Bioresource Technology 96 (2005) 443450

Adsorption behaviour of Fe(II) and Fe(III) ions in aqueous

solution on chitosan and cross-linked chitosan beads
W.S. Wan Ngah *, S. Ab Ghani, A. Kamari
School of Chemical Sciences, Universiti Sains Malaysia, 11800 Penang, Malaysia
Received in revised form 6 May 2004; accepted 20 May 2004

Abstract
A batch adsorption system was applied to study the adsorption of Fe(II) and Fe(III) ions from aqueous solution by chitosan and
cross-linked chitosan beads. The adsorption capacities and rates of Fe(II) and Fe(III) ions onto chitosan and cross-linked chitosan
beads were evaluated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol
diglycidyl ether (EGDE) in order to enhance the chemical resistance and mechanical strength of chitosan beads. Experiments were
carried out as function of pH, agitation period, agitation rate and concentration of Fe(II) and Fe(III) ions. Langmuir and Fre-
undlich adsorption models were applied to describe the isotherms and isotherm constants. Equilibrium data agreed very well with
the Langmuir model. The kinetic experimental data correlated well with the second-order kinetic model, indicating that the chemical
sorption was the rate-limiting step. Results also showed that chitosan and cross-linked chitosan beads were favourable adsorbers.

2004 Elsevier Ltd. All rights reserved.

Keywords: Chitosan beads; Cross-linked chitosan beads; Adsorption capacities; Adsorption rates; Adsorption isotherm

1. Introduction minerals both as Fe(II) and Fe(III). Fe(II) is required

Water pollution by toxic metals remains a serious
environmental problem and can be detrimental to living
systems. Metals can be toxic pollutants that are non-
biodegradable, undergo transformations, and have great
environmental, public health, and economic impacts
(Gupta and Sharma, 2002). In the environment, one
element can be present in dierent chemical forms,
which dier in their chemical behaviour, bioavailability
and toxicity. Some elements such as iron (Mulaudzi
et al., 2002), arsenic (Balaji and Matsunaga, 2002),
manganese (Xue et al., 2001) and chromium (Xue et al.,
2000) are mainly present in natural water as two oxi-
dation states. For instance Cr(VI), As(III) and As(V)
are known carcinogens, while Fe(II), Fe(III), Mn(II),
Mn(VII) and Cr(III) are essential micronutrients for
organisms and plants. However, they become toxic at
higher levels.
Iron is the fourth most abundant element in the
earths crust, it is present in a variety of rock and soil
*
Corresponding author. Fax: +60-465-74854.
E-mail address: wsaime@usm.my (W.S.W. Ngah).
for proper transport and storage of oxygen by means of
hemoglobin and myoglobin while its oxidized forms,
methemoglobin and metmyoglobin, which contain
Fe(III), will not bind oxygen (Safavi and Abdollahi,
1999). Iron plays an essential role in photosynthesis and
is the limiting growth nutrient for phytoplanktons in
some parts of the ocean (Kieber et al., 2001). Both Fe(II)
and Fe(III) are important in the biosphere, serving as an
active centre of a wide range of proteins such as oxi-
dases, reductases and dehydrases. Waste euents from
steel tempering, coal coking and mining industries, for
example, contain signicant quantities of iron, nickel,
copper and zinc (Aksu et al., 1999).
Among the many methods available for the removal
of trace metals from water namely: chemical precipita-
tion, ion exchange, coagulation, solvent extraction and
membrane processes, adsorption has been shown to be
an economically feasible alternative. Activated carbon
has undoubtedly been one of the most popular adsor-
bents for the removal of metal ions from aqueous
solution and is widely used in wastewater treatment
applications throughout the world (El-Shafey et al.,
2002). In spite of its prolic use, activated carbon

