Biosorption of Basic Orange from aqueous solution onto dried A.

liculoides biomass:
Equilibrium, kinetic and FTIR studies
Cai-yun Tan
a
, Min Li
b
, Yu-Man Lin
a
, Xiao-Qiao Lu
a
, Zu-liang Chen
a,

a
School of Chemistry and Material Sciences, Fujian Normal University, Fuzhou 350007, China
b
School of Biology, Fujian Normal University, Fuzhou 350007, China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 10 February 2010
Received in revised form 4 August 2010
Accepted 4 August 2010
Available online 25 August 2010
Keywords:
Biosorption
Basic Orange (BO)
A. liculoides
Kinetics
FT-IR
A dried Azolla liculoides (A. liculoides ) biomass was used to remove Basic Orange (BO) dye from aqueous
solution using batch experiments. The kinetic results demonstrated that the biosorption of BO onto the dried
A. liculoides was well described by the pseudo-second-order kinetic model. The maximum biosorption
capacity for BO was 833.33 mg/g based on the Langmuir equation at a temperature of 303 K, a solution pH of
7.0, a biosorbent dosage of 5 g/L and a contact time of 4 h. From the D-R isotherm equation, mean free energy
was calculated to be 8.69 kJ/mol at 303 K, suggesting that the biosorption of BO onto the dried A. liculoide
involved chemisorption. The thermodynamic values, including G, H and S obtained from the calculation,
suggest that the biosorption of BO on the dried A. liculoides biomass is feasible, spontaneous and
endothermic under the experimental conditions in this study. Fourier transform infrared (FT-IR) spectros-
copy was used to examine functional groups that may participate in the interaction between BO and dried
A. liculoides biomass. Results showed that the amino, carboxyl, and hydroxyl groups may be responsible for
the biosorption of BO on the biomass.
2010 Elsevier B.V. All rights reserved.
1. Introduction
In recent years, removal of highly colored dyes in efuents
produced by textile industries has attracted much attention because
these highly colored efuents are extremely damaging to the
environment [1]. Of particular environmental concern, is the presence
of complex aromatic compounds in the dyes, that are highly resistant
to photo, chemical and microbial degradations [2,3]. Various methods,
including physical, chemical and biological treatments are available to
remove the highly colored dyes from the textile efuents [2,4]. These
conventional physical and chemical treatments however have various
limitations, including high operational costs, formation of hazardous
by-products and greater energy consumption [5]. Recently, many
biosorption methods using biomass as biosorbents to remove the dyes
from the textile efuents have been reported as a low-cost and
environmentally friendly means of treatment [6]. Functional groups of
amino, carboxyl, thiol and phosphate present on the cell wall of the
biosorbent are responsible for removal of dyes from the textile
efuents [7]. Biosorption of the dyes on the cell surface appears to be a
quick process and often completes in a matter of hours [8]. Various
low-cost biomasses, including peat [9], wheat shells [10] and dried
algae [1113], have been used as the potential biomass materials to
remove dyes from textile efuents. These biosorbents have shown a
high efciency for removal of dyes from aqueous solutions.
Azolla liculoides is a oating water fern abundant in many aquatic
environments all over the world. It is commonly found in ditches,
ponds and slowly moving streams. This species is capable of
colonizing rapidly to form dense mats over water surface, imposing
negative effects on the aquatic ecology [14]. A. liculoides has recently
received attention because it can be used as a potential biosorbent for
the treatment of metal-bearing efuents [1521]. There are few
reports however on the removal of dyes fromtextile efuents using A.
liculoides. Batch and column studies on biosorption of acid dyes
showed that the biosorption capacity was pH dependent, a maximum
value for Acid Red 88 was 109.0 mg/g at pH 7, while for Acid Green 3
and Acid Orange 7 at pH3 was 133.5 and 109.6 mg/g respectively [14].
Removal of Rhodamine B and Methylene Blue using A. liculoides have
also been reported using a batch reactor and a xed-bed column
system with a maximum removal of 166.7 mg/g for Rhodamine B and
91.8 mg/g for Methylene Blue based on the calculation using
Langmuir equation [22,23].
In this paper, the equilibrium, kinetic and thermodynamic studies
for removal of Basic Orange (BO) using the dried A. liculoides biomass
as a biosorbent were conducted in order to develop models that can
be used to describe biosorption of BO on the cell wall of the biomass
either qualitatively or semi-quantitatively. Equilibrium, kinetic and
