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Environmental Application of Chitosan Resins for the Treatment of Water

and Wastewater: A Review
Khalid Z. Elwakeel a
a
Egyptian Water and Wastewater Regulatory Agency, New Cairo City, Egypt

Online publication date: 23 February 2010

To cite this Article Elwakeel, Khalid Z.(2010) 'Environmental Application of Chitosan Resins for the Treatment of Water
and Wastewater: A Review', Journal of Dispersion Science and Technology, 31: 3, 273 — 288
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 Journal of Dispersion Science and Technology, 31:273–288, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903167178

Environmental Application of Chitosan Resins for the

Treatment of Water and Wastewater: A Review
Khalid Z. Elwakeel
Egyptian Water and Wastewater Regulatory Agency, New Cairo City, Egypt

Chitosan is a polysaccharide formed mainly from repeating residues of D-glucosamine, having

primary amino groups. It is of great interest not only as an underutilized resource, but also as
a new functional material of high potential in various fields, and recent progress in chitin chem-
istry is quite noteworthy. The purpose of this review is to take a closer look at chitosan appli-
cation in water technology based on (a) its ability to bind toxic pollutants, (b) the mod of
chitosan modification, (c) the nature of the interaction of chitosan with different pollutants,
and (d) chitosan regeneration and recycling.
Keywords Adsorption, chelating resins, chitosan environmental application
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010

1. INTRODUCTION (heparinoids),[18] photography,[19] cosmetics,[2] artificial

Chelating resins have high potential applications for the
selective removal of metal ions from industrial waste
solutions and water treatment.[1] Many chelating resins with
different functionalities have been used to bind various metal
ions from wastewater and drinking water. Among these
functionalities, those which contain oxygen, nitrogen and
sulphur atoms as active sites such as iminoacetic acid[2] Schiff
bases,[3] hydroxamic acid,[4] amidoxime,[5] thiol,[6] amine,[7]
etc. Many studies have been done to show the behavior of
those chelating resins toward different metal ions.[8–14]
Chelating resins can be obtained from naturally
occurring polymeric matrix or synthetic polymeric matrix.
Different metal-complexing ligands loaded on synthetic
and natural adsorbents have been reported in the literature
for heavy metal removal.
Chitosan is a natural polymer obtained from chitin,
through deacetylation in alkaline medium.[15] The chemical
structures of chitin and chitosan as shown in Figure 1.
Chitosan itself is a nontoxic biopolymer and has a wide
variety of applications in the fields of biotechnology,
biomedical, environmental, microbiology, and pharmaceu-
tical sttudies.[16,17]
Chitosan has been used in the preparation of some
biotechnological materials such as cell-stimulating materi-
als,[16] antibacterial agents,[16] blood anti-coagulants
Received 20 September 2008; accepted 12 November 2008.
The author is grateful to his wife, Eng. Hanady K. Yassin, for
her moral support.
Address correspondence to Khalid Z. Elwakeel, Egyptian
Water and Wastewater Regulatory Agency, Masraweya District,
5th Community, New Cairo City, Egypt. E-mail: Khalid_elwakeel@
yahoo.com
skin,[20] chitin and chitosan based dressings,[21] food and
nutrition,[22] opthalmology,[16] paper finishing,[23] solid-
state batteries,[24] drug-delivery systems.[25,26]
2. MODIFICATION OF CHITOSAN
One of the most interesting advantages of chitosan is its
preparation in different physical forms such as powder,
nanoparticles,[27] gel beads,[28] membranes,[29] sponge,[30]
fibers,[31] or hollow fibers.[32] Some physical and chemical
modifications of chitosan have been carried out to improve
its affinity and selectivity toward different sorbates.[33]
Kurita,[34] prepared a review article on the chemical
modification of chitosan for metal ion adsorption. The
modification was controlled by two objectives: (a) prevent-
ing the dissolution of the polymer when metal ion sorption
(or desorption) was carried out in acidic medium, (b)
improvement of sorption characteristics such as, rate of
adsorption, selectivity, etc.[35–39] Poly(ethylenimine) has
been successfully grafted on chitosan using for example,
glutaraldehyde,[40] hexamethylenediisocyanate,[41,42] epi-
chlorhydrin,[43,44] as linker=spacer agents. The grafting of
carboxylic functional group on chitosan was also interest-
ing modification for increasing the sorption properties of
chitosan.[45] Carboxymethyl chitosan has been prepared
by reaction of chitosan with chloroacetic acid in a suitable
solvent.[46] Carboxylic acids have also been grafted on
chitosan through Schiff’s base condensation reactions.[47]
Another way for incorporation of carbonyl and carboxy-
late functionalities into chitosan was achieved through its
reaction with acid anhydride[48] in the last two decades, a
great attention has been paid to the grafting of crown ether
on chitosan using a Schiff’s base reaction.[49,50]

273
 274 K. Z. ELWAKEEL
FIG. 1. Chemical structures of chitin and chitosan.
The preparation of cross-linked chitosan is very impor-
tant to increase its stability against dissolution in acid
medium. The cross-linking reaction proceeds via the
reaction of chitosan with bifunctional reagents such as
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
glutaraldehyde,[51,52] 1,1,3,3-tetramethoxypropane,[53]
oxidized b-cyclodextrin (b-cyclodextrin polyaldehyde),[54]
ethyleneglycol diglycidyl ether,[55] or glycerolpolyglycidy-
lether.[56] Tri-polyphosphate has also been selected as a
cross-linking agent, which can be used for the preparation
of chitosan gel beads by the coagulation=neutralization
effects.[57] Generally, the cross-linking step may cause a
significant decrease in the metal ion uptake efficiency and
sorption capacities, especially in the case of chemical reac-
tions involving amine groups.[58] At higher levels of cross-
linking (e.g., glutaraldehyde), the precipitates had lower
swelling properties and, therefore, lower accessibilities
due to the extensive three-dimensional network as well as
hydrophobic character. For example increasing the
glutaraldehyde–amine ratio beyond 0.7 for cross-linked
chitosan led to decrease in the binding capacity.[59,60]
The use of chitosan beads, chitosan–glutaraldehyde 1:1
and 2:1 ratio beads, and chitosan–alginate beads for the
removal of Cu2þ ions from aqueous solution at different
initial pH, agitation periods, adsorbent dosage, and initial
concentrations has been investigated.[61]
Cross-linked chitosans synthesized with epichlorohydrin
were used for adsorption of three metals of Cu2þ, Pb2þ,
and Zn2þ ions in an aqueous solution.[62] The results
obtained from the equilibrium isotherms adsorption stu-
dies were analyzed in three adsorption models, namely,
Langmuir, Freundlich, and Dubinnin-Radushkevich iso-
therm equations. The data indicated to be well fitted to
the Langmuir isotherm equation under the concentration
range studied. The order of the adsorption capacity for
three metal ions was as follows: Cu2þ > Pb2þ > Zn2þ.
Chitosan was used for the removal of Cu2þ, Hg2þ, Ni2þ,
and Zn2þ.[63,64] Maruca et al.[65] used chitosan flakes of
0.4–4 mm for the removal of Cr3þ from wastewater. The
adsorption capacity was found to be increased with the
decrease in the size of the flakes. Chitosan has an extremely
high affinity for many dyes, including disperse, direct,
reactive, acid, sulfur, and naphthol dyes.[66]
Yang et al.[67] studied the treatment of chitosan with
glyoxal solution as across-linking agent at different reac-
tion conditions. The influence of the degree of cross-linking
(DCL) on chitosan beads was studied.[68] The beads water
contents and pKa were found to decrease with increasing
DCL. The equilibrium properties of copper adsorption
onto the cross-linked beads were also studied.
Chitosan nanoparticles with different mean size ranging
from 40 to 100 nm were prepared by ionic gelation of chit-
osan and tripolyphosphate (CS-TPP).[69] Physicochemical
properties of nanoparticles obtained were investigated by
zeta-potential analyzer, atomic force microscopy, FTIR
spectra, and x-ray powder diffraction. The sorption
capacity toward lead ions were studied. Factors such as
initial concentration of lead ions, sorbent amount, tem-
perature, sorbent size, agitation period, and pH value of
solution that influence sorption capacity were investigated.
It was found that chitosan nanoparticles could sorb lead
ions effectively, the sorption rate was affected significantly
by initial concentrations of solutions, sorbent amount,
agitation speed, and pH value of solution.
Twu et al.[70] examined the metal ion sorption properties
of chitosan=cellulose against Cu2þ, Fe3þ, and Ni2þ ions.
The studies showed that chitosan=cellulose blend beads
have potential applications for metal ions adsorption.
Chelating adsorbent was prepared from chitosan micro-
spheres cross-linked with glutaraldehyde by spray drying
using 8-hydroxyquinoline-5 sulphonic acid as chelant agent
(CTS-SX-CL).[71] Microspheres of the adsorbent obtained
were characterized by Raman spectroscopy, scanning elec-
tron microscopy (SEM) and energy-dispersive x-ray micro-
analysis (EDX). The effect of pH, contact time and
concentration of metallic ions in solution on the adsorption
behavior of Cd2þ and Zn2þ by CTS-SX-CL were evalu-
ated. Adsorption was found to be maximum for both
Cd2þ and Zn2þ at pH 8.0. Adsorption kinetic curves were
obtained and found to be fit by the pseudo-second order
adsorption model.
Laus et al.[72] prepared chitosan microspheres by the
phase inversion method. Water samples from coal mining
effluents were treated using different amounts of micro-
spheres for removal of Fe3þ, Al3þ, and Cu2þ.
Chitosan and 20%-lanthanum incorporated chitosan
(20% La-chitosan) were applied as adsorbents for the
removal of excess fluoride from drinking water.[73] The
effects of various physicochemical parameters such as
pH, adsorbent dose, initial fluoride concentration and the
presence of interfering ions on adsorption of fluoride were
also studied.
The application of chitosan–cellulose hydrogel beads as
an adsorbent for Cu2þ adsorption from aqueous solutions
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
was examined.[74] Chitosan was blended with cellulose to
make chitosan–cellulose hydrogel beads and the hydrogel
beads were cross-linked with ethyleneglycol diglycidyl ether
(EGDE). It was found that the addition of cellulose to chit-
osan made the hydrogel beads materially denser and the
cross-linking reaction improved the chemical stability of
the chitosan–cellulose beads in solutions with pH values
down to 1. Batch adsorption experiments indicated that
both the chitosan–cellulose and the cross-linked chitosan–
cellulose hydrogel beads had high adsorption capacities
for Cu2þ removal.
Cross-linked chitosan with dihydroxyazacrown ether as
the cross-linking agent was prepared.[75] Its structure was
confirmed by elemental analysis, FTIR, solid-state 13C
nuclear magnetic resonance (NMR) analysis, and x-ray dif-
fraction analysis. Its static adsorption properties toward
Agþ, Cd2þ, Hg2þ, and Co2þ were studied. The experi-
mental results showed that the dihydroxyazacrown ether
cross-linked chitosan has good adsorption capacities and
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
high selectivity for adsorption of Agþ with the coexistence
of Hg2þ and Co2þ.
