2011 2nd International Conference on Environmental Science and Technology
IPCBEE vol.6 (2011) © (2011) IACSIT Press, Singapore
Removal of Dissolved Hexavalent Chromium using Synthetic Biopolymer
Ghodratallah Shams Khorramabadi
Department of Environmental Health
Lorestan University of Medical Sciences
Khorramabad, Iran
e-mail: Shams_lums@ yahoo.com
Reza Darvishi Cheshmeh Soltani
Department of Environmental Health
Tarbiat Modares University
Tehran, Iran
e-mail: rezadarvish86@ yahoo.com
Abstract—The objective of this investigation was to study the
biosorption of Cr (VI) on calcium alginate as synthetic
biopolymer and to determine the isotherms and kinetics of
chromium biosorption. Using a batch system, the capacity for
Cr (VI) biosorption was investigated as a function of pH and
shaking time. The optimal pH for Cr (VI) biosorption by
calcium alginate was 4.0. Compared to the Langmuir isotherm
model, the Freundlich model best fit the experimental data
(R2>0.98). Moreover, the maximum biosorption capacity of
calcium alginate was 84.75 mg/g. The results of this study
demonstrated that the pseudo-second order model was more
suitable than pseudo-first order model for Cr (VI) biosorption
onto calcium alginate.
Keywords-Biosorption; Chromium; Calcium alginate;
Isotherm; Kinetic
I. INTRODUCTION
Heavy metal ions can be discharged into the
environment from a variety of industrial activities [1].
Heavy metal ions incline to persist and accumulate in
every part of the food chain resulting to a serious threat
to animals and human being [2]. Chromium is a heavy
metal with oxidation states that vary from −2 to +6;
however, the +3 and +6 states are common in aqueous
solutions. The Cr(VI) is much more toxic than the
Cr(III) species. Moreover, chromium (VI) has been
categorized as a human carcinogen [3, 4]. Many
conventional methods have been used to remove heavy
metals from solution, including chemical precipitation
and filtration, electrochemical treatments, solvent
extraction, application of membrane technology, ion
exchange and activated carbon adsorption [5, 6]. The
removal of heavy metals by passive binding to non-
living biomaterials, commonly referred to as
biosorption, has gained a considerable amount of
attention in recent decades because biosorption has
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Abbas Rezaee
Department of Environmental Health
Tarbiat Modares University
Tehran, Iran
e-mail: abbasrezaee@ yahoo.com
Hatam Godini
Department of Environmental Health
Lorestan University of Medical Sciences
Khorramabad, Iran
e-mail: h_godini@ yahoo.com
many advantages over traditional methods. For
instance, biosorption is environmentally friendly, cost
efficient, readily available, easy to conduct and highly
selective [1, 7, 8]. Biopolymers such as sodium alginate
can uptake metal ions from aqueous solutions.