thermodynamic studies are useful to understand biosorption of BO
from aqueous solution and experimental isotherms are useful for
describing adsorption capacity. To the best of our knowledge, this is
Desalination 266 (2011) 5662
Corresponding author. Tel./fax: +86 591 83465689.
E-mail address: zlchen@fjnu.edu.cn (Z. Chen).
0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.08.002
Contents lists available at ScienceDirect
Desalination
j our nal homepage: www. el sevi er. com/ l ocat e/ desal
the rst example where A. liculoides has been investigated as a
potential biomass source to remove BO from aqueous solution
complete with description of the biosorption mechanism involved.
This study focuses on the equilibrium, kinetic and thermodynamic
reactions on biosorption of BO on the dried A. liculoides biomass. To
obtain a better understanding of the biosorption mechanisms of
removal of BO from aqueous solution, the objectives of this study
included (1) to establish kinetic model for the biosorption of BO on
the dried A. liculoides biomass; (2) to investigate the biosorption
isotherms, and to describe the biosorption thermodynamics; (3) using
Fourier transforminfrared (FT-IR) spectroscopy to examine functional
groups of the biosorbent that may be involved in biosorption
mechanisms.
2. Materials and methods
2.1. Materials
A. liculoides, used as a biosorbent in this study, was obtained from
Azolla Research Center, Fujian Academy of Agricultural Sciences,
Fuzhou, China. Biomass of A. liculoides was oven dried at 60 C for
48 h to constant weight, then grounded and sieved through a 110
mesh sieve to obtain particle sizes less than 0.135 mm. Prior to use,
material was placed in a polyethylene bag and stored in a desiccator.
Characterization analysis of the dried A. liculoides, the specic surface
area analysis (Methylene Blue adsorption method) [24] and the cation
exchange capacity (CEC) analysis [25], showed that the dried A.
liculoides had a high cation exchange capacity (CEC, 93.6 mmol/
100 g) and porosity structure with a large specic surface area
(80.4 m
2
/g).
All chemicals used in this work, were of analytical reagent grade and
were used without further purication. Basic Orange (C
12
H
12
N
4
HCl) is
a cationic dye, with a molecular weight of 248.72 g/mol, a
max
of
448 nm, and chemical structure as shown in Fig. 1.
2.2. Batch experimental procedure
A0.1 g sample of A. liculoides was mixed with20 mL of test solution
at initial pH of 7.0 in a 50 mL polypropylene centrifuge tube, and then
shaken in an electrical thermostatic reciprocating shaker at 250 rpm.
Biosorption kinetic study was conducted with an initial BO concentra-
tion of 100 mg/L at temperatures of 293, 303, 313 and 323 K,
respectively. Samples were collected at various shaking time intervals
until the concentration of BO in the dilute phase became constant.
Biosorption experiments were also carried out with different initial BO
concentrations varying from 10 to 1000 mg/L at 313 K for 4 h. In these
batch experiments, solutions with different initial concentrations of BO
were prepared by adding the stock solution of 1000 mg/L BO standard.
At the end of shaking, tubes were centrifuged at 6800 rpm for 10 min
and supernatant collected. Solutions without dried A. liculoides were
used for the determination of BO concentrations using UV-Spectropho-
tometer (721 S, Tianjin, China) at
max
of 448 nm (obtained from
preliminary experiments). The content of BO biosorbed (q) and
percentage of BO removed (R
E
) by dried A. liculoides was calculated
fromthe difference between the initial and nal concentrations of BOin
solution. All the batchexperiments were carriedout intriplicate, andthe
results were presented as average values.
2.3. FT-IR spectroscopy analysis
Dried A. liculoides samples used before and after removal of Basic
Orange under the optimization conditions were examined using the
Fourier transforminfrared (FT-IR) spectroscopy method. The optimiza-
tionconditions includedaninitial pHof 7.0, a biosorbent dosage of 0.1 g,
a 20 mL solution containing the initial BO concentration of 100 mg/L, a
biosorption time of 4 h at 250 rpm and a temperature at 303 K. The
A. liculoides before and after use were lleted. Dried A. liculoides was
rinsedwithdistilled water thoroughly, then ovendried at 60 C for 48 h.
Once dried the A. liculoides sample was crushed into ne particles,
transferred into a polythylene bag and stored in a desiccator before
characterization. The treated A. liculoides before and after use were
examined using a FT-IR spectroscopy in wave numbers ranging from
400 cm
1
to 4000 cm
1
on the Nicolet 5700 instrument (Thermo corp,
U.S.A).