Rhazi et al.[76] studied the selective adsorption of chito-
san toward different metal ions. Chitosan was cross-linked
using the complexing agent N-N0 -[bis(2-hydroxy-3-
formyl-5-methylbenzyl-dimethyl)]-ethylenediamine.[77] The
chemical modification was confirmed by Raman spec-
troscopy and thermogravimetric analysis (TGA). The che-
lating polymer obtained was used for adsorption of Cu2þ
from aqueous solution. The results showed that adsorption
was dependent on the pH of the solution. The maximum
capacity was found to 113.6 mg=g (1.79 mmol=g) at pH
6.0. The adsorption kinetics data were found to best fitted
with the pseudo-second order model.
Cheung et al.[78] studied the removal of Cu2þ ions from
aqueous effluents by chitosan. The sorption capacities of
chitosan for Cu2þ ions are 1.26 and 1.12 mmol=g at pH
3.5 and 4.5, respectively. The equilibrium experimental
data were best correlated by the Langmuir equation. The
kinetics of sorption were studied at an initial solution
pH of 4.5 and a chitosan particle size of 355–500 mm. The
kinetics were analyzed using four models: the pseudo-first
order, pseudo-second order, modified second-order, and
Elovich equations.
Ng et al.[79] studied the sorption of Cu2þ ions from sol-
ution onto chitosan at two pHs. DSC, TGA, surface area,
SEM, and NMR studies have been used to report the pure
physical states of chitosan and the chitosan–copper com-
plex. The experimental isotherm data were analyzed using
the Langmuir, Freundlich, and Redlich–Peterson equations.
Chitosan coated perlite beads were prepared and used for
adsorption of Cu2þ.[80] The adsorption experiments were
carried out in the concentration range of 50–4100 mg=L
(0.78–64.1 mM). Adsorption capacity found to be pH
dependent. The maximum uptake is 104 mg=g and was
275
obtained at pH 4.5. Anions in the solution had minimal
effect on Cu2þ adsorption. EDTA was used effectively for
the regeneration of the bed. The diffusion coefficient of
Cu2þ onto chitosan coated beads was calculated from the
breakthrough curve and was found to be 2.02
108 cm2=s.
Chitosan functionalized with 2-pyridinecarboxaldehyde
and 4-pyridinecarboxaldehyde were used for Cu2þ adsorp-
tion from aqueous solutions.[81] The degree of substitution
of NH2 groups of the chitosan was 85%. The adsorption
parameters KL (Langmuir constant) and maximum value
of adsorbed Cu2þ ions were calculated using Langmuir’s
equation by nonlinear regression methods. KL and maximum
value of adsorbed Cu2þ for N-(2-pyridyl-methyl)chitosan
systems were higher than those for N-(4-pyridyl-
methyl)chitosan. The difference is related to the nitrogen
position at the pyridine ring.
The influence of particle size, temperature and agitation
speed on Cd2þ sorption using chitosan flakes and chitosan
gel beads were investigated.[82]
Removal of Ni2þ from aqueous solutions through
adsorption on to biopolymer sorbents, such as chitosan
calcium alginate (CA), coated calcium alginate (CCCA),
and chitosan coated silica (CCS), was studied using equilib-
rium batch and column flow techniques.[83] The biosor-
bents were characterized by FTIR, SEM, TGA, and
surface area analysis. The extent of adsorption was found
to be a function of the pH of the solution, contact time,
sorbate concentration and adsorbent dose. Ni2þ loaded
biosorbents were regenerated using 0.1 M EDTA solution.
Paulino et al.[84] investigated the best chitosan deacetyla-
tion time (DT) for the removal of Pb2þ and Cu2þ from
battery manufacture wastewater. Bath experiments were
used to determine the best adsorption conditions. The best
DT for Cu2þ removal was 180 minutes (92% deacetylation)
and for Pb2þ removal was 90 minutes (80% deacetylation).
The maximum adsorption capacities of Pb2þ and Cu2þ were
0.4 mmol=g and 1.5 mmol=g, respectively, for contact time
of 24 hours, pH 5.0, particle size from 300 to 425 mm, and
temperature of 20  0.1 C. Metal adsorption onto chitosan
was evaluated by Langmuir and Freundlich isotherms. An
experimental column packed with chitosan was used to
remove Fe3þ, Cu2þ, and Pb2þ from battery wastewater.
Chitosan was chemically modified by introducing xan-
thate group onto its backbone using carbondisulfide under
alkaline conditions.[85] The chemically modified chitosan
flakes (CMC) was used as an adsorbent for the removal of
cadmium ions from electroplating waste effluent under lab-
oratory conditions. CMC was found to be far more efficient
than the conventionally used adsorbent activated carbon.
The maximum uptake of Cd2þ ions by CMC in batch studies
was found to be 357.14 mg=g at an optimum pH of 8.0
whereas for plain chitosan flakes it was 85.47 mg=g.
Removal of Cr3þ ions from aqueous solutions by using
natural and cross-linked chitosan membranes was achieved
 276 K. Z. ELWAKEEL
using batch adsorption experiments.[86] The effect of pH
(6.0 and 2.0), concentration of Cr3þ ions and cross-linking
agents on the adsorption properties of chitosan membranes
was analyzed.
A comparison between the removal efficiency of heavy
metals from wastewater by using activated alumina and
chitosan as adsorbents was evaluated.[87] Cd2þ and Cr3þ
ions were employed as models of the behavior of divalent
and trivalent metal ions. The adsorption of Cd2þ and
Cr3þ onto the adsorbents was studied as a function of
pH, time, amount of adsorbent, concentration of metal
ions and sample volume. The results indicated that chito-
san is more preferable than alumina due to the reduced
price of chitosan and the absence of side-pollution effects.
The effect of particle size and pH of the solution on the
uptake of Hg2þ by chitosan has been investigated.[88] Jeon
and Ha Park[89] studied the adsorption behavior of
mercury ions on aminated chitosan beads. The adsorption
process was found to be exothermic. The adsorption was
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
almost completed within 100 minutes. EDTA was used
for desorption of mercury from loaded chitosan with
efficiency of 95% up to five cycles. Ethylenediamine con-
taining cross-linked chitosan was prepared by Atia.[90]
The modified chitosan obtained was tested for the removal
of Hg2þ and UO2þ 2 from their aqueous solutions. The
uptake capacity was found to be high. Selective separation
chitosan=amine resin showed high uptake toward Hg2þ
and UO2þ 2 . Selective separation of Hg
2þ
from UO2 was
2þ
achieved at pH < 2. Hg was eluted from the resin using
H2SO4. Vieira and Beppu[91] studied the effect of
cross-linker and shape of particle on the adsorption beha-
vior of chitosan toward Hg2þ. The adsorption process
was found to proceed according to Langmuir model.
Aminated chitosan beads with ethylenediamine have a
high uptake capacity of about 2.3 mmol=g at pH 7 toward
mercury.[92] The increased number of amine groups was
confirmed by IR analysis and measuring the saturation
capacities for adsorption of HCl. The surface condition
and existence of mercury ions on the beads was confirmed
by the environmental scanning electron microscope and
energy dispersive x-ray spectroscopy. Fundamental investi-
gation on adsorption and desorption of Hg2þ ions on chit-
osan membranes was performed by Vieira and Beppu.[93]
The adsorption properties of the dihydroxyl mesocyclic
diamine grafted chitosan for Agþ, Pb2þ, Cd2þ, and Cr3þ
were studied.[94] The experimented results showed that
the novel chitosan derivative has good adsorption capacity
and high selectivity toward Agþ in the presence of Pb2þ,
Cd2þ, and Cr3þ.
Modified chitosan was obtained from treatment with
glutaraldehyde and poly(ethyleneimine).[95] These sorbents
were tested for the recovery of platinum group from bicom-
ponent mixtures at pH 2. The sorbents have a marked pref-
erence for Pd2þ over Pt4þ. In most cases, metal desorption
was tested using several eluants, none of which allowed the
complete removal of the metals from loaded sorbent nor
the selective desorption. A complete separation of the
metals was not obtained. Ruiz et al. studied the kinetic
behavior of adsorption reaction of Pd2þ by modified
chitosan.[96]
Sabarudin et al.[97] synthesized chelating resin using chit-
osan as a base material. Functional moiety of 2-amino-5-
hydroxy benzoic acid (AHBA) was chemically bonded to
the amino group of cross-linked chitosan (CCTS) through
the arm of chloromethyloxirane (CCTS-AHBA resin).
Several elements, such as Agþ, Cd2þ, Co2þ, Cu2þ, Ni2þ,
Pb2þ, and rare earth elements, could be adsorbed on the
resin obtained.
Becker et al.[98] carried out further chemical modifica-
tions for chitosan to improve the metal ion capacities and
selectivities. The capacities for Ni2þ, Zn2þ, and Cd2þ ions
were measured in aqueous nitrate, chloride and sulphate
solutions at pH 6. The selectivities were determined in mix-
tures of Ni2þ, Zn2þ, Cd2þ, Mg2þ, and Ca2þ and were
recorded as a function of the pH value and the counterion.
Some of the prepared chitosan derivatives showed higher
metal uptake rates in sulphate solution than in nitrate or
chloride ones.
Erosa et al.[99] investigated the influence of particle size,
temperature and agitation speed on metal sorption using
chitosan flakes and chitosan gel beads. Temperature and
agitation speed hardly influence equilibria and kinetics in
the selected experimental conditions corresponding to a
large sorbent dosage. The major effect on sorption
performance is due to sorbent particle size, especially for
chitosan flakes.
The adsorption studies of cross-linked chitosan toward
Cr6þ, V4þ and W6þ were studied.[100,101] Chitosan is very
efficient at removing of vanadium from dilute solutions.[102]
Sorption capacity is 400–450 mg=g under optimum experi-
mental conditions. In acidic solutions, the chitosan’s amine
groups are protonated, and vanadate anions can be
exchanged with counter ions bound to NHþ 3 sites.
A chitosan resin functionalized with threonine moiety
was synthesized, and applied to the collection=concentration
of Mo6þ, V4þ, and Cu2þ in environmental water samples.
The synthesized resin showed good adsorption behavior
toward trace amounts of Mo6þ, V4þ, and Cu2þ in a wide
pH range. The adsorbed elements can be easily eluted using
2 M HNO3, and their recoveries were found to be
90–100%.[103]
A chitosan resin functionalized with 3-nitro-4-amino
benzoic acid moiety was synthesized for the collection=
concentration of trace Mo6þ oxyanions.[104] The carboxyl
group of the moiety was chemically attached to amino
group of cross-linked chitosan through amide bond forma-
tion. The adsorption behavior of Mo6þ as well as other 60
elements on the resin was examined by passing the sample
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
solutions through a mini-column packed with the resin.
After the elution of the elements collected on the resin with
1 M HNO3.
Molybdate ion uptake by raw chitosan and by glutaral-
dehyde cross-linked chitosan beads was investigated.[105]
Although the amine functions of glucosamine residues
remain the major sites of interaction with the metal species,
other functional groups can also be involved. It is certainly
the case with carbonyl functions provided by the glutaral-
dehyde structure in cross-linked sorbents. Due to the large
size of the polynuclear hydrolysed molybdate species, the
sorption may involve several monomer units, resulting in
additional linkages between the polymer chains.
A chitosan resin modified with N-methyl-d-glucamine
(CCTS-NMDG) was synthesized by using a cross-linked
chitosan (CCTS) as base material.[106] The N-methyl-d-
glucamine (NMDG) moiety was attached to the amino
group of CCTS through the arm of chloromethyloxirane.