Biopolymers possess all of biosorbent advantages and
compete with other traditional methods such as ion-
exchange and activated carbon [2]. One of the
important and most widely used biopolymer for metal
ions biosorption from aqueous solutions have been
alginate [9]. Therefore, the biosorption of chromium
(VI) from aqueous solution using pure calcium alginate
beads was investigated in this study. The equilibrium
between adsorbed metal ions and free metal ions in
solution can be described by adsorption isotherm
models such as the Langmuir, Freundlich and
Freundlich-Langmuir model. Eq.(2) illustrates the
linear form of the Langmuir isotherm model:
Ce 1 C
= + e Eq.(2)
qe Kq m q m
where qe (mg/g) is the amount of adsorbed metal ions
per unit weight of biosorbent and Ce (mg/L) is
concentration of free metal ions in solution. Qm (mg/g)
is the amount of biosorbate per unit weight of
biosorbent that is required to form a monolayer on the
surface of the biosorbent and K (L/mg) is related to the
affinity of the binding sites. The linear form of the
Freundlich isotherm model is shown in Eq.(3):
1
log q e = log K F + log C e Eq.(3)
n
where n and KF are the Freundlich constants, and are
related to the sorption intensity and sorption capacity,
respectively [10]. The linear form of the Freundlich-
Langmuir equation is shown in Eq.(4):
 ⎛1 1 ⎞ ⎛ 1 ⎞ 1 ⎛ 1
log ⎜⎜ − ⎟⎟ = log ⎜⎜ ⎟⎟ + log ⎜⎜
⎝ q qm ⎠ ⎝ bq m ⎠ n ⎝ Ce
The pseudo-first order and pseudo-second order
kinetic models were used to evaluate the mechanism of
biosorption. The linear form of the pseudo-first order
kinetic equation is:
k
log(qe − q) = log qe − 1,ad t Eq.(5)
2.303
where q (mg/g) is the amount of adsorbed metal ions at
time t and k1ads (1/min) is the rate constant. A straight
line of log (qe−q) versus time indicates that the pseudo-
first order model is a suitable representation of the
adsorption process [2]. The linear form of the pseudo-
second order kinetic equation is:
t 1 1 100 mg/l, respectively. The egg-box model was used to
= 2
+ t Eq.(6)
q k 2 , ad q e qe
where k2ads (g/mg.min) is the rate constant. If the
pseudo-second order kinetic is applicable to the
adsorption process, a plot of t/q versus t should provide
a straight line [10, 11].
II. METHODS
Pure sodium alginate was mixed in deionized water
to achieve a 2% sodium alginate solution. The resulting
solution was thoroughly mixed for 1 h to achieve
homogeneity. After obtaining a homogeneous mixture,
the solution was added via syringe to a solution of
CaCl2 (0.5 M) under constant agitation. After formation
of calcium alginate beads, the beads were cured in a
CaCl2 solution for 24 h and were washed twice with
sterile distilled water. Finally, the beads were filtered to
remove excess water and were dried at room
temperature [2, 12]. Batch experiments were performed
in 100 mL Erlenmeyer flasks at 150 rpm to explore the
effects of solution pH and contact time at room
temperature (25±1°C). The optimum pH and contact
time for the biosorption of Cr (VI) were determined,
and subsequent experiments were conducted under the
optimized conditions. To obtain the desired
concentration of Cr (VI) ions, a 1000 mg/L stock
solution of K2Cr2O7 was prepared. In subsequent
experiments, the concentration of biosorbent and Cr (VI)
was set to 1 g/L and 50 mg/L, respectively. The pH
was adjusted to the desired value with 0.01 M HCl and
0.01 M NaOH at the beginning of each experiment. A
control flask without biosorbent was used to determine
Cr (VI) removal in the absence of the biosorbent. The
samples were collected from the Erlenmeyer flasks and
were filtered to remove solid material. The filtrates
were analyzed for residual Cr (VI) ions via a
colorimetric method using a UV/Visible
spectrophotometer (UNICO 2100) set to 540 nm,
⎞ Eq.(4)
according to standard methods for the analysis of water
⎟⎟ and wastewater [13].
⎠
III. RESULTS AND DISCUSSIONS
A. pH effect
Figure 1 displays the concentration of biosorbed Cr
(VI) ions as the pH of the solution increased from 2 to
6. In the biosorption of Cr (IV) onto calcium alginate,
Cr (VI) ion uptake increased as the pH increased from
2 to 4, then decreased as the pH increased from 4 to 6.