0960-8524/$ - see front matter
2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2004.05.022
444 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450
remains an expensive material since the higher the qual-
ity of the activated carbon, the greater its cost. Research
interest into the production of alternative adsorbents to
replace the costly activated carbon has intensied in
recent years. Attention has been focused on various
adsorbents which have metal-binding capacities and are
able to remove unwanted heavy metals from contami-
nated water at low cost. Because of their low cost and
local availability, natural materials such as chitosan,
zeolites, clay or certain waste products from industrial
operations such as y ash, coal and oxides are classied
as low-cost adsorbents (Babel and Kurniawan, 2003).
Low et al. (2000) dened a low-cost sorbent as one
which is abundant in nature, or as a by-product or waste
material from another industry.
Chitin, poly(1 4)-2-acetamido-2-deoxy-b-D -glucan
is a naturally occurring polymer extracted from crusta-
cean shells, such as prawns, crabs, krill, insects and
shrimps, and the second most abundant biopolymer
next to cellulose. Chitosan is prepared from chitin by
partially deacetylating its acetamido groups with a
strong alkaline solution. Chitosan has been reported to
have high potential for adsorption of metal ions (Guibal
et al., 1998, Ngah et al., 2002a), dyes (Chiou and Li,
2002) and proteins (Zeng and Ruckenstein, 1998).
Chitosan is non-toxic, hydrophilic, biocompatible, bio-
degradable and anti-bacterial, which has led to a very
diverse range of applications in the biomedical eld and
in cosmetic, food and textile industries. The presence of
a large number of amine groups on the chitosan chain
increases the adsorption capacity of chitosan compared
to that of chitin, which only has a small percentage of
amino groups (Evans et al., 2002; Wu et al., 2000; Lu
et al., 2001). Chitosan has both hydroxyl and amine
groups that can be chemically modied. Several meth-
ods have been used to modify raw chitosan ake either
physical or chemical modications (Guibal et al., 1999;
Ngah and Liang, 1999; Yang et al., 2002). Physical
modications (Onsoyen and Skaugrud, 1990) may in-
crease the sorption properties: gel formation decreases
the crystallinity of the sorbent and involves an expan-
sion of the porous network. Chemical modications also
oer a wide spectrum of tools to enhance the sorption
properties of chitosan for metals. They may increase the
chemical stability of the sorbent in acid media and,
especially, decrease the solubility in most mineral and
organic acids. They also increase its resistance to bio-
chemical and microbiological degradation (Guibal et al.,
2000; Yang and Yuan, 2001). A cross-linking step is
required to reinforce the chemical stability of the bio-
sorbents in such acidic solutions. Although cross-linking
reduces the adsorption capacity, it enhances the resis-
tance of chitosan against acid, alkali and chemicals.
This work concentrates on the study of ferrous and
ferric ions sorption onto chitosan and cross-linked
chitosan beads. The inuence of experimental condi-
tions such as pH, agitation period, agitation rate and
concentration of Fe(II) and Fe(III) ions was studied.
The Langmuir and Freundlich equations were used to t
the equilibrium isotherm. The adsorption rates were
determined quantitatively and compared by the rst-
order, second-order and the intraparticle diusion
model. This information will be useful for further
applications of system design in the treatment of prac-
tical waste euents.
2. Methods
2.1. Material
Samples of chitosan akes with average molecular
weights 105 106 and with a deacetylation percentage of
approximately 55.94% (dened by an IR method), pre-
pared from shells of prawns, were kindly donated by
the Chitin-Chitosan Research Centre, Universiti Ke-
bangsaan Malaysia, Bangi. Glutaraldehyde (GLA), epi-
chlorohydrin (ECH) and ethylene glycol diglycidyl ether
(EGDE) purchased from Fluka were analytical-reagent
grade. Doubly distilled water was used to prepare all the
solutions.
2.2. Preparation of chitosan beads
Chitosan solution was prepared by dissolving 2.00 g
of chitosan akes in 60 ml of 5% (v/v) acetic acid solu-
tion. The chitosan solution was sprayed into a precipi-
tation bath containing 500 ml of 0.50 M NaOH, which
neutralized the acetic acid within the chitosan gel and
thereby coagulated the chitosan gel to spherical uniform
chitosan gel beads. A magnetic stirrer was used to stir
the aqueous NaOH solution. The wet chitosan gel beads
were extensively rinsed with distilled water to remove
any NaOH, ltered and nally air-dried to remove the
water from the pore structure (hereafter called chitosan
beads). The beads were then ground by using a labo-
ratory jar mill and sieved to a constant size (<250 lm)
before use.
2.3. Preparation of cross-linked chitosan beads
Cross-linked chitosan beads were prepared according
to the same procedure described previously (Ngah et al.,
2002b). In this work, three dierent cross-linking agents
were used to modify chitosan at a ratio of 1:1 (cross-
linking agent:chitosan).
2.3.1. Glutaraldehyde (GLA)
Recently prepared wet chitosan beads were sus-
pended in 0.025 M glutaraldehyde solution to obtain a