The adsorption behavior of 59 elements on the synthesized
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
resin was systematically examined by using the resin packed
in a mini-column, passing water samples through it and
measuring the adsorbed elements in eluates by ICP-MS.
Chitosan-amino acid conjugates were prepared by coup-
ling amino acid esters to the carboxyl group of glyoxylic
acid-substituted chitosan.[107] The removal of heavy metals
(Cu2þ, Ni2þ, Co2þ and Mn2þ) was increased by introduc-
tion of amino acids to chitosan, especially for Mn2þ. Heavy
metals were almost completely removed by chitosan-amino
acid conjugates from solutions at an initial concentration
of 100 parts per million.
Beppu et al.[108] studied the influence of functionalization
of macroporous chitosan membranes with histidine on their
ability to remove copper ions from aqueous solution in the
range of pH 4 to pH 6. The maximum adsorption capacity
for Cu2þ was 2.5 mmol=g. Under this condition, no influ-
ence of membrane porosity was observed.
The adsorption of Au3þ, Pt4þ and Pd2þ onto glycine
modified cross-linked chitosan resin (GMCCR) has been
investigated.[109] The parameters studied include the effects
of pH, contact time, ionic strength and the initial metal ion
concentrations by batch method. The optimal pH for the
adsorption of Au3þ, Pt4þ, and Pd2þ was found to range
from 1.0 to 4.0 and the maximum uptake was obtained
at pH 2.0 for Au3þ, Pt4þ, and Pd2þ. The results obtained
from equilibrium adsorption studies are fitted in various
adsorption models such as Langmuir and Freundlich.
The model parameters have been calculated. The maximum
adsorption capacity of GMCCR for Au3þ, Pt4þ, and Pd2þ
was found to be 169.98, 122.47, and 120.39 mg=g, respect-
ively. The kinetic data was tested using pseudo-first-order
and pseudo-second-order kinetic models and an intraparti-
cle diffusion model.
Cross-linked chitosan resin chemically modified with
L-lysine has been used for adsorption of Au3þ, Pt4þ and
277
Pd2þ[110] from aqueous solutions. Batch adsorption studies
were carried out at various conditions, such as initial metal
ion concentration, contact time, pH and temperature. The
maximum adsorption capacity was found at pH 1.0 for
Pt4þ and pH 2.0 for Au3þ and Pd2þ. Langmuir and
Freundlich isotherm models were applied to analyze the
experimental data. The best interpretation of experimental
data was given by the Langmuir isotherm and the maximum
adsorption capacity was found to be 129.26 mg=g for Pt4þ,
109.47 mg=g for Pd2þ and 70.34 mg=g for Au3þ. The kinetic
data were tested using pseudo-first order and pseudo-second
order models. Thermodynamic parameters like Gibbs free
energy (DG ), enthalpy (DH ), and entropy (DS ) were
evaluated by applying the Van’t Hoff equation. The ther-
modynamic study indicated that the adsorption process is
spontaneous and exothermic in nature. The desorption
studies were carried out using various reagents such as
0.7 M thiourea and 2 M HCl.
Adsorption of Co2þ, Ni2þ, Cu2þ and Zn2þ by chitosan
was studied by Lima and Airoldi.[111] The exothermic
enthalpy, the negative Gibbs free energy and the positive
entropic values are in agreement with a favorable
thermodynamic condition for cation–chitosan amine group
interaction.
Cárdenas et al.[112] developed a good method to prepare
chitosan mercaptanes derivatives using mercaptoacetic acid
and 1-chloro-2,3-epoxy propane propionic acid. The
evaluation of the retention capacities using several concen-
trations of copper and mercury solutions with concentra-
tions ranging from 10 to 104 ppm at pH 2.5 and 4.5 are
tested.
Merrifield et al.[113] studied the synthesis and character-
ization of thiol-grafted chitosan. The beads were tested
for adsorption of Hg2þ. Cysteine was grafted onto the
beads in order to improve the adsorption affinity of Hg2þ
to the beads. Equilibrium and kinetic characteristics of
uptake were investigated. The adsorption capacity was
approximately 8.0 mmol=g at pH 7, and decreased with
decreasing pH.
Modified chitosans have been synthesized by reacting
chitosan with ethylenediaminetetraacetic acid (EDTA)
anhydride and diethylenetriaminepentaacetic acid (DTPA)
anhydride. A comparative study for adsorption of glycine–
chitosan, iminodiactic acid–chitosan, EDTA–chitosan and
DTPA–chitosan toward different metal ions was carried
out.[114–116]
Functionalized chitosan with serinediacetic acid
moiety was synthesized and applied to the collection=
concentration of trace elements in environmental water
samples.[117] Cross-linked chitosan serinediacetic acid
(CCTS-SDA), showed good adsorption behavior toward
trace amounts of Cd2þ, Pb2þ, Cu2þ, Ni2þ, and V4þ in a
wide pH range. Additionally, rare earth elements also can
be retained on the resin at neutral pH. The adsorbed
 278 K. Z. ELWAKEEL
elements can be easily eluted with 1 M of nitric acid, and
their recoveries were found to be 90% to 100%.
Modified chitosan with ascorbic acid and other func-
tionalities was prepared and applied for adsorption of
metal ions.[118]
Chitosan-based adsorbent materials were synthesized
using a higher fatty diacid diglycidyl as a cross-linking
agent.[119] Selective adsorption for Cu2þ in comparison
with other divalent metal ions, such as Ni2þ, Pb2þ, Cd2þ,
and Ca2þ was carried out at pH 6. The addition of ethyle-
nediaminetetraacetic acid (EDTA) residues to the
cross-linked chitosan significantly enhanced the adsorption
power for metal ions, especially for Ca2þ. The newly
synthesized adsorbent could be used for the recovery of
metal ions from industrial waste solutions with a relatively
wide range of pHs.
The chelating ability of N-carboxymethyl chitosan
was assessed for dilute solutions of Cu2þ and Pb2þ by
Delben.[120] The binding of metal cations by N-carboxy-
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methyl chitosan in dilute aqueous solution was studied as
a function of charge density, temperature and pH.
Guzman et al.[121] studied the sorption of copper by chit-
osan in the presence of citrate at different metal=ligand
ratios. Cu2þ uptake in acidic solution takes place through
electrostatic attraction between the protonated amine
groups of chitosan and anionic copper-citrate complexes
(mainly Cu(OH)L2).
Wan et al.[122] synthesized N-benzylidene chitosan
(CTB) by the reaction of benzaldehyde with chitosan
(CTS). Chitosan-dibenzo-18-crown-6 crown ether bearing
Schiff-base group (CTBD) and chitosan-dibenzo-18-
crown-6 crown ether (CTSD) were prepared by the reac-
tion of 4,40 -dibromodibenzo-18-crown-6 crown ether with
CTB and CTS, respectively. These crown ether cross-linked
CTSs have stronger complexation power and better selec-
tivity for metal ions. Moreover, these CTS derivatives
can be used to separate and preconcentrate heavy or pre-
cious metal ions from aqueous solutions. The adsorption
and selective properties of CTB, CTBD, and CTSD for
Agþ, Cu2þ, Pb2þ, and Ni2þ were studied. The experimental
results showed that CTBD had better adsorption proper-
ties and higher selectivity for metal ions than CTSD.
Three chitosan crown ethers, N-Schiff base-type chito-
san crown ethers and N-secondary amino type chitosan
crown ether were prepared.[123] The adsorption and selec-
tivity of modified chitosan for Pd2þ, Au3þ, Pt4þ, Agþ,
Cu2þ, and Hg2þ were studied. Experimental results showed
these adsorbents not only had good adsorption capacities
for noble metal ions Pd2þ, Au3þ, Pt4þ, and Agþ, but also
high selectivity for the adsorption of Pd2þ with the coexist-
ence of Cu2þ and Hg2þ.
A polyaminated highly porous resin has been prepared
from porous beads of chitosan by cross-linking with
ethyleneglycoldiglycidyl ether and then reacting the
cross-linked beads with epichlorohydrin and polyethylenei-
mine, respectively.[124] The structure of the resin is as
shown in Figure 2.
The order of selectivity of adsorption of metal ions onto
the resin at pH 7.0 was Hg2þ > UO2þ 2 > Cd
2þ
>
Zn > Cu > Ni , Mg . Ca , Ga , As , and Sr2þ
2þ 2þ 2þ 2þ 2þ 3þ 3þ
were not adsorbed on the resin at all. The selectivity is
depended on the pH. The resin was found to have higher
adsorption as compared to commercial chelate resin. The
mechanism of adsorption was shown to be pore diffusion
as well as surface diffusion in polyethyleneimine–chitosan
particles. The resin could be effectively reused after
repeated cycles of adsorption and elution. Elution of
Hg2þ was effected by sulphuric acid.[124]
Modified chitosans with different mono- as well as
disaccharides were prepared and applied for adsorption
of different metal ions. The order of adsorptivity for
trivalent metals was Ga3þ > In3þ > Nb3þ > Eu3þ and
Cu2þ > Ni2þ > Co2þ for divalent metals. The pH depen-
dency on the distribution ratio was affected by valency of
metal ion.[125,126]
Martins et al.[127] described the functionalization of
chitosan by 8-hydroxyquinoline. The efficiency of the
chelating resin obtained for analysis of potable water, lake
water, seawater and a certified sample of oyster tissue was
evaluated. The chelating resin showed chemical stability
within a wide range of pH and the efficiency was not
altered for the preconcentration of the metal ions during
all the experiments.
Amidoximated chitosan[128] had a higher adsorption
affinity for Cu2þ, Mn2þ, and Pb2þ compared to cross-
linked chitosan. The adsorption capacity had a linear
dependence on pH in cases of Cu2þ and Pb2þ. However,
a slight decrease in the adsorption capacity was observed
in case of Zn2þ and Cd2þ.
Chitosan was entrapped in polyacrylamide (PAA) by
direct polymerization of acrylamide in a suspension of chit-
osan. The adsorptive features of PAA–chitosan and chito-
san were then investigated for Pb2þ, UO2þ 2 and Th .
4þ [129]
Chitosan was modified with coconut shell carbon to
produce composite adsorbent. The adsorption efficiency
of the adsorbent was evaluated by measuring the extent
of adsorption of Zn2þ in synthetic beverage industrial
wastewater.[130]
FIG. 2. Structure of chitosan cross-linked with ethylene glycol ether
(EDGE) and aminated with polyethyleneimine (PEI).
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
A series of snake-cage resins were synthesized using
carboxymethyl chitosan (CM-CTS) as the snake resin
and urea–formaldehyde resin (UF) as the cage one.[131]
The saturated sorption capacities of the resins for Cu2þ,
Ni2þ, Zn2þ and Pb2þ were 1.48, 0.78, 0.13, and 0.02 mmol=
g, respectively.
Adsorption of Cr6þ oxyanions by chitosan was determ-
ined using a stirred-batch method at constant pH.[132]
Wong et al.[133] investigated the adsorption of five acid
dyes onto chitosan from aqueous solutions. The equilib-
rium isotherms were measured and analyzed with the
Langmuir, Freundlich, and Redlich–Peterson equations;
the results correlated well with the Langmuir equation.
Kinetic studies were also performed in an agitated batch
adsorbent to study the effect of the initial dye concen-
tration and the mass of chitosan. The kinetics were ana-
lyzed with the pseudo-first order rate equation, and the
rate constants were determined.