The optimal pH for Cr (VI) biosorption onto calcium
alginate was 4.0 with Cr (VI) uptake rate of 6.1, 17.04
and 33.53 mg/g for Cr (VI) concentration of 10, 50 and
illustrate the structure of calcium alginate, which
contains free carboxylic groups that can interact with
metal ions. The carboxyl groups of calcium alginate are
ionized at pH values greater than 4.0, and the rate of Cr
(VI) uptake decreased at high pHs. In a previous study
by Papageorgiou et al. [14] the optimal pH for
biosorption of Cu2+, Cd2+ and Pb2+ onto alginate was
4.5. The difference in the optimal pH for maximum
metal ion adsorption by the biosorbent indicated that
the mechanism of metal binding may be dependent on
the material [1]. Based on the results of this
investigation, the pH of the solution in subsequent
experiments was set to 4.0 because the removal rate of
Cr (VI) by calcium alginate was significant at this pH.
40
Biosorption rate (mg/g)
35
30
10 mg/l
50 mg/l
25 100 mg/l
20
15
10
5
0
1 2 3 4 5 6 7
pH values
Figure 1. The concentration of adsorbed Cr (VI) ions versus the pH of the
solution. pH range=2-6, contact time=360 min, agitation speed=150 rpm,
initial Cr (VI) concentration=10-100 mg/L, biosorbent concentration=1 g/L.
B. Equilibrium time
The concentration of adsorbed Cr (VI) onto calcium
alginate over time is depicted in Figure 2. As shown in
the figure, the amount of adsorbed Cr (VI) ions
increased with an increase in time, and equilibrium was
attained at approximately 120 min. At equilibrium, the
cumulative removal percentage for Cr(VI)
concentration of 10, 50 and 100 mg/L was 57.8, 42.9
and 35.14%, respectively. As shown in Figure 2, the
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rate of biosorption onto pure calcium alginate (as mg/g)
increased from 5.78 to 35.14 as the concentration of Cr
(VI) ions increased from 10 to 100 mg/L, respectively.
Considering the low volume of the reactor, the
equilibrium time obtained in this study suggested that
the rate of Cr(VI) biosorption onto calcium alginate
was moderate. As a result, low volumes of solution are
required in the reactor and the full-scale operation is
cost efficient. Similarly, Abu Al-Rub et al. [5] showed
that equilibrium of nickel biosorption onto blank
alginate beads was attained in approximately 120 min.
In another study, Nityanandi and Subbhuraam [15]
reported that the biosorption of Cr(VI) by puresorbe
reached equilibrium after 230 min.
40
biosorption rate (mgg )
35
-1
30
25
20
15
10 mg/l 50 mg/l
10
5
0
0 50 100 150 200 250
Time (min)
Figure 2. The concentration of adsorbed Cr (VI) ions versus time. Contact
time=360 min, pH=4.0, agitation speed=150 rpm, initial Cr (VI)
concentration=10-100 mg/L, biosorbent dosage=1 g/L.
C. Isotherm study
To evaluate the isotherm models, 1 g/L of the
biosorbent were stirred in a solution of Cr (VI) at a pH
of 4.0 and an initial Cr (VI) concentration ranging from
10 to 300 mg/L for 120 min. The Langmuir, Freundlich
and Freundlich-Langmuir equations were used to model
the concentration of adsorbed metal ions and residual
metal ions in solution. The values of the isotherm
constants and maximum biosorption capacities (qmax)
are provided in Table 1. As shown in Table 1, the
values of the correlation coefficients indicated that the
Freundlich model best fit Cr (VI) biosorption onto
calcium alginate. The Freundlich isotherm model
provides a more realistic description of adsorption by
organic material because it accounts for different types
of binding sites and their interactions, surface
heterogeneity and the energy of the biosorbent surface
[1, 16, 17]. Similarly, Li et al. [18] showed that the
biosorption of Cr (VI) by Synechococcus sp. obeys the
Freundlich model. The correlation coefficient for the
Langmuir model was >0.95; therefore, the value of qmax
from the Langmuir model can be used to evaluate the
adsorption capacity of the biosorbent. The data were
fitted to the Langmuir model, and the results indicated
that the maximum Cr (IV) biosorption capacity of
calcium alginate was 84.75 mg/g. Yakup Arıca et al.
