to reach equilibrium
(compared to 24 h for HNO3 solutions). The presence
of chloride ions may displace speciation equilibrium
for gold to the formation of readily adsorbable spe-
cies. Sorption kinetics was then enhanced for all
sorbents. The positive effect of metal speciation was
thus not only detectable for sorbents involving ion
exchange reactions in the uptake mechanism. In this
case, it is interesting to observe that sulfur grafting
enhanced sorption kinetics compared to cross-linked
material, independently of HMDI treatment. Within
the first hours of contact, sorption kinetics was com-
parable with RADC, CHMDI and RADC-HMDI
sorbents and significantly better than with GCC. In
the case of GCC, within the first 6 h of contact, the
residual relative concentration (C(t)/Co) varied as a
linear function of time. This means that in the first
stage of the process, the kinetics may be surprisingly
described by a pseudo-first-order equation. For large
contact time, in the case of CHMDI, the residual
.
198 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200

Fig. 6. Gold sorption kinetics at pH 2 (controlled with hydrochloric acid) on GCC (5), CHMDI (n), RADC (o) and RADC-HMDI ( ) .
(Co(Au): 25 mg Au L 1; sorbent dosage, SD: 50 mg L 1).

concentration increased again, perhaps due to the
instability of the sorbent or to the weakness of the
linkage between gold and the sorption site.
At pH 3.2, despite a higher sorbent dosage (100 mg
sorbent L 1) and a pH controlled with HCl, the
sorption kinetics was significantly slower than those
obtained at pH 2 (Fig. 7). It is interesting to observe
that sorption kinetics was significantly faster for
RADC than for GCC. The strong reactivity of sulfur
at pH 3.2 (in comparison to the affinity of cross-linked
chitosan for gold at this pH) may explain the fast
kinetics. Byerley et al. (1989) observed very fast
kinetics for gold sorption on un-cross-linked chitosan;
however, some experimental details (particle size,
which has a drastic effect on sorption kinetics through
diffusion mechanisms) were not reported for a direct
comparison of the kinetics. They established several
kinetic models based on pure sorption, pure reduction
and dual sorption/reduction mechanisms. They con-
cluded that gold uptake was kinetically controlled by
a dual sorption/reduction mechanism. Remoudaki et
al. (1999) also concluded that palladium uptake
occurs through a dual mechanism including sorption
by chemical bonds followed by a reduction. Their
conclusions are consistent with previous results on
gold deposition on the cell walls of Sargassum natans
(Kuyucak and Volesky, 1988). The potential of chito-
san to reduce some metals (especially under light/sun
exposure) have been characterized (Guibal et al.,
1996). Recently, XPS analyses on chitosan gel beads
have confirmed the reduction of metal ions during (or
after) metal sorption, depending on the electrochem-

1
Fig. 7. Gold sorption kinetics at pH 3.2 (controlled with hydrochloric acid) on GCC (5) and RADC (o) (Co(Au): 25 mg Au L ; sorbent
dosage, SD: 100 mg L 1).
 M.L. Arrascue et al. / Hydrometallurgy 71 (2003) 191–200
ical properties of the metals (ca. standard reduction
potential) (Dambies et al., 2001).
4. Conclusion
Chitosan derivatives are very efficient at removing
gold from dilute acidic solutions: Maximum uptake
capacity reaches 600 mg Au g 1 (about 3 mmol g 1).
The speciation of gold (under chloride and hydrox-
ide – chloride forms) appears to be a predominant
parameter influencing uptake. In acidic solutions,
chitosan is protonated and protonated amine groups
are available for the sorption of anionic gold species.
The optimum pH range is pH 2– 3 for glutaraldehyde
cross-linked chitosan, but the sorption capacity
strongly decreases with increasing pH. Rubeanic acid
grafting decreases the influence of pH on gold sorp-
tion. Sulfur grafting increases the polymer chelating
sites that are less influenced by pH than ion exchange
sites (protonated amines) involved in ion-pair forma-
tion. Sorption kinetics is influenced by pH and the
type of chitosan derivatives. The grafting of sulfur
compounds and the hexamethylene diisocyanate
cross-linking enhance sorption kinetics probably due
to the presence of highly reactive chelating sites and
to better diffusion properties.
Acknowledgements
The authors thank the cooperation program Raul
Porras Barrenechea (Ministère des Affaires Etrangères
in France, and Ministerio de Relaciones Internacio-
nales in Peru) for the financial support. EG also
thanks the European Union for the financial support
(EU contract GRD-CT-2000-00300).
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