Poly(ethyleneglycol) (PEG) samples of different molecu-
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lar weights were reacted with a diisocyanate ester and poly-
urethane (PU). The product obtained was then mixed with
chitosan to form a polymer adsorbent,[134] which was tested
for adsorption of acidic dyestuffs under various conditions.
The results showed that under all the tested conditions, the
blended polymer adsorbent possessed a better adsorbing
ability than chitosan itself.
The adsorption of indigo carmine dye onto chitin and
chitosan from aqueous solutions was carried out using a
batch system.[135]
The adsorption of eosin Y from aqueous solution using
modified nanoparticles chitosan was investigated.[136] The
nanoparticles were characterized by atomic force microscopy
(AFM) and zeta potential analysis. A batch method was
applied to study the adsorption reaction. The results showed
that the adsorption of eosin Y on chitosan nanoparticles was
affected by contact time, eosin Y concentration, pH and
temperature. The adsorption reaction follows Langmuir
isotherm model and the adsorption capacity was found to
be 3.3 g=g. The adsorption process was endothermic in nature
with an enthalpy change (DH ) of 16.7 kJ=mol at 20–50 C.
The optimum pH value for eosin Y removal was found to
be 2–6. The dye was desorbed from the chitosan nanoparti-
cles by increasing the pH of the solution.
Physicochemical investigation on adsorption of congo
red, (an anionic azo dye) by chitosan hydrobeads has been
carried out.[137] Adsorption process has been found to be
dependent on temperature with optimum activity at
30 C. Both ionic interaction as well as physical forces
is responsible for binding of congo red with chitosan.
Theoretical correlation of the experimental equilibrium
adsorption data for congo red–chitosan hydrobeads system
would be best explained by linearized form of Langmuir
isotherm model. The kinetic results follow pseudo
second-order rate equation.
279
Acid Green 25, which is a diazoic dye bearing two sulfo-
nic groups, is efficiently sorbed on chitosan.[138] The proto-
nation of chitosan may explain the electrostatic attraction
of this anionic dye.
Chiou and Li[139] studied the adsorption of reactive
dye (reactive red 189) from aqueous solutions on cross-
linked chitosan beads in a batch system. Langmuir and
Freundlich adsorption models were applied to describe
the adsorption isotherm. The pseudo first- and second-
order kinetic models were used to describe the kinetic
behavior.
Chiou and Li[140] studied also the effect of cross-linker
on adsorption of reactive dye (reactive red 189) from aque-
ous solutions. The ionic cross-linking reagent sodium tripo-
lyphosphate was used to obtain more rigid chitosan beads.
To stabilize chitosan in acidic solutions, cross-linking
reagents such as epichlorohydrin (ECH), glutaraldehyde
and ethyleneglycol diglycidyl ether were used. Thermodyn-
amic parameters of adsorption process such as change in
free energy (DG ), enthalpy (DH ), and entropy (DS )
energy were determined. The adsorption mechanism is
shown to be the electrostatic interactions between the dye
and chitosan beads.
N,O-carboxymethyl-chitosans (N,O-CMC) with differ-
ent degree of substitution (DS) were synthesized under
heterogeneous conditions by controlling the reaction tem-
perature.[141] The factors influencing adsorption capacity
of N,O-CMC toward congo red (CR) such as the DS of
N,O-CMC, initial pH value of the dye solution, and
adsorption temperature.
The adsorption of Remazol black 13 (reactive) dye onto
chitosan in aqueous solutions was investigated.[142] The
equilibrium adsorption data of reactive dye on chitosan
were analyzed by Langmuir and Freundlich models. The
maximum adsorption capacity (qm) has been found to be
91.47–130.0 mg=g. The kinetics of reactive dye adsorption
followed the pseudo-first and second-order rate expression,
which demonstrates that intraparticle diffusion plays a sig-
nificant role in the adsorption mechanism. Isotherms have
also been used to obtain the thermodynamic parameters
such as free energy, enthalpy, and entropy of adsorption.
The positive value of the enthalpy change (0.212 kJ=mol)
indicated that the adsorption is endothermic process. The
results indicate that chitosan is suitable as adsorbent
material for adsorption of reactive dye form aqueous
solutions.
The sorption of methyl orange by chitosan cross-linked
particles was studied.[143] Zeta potential measurements
indicated that electrostatic interactions were important
for the sorption process.
The evaluatation of the adsorption of two reactive dyes,
methylene blue (MB) and benzopurpurin (BP), from
aqueous solutions by the utilization of chitosan-TiO micro-
porous was carried out.[144]
 280 K. Z. ELWAKEEL
Adsorption of five acid dyes onto chitosan was
studied.[145] The rate of batch adsorption was controlled
by the intraparticle diffusion.
Modified chitosan beads were used for the removal of
cationic dye malachite green (MG) from aqueous sol-
ution.[146] The sorption data were analyzed using linear
form of Langmuir and Freundlich equation. Ninety-nine
percent of MG was removed at the optimum pH value of
8. The sorption process followed the pseudo-second order
kinetic model. The sorption process is spontaneous. The
interactions between MG and chitosan bead was investi-
gated by FTIR analysis.
The immobilization of reactive blue 2 (RB2) dye on
chitosan microspheres was carried out.[147] The adsorption
behavior of the immobilized chitosan toward Cu2þ and
Ni2þ was also studied. Langmuir model resulted in the best
fit for both metals and maximum adsorption was 57.0 mg=
g (0.90 mmol=g) for Cu2þ and 11.2 mg=g (0.19 mmol=g) for
Ni2þ. The Cu2þ and Ni2þ ions were desorbed from
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chitosan-RB2 with aqueous solutions of EDTA and
H2SO4, respectively.
The adsorption isotherms and rates of adsorption of two
dyes and humic acid from aqueous solutions onto chitosan-
encapsulated activated carbon (CEAC) beads were mea-
sured at 30 C.[148] It was shown that the isotherms of dyes
and humic acid were well fitted by the Freundlich equation.
The adsorption capacity and rate were enhanced when acti-
vated carbon was encapsulated with chitosan.
Adsorption of reactive dye from aqueous solution onto
cross-linked chitosan=oil palm ash composite beads (CC=
OPA) was investigated.[149] Kinetic and isotherm studies
were carried out at different experimental conditions, such
as initial concentration (50–500 mg=L), contact time, pH
(2–13), and temperature (30, 40, 50 C). It was found that
the dye uptakes were much higher in acidic solutions than
those in neutral and alkaline conditions. Langmuir,
Freundlich, Redlich–Peterson, and Temkin isotherms
were models were applied to analyze the equilibrium data
at different temperatures. Kinetic studies showed that
the adsorption followed a pseudo-second order model.
Thermodynamic parameters such as standard Gibbs free
energy (DG ), standard enthalpy (DH ), and standard
entropy (DS ) were calculated by applying the Van’t Hoff
equation.
3. MAGNETIC CHITOSAN BEADS
Magnetic chitosans have great applications in the field
of pollutants removal due to the easy separation from the
removal medium.[150–154]
Chang and Chen[155] prepared chitosan-bound Fe3O4
nanoparticles as a magnetic nanoadsorbent for the removal
of heavy metal ions. The chitosan-bound Fe3O4 nano-
particles were used for the removal of Cu2þ at pH > 2.
The adsorption rate was so fast that the equilibrium was
achieved within 1 minute due to the absence of internal
diffusion resistance. Magnetic chitosan particles were pre-
pared from chitosan coated on magnetic powder and cross-
linked by glutaraldehyde and then epichlorohydrin.[156]
A chitosan-based ferrimagnetic membrane (Chitosan=
NiFe2O4) was prepared and applied for removal of Hg2þ,
Cu2þ and Zn2þ ions from aqueous solutions.[157] The
results indicate that the chitosan=NiFe2O4 is a good candi-
date for removal of heavy metals from polluted water. Its
recovery can be done by an electromagnet.
The removal of Zn2þ using a magnetic nanoadsorbent
modified chitosan was carried out.[158] The adsorption rate
was so rapid that the equilibrium was achieved within 2
minutes. The thermodynamic studies indicated that the
adsorption process was exothermic.
4. INTERACTION MECHANISMS
Despite the large number of papers dedicated to the
sorption of metal ions, most of them focus on the evalu-
ation of sorption performances and only a few of them
aim at gaining a better understanding of sorption mechan-
isms. However, it is accepted that amine sites are the main
reactive groups for metal ions, though hydroxyl groups
(especially in the C-3 position) may contribute to sorption.
These reactive groups may interact with metal ions through
different mechanisms depending on the metal, the pH, and
the matrix of the solution. The free electron doublet on
nitrogen may bind metal cations at pH close to neutrality
(or weak acidity).[159–161] On the other hand, the protona-
tion of amine groups in acidic solutions gives the polymer
a cationic behavior and consequently the potential for
attracting metal anions.[54,162] It is important to observe
that the sorption of a metal may involve different mechan-
isms (chelation versus electrostatic attraction) depending
on the composition of the solution, the pH, since these
parameters may affect the protonation of the polymer
(repulsion of metal cations) and the speciation of metal
ions. The chelation of metal cations by ligands in solution
may result in the formation of metal anions, which there-
fore turns the chelation mechanism on chitosan to an elec-
trostatic attraction mechanism on protonated amine
groups of the polymer.
Rhazi et al.[163] found that the coordination number for
chitosan (ligand–metal molar ratio) varied from 1 at pH 5.3
to 2 at pH 5.8. The change in the conformation of the poly-
mer (dissolved state, solid state, etc.) may be a cause of a
change in the coordination mechanism and more specifi-
cally the kind of complex formed between Cu2þ and amine
groups. Most of the studies were performed with chitosan
solutions using oligomers or polymers and it was generally
concluded that the monomer (glucosamine unit) is not very
efficient at complexing Cu2þ. Oligomers proved more
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
efficient, though the minimum degree of polymerization
required for efficient sorption varies according to the
author. Shahgoli et al.[164] observed strong chelation of
copper with chitosan tetrasaccharide, while Rhazi
et al.[163] found that that the threshold value for the poly-
merization degree was 6. The need for polymerization is
another piece of evidence for the contribution of several
glucosamine units in the sequestration mechanism,
undoubtedly due to the contribution of hydroxyl groups
of vicinal units together with amine groups of a given
monomer. Few studies have been published on the
interpretation of the chelation mechanisms of chitosan
with other metals. Hirano et al.[165] described the formation
of a 1:1 complex between the amine groups of chitosan
and uranyl ions: elemental analysis obtained a U=N ratio
close to 1.
Piron and Domard[166] found that uranium is adsorbed
on chitosan in a pendant mode by reaction of amine groups
with uranyl divalent cations together with 2 OH groups,
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the fourth site being occupied by either a water molecule
or the OH group in C-3 position in the glucosamine unit.
The saturation of the polymer by uranyl ions showed that
approximately 1 mol of uranyl ions was sorbed for 2 mol of
amino groups contained in the amorphous domain. This
result can be related to the intrinsic properties of chitosan.