3. Results and discussion
3.1. The effect of experimental parameters on the biosorption
Preliminary results showed an increase in BO biosorption to the
dried A. liculoides with increasing solution initial pH from 2.0 to 4.0
(Fig. 2(a)). Biosorption however remained unchanged when initial pH
was increased further from4.0 to 10.0, where 93 % of BO was removed
from the solution containing 100 mg/L of the dye. Thus, the initial pH
of 7.0 was selected for the rest of experiments conducted in this study.
The effect of contact time and temperature study was conducted with
an initial BO concentration of 100 mg/L at different temperatures of
293, 303, 313 and 323 K respectively as shown in Fig. 2(b). It can be
seen that there was an accordant trend of BO biosorption with
increasing temperatures. The content of the BO biosorption onto the
dried A. liculoides increased rapidly within the rst 30 min, and then
slowed down from 30 min to 2 h, and remained constant from 2 h up
to 8 h. The contents of the BO biosorbed at the equilibrium increased
steadily from 18.25 to 19.14 mg/g with increasing temperatures from
293 to 323 K, indicating that even minimal increases in temperature
increased BO biosorption. This may be due to the relatively fast
biosorption of BO onto the dried A. liculoides, a process that is
endothermic in nature. The inuence of initial BO concentrations,
ranging from 10 to 1000 mg/L, on the BO biosorption on the dried
A. liculoides was investigated. As shown in Fig. 2(c), the biosorption
increases signicantly from 1.87 to 170.89 mg/g when initial
concentrations of BO increases from 10 to 1000 mg/L, while the BO
removal efciency decreases from 95% to 85%. The optimal conditions
included a solution pHof 7.0, a biosorbent dosage of 5 g/L, an initial BO
concentration of 100 mg/L and a contact time of 4 h.
3.2. Biosorption kinetics
In order to examine possible mechanismthat control the dynamics
of biosorption, different kinetic models that can suitably describe the
mechanism of the biosorption were used. These models are highly
dependent on the physical and/or chemical characteristics of the
biomass [22]. Pseudo-rst-order and pseudo-second-order models,
used to describe the biosorption kinetics [26], were subsequentially
used in analysis of the experimental data obtained in this study. The
linear form of the pseudo-rst-order equation is given as below:
ln q
e
q
t
= lnq
e
k
1
t 1
where q
e
and q
t
(mg/g) are the amounts of a dye biosorbed at the
equilibrium and at the time t; k
1
(min
1
) is the equilibrium rate
constant, which can be calculated from the linear plot of ln(q
e
q
t
)
against t.
N N
H
2
N
NH
2
HCl
Fig. 1. The chemical structure of Basic Orange.
57 C. Tan et al. / Desalination 266 (2011) 5662
The pseudo-second-order model can be used to predict kinetics of
biosorption, where chemical sorption is the rate-controlling step. The
rate of occupation of biosorption sites is proportional to the square of
the number of unoccupied sites [15]. The linear form of the pseudo-
second-order model can be described as below [27]:
t
q
t
=
1
k
2
q
2
e
+
1
q
e
t 2
where q
e
and q
t
are the amounts of a dye biosorbed by biosorbent at
the equilibrium and at the time t, respectively, k
2
is the rate constant
(g/(mg min). q
e
and k
2
can be calculated fromthe slope (1/q
e
) and the
intercept (1/kq
e
2
) derived from the plots of t/q
t
against t
.
The results obtained from the pseudo-rst-order model and the
pseudo-second-order models at temperatures ranging from 293 to
323 K are shown in Fig. 3(a) and (b) respectively. The associated
constants calculated from both models are given in Table 1. The
correlation coefcients obtained from the pseudo-second-order model
are quite high (R
2
2
=0.9991.00) compared to those obtained from the
pseudo-rst-order model (R
1
2
=0.8920.955) within the contact time of
0 to 2 h when biosorption reached equilibrium. The results suggest that
the biosorption of BO onto the dried A. liculoides ts with the pseudo-
second-order model better thanwiththe pseudo-rst-order model. This
is also conrmed with an agreement between the theoretical q
e
value
derived from the pseudo-second-order model and the experimental
value given in Table 1. Similar observation of dyes adsorbed onto
different biomaterials has been reported in the literature [14,28].
Furthermore, the initial biosorption rate (u) and the half-adsorption
time (t
1/2
) are given based on the pseudo-second-order model, and are
described by the following equations [29]:
u = k
2
q
2
e
3
t
1=2
=
1
k
2
q
e
4
0 200 400 600 800 1000
0
30
60
90
120
150
180
BO biosorption
BO removal percent
Initial BO concentration C
0
(mg/L)
Initial BO concentration C
0
(mg/L)
B
O