ratio of 1:1 with chitosan (mol GLA:mol NH2 ). The
chitosan beads in resulting glutaraldehyde solution were
 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450
left standing for 24 h at room temperature. After 24 h
the cross-linked chitosan beads were intensively washed
with distilled water, ltered and air-dried. The newly
formed beads (hereafter called chitosan-GLA beads)
were ground and sieved to a constant size (<250 lm)
before use. The chitosan-GLA beads obtained were
conrmed by a Perkin-Elmer FT-IR System 2000 Model
spectrometer.
2.3.2. Epichlorohydrin (ECH)
A solution of 0.10 M epichlorohydrin containing
0.067 M sodium hydroxide was prepared (pH 10).
Freshly prepared wet chitosan beads were added to the
epichlorohydrin solution to obtain a ratio of 1:1 with
chitosan (mol ECH:mol CH2 OH). The chitosan beads in
epichlorohydrin were heated to a temperature between
40 and 50 C for 2 h and stirred continuously using a
magnetic stirrer. After 2 h the beads were ltered and
washed intensively with distilled water to remove any
unreacted epichlorohydrin, then ltered and air-dried.
The newly formed beads (hereafter called chitosan-ECH
beads) were ground and sieved to a constant size (<250
lm) before use. The chitosan-ECH beads obtained were
conrmed by a Perkin-Elmer FT-IR System 2000 Model
spectrometer.
2.3.3. Ethylene glycol diglycidyl ether (EGDE)
Wet chitosan beads were added to a solution of 0.025
M EGDE to obtain a ratio of 1:1 with chitosan (mol
EGDE:mol NH2 ). The solution was heated to a tem-
perature of 5060 C for 3 h and stirred continuously.
After 3 h, the newly cross-linked chitosan beads were
intensively washed and air-dried. The beads (hereafter
called chitosan-EGDE beads) were ground and sieved to
a constant size (<250 lm) before use. The chitosan-
EGDE beads obtained were conrmed by a Perkin-
Elmer FT-IR System 2000 Model spectrometer.
2.4. Characterization of chitosan and cross-linked chito-
san
Some physical properties of chitosan and cross-linked
chitosan beads were measured in this work. The ana-
lyses were performed using a Micromeritics ASAP 2010
gas adsorption surface analyzer according to the BET
equation. The CHN analyses of the beads were deter-
mined using a Perkin-Elmer Series II 2400 CHNS/O
Analyzer.
2.5. Batch adsorption experiments
Stock solutions (1000 ppm) of Fe(II) and Fe(III) ions
were prepared by using FeSO4 7H2 O (R&M Chemicals)
and FeCl3 (R&M Chemicals), respectively. The stock
445
solutions were then diluted to give standard solutions of
appropriate concentrations. Batch experiments were
conducted in 250 ml beakers and equilibrated using a
magnetic stirrer. Then 100 ml aliquots of these standard
solutions were placed in 250 ml beakers and 0.010 g of
chitosan or cross-linked chitosan beads was added.
After ltration, the concentrations of Fe(II) and Fe(III)
in supernatant were analyzed at wavelength 248 nm
using an atomic absorption spectrophotometer (Perkin-
Elmer 3100 Model). The eect of Fe(II) and Fe(III)
adsorption was studied in pH range 15. The pH of the
initial solution was adjusted to the required pH value
using either 0.10 M HCl or 0.10 M NaOH. Chitosan and
cross-linked chitosan beads were equilibrated at the
particular pH for about 30 min at 500 rpm and at an
initial Fe(II) and Fe(III) concentration of 6 ppm. The
eect of agitation period and agitation rate was also
studied to determine the optimum conditions for
adsorption of Fe(II) and Fe(III) ions.
Adsorption equilibrium studies were conducted under
optimum conditions. For the Fe(II) adsorption equi-
librium studies, a contact time of 40 min at pH 5 for
chitosan, chitosan-GLA and chitosan-ECH beads was
employed, whereas for chitosan-EGDE beads, contact
time was 60 min at pH 5. For the Fe(III) adsorption
equilibrium studies, a contact time of 40 min at pH 3
was used for chitosan, chitosan-GLA and chitosan-
ECH beads, whereas for chitosan-EGDE beads, contact
time was 60 min at pH 3. Isotherm studies were con-
ducted with a constant chitosan and cross-linked
chitosan beads weight (0.010 g) and varying initial
concentrations of Fe(II) and Fe(III) in the range of 214
ppm. The amounts of adsorption were calculated based
on the dierence of Fe(II) and Fe(III) concentrations in
aqueous solutions before and after adsorption, the vol-
ume of aqueous solution (100 ml) and the weight of the
beads (0.010 g) according to:
C0
Ce V
Adsorption capacity qe 1
W
where C0 is the initial Fe(II) and Fe(III) concentration
(ppm), Ce is the nal or equilibrium Fe(II) and Fe(III)
concentration (ppm), V is the volume of the Fe(II) and
Fe(III) solution (ml) and W is the weight of the chitosan
and cross-linked chitosan beads (g).
For batch kinetic studies, 0.010 g chitosan and cross-
linked chitosan beads (<250 lm) were equilibrated
under optimum conditions as mentioned earlier. The
beads and 100 ml of Fe(II) and Fe(III) solutions (6 ppm)
were placed in 250 ml beakers and stirred by a magnetic
stirrer. The sorption time was varied between 2 and
90 min. At predetermined times, the solutions in the
beakers were separated from the beads by ltration.
After ltration, the concentrations of Fe(II) and Fe(III)
in supernatant were determined at wavelength 248 nm.
446 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450