Desorption experiments are in favor of strong interaction,
in fact, no desorption was observed whatever the experi-
mental conditions. Spectroscopic characterization was per-
formed on complexes in solution and in the solid state. On
the other hand, the correlation of optimum sorption with
experimental conditions corresponding to the predomi-
nance of hydrolyzed uranyl species ((UO2)3(OH)5þ) has
been used for identifying these hydrolyzed species as the
adsorbable species.[118] The large size of this species may
introduce diffusion limitations but the sorption of one
polymer unit corresponds to the sorption of three uranyl
units, which may explain the high sorption capacities
reached with this ion. A first attempt at using molecular
mechanical modeling has recently been made in order to
correlate experimental sorption data to chelation mechan-
isms for the sorption of lead and mercury using chitosan
and pectic acid.[167,168] The authors arrive at contrasting
conclusions, showing the difficulty of using simple models
for the interpretation of the interactions of these polymeric
materials with metals. They conclude that several sorption
sites may be involved in the sorption of these metal cations,
complementary studies seem to be necessary in order to
obtain a better insight into the sorption mechanisms. Simi-
larly debatable conclusions have been reached using den-
sity functional theory for the interpretation of copper
and nickel sorption on chitosan: Braier and Jishi[169] pro-
posed a model whereby the sorption of metal ions takes
place in the vicinity of the glycosidic oxygen with contribu-
tions from nitrogen and OH groups, but these hypotheses
281
are not supported by gas phase mass spectrometry.[164] It
is interesting to observe that chitosan has very limited affin-
ity for alkaline and alkaline earth metals due to the absence
of d and f unsaturated orbitals (unlike transition
metals).[28] Therefore, chitosan is selective of transition
metals over common nontransition metals. However, these
metal ions can be sorbed on chitosan derivatives when
phosphorylated groups are grafted on the polymer.[170]
Sorlier et al.[171] extensively studied the acid-base
properties of chitosan in function of the degree of acety-
lation and the dissociation degree. These properties are
key parameters for the understanding of the electrostatic
properties of chitosan and its cationic behavior, which in
turn may influence its ability to bind anions through elec-
trostatic attraction. A number of studies have focused on
the sorption of metal anions and anionic dyes on chitosan
and derivative materials. At neutral pH, about 50% of total
amine groups remain protonated and theoretically avail-
able for the sorption of metal anions. However, the exist-
ence of free amine groups may cause direct chelation of
metal cations (which may co-exist with anionic species,
depending on the speciation of the metal). As the pH
decreases, the protonation of amine groups increases,
together with the efficiency. The distribution coefficient
can be defined as the ratio of sorption capacity q (concen-
tration of the metal on the sorbent, mol=g) to the equilib-
rium concentration of the metal in the solution (Ce, M).
Usually the logarithm of the distribution coefficient can
be plotted versus the pH and the slope of the curve can
be used to determine the stoichiometry of ion exchange
(the amount of metal adsorbed per mole of protonated
amine groups).[172] Actually, in most cases, with raw chito-
san, the distribution coefficient reaches a maximum before
it decreases at low pH. This decrease may be explained by a
strong competitor effect of the anions brought about by the
dissociation of the acid used for pH control, or present in
the matrix of the solution. The optimum pH is frequently
found around pH 2–4.[173–175] Below this limit value,
usually a large excess of competitor anions limits sorption
efficiency. This competitor effect is the subject of many stu-
dies aiming to develop chitosan derivatives that are less
sensitive to the presence of competitor anions.[176,177] This
electrostatic attraction may occur by direct interaction with
free metal anions, but that mechanism may be also
involved in the sorption of metal complexes, as a result
of the interaction of metal cations with ligands in the sol-
ution.[178] Actually, the formation of complexes, with
ligands and=or OH influences the speciation of metals
ions and thus the sorption efficiency and uptake mech-
anism. This property of electrostatic interaction between
protonated amine groups and anions has been used for
the gelation of chitosan.[179] For example, in the case of
molybdate, polynuclear species may interact with several
amine groups from the same chain or different chains,
 282 K. Z. ELWAKEEL
strengthening the structure of the polymer and preventing
it from dissolving in moderate acidic solutions. Polyoxoa-
nions and polyphosphate anions are very efficient for the
formation of these multiple bonds.[180]
Since alkaline and alkaline-earth metals are not signifi-
cantly sorbed on raw chitosan, it is necessary to graft
phosphate or phosphonic groups on the chitosan back-
bone.[170,181,182] Another possibility was recently developed
by Domard’s group for the uptake of calcium and stron-
tium on raw chitosan.[166,183–185] The mechanism involves
the formation of a ternary complex between calcium, chit-
osan and sodium undecylenate. One calcium ion is involved
in the formation of an ion pair with two carboxylate
groups of undecylenate before the ion pair complexes with
the amine groups of chitosan.[183] They found that the
interaction is significantly weaker than that involved in
coordination mechanisms. Piron et al.[184] developed a
similar approach for the uptake of 85Sr found in waste
streams from nuclear power plants. While strontium was
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not adsorbed on chitosan, the addition of carbonate led
to the sorption of strontium. Experiments performed at
different ionic strengths confirmed that the interaction
was not based on an electrostatic attraction mechanism,
and the interaction of –NH2 groups with ðSr2þ ; CO2 3 Þ
ion pairs appeared the most probable mechanism.
5. SELECTIVITY AND COMPETITOR EFFECTS
Only a limited number of studies have been carried out
on the sorption of metals in multi-component solutions
using chitosan, and, generally, these studies were per-
formed in experimental conditions that do not really allow
the selectivity of the sorption to be determined. Indeed, the
precipitation phenomena that may occur under different
pH and concentration ranges for the different metals can
lead to misunderstandings and inaccurate interpretation
of sorption phenomena. Moreover, the comparison of
sorption performance would require a full study at differ-
ent pHs corresponding to the optimum pHs for sorption
of the different metals before a well-established conclusion
could be reached. For example, in acidic solutions chitosan
protonation enables adsorption of metal anions but signifi-
cantly reduces the affinity of the sorbent for the uptake of
metal cations. Hence, metal anions (precious metal ions,
for example) can be recovered selectively from transition
metals (base metals).[58] Generally, except in the case of for-
mation of ternary complexes, chitosan has no affinity for
alkaline and alkaline-earth metals, therefore it is possible
to separate transition metals from these background
metals. The presence of anions (chloride, nitrate, etc.) in
excess can significantly decrease the efficiency of metal
anion sorption due to their competitor effect for
interaction with protonated amine groups. While the
presence of chloride at low concentration allowed the
formation of chloro-anionic species for platinum and
palladium, thus improving sorption capacities, at high con-
centration it greatly reduced metal recovery on glutaralde-
hyde cross-linked chitosan.[186] This competitor effect may
be reduced by chemical modification of the chitosan (graft-
ing of chelation groups, such as sulfur and nitrogen
compounds).[58] The selective separation of metals can
also be increased by modification of the chemical structure
of the polymer using, for example, a template formation
procedure.[187]
Metal-loaded sorbents may be used for complementary
sorption processes, taking advantage of the ability of the
metal loaded on chitosan to sorb other solutes. For
example, in the case of molybdate-loaded chitosan beads,
the chelating affinity of molybdate for arsenic has been
used for the recovery of As5þ and As3þ from dilute
solutions.[188,189]
Arsenate ions were strongly adsorbed in the pH range
from 2 to 4 with a minimum release of molybdate ions.[188]
The sorption mechanism is a complexation between arsen-
ate ions and molybdate anions. Even at low equilibrium
concentration, the sorption capacity is high, and allows
the process to be used as a finishing treatment. Phosphate
ions significantly depressed arsenate collection because of
a competing reaction for the active sites. Simultaneously
with the arsenate sorption, molybdate is released to a sig-
nificant extent. This release can be reduced using a treat-
ment of molybdate impregnated chitosan beads with
orthophosphoric acid (to obtain MICB-PO4). The treat-
ment allows weakly bound molybdenum to be removed
from the sorbent during As5þ sorption: molybdate release
does not exceed 2%. The Langmuir equation fits best the
experimental data for As5þ sorption on MICB-PO4 at
pH 3 up to equilibrium concentration of 80 mg=L. A selec-
tive and total elution can be carried out using a 0.05–1 M
orthophosphoric acid solution. Three sorption:desorption
cycles were performed with no significant decrease in
uptake performance.
The adsorption behavior of N-succinyl-chitosan (NSC)
for Cu2þ ion was investigated.[190] The equilibrium adsorp-
tion data of NSC have been found to fit the Langmuir
adsorption isotherm, and the saturation adsorption
capacity is 2.74 mmol=g. Based on the obtained optimum
condition of the influences of the pH, the adsorption tem-
perature and time, the degree of substitute (DS) of NSC
and the dosage of cross-linking agent, a new perfect
adsorbent material, cross-linked NSC resins with Cu2þ as
template ions (cross-linked NSC template) was synthesized.
The adsorption experiments indicated that the cross-linked
NSC template and NSC can selectively adsorbed Cu2þ ions
from the solution of Cu2þ, Zn2þ, Co2þ, and Ni2þ ions
coexistence, but the selectivity of the cross-linked NSC
template is higher than that of NSC. Furthermore, the
cross-linked NSC template has shown a good reusability.
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
The FTIR analysis results revealed that the adsorption sites
mainly occur on the carboxyl groups of the succinyl groups
of the cross-linked NSC template in the Cu2þ adsorption
process.
The influence factors of the pH value, the degree of sub-
stitution of carboxymethyl-chitosan (CMC) and the dosage
of cross-linking agent on the adsorption for Zn2þ ion were
investigated, and then the cross-linked CMC resin with
Zn2þ as template ion was synthesized at the optimum
adsorption conditions for Zn2þ ions.[191] The adsorption
properties and selectivity for Cu2þ, Co2þ, Ni2þ, Zn2þ,
Cd2þ, and Hg2þ ion were discussed. The results showed
that the adsorption capacities of the resin for above metal
ions are lower than those of CMC, but the selectivity for
Zn2þ was greatly increased. The adsorption mechanisms
of CMC and the resin for zinc sulfate have also been inves-
tigated by means of x-ray photoelectron spectroscopy
(XPS), IR spectra and SEM. The XPS and FT-IR spectra
reveal that CMC and the resin coordinated with Zn2þ
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
mainly through oxygen atom in the CH2COO and
OH groups, and nitrogen atom in the NH2 group of
the polymer chain. The SEM results show that the Zn2þ
distribute on the surface of the resin–Zn2þ complex
uniformly, while distribute on the surface of CMC–Zn2þ
complex in the bulk.
Two different processes have been used for the prep-
aration of molybdate-impregnated chitosan beads: the
sorption process,[189] and the coagulation process.[192] The
critical parameter is the strength of the chitosan-molybdate
interaction, since it controls the release of molybdate dur-
ing the arsenic sorption process. A partial release of molyb-
date in the solution leads to the formation of an
arsenic-molybdate complex that is not adsorbable on chit-
osan. Therefore, arsenic sorption is decreased and there is a
supplementary contamination of the solution with molyb-
date ions. This release effect is limited when molybdate-
impregnated chitosan beads are treated with phosphoric
acid: this pretreatment enables the labile molybdate frac-
tion to be removed from the beads. The coagulation pro-
cess increases the stability of the molybdate on the beads.
Under optimum experimental conditions, sorption capaci-
ties can reach up to 200 mg As=g Mo. Yoshizuka et al.
prepared silver-loaded chitosan for the recovery of pesti-
cides.[193] Indeed, some pesticides such as parathion bear
sulfur functions that can interact with silver ions immobi-
lized on the polymer support. Recently, Shi et al.[194] used
silica coated with chitosan for the preparation of immobi-
lized metal affinity support for the recovery of protein.
These supports were characterized by their high stability
in alkaline media and for repeated uses.