b
i
o
s
o
r
p
t
i
o
n

(
m
g
/
g
)
50
60
70
80
90
100
B
O

r
e
m
o
v
a
l

p
e
r
c
e
n
t

(
%
)
(a)
0 60 120 180 240 300 360 420 480
13
14
15
16
17
18
19
293 K
303 K
313 K
323 K
B
O

b
i
o
s
o
r
p
t
i
o
n

(
m
g
/
g
)
Contact time (min)
(b)
0 200 400 600 800 1000
0
30
60
90
120
150
180
BO biosorption
BO removal percent
B
O

b
i
o
s
o
r
p
t
i
o
n

(
m
g
/
g
)
50
60
70
80
90
100
B
O

r
e
m
o
v
a
l

p
e
r
c
e
n
t

(
%
)
(c)
Fig. 2. The effect of experimental parameters on the biosorption of BO onto
A. liculoides: effect of initial solutions pH (a), effect of contact time and temperature
(b), and effect of initial BO concentration (c).
0 20 40 60 80 100 120
0
1
2
3
4
5
6
7
t
/
q
t
t
(b)
0 20 40 60 80 100 120
-5
-4
-3
-2
-1
0
1
2
l
n
(
q
e
-
q
t
)
t
(a)
Fig. 3. Pseudo-rst and second-order biosorption kinetics of BO on the dried
A. liculoides: Pseudo-rst-order (a), Pseudo-second-order (b); 293 K (), 303 K (),
313 K (), 323 K (). Conditions: C
o
=100 mg/L, initial pH of 7, dosage of 5 g/L.
58 C. Tan et al. / Desalination 266 (2011) 5662
where t
1/2
is the time required to take up half as much dye as its
equilibrium value. The values of the half-adsorption time are listed in
Table 1. The lower the value of t
1/2,
the faster the rate of BO adsorbed
onto the dried A. liculoides. In addition, increasing temperature
increases the values of k
2
and u, but decreases the values of t
1/2
,
indicating that an increase of temperature enhances the biosorption of
BO onto the dried A. liculoides.
If the movement of the solute from the bulk liquid to the lm
surrounding the adsorbent is ignored, the adsorption process on
porous solids can be considered to have three steps: (1) external
binding or boundary layer diffusion, (2) intraparticle diffusion, and
(3) adsorption and desorption onto the interior sites [30,31]. In
addition, studies have shown that the third step is a fast process for
the adsorption of organic molecules onto the porous adsorbents [32].
Thus either external diffusion or intraparticle diffusion may be the
rate-controlling step. To examine the possible mechanisms control-
ling the biosorption, an intraparticle mass transfer diffusion model
was used. The equation is given as below [33]:
q
t
= k
ip
t
1=2
+ C 5
where q
t
(mg/L) is the content of the biosorption at the time t
(min); k
ip
(mg/(g min
1/2
)) is the rate constant of intraparticle
diffusion; and C (intercept) is the constant associated with thickness
of the boundary layer. The larger the value of C, the less the
intraparticle diffusion affects.
The plot of q
t
versus t
1/2
based on the data obtained at 303 K using
the intraparticle diffusion model is shown in Fig. 4. Similar plots were
obtained for other temperatures studied. As shown in Fig. 4, the plot is
not linear over the full time range; however, it exhibits a tri-linearity,
suggesting three successive steps of the biosorption. The rst linearity
may correspond to boundary layer diffusion, the second part may be
attributed to the intraparticle diffusion step, and the third linearity is
related to adsorption and desorption: the equilibriumstep. Due to the
boundary layer effect, the shape of q
t
versus t
1/2
plot is curved at a
small time limit [34], and causes the second linear part to deviate
remarkably from the origin (C=15.45). This clearly indicates the
involvement of intraparticle diffusion in biosorption of BO onto the
dried A. liculoides, yet this is not a rate-controlling step.
Based on all kinetic studies, it can be concluded that the
biosorption of BO onto the dried A. liculoides may involve a multi-
step process, including external biosorption of BO molecules onto the
sites of the dried A. liculoides, and intraparticle diffusion. The
chemical biosorption on the external surface however, is the rate-
controlling step, and may take place as a result of an interaction,