3. Results and discussion 50

3.1. Characterization of chitosan and cross-linked chito- 40

san beads

qFe(II) (mg g-1)

Chitosan (Cs)
30
Table 1 lists the characteristics of chitosan and cross- Cs-ECH
linked chitosan beads. According to the International Cs-GLA
20
Union of Pure and Applied Chemistry (IUPAC) classi- Cs-EGDE
cations, the pores can be divided in broad terms
according to diameter (d) into macropores (d > 50 nm), 10
mesopores (2 < d < 50 nm) and micropores (d < 2 nm).
As shown in Table 1, chitosan and cross-linked chitosan 0
beads correspond to micropores. 0 2 4 6
pH
The CHN composition of chitosan and cross-linked
chitosan beads as determined by CHN analyzer is given Fig. 1. Eect of pH on the adsorption of Fe(II) on chitosan and cross-
in Table 2. It was found that modication with cross- linked chitosan beads.
linking agents decreased the percentage of free N atom
on the chitosan chain. This is due to the chemical
reaction between the cross-linking agents and chitosan. 70
The cross-linking agents mainly, react with NH2 60
groups and, as a result, the residual free N atoms are
eliminated. qFe(III) (mg g-1) 50
Chitosan (Cs)
40 Cs-ECH
3.2. Adsorption equilibrium Cs-GLA
30
Cs-EGDE
The pH of a solution strongly aects the adsorption 20
capacity of the chitosan and cross-linked chitosan beads.
Figs. 1 and 2 show that the adsorption of Fe(II) and 10
Fe(III) increased with increasing pH of the solution. In 0
acidic solutions, more protons will be available to pro- 0 1 2 3 4
tonate amine groups to form groups NH 3 , reducing
pH
the number of binding sites for the adsorption of Fe(II)
and Fe(III). While, at higher pH adsorption of Fe(II) Fig. 2. Eect of pH on the adsorption of Fe(III) on chitosan and
and Fe(III) increases due to the decreased inhibitory cross-linked chitosan beads.
eect of H , which decreases with the increase in pH. At
pH values higher than 7, Fe(II) and Fe(III) precipitation
occurred simultaneously. The maximum adsorptions of
Fe(II) and Fe(III) ions on chitosan and cross-linked
Table 1 chitosan beads were found at pH 5.0 and 3.0, respec-
Physical characteristics of chitosan and cross-linked chitosan beads tively.
Beads BET surface Average pore Figs. 3 and 4 show the eect of agitation period on
area (m2 g
1 ) 
diameter (A) the adsorption of Fe(II) and Fe(III) by chitosan and
Chitosan 1.46 50.96 cross-linked chitosan beads. The adsorption of Fe(II)
Chitosan-ECH 1.33 69.85 and Fe(III) increased with agitation period and attained
Chitosan-GLA 1.45 46.52 equilibrium at about 40 min for chitosan and 60 min for
Chitosan-EGDE 1.24 68.18
cross-linked chitosan beads. The adsorption of Fe(II)
and Fe(III) remained constant after 40 min for chitosan
and 60 min for cross-linked chitosan beads, implying
Table 2 that equilibrium had been reached.
CHN analyses of chitosan and cross-linked chitosan beads Figs. 5 and 6 show the adsorption isotherms of Fe(II)
Beads Percentage of composition (%) and Fe(III) on the chitosan and cross-linked chitosan
C H N beads. The Langmuir and Freundlich models are often
Chitosan 39.53 7.26 6.10 used to describe equilibrium sorption isotherms. The
Chitosan-ECH 40.41 7.14 5.93 most widely used Langmuir equation, which is valid for
Chitosan-GLA 40.35 7.18 5.45 monolayer sorption on to a surface with a nite number
Chitosan-EGDE 37.56 6.86 5.84
of identical sites, is given by:
 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450 447