[19] obtained a maximum biosorption capacity of 21.2
mg Cr (VI) per g of dried acid-treated microalgae
(Chlamydomonas reinhardtii), which is significantly
lower than the maximum biosorption capacity of
calcium alginate.
TABLE 1. ISOTHERM PARAMETERS FOR CR (VI) IONS BIOSORPTION
ONTO CALCIUM ALGINATE.
Type of isotherm models Value of parameters
Langmuir isotherm
qm (mg/g) 84.75
K (L/mg) 0.013
R2 0.9585
Freundlich isotherm
Kf 2.08
n 1.56
R2 0.9820
100 mg/l Freundlich-Langmuir isotherm
R2
0.9826
300 350 400 D. Kinetic study
The kinetics of biosorption were investigated at an
initial Cr (VI) concentration of 50 mg/L, a biosorbent
concentration of 1 g/L, a pH of 4.0 and a contact time
of 120 min. The pseudo-first order and pseudo-second
order models were fit to the experimental data. The
kinetic parameters and correlation coefficients of the
models are shown in Table 2. For the biosorption of Cr
(VI) onto calcium alginate, the correlation coefficient of
the pseudo-second order model was higher than that of
the pseudo-first order model, which suggested that the
pseudo-second order model best fit the experimental
data. If metal biosorption is controlled by diffusion
through a boundary layer, the kinetics of the adsorption
process should fit to the pseudo-first order model [9].
However, biosorption involves various mechanisms
such as electrostatic and chemical interactions between
functional groups and metal ions. Therefore, the
pseudo-second order model usually provides the best
fit for biosorption processes. The pseudo-second order
model assumes that biosorption occurs via two distinct
reactions. In the biosorption of Cr (VI) onto calcium
alginate, the first reaction is relatively fast, and the
second reaction is slow and requires long exposure
times [20], as shown in Figure 2. To predict the
kinetics of chemical biosorption, two steps were
assume to control the pseudo-second order model,
including the dissociation of hydrated complexes and
the interaction of dissociated metal ions with active
sites on the biosorbent [12]. As shown in Table 2, the
value of qe for the pseudo-second order model was
23.81 mg/g for pure calcium alginate. Compared to
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other biosorbents such as marine algae biomass,
immobilized fungus, chitosan beads, peat, pine bark
and bone char, calcium alginate possess a relatively
high capacity for Cr metal ions [14]. According to the
egg-box model of the gel matrix, Cr (VI) ions can be
sequestered into holes and cavities formed in the
alginate gel, where calcium ions are located in the
electronegative cavities like eggs in an egg-box.
Moreover, the presence of calcium salts generates a
channeling effect, which increases the rate of Cr (VI)
penetration into the internal layers of the alginate
matrix [9, 14].
TABLE 2. KINETIC PARAMETERS FOR CR (VI) IONS BIOSORPTION
ONTO CALCIUM ALGINATE.
Type of kinetic model Value
Pseudo-first order model
R2 0.9326
k1,ad (min-1) 0.02
qe (mgg-1) 15.11
Pseudo-second order model
(mgg-1)
R2 0.9721
K2,ad (gmg-1min-1) 0.00198
qe (mgg-1) 23.81
IV. CONCLUSION
In this study, Cr (VI) biosorption onto calcium
alginate was evaluated. According to the results of this
investigation, the optimal pH for Cr (VI) biosorption
onto calcium alginate was 4.0. In the biosorption of Cr
(VI) equilibrium was achieved within 120 min. As a
result, low volumes of solution are required in the
reactor and the full-scale operation is cost efficient.
Among isotherm models, the Freundlich isotherm best
fit the experimental data, compared to the Langmuir
and BET models. The results of this study
demonstrated that the pseudo-second order model was
more suitable than pseudo-first order model for Cr (VI)
biosorption onto calcium alginate.
ACKNOWLEDGMENT
The authors acknowledge the support of Lorestan
University of Medical Sciences and Tarbiat Modares
University.
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