Chitosan (CS) gel beads were prepared by using phase
inversion and precipitation technique.[195] The gel beads
could bind Cu2þ, by which Cu2þ ion-immobilized chitosan
gel beads (CS-Cu2þ gel beads) were prepared, and the
283
amount of the immobilized Cu2þ was about 35 mg=g when
the CS gel beads were incubated in 150 ppm cupric sulfate
solution. The CS-Cu2þ gel beads could selectively adsorb
histidine (His) from the mixed solution containing His
and tryptophan (Trp); and the selective coefficient which
was defined as the adsorbed amount ratio of His to Trp
was about 8.0 at the pH value of 7.4. The effect of the
pH value on the amino acid adsorption was also studied.
Silica gel bead coated with macroporous chitosan layer
(CTS-SiO2) was prepared, and the metal immobilized affin-
ity chromatographic (IMAC) adsorbents could be obtained
by chelating Cu2þ, Zn2þ, Ni2þ ions, respectively, on
CTS-SiO2, and trypsin could be adsorbed on the IMAC
adsorbent through metal–protein interaction forces.[196]
Batch adsorption experiments show that adsorption
capacity for trypsin on these IMAC adsorbent variated
with change of pH. The maximal adsorption reached when
the solution was in near neutral pH in all three IMAC
adsorbents. Trypsin immobilized on the IMAC beads
could not be desorbed by water, buffer and salt solution
if the pH was kept in the range of 5–10, and could be easily
desorbed from the IMAC beads by acidic solution and
metal chelating species such as EDTA and imidazole.
6. DESORPTION AND SORBENT RECYCLING
The use of chitosan for metal recovery can be limited by
the cost of the polymer compared to other waste materials.
Except in the case of precious metals for which the cost of
the sorbent is not a limiting criterion (taking into account
the high sorption capacities that can be achieved), the recy-
cling of the polymer is a required step in the design of the
process. The recovery of the metal is also an important
parameter for the economics of the process.[197] This aspect
has not been adequately studied and there is very little
literature focusing on this topic. However, the sorption
mechanisms involved in metal uptake can provide an orien-
tation for the design of the desorption strategy. In the case
of the sorption of metal cations, the chelation mechanism is
very sensitive to pH and usually sorption does not occur at
low pH. Therefore, a simple change in the pH of the sol-
ution may reverse the reaction. However, to prevent the
polymer dissolving it will be necessary to use sulfuric
acid.[198] It would be also possible to use a strong chelating
agent (such as EDTA): the complexation of the metal by
the ligand can displace the metal from the sorbent.[199]
However, this method is more complex and the eluate con-
tains chelated metal, which is less easy to recycle. The
method of pH change has also been successfully used for
desorbing metal anions from loaded sorbent. However, in
this case it was necessary to increase the pH using sodium
hydroxide (or ammonium hydroxide).[200] Molybdate was
completely recovered from loaded phases using NH4OH=
NH4CL buffer pH 10. The sorbent can be successfully
 284 K. Z. ELWAKEEL
re-used with no significant decrease in sorption capaci-
ties,[200] but its recycling requires re-conditioning of the
polymer in acidic conditions prior to subsequent cycles of
metal sorption. However, desorption of metal anions can-
not be systematically achieved in alkaline conditions. For
example, in the case of precious metal sorption, the
strength of sorbent-metal interactions does not allow a sig-
nificant fraction of the metal to be recovered and better
desorption is achieved using very acidic solutions (HCl
for example at concentration higher than 3 M) or strong
chelating agents such as thiourea.[201]
The industrial user can be additionally rebutted by some
commercial external parameters related to the price of raw
material that may limit the competitiveness of chitosan ver-
sus styrene-DVB conventional resins (commercial resins),
especially when the process is targeted to the recovery of
common heavy metals and for the treatment of large flow
rates. For this reason the chitosan process seems to be more
appropriate (a) for polishing treatment; (b) for specific treat-
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
ments involving valuable metals; or (c) when chitosan is
shown to be highly selective (compared to conventional pro-
cesses, as pointed out above). The cost of raw material is
partly controlled by the lack of large market that would
imply the development of large-capacity production units
(which would result in turn to a decrease of the cost of the
material) and the competition in use for cosmetic and medi-
cal applications that require high quality chitosan with large
added value.[16] There is also a need for a better standardiza-
tion of production process to be able to prepare reproduc-
ible chitosan batches. Sorption properties are strongly
controlled as pointed out above by the characteristics of
chitosan. Changes in the specifications of the polymer may
significantly change sorption performance and would
required adaptation of process design that is not favorable
to a wide spreading of chitosan-based technology. For these
reasons, it sounds that a greater attention should be paid to
using these interaction properties of chitosan with metal
ions for the preparation of new materials.
7. CONCLUSIONS AND RECOMMENDATIONS FOR
FUTURE STUDIES
This review reports the main advances published over
the last two decades. The use of chitosan resins for remov-
ing various pollutants from water and wastewater presents
many attractive features such as the outstanding adsorp-
tion capacity, especially for metal ions and dyes, and the
fact that these materials are low cost, nontoxic and bio-
compatible. However, their affinity for other pollutants
(e.g., phenols, anions, pesticides, humic substances) needs
extensive research. Although the amount of available
literature data for chitosan application in water and waste-
water treatment is increasing at a tremendous pace, the
development in the field of water and wastewater treatment
process using chitosan essentially requires further investi-
gation of testing these materials with real industrial efflu-
ents. It is further suggested that the research should not
limit to only lab scale batch studies, but pilot-plant studies
should also be conducted with the following issues.
(1) Selection and identification of an appropriate form of
chitosan is one of the key issues to achieve the
maximum removal of specific type of pollutant.
(2) The conditions for the production of chitosan loaded
with high concentration of active sites on its surface
need to be optimized, which consequently would
increase the removal efficiency of the resin.
(3) Regeneration studies need to be studied in detail to
recover the metals as well as adsorbent. It will enhance
the economic feasibility of the process.
(4) Cost analysis should be studied. Low production cost
with a higher removal efficiency would make the
process economical and efficient.
If it is possible to develop such adsorbents having all
the above-mentioned characteristics, these adsorbents
may offer significant advantages over currently available
commercially expensive activated carbons and, in addition
contribute to an overall waste minimization strategy.
REFERENCES
[1] Watera, L.G.A., Driessena, W.L., Glennyb, M.W.,
Reedijka, J., and Schroaderb, M. (2002) React. Funct.
Polym., 51: 33.
[2] Yuchi, A., Mukaie, K., Sotomura, Y., Yamada, H., and
Wada, H. (2002) Anal. Sci., 8: 575.
[3] Samala, S., Acharyaa, S., Dey, R.K., and Rayb, A.R.
(2002) Talanta, 57: 1075.
[4] Taek-Seung, L., Dong-Won, J., Jai-Kyeong, K., and Sung,
H. (2001) Fib. Polym., 2: 13.
[5] Egawa, H., Nonaka, T., and Nakayama, M. (1988)
J. Macromol. Sci. Chem., 11: 1407.
[6] Masahiko, C., Morio, N., Tomoo, T., and Hisashi, T.
(1979) Talanta, 26: 911.
[7] Mukherjee, A. and Biswas, M. (1993) Appl. Polym. Sci., 50:
1485.
[8] Nakayama, M., Chikuma, M., Tanaka, H., and Tanaka, T.
(1982) Talanta, 29: 503.
[9] Egawa, H., Nonaka, T., and Maeda, H. (1985) Sep. Sci.
Techn., 20: 653.
[10] Trochimczuk, A.W., Kol, B.N., and Bartkowiak, D.J. Eur.
Polym. J., 37: 559.
[11] Polakovi, J. and Kubov, J. Anal. Chim. Acta, 488: 123.
[12] Fortes, M.C.B., Martins, A.H., and Benedettoa, J.S. (2003)
Miner. Eng., 16: 659.
[13] Prabhakar, L.D. and Marysaral, A. (1997) Polym. Int., 42:
149.
[14] Haron, M.J., Wan Yunus, W.M.Z., and Yong, N.L. (1999)
Chemosphere, 39: 2459.
[15] Ramos, V.M., Rodrıguez, N.M., Rodrıguez, M.S., Heras,
A., and Agullo, E. (2003) Carbohydr. Polym., 51: 425.
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS 285

[16] Ravi Kumar, M.N.V. (2000) React. Funct. Polym., 46: 1. [51] Ngah, W.S.W., Ghani, S.A., and Kamari, A. (2005) Biore-
[17] Sashiwa, H. and Aiba, S. (2004) Prog. Polym. Sci., 29: 887. sour. Technol., 96: 443.
[18] Hirano, S. (1999) Polym. Int., 48: 732. [52] Monteiro Jr., O.A.C. and Airoldi, C. (1999) Int. J. Biol.
[19] Muzzarelli, R.A.A. (1997) Cell Mol. Biol. Life Sci., 53: 131. Macromol., 26: 119.
[20] Yannas, I.V., Burke, H.F., Orgill, D.P., and Skrabut, E.M. [53] Capitani, D., De Angelis, A.A., Crescenzi, V., Masci, G.,
(1982) Science, 215: 174. and Segre, A.L. (2001) Carbohydr. Polym., 45: 245.
[21] Le, Y., Anand, S.C., and Horrocks, A.R. (1997) Ind. J. [54] Paradossi, G., Cavalieri, F., and Crescenzi, V. (1997) Carbo-
Fibre Textile Res., 22: 337. hydr. Res., 300: 77.
[22] Bourtoom, T. and Chinnan, M.S. (2008) LWT-Food Sci. [55] Kawamura, Y., Yoshida, H., Asai, S., and Tanibe, H.
Technol., 41: 1633. (1997) Water Sci. Technol., 35: 97.
[23] Kamel, S., El-Sakhawy, M., and Nada, A.M.A. (2004) [56] Alam, M.S., Inoue, K., and Yoshizuka, K. (1998) Hydrome-
Thermochimica Acta, 421: 81. tallurgy, 49: 213.
[24] Mukoma, P., Jooste, B.R., and Vosloo, H.C.M. (2004) J. [57] Mi, F.-L., Shyu, S.-S., Lee, S.-T., and Wong, T.-B. (1999) J.
Power Sources, 136: 16. Polym. Sci. Polym. Phys., 37: 1551.
[25] Wang, X., Ma, J., Wang, Y., and He, B. (2002) Biomater- [58] Erosa, M.S.D., Medina, T.I.S., Mendoza, R.N., Rodriguez,
ials, 23: 4167. M.A., and Guibal, E. (2001) Hydrometallurgy, 61: 157.
[26] Miyazaki, S., Ishii, K., and Nadai, T. (1981) Chem. Pharm. [59] Kurita, K., Koyama, Y., and Taniguchi, A. (1986) J. Appl.
Bull., 29: 3067. Polym. Sci., 31: 1951.
[27] Chang, Y.-C., Chang, S.-W., and Chen, D.-H. (2006) React. [60] Guibal, E. (2004) Sep. Purif. Technol., 38: 43.
Funct. Polym., 66: 335. [61] Wan Ngah, W.S. and Fatinathan, S. (2008) Chem. Eng. J.,
[28] Hsien, T.-Y. and Rorrer, G.L. Sep. Sci. Technol., 30: 2455. 143: 62.