60 100

50 80

40 Chitosan (Cs)
qFe(II) (mg g-1)

qe (mg g-1)
Chitosan (Cs) 60
Cs-ECH
Cs-ECH
30 Cs-GLA
Cs-GLA 40
Cs-EGDE
Cs-EGDE
20
20
10
0
0 0 2 4 6 8
0 20 40 60 80 100 Ce (ppm)
Agitation period (min)
Fig. 6. Adsorption isotherms of Fe(III) on chitosan and cross-linked
Fig. 3. Eect of agitation period on the adsorption of Fe(II) on chitosan beads.
chitosan and cross-linked chitosan beads.
Fe(III) (ppm), qe is the amount of Fe(II) or Fe(III) ad-
70 sorbed per unit weight of chitosan and cross-linked
chitosan beads at equilibrium concentration and b is the
60
Langmuir constant related to the anity of binding sites
50 (ml mg
1 ) and is a measure of the energy of adsorption.
qFe(III) (mg g-1)

Chitosan (Cs) A linearized plot of Ce =qe against Ce gives Q and b.

40 Cs-ECH The widely used empirical Freundlich equation based
30 Cs-GLA on sorption on a heterogeneous surface is given by:
Cs-EGDE
1
20 log qe log KF log Ce 3
n
10 where KF and n are Freundlich constants indicating
0 sorption capacity and intensity, respectively. KF and n
0 20 40 60 80 100 can be determined from a linear plot of log qe against
Agitation period (min) log Ce . The calculated results of the Langmuir and
Fig. 4. Eect of agitation period on the adsorption of Fe(III) on
Freundlich isotherm constants are given in Table 3. It is
chitosan and cross-linked chitosan beads. found that the adsorptions of Fe(II) and Fe(III) on the
chitosan and cross-linked chitosan beads correlated well
(R > 0:99) with the Langmuir equation as compared to
60
the Freundlich equation under the concentration range
50
studied.
The essential features of a Langmuir isotherm can be
40 Chitosan (Cs)
expressed in terms of a dimensionless constant separa-
qe (mg g-1)

Cs-ECH
tion factor or equilibrium parameter, RL which is used to
30 predict if an adsorption system is favourable or
Cs-GLA
Cs-EGDE unfavourable. The separation factor, RL is dened by:
20
1
RL 4
10 1 bC0
0 where C0 is the initial Fe(II) or Fe(III) concentration
0 2 4 6 8 (ppm) and b is the Langmuir adsorption equilibrium
Ce (ppm)
constant (ml mg
1 ). Table 4 lists the calculated results.
Fig. 5. Adsorption isotherms of Fe(II) on chitosan and cross-linked Based on the eect of separation factor on isotherm
chitosan beads. shape, the RL values are in the range of 0 < RL < 1,
which indicates that the adsorptions of Fe(II) and
Ce Ce 1 Fe(III) on chitosan and cross-linked chitosan beads
2 are favourable. Thus, chitosan and cross-linked
qe Q Qb
chitosan beads are favourable adsorbers. As mentioned
where Q is the maximum adsorption at monolayer earlier, chitosan and cross-linked chitosan beads are
(mg g
1 ), Ce is the equilibrium concentration of Fe(II) or microporous biopolymers, therefore pores are large en-
448 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450