specically, between negatively charged groups of the biosorbent
surface and the positively charged molecules of the dye [35] or take
place as a result of ion-exchange between alkaline-earth ions (Ca
2+
or
Mg
2+
) on the surface sites of the dried A. liculoides and BO cations
[15].
3.3. Biosorption isotherms
To describe the biosorption equilibriumbetween an adsorbent and
a sorbate, three models were used, including the Langmuir isotherm,
the Freundlich equation and the DubininRadushkevich (DR)
equation. The Langmuir isotherm assumes a monolayer coverage of
sorbate on the solid surface of the adsorbent, uniform energy of
sorption, and no transmigration of sorbate in the surface [28]. At
equilibrium, the Langmuir isotherm can be expressed as:
1
q
e
=
1
K
L
q
m
1
C
e
+
1
q
m
6
where q
e
is a sorbate biosorbed at the equilibrium(mg/g); C
e
is the
equilibriumconcentration of the sorbate or the sorbate unadsorbed in
the solution (mg/L); q
m
(mg/g) is a maximum biosorption capacity
where it could not be reached in the experiments; and K
L
(L/mg) is a
measure of biosorption energy, indicating an afnity between the
biosorbent and the sorbate. The equilibrium constants of biosorption,
q
m
and K
L
, can be calculated fromthe plot of 1/q
e
versus 1/C
e
, where q
m
is 1/intercept and K
L
is intercept/slope. The dimensionless parameter
of the equilibrium or the adsorption intensity based on the Langmuir
isotherm can be expressed by the following equation [35]:
R
L
=
1
1 + K
L
C
0
7
where C
0
(mg/L) is the initial concentration of a sorbate in
solution. The parameter, R
L,
is considered as a reliable indicator of the
adsorption, representing favourability and feasibility nature of the
adsorption. Usually, there are four probabilities: R
L
=0, irreversible
adsorption; 0bR
L
b1, favourable adsorption; R
L
=1, linear adsorption;
and R
L
N1, unfavourable adsorption [26].
Fig. 5 shows a linear plot obtained from the Langmuir isotherm for
the biosorption of BO onto the dried A. liculoides at 303 K. The
correlation coefcient (R
2
) obtained is 0.996, which indicates that the
Table 1
Kinetic parameters derived from the pseudo-rst and second-order for the biosorption of BO on the dried A. liculoides at various temperatures.
T (K) Pseudo-rst-order Pseudo-second-order q
e. exp
(mg/g)
k
1
(min
1
) q
e.cal
(mg/g) R
1
2
k
2
(g/(mg min)) q
e.cal
(mg/g) R
2
2
u (mg/(g min)) t
1/2
(min)
293 0.031 3.67 0.892 0.023 18.52 0.999 7.770 2.383 18.25
303 0.053 3.39 0.939 0.032 19.01 0.999 11.587 1.641 18.70
313 0.041 2.39 0.92 0.042 19.05 1.000 15.291 1.246 18.87
323 0.034 2.25 0.955 0.043 19.27 0.999 15.949 1.208 19.14
2 4 6 8 10 12
13
14
15
16
17
18
19
q
e
t
1/2
Fig. 4. Intraparticle diffusion biosorption kinetics of BO on the dried A. liculoides at
303 K. Conditions: C
o
=100 mg/L, initial pH of 7, dosage of 5 g/L, and contact time of
4 h.
59 C. Tan et al. / Desalination 266 (2011) 5662
equilibrium ts well for the Langmuir isotherm. The Langmuir
biosorption constants of the maximum biosorption capacity (q
m
)
and K
L
calculated are 833.33 mg/g and 3.6710
3
L/mg respectively.
The biosorption intensity (R
L
) varied from 0.965 to 0.214 when the
initial concentration of BO was increased from 10 to 1000 mg/L. R
L
value within the range of 01 indicate that biosorption of BO onto the
dried A. liculoides is favourable. Due to its favourability and a high
biosorption capacity for BO (q
m
=833.33 mg/g), it could be concluded
that dried A. liculoides shows considerable potential for the removal
of BO from aqueous solutions.
The Freundlich equation is often used as an empirical relationship
between the concentration of a sorbate on the surface of an adsorbent
and the concentration of the sorbate in the solution. The Freundlich
equation based on the hypothesis of multi-layer