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010

[29] Vieira, R.S. and Beppu, M.M. (2006) Colloids Surf. A, 279: [62] Chen, A.-H., Liu, S.-C., Chen, C.-Y., and Chen, C.-Y. (2008)
196. J. Hazard. Mater., doi: 10.1016=j.jhazmat.2007.10.009
[30] Denkbas, E.B. and Odabasi, M. J. Appl. Polym. Sci., 76: [63] McKay, G., Blair, H.S., and Gardner, J.R. (1989) J. Appl.
1637. Polym. Sci., 27: 3043.
[31] Agboh, O.C. and Quin, Y. (1997) Polym. Adv. Technol., 8: [64] Ngah, W.S.W., Endud, C.S., and Mayanar, R. (2002)
355. React. Funct. Polym., 50: 181.
[32] Vincent, T. and Guibal, E. (2002) Solvent Extr. Ion Exch., [65] Maruca, R., Suder, B.J., and Wightmen, J.P. (1982) J. Appl.
18: 1241. Polym. Sci., 27: 4827.
[33] Inoue, K., Hirakawa, H., Ishikawa, Y., Yamaguchi, T., [66] Wong, Y.C., Szeto, Y.S., Cheung, W.H., and McKay, G.
Nagata, J., Ohto, K., and Yoshizuka, K. (1996) Sep. Sci. (2003) Langmuir, 19: 7888.
Technol., 31: 2273. [67] Yang, Q., Dou, F., Liang, B., and Shen, Q. (2005) Carbo-
[34] Kurita, K. (2001) Prog. Polym. Sci., 26: 1921. hyd. Polym., 61: 393.
[35] Inoue, K. and Baba, Y. (1997) J. Ion Exch., 8: 115. [68] Osifo, P.O., Webster, A., Merwe, H., Neomagus, H.W.,
[36] Inoue, K., Yoshizuka, K., and Baba, Y. (1997) J. Ion Exch., Gun, M.A., and Grant, D.M. (2008) Bioresour. Technol.,
8: 180. 99: 2377.
[37] Baba, Y. and Inoue, K. (1997) J. Ion Exch., 8: 227. [69] Qi, L. and Xu, Z. (2004) Colloids Surf. A, 251: 186.
[38] Inoue, K., Ohto, K., and Baba, Y. (1998) J. Ion Exch., 9: [70] Twu, Y-K., Huang, H., Chang, S.-Y., and Wang, S.-L.
115. (2003) Carbohydr. Polym., 54: 425.
[39] Trimukhe, K.D. and Varma, A.J. (2008) Carbohydr. [71] Vitali, L., Laranjeira, M.C.M., Gonçalves, N.S., and
Polym., 71: 698. Fávere, V.T. (2008) Int. J. Biol. Macromol., 42: 152.
[40] Ruiz, M., Sastre, A.M., and Guibal, E. (2002) Sep. Sci. [72] Laus, R., Geremias, R., Vasconcelos, H.L., Laranjeira,
Technol., 37: 2385. M.C.M., and Fávere, V.T. (2007) J. Hazard. Mater., 149:
[41] Sreenivasan, K. J. Appl. Polym. Sci., 69: 1051. 471.
[42] Tojima, T., Katsura, H., Nishiki, M., Tokura, S., and [73] Kamble, S.P., Jagtap, S., Labhsetwar, N.K., Thakare, D.,
Sakairi, N. Carbohydr. Polym., 40: 17. Godfrey, S., Devotta, S., and Rayalu, S.S. (2007) Chem.
[43] Juang, R.-S. and Ju, C.-Y. Ind. Eng. Chem. Res., 36: 5403. Eng. J., 129: 173.
[44] Juang, R.-S. and Ju, C.-Y. Ind. Eng. Chem. Res., 37: 3463. [74] Li, N. and Bai, R. (2005) Sep. Purif. Technol., 42: 237.
[45] Muzzarelli, R.A.A. Carbohydr. Polym., 8: 1. [75] Don, T.-M., Hsu, S.-C., and Chiu, W.-Y. (2001) J. Appl.
[46] Tang, L.-G. and Hon, D.N.S. J. Appl. Polym. Sci., 79: 1476. Polym. Sci. A, 39: 646.
[47] Muzzarelli, R.A.A. Carbohydr. Polym., 5: 85. [76] Rhazi, M., Desbrieres, J., Tolaimate, A., Rinaudo, M.,
[48] Shigemasa, Y., Usui, H., Morimoto, M., Saimoto, H., Vottero, P., Alagui, A., and El Meray, M. (2002) Eur.
Okamoto, Y., Minami, S., and Sahiwa, H. (1999) Carbo- Polym. J., 38: 1523.
hydr. Polym., 39: 237. [77] Vasconcelos, H.L., Camargo, T.P., Gonçalves, N.S., Neves,
[49] Peng, C., Wang, Y., and Tang, Y. (1998) J. Appl. Polym. A., Laranjeira, M.C.M., and Fávere, V.T. (2008) React.
Sci., 70: 501. Funct. Polym., 68: 572.
[50] Tan, S., Wang, Y., Peng, C., and Tang, Y. (1999) J. Appl. [78] Cheung, W.H., Ng, J.C.Y., and Mckay, G. (2003) J. Chem.
Polym. Sci., 71: 2069. Technol. Biotechnol., 78: 562.
 286 K. Z. ELWAKEEL
[79] Ng, J.C.Y., Cheung, W.H., and McKay, G. (2002) J.
Colloid Interface Sci., 255: 64.
[80] Hasan, S., Ghosh, T.K., Viswanath, D.S., and Boddu, V.M.
(2008) J. Hazard. Mater., 152: 826.
[81] Rodrigues, C.A., Laranjeira, M.C.M., Favere, V.T., and
Stadler, E. (1998) Polymer, 39: 5121.
[82] Erosa, M.S.D., Medina, T.I.S., Mendoza, R.N.,
Rodriguez, M.A., and Guibal, E. (2001) Hydrometallurgy,
61: 157.
[83] Vijaya, Y., Popuri, S.R., Boddu, V.M., and Krishnaiah, A.
(2008) Carbohydr. Polym., 72: 261.
[84] Paulino, A.T., Santos, L.B., and Nozaki, J. (2008) React.
Funct. Polym., 68: 634.
[85] Sankararamakrishnan, N., Sharma, A.K., and Sanghi, R.
(2007) J. Hazard. Mater., 148: 353.
[86] Baroni, P., Vieira, R.S., Meneghetti, E., da Silva, M.G.C.,
and Beppu, M.M. (2008) J. Hazard. Mater., 152: 1155.
[87] Cervera, M.L., Arnal, M.C., and de la Guardia, M. (2003)
Anal. Bioanalytical Chem., 375: 820.
[88] Shafaei, A., Ashtiani, F.Z., and Kaghazchi, T. (2007) Chem.
Eng. J., 133: 311.
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
[89] Jeon, C. and Ha Park, K. (2005) Water Res., 39: 3938.
[90] Atia, A.A. (2005) Hydrometallurgy, 80: 13.
[91] Vieira, R.S. and Beppu, M.M. (2006) Water Res., 40: 1726.
[92] Jeon, C. and Oll, W.H.H. (2003) Water Res., 37: 4770.
[93] Vieira, R.S. and Beppu, M.M. (2006) Colloids Surf. A, 279:
196.
[94] Yang, Z. and Li, J. (2002) J. Appl. Polym. Sci., 86: 2677.
[95] Chassary, P., Vincent, T., Marcano, J.S., Macaskie, L.E.,
and Guibal, E. (2005) Hydrometallurgy, 76: 131.
[96] Ruiz, M., Sastre, A.M., and Guibal, E. (2000) React. Funct.
Polym., 45: 155.
[97] Sabarudin, A., Lenghor, N., Oshima, M., Hakim, L.,
Takayanagi, T., Gao, Y.-H., and Motomizu, S. (2007)
Talanta, 72: 1609.
[98] Becker, T., Schlaak, M., and Strasdeit, H. (2000) React.
Funct. Polym., 44: 289.
[99] Erosa, M.S.D., Medina, T.I.S., Mendoza, R.N.,
Rodriguez, M.A., and Guibal, E. (2001) Hydrometallurgy,
61: 157.
[100] Rojas, G., Silva, J., Flores, J.A., Rodriguez, A., Ly, M., and
Maldonadob, H. (2005) Sep. Purif. Technol., 44: 31.
[101] Qian, S., Wang, H., Huang, G., Mo, S., and Wei, W. (2004)
J. Appl. Polym. Sci., 92: 1584.
[102] Guzman, J., Saucedo, I., Navarro, R., Revilla, J., and
Guibal, E. (2002) Langmuir, 18: 1567.
[103] Hakim, L., Sabarudin, A., Oshita, K., Oshima, M., and
Motomizu, S. (2008) Talanta, 74: 977.
[104] Sabarudin, A., Oshima, M., Noguchi, O., and Motomizu, S.
(2007) Talanta, 73: 831.
[105] Guibal, E., Milot, C., Eterradossi, O., Gauffier, C., and
Domard, A. (1999) Int. J. Biol. Macromol., 24: 49.
[106] Sabarudin, A., Oshita, K., Oshima, M., and Motomizu, S.
(2005) Talanta, 66: 136.
[107] Ishii, H., Minegishi, M., Lavitpichayawong, B., and Mitani,
T. (1995) Int. J. Biol. Macromol., 17: 21.
[108] Beppu, M.M., Arrud, E.J., Vieira, R.S., and Santos, N.N.
(2004) J. Membr. Sci., 240: 227.
[109] Ramesh, A., Hasegawa, H., Sugimoto, W., Maki, T., and
Ueda, K. (2008) Bioresour. Technol., 99: 3801.
[110] Fujiwara, K., Ramesh, A., Maki, T., Hasegawa, H., and
Ueda, K. (2007) J. Hazard. Mater., 146: 39.
[111] Lima, I.S. and Airoldi, C. (2004) Thermochimica Acta, 421:
133.
[112] Cardenas, G., Orlando, P., and Edelio, T. (2001) Int. J. Biol.
Macromol., 28: 167.
[113] Merrifield, J.D., Davids, W.G., MacRae, J.D., and
Amirbahman, A. (2004) Water Res., 38: 3132.
[114] Inoue, K., Yamaguchi, T., Shinbaru, R., Hirakawa, H.,
Yoshizuka, K., and Ohto, K. (1996) Adv. Chitin Sci., 1: 271.
[115] Schnurch, A.B., Paikl, C., and Valenta, C. (1997) Pharma-
col. Res., 14 (7): 917.
[116] Inoue, K., Ohto, K., Yoshizuka, K., Yamaguchi, T., and
Tanaka, T. (1997) Bull. Chem. Soc. Jpn., 70: 2443.
[117] Hakim, L., Sabarudin, A., Oshima, M., and Motomizu, S.
(2007) Anal. Chim. Acta, 588: 73.
[118] Guibal, E., Saucedo, I., Roussy, J., and Le Cloirec, P.
(1994) React. Polym., 23: 147.
[119] Shimizu, Y., Izumi, S., Saito, Y., and Yamaoka, H. (2004)
J. Appl. Polym. Sci., 92: 2758.
[120] Delben, F. (1989) Carbohydr. Polym., 11: 205.
[121] Guzman, J., Revilla, J., Navarro, R., and Guibal, E. (2003)
Int. J. Biol. Macromol., 33: 57.
[122] Wan, L., Wang, Y., and Qian, S. (2002) J. Appl. Polym.
Sci., 84: 29.