Table 3
Langmuir and Freundlich isotherm constants and correlation coecients
Iron Beads Langmuir Freundlich
Q (mg g
1 ) b (ml mg
1 ) R KF (mg g
1 ) n R
Fe(II) Chitosan 64.10 2197 0.9986 42.74 4.77 0.7730
Chitosan-ECH 57.47 1891 0.9998 33.25 3.19 0.9597
Chitosan-GLA 45.25 1023 0.9995 21.84 2.71 0.9744
Chitosan-EGDE 38.61 762 0.9985 17.15 2.79 0.9985
Fe(III) Chitosan 90.09 2413 0.9989 55.27 3.32 0.9824
Chitosan-ECH 72.46 1550 0.9987 39.35 2.98 0.9788
Chitosan-GLA 51.55 1405 0.9989 28.63 3.47 0.9881
Chitosan-EGDE 46.30 2076 0.9991 28.36 3.61 0.8982

Table 4
RL values based on the Langmuir equation
Iron Initial concentration RL value
(ppm) Chitosan Chitosan-ECH Chitosan-GLA Chitosan-EGDE
Fe(II) 3 0.1317 0.1498 0.2457 0.3044
6 0.0705 0.0810 0.1401 0.1795
9 0.0481 0.0555 0.0980 0.1273
Fe(III) 3 0.1214 0.1769 0.1917 0.1383
6 0.0646 0.0971 0.1060 0.0743
9 0.0440 0.0669 0.0732 0.0508

ough to let Fe(II) and Fe(III) ions through. The mech-
anism of ion adsorption on porous adsorbents may in-
volve three steps (Peniche-Covas et al., 1992): (i)
diusion of the ions to the external surface of adsorbent;
(ii) diusion of ions into the pores of adsorbent; (iii)
adsorption of the ions on the internal surface of adsor-
bent. The rst step of adsorption may be aected by
metal ion concentration and agitation period. The last
step is relatively a rapid process.
3.3. Kinetics of adsorption
Figs. 7 and 8 show the time proles of Fe(II) and
Fe(III) adsorption onto chitosan and cross-linked
chitosan beads with an initial concentration of 6 ppm.
It indicates that the adsorption capacity of the beads
decreases in the order chitosan > chitosan-ECH > chito-
san-GLA > chitosan-EGDE. It is known that the amine
groups (NH2 ) on the chitosan chain act as electron
donors. The nitrogen electrons present in the amine
groups can establish dative bonds with transition
metal ions. But, cross-linking results in a signicant
decrease in the adsorption capacity, due to the forma-
tion of chemical bonds at adsorption sites (Inoue et al.,
1993).
In order to investigate the controlling mechanisms of
adsorption processes such as mass transfer and chemical
reaction, the rst-order, second-order and intraparticle

50
100

40
80

Chitosan (Cs)
qt (mg g-1)

30 Chitosan (Cs)
qt (mg g-1)

Cs-ECH 60
Cs-ECH
Cs-GLA
20 Cs-GLA
Cs-EGDE 40
Cs-EGDE

10 20

0 0
0 20 40 60 80 100 0 20 40 60 80 100
t (min) t (min)

Fig. 7. Time proles of Fe(II) adsorption on chitosan and cross-linked Fig. 8. Time proles of Fe(III) adsorption on chitosan and cross-
chitosan beads. linked chitosan beads.
 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450 449

Table 5
Kinetic parameters for Fe(II) and Fe(III) adsorption onto chitosan and cross-linked chitosan beads at agitation period 90 min (C0 6 ppm)
Iron Beads First-order Second-order Intraparticle diusion
k1 (min
1 ) R k2 (g mg
1 min
1 ) R ki (mg g
1 min
0:5 ) R
Fe(II) Chitosan 1.99 10
2 0.9755 1.05 10
3 0.9992 4.65 0.9866
Chitosan-ECH 1.82 10
2 0.9726 9.86 10
4 0.9991 3.97 0.9894
Chitosan-GLA 8.63 10
2 0.9782 1.72 10
3 0.9996 2.59 0.9879
Chitosan-EGDE 9.80 10
3 0.9951 4.74 10
4 0.9993 2.05 0.9914
Fe(III) Chitosan 3.06 10
2 0.9622 3.21 10
3 0.9998 5.04 0.9978
Chitosan-ECH 1.98 10
2 0.9727 1.07 10
3 0.9997 4.52 0.9953
Chitosan-GLA 2.33 10
2 0.9755 2.33 10
3 0.9995 3.15 0.9817
Chitosan-EGDE 1.66 10
2 0.9803 1.26 10
3 0.9997 2.51 0.9892

diusion equations were used to test the experimen-
tal data. The rst-order kinetic model of Chiou and
Li (2003) and Annadurai and Krishnan (1997) is
given as:
k1
logqe
qt log qe
t 5
2:303
where qe and qt are the amounts of Fe(II) or Fe(III) ad-
sorbed on adsorbent (mg g
1 ) at equilibrium and at time
t, respectively and k1 is the rate constant of rst-order
adsorption (min
1 ). Straight line plots of logqe
qt
against t were used to determine the rate constant, k1 and
correlation coecient, R values for Fe(II) and Fe(III)
under dierent concentration range conditions. The sec-
ond-order equation (McKay and Ho, 1999) may be
expressed as:
t 1 t muir equation. The adsorption capacity of chitosan
2
qt k 2 qe qe
where k2 is the rate constant of second-order adsorption
(g mg
1 min
1 ). Straight-line plots of t=qt against t were
tested to obtain rate parameters and the results sug-
gested the applicability of this kinetic model to t the
experimental data. The intraparticle diusion rate
(Chiou and Li, 2003) can be described as:
qt ki t0:5
where ki is intraparticle diusion rate (mg g
1 min
0:5 ).
The ki is the slope of straight-line portions of the plot of
qt against t0:5 .
The results of the kinetic parameters for Fe(II) and
Fe(II) adsorption are given in Table 5. Based on the
correlation coecients, the adsorptions of Fe(II) and
Fe(III) are best described by the second-order equation.
Many studies reported the rst-order equation of La-
gergren does not t well to the initial stages of the
adsorption processes (Chiou and Li, 2003). The rst-
order kinetic process has been used for reversible reac-
tion with an equilibrium being established between
liquid and solid phases (Low et al., 2000). Whereas, the
second-order kinetic model assumes that the rate-limit-
ing step may be chemical adsorption (Wu et al., 2001).
In many cases, the second-order equation correlates
well to the adsorption studies (Sag and Aktay, 2002).
It is more likely to predict that the adsorption behav-
iour may involve valency forces through sharing of
electrons between transition metal cations and adsor-
bent.
4. Conclusion
In this study, the capacity of chitosan and cross-linked
chitosan beads with glutaraldehyde, epichlorohydrin and
ethylene glycol diglycidyl ether as cross-linkers to adsorb
Fe(II) and Fe(III) ions from aqueous solutions was
examined, including equilibrium and kinetic studies. The
adsorption isotherms could be well tted by the Lang-
6 beads is higher than that of cross-linked chitosan beads,
but cross-linked chitosan beads are insoluble in both
acidic and basic media. The adsorption process could be
best described by the second-order equation. This sug-
gests that the rate-limiting step may be the chemical
adsorption (chemisorption) not the mass transport. The
capacity of Fe(III) adsorption using chitosan and cross-
linked chitosan beads was greater than Fe(II) adsorp-
tion. The results showed that the adsorption behaviour
7
of Fe(II) and Fe(III) on chitosan and cross-linked
chitosan beads used in this study was not aected by
physical properties, but was mainly aected by chemical
interaction. It can be concluded that chitosan and cross-
linked chitosan beads are eective adsorbents for the
collection of metal ions.
Acknowledgements
The authors thank Chitin-Chitosan Research Centre,
Universiti Kebangsaan Malaysia, Bangi, Malaysia, for
supplying samples of chitosan. The authors also thank
Universiti Sains Malaysia for the nancial support
under IRPA Short Term Research Grant (grant no. 305/
PKIMIA/622183).
450 W.S.W. Ngah et al. / Bioresource Technology 96 (2005) 443450
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