[123] Tang, X.-H., Tan, S.-Y., and Wang, Y.-T. (2002) J. Appl.
Polym. Sci., 83: 1886.
[124] Kawamura, Y., Mitsuhashi, M., Tanibe, H., and Yoshida,
H. (1993) Ind. Eng. Chem. Res., 32: 386.
[125] Chiessi, E., Palleschi, A., Paradossi, G., Venanzi, M., and
Pispisa, B. (1991) J. Chem. Res. Synop., 9: 248.
[126] Kondo, K., Sumi, H., and Matsumoto, M. (1996) Sep. Sci.
Technol., 31: 1771.
[127] Martins, A.O., da Silva, E.L., Carasek, E., Gonçalves, N.S.,
Laranjeira, M.C.M., and de Favere, V.T. (2004) Anal.
Chim. Acta, 521: 157.
[128] Kang, D.W., Choi, H.R., and Kweon, D.K. (1999) J. Appl.
Polym. Sci., 73: 469.
[129] Akkaya, R. and Ulusoy, U. (2008) J. Hazard. Mater., 151:
380.
[130] Amuda, O.S., Giwa, A.A., and Bello, I.A. (2007) Biochem.
Eng. J., 36: 174.
[131] Qu, R., Sun, Y., Wang, C., Lu, S., Yu, H., and Cheng, G.
(2002) J. Appl. Polym. Sci., 84: 310.
[132] Lasko, C.L., Adams, K.H., Benedet, E.M., and West, P.A.
(2004) J. Appl. Polym. Sci., 93: 2808.
[133] Wong, Y.C., Szeto, Y.S., Cheung, W.H., and McKay, G.
(2004) J. Appl. Polym. Sci., 92: 1633.
[134] Shih, C.-Y., Chen, C.-W., and Huang, K.-S. (2004) J. Appl.
Polym. Sci., 91: 3991.
[135] Prado, A.G.S., Torres, J.D., Faria, E.A., and Dias, S.C.L.
(2004) J. Colloid Interface Sci., 277: 43.
[136] Du, W.L., Xu, Z.R., Han, X.Y., Xu, Y.L., and Miao, Z.G.
(2008) J. Hazard. Mater., 153: 152.
[137] Chatterjee, S., Chatterjee, S., Chatterjee, B.P., and Guha,
A.K. (2007) Colloids Surf. A, 299: 146.
 ENVIRONMENTAL APPLICATION OF CHITOSAN RESINS
[138] Gibbs, G., Tobin, J.M., and Guibal, E. (2003) J. Appl.
Polym. Sci., 90: 1073.
[139] Chiou, M.-S. and Li, H.-Y. (2002) J. Hazard. Mater., 93:
233.
[140] Chiou, M.-S. and Li, H.-Y. (2003) Chemosphere, 50: 1095.
[141] Wang, L. and Wang, A. (2008) Bioresour. Technol., 99:
1403.
[142] Annadurai, G., Ling, L.Y., and Lee, J.-F. (2008) J. Hazard.
Mater., 152: 337.
[143] Morais, W.A., Fernandes, A.L.P., Dantas, T.N.C., Pereira,
M.R., and Fonseca, J.L.C. (2007) Colloids Surf. A, 310: 20.
[144] Zubieta, C.E., Messina, P.V., Luengo, C., Dennehy, M.,
Pieroni, O., and Schulz, P.C. (2008) J. Hazard. Mater.,
152: 765.
[145] Cheung, W.H., Szeto, Y.S., and McKay, G. (2007) Biore-
sour. Technol., 98: 2897.
[146] Bekçi, Z., Özveri, C., Seki, Y., and Yurdakoç, K. (2008)
J. Hazard. Mater., 154: 254.
[147] Vasconcelos, H.L., Fávere, V.T., Gonçalves, N.S., and
Laranjeira, M.C.M. (2007) React. Funct. Polym., 67:
1052.
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
[148] Wu, F.-C., Tseng, R.-L., and Juang, R.-S. (2002) J. Chem.
Technol. Biotechnol., 77: 1269.
[149] Hasan, M., Ahmad, A.L., and Hameed, B.H. (2008) Chem.
Eng. J., 136: 164.
[150] Denkbas, E.B., Kiliçay, E., Birlikseven, C., and Oztürk, E.
(2002) React. Funct. Polym., 50: 225.
[151] Safarik, I. (1995) Water Res., 29: 101.
[152] Safaik, I. and Safaiková, M. (1996) International Journal of
Biodeterioration and Biodegradation, 37: 251.
[153] Cumbal, L., Greenleaf, J.E., Leun, D., and SenGupta, A.
(2003) React. Funct. Polym., 54: 167.
[154] Marco, M.J.D., Gupta, A.S., and Greenleaf, J.E. (2003)
Water. Res., 37: 164.
[155] Chang, Y.-C. and Chen, D.-H. (2005) J. Colloid Interface
Sci., 283: 446.
[156] An, X. and Su, Z. (2001) J. Appl. Polym. Sci., 81: 1175.
[157] Macêdo, M.A., Silva, M.N.B., Cestari, A.R., Vieira, E.F.S.,
Sasaki, J.M., Góes, J.C., and Albino Aguiar, J. (2004)
Physica B, 354: 171.
[158] Zhou, L., Wang, Y., Liu, Z., and Huang, Q. (2006) Acta
Physico-Chimica Sinica, 22: 1342.
[159] Randall, J.M., Randall, V.G., McDonald, G.M., Young,
R.N., and Masri, M.S. (1979) J. Appl. Polym. Sci., 23: 727.
[160] Peniche-Covas, C., Alvarez, L.W., and Argüelles-Monal,
W. (1992) J. Appl. Polym. Sci., 46: 1147.
[161] Vasconcelos, M.T., Leal, M.F., and Soares, H.M.V.M.
(1996) Anal. Chim. Acta, 330: 273.
[162] Guibal, E., Ruiz, M., Vincent, T., Sastre, A., and Navarro
Mendoza, R. (2001) Sep. Sci. Technol., 36: 1017.
[163] Rhazi, M., Desbrières, J., Tolaimate, A., Rinaudo, M.,
Vottero, P., and Alagui, A. (2002) Polymer, 43: 1267.
[164] Shahgholi, M., Callahan, J.H., Rappoli, B.J., and Rowley,
D.A. (1997) J. Mass Spectrom., 32: 1080.
[165] Hirano, S., Kondo, Y., and Nakazawa, Y. (1982) Carbo-
hydr. Res., 100: 431.
[166] Piron, E. and Domard, A. (1998) Int. J. Biol. Macromol.,
22: 33.
287
[167] Ferreira, M.L. and Gschaider, M.E. (2001) Macromol.
Bioscience, 1: 233.
[168] Debbaudt, A., Zalba, M., Ferreira, M.L., and Gschaider,
M.E. (2001) Macromol. Biosci., 1: 249.
[169] Braier, N.C. and Jishi, R.A. (2000) J. Mol. Struct. Theo-
chem., 499: 51.
[170] Nishi, N., Ebina, A., Nishimura, S.-I., Tsutsumi, A.,
Hasegawa, O., and Tokura, S. (1986) Int. J. Biol. Macro-
mol., 8: 311.
[171] Sorlier, P., Denuzière, A., Viton, C., and Domard, A. (2001)
Biomacromolecules, 2: 765.
[172] Gibbs, G., Tobin, J.M., and Guibal, E. (2004) Ind. Eng.
Chem. Res., 43: 1.
[173] Arrascue, M.L., Maldonado Garcia, H., Horna, O., and
Guibal, E. (2003) Hydrometallurgy, 71: 191.
[174] Guibal, E., Milot, C., and Roussy, J. (2000) Sep. Sci. Tech-
nol., 35: 1021.
[175] Guzman, J., Saucedo, I., Revilla, J., Navarro, R., and
Guibal, E. (2002) Langmuir, 18: 1567.
[176] Ruiz, M., Sastre, A.M., and Guibal, E. (2003) Solvent Extr.
Ion Exch., 21: 307.
[177] Guibal, E., Van Offenberg Sweeney, N., Vincent, T., and
Tobin, J.M. (2002) React. Funct. Polym., 50: 149.
[178] Lasko, C.L. and Hurst, M.P. (1999) Environ. Sci. Technol.,
33: 3622.
[179] Brack, H.P., Tirmizi, S.A., and Risen, W.M.J. (1997)
Polymer, 38: 2351.
[180] Lee, S.-T., Mi, F.-L., Shen, Y.-J., and Shyu, S.-S. (2001)
Polymer, 42: 1879.
[181] Nishi, N., Maekita, Y., Nishimura, S.-I., Hasegawa, O., and
Tokura, S. (1987) Int. J. Biol. Macromol., 9: 109.
[182] Heras, A., Rodriguez, N.M., Ramos, V.M., and Agullo, E.
(2001) Carbohydr. Polym., 44: 1.
[183] Demarger, S. and Domard, A. (1995) Carbohydr. Res., 27:
101.
[184] Piron, E. and Domard, A. (1998) Int. J. Biol. Macromol.,
23: 113.
[185] Guibal, E., Milot, C., and Tobin, J.M. (1998) Ind. Eng.
Chem. Res., 37: 1454.
[186] Gavilan, K.C., Pestov, A.V., Garcia, H.M., Yatluk, Y.,
Roussy, J., and Guibal, E. (2009) J. Hazard. Mater., 165: 415.
[187] Alam, M.S., Inoue, K., Yoshizuka, K., and Ishibashi, H.
(1998) Sep. Sci. Technol., 33: 655.
[188] Dambies, L., Guibal, E., and Roze, A. (2000) Colloids Surf.
A, 170: 19.
[189] Dambies, L., Vincent, T., and Guibal, E. (2002) Water Res.,
36: 3699.
[190] Sun, S., Wang, Q., and Wang, A. (2007) Biochem. Eng. J.,
36: 131.
[191] Sun, S. and Wang, A. (2006) React. Funt. Polym., 66: 819.
[192] Dambies, L., Vincent, T., Domard, A., and Guibal, E.
(2001) Biomacromolecules, 2: 1198.
[193] Yoshizuka, K., Lou, Z., and Inoue, K. (2000) React. Funct.
Polym., 44: 47.
[194] Shi, Q.-H., Tian, Y., Dong, X.-Y., Bai, S., and Sun, Y.
(2003) Biochem. Eng. J., 16: 317.
[195] Bai, P., Cao, F., Lan, X., Zhao, F., Ma, Y., and Zhao, C.
(2008) J. Biochem. Biophys. Methods, 70: 903.
 288 K. Z. ELWAKEEL

[196] Wu, J., Luan, M., and Zhao, J. (2006) Int. J. Biol. Macro-
mol., 39: 185.
[197] Coughlin, R.W., Deshaies, M.R., and Davis, E.M. (1990)
Environ. Prog., 9: 35.
[198] McKay, G., Blair, H.S., and Grant, S. (1987) J. Appl.
Polym. Sci., 40: 63.
Downloaded By: [Elwakeel, Khalid Z.] At: 10:27 24 February 2010
[199] Atia, A.A., Donia, A.M., El-Enein, S.A., and Yousif, A.M.
(2007) Sep. Sci. Technol., 42: 403.
[200] Atia, A.A. (2007) Appl. Clay. Sci., 41: 73.
[201] Donia, A.M., Atia, A.A., and Elwakeel, K.Z. (2005) Sep.
Purif. Technol., 42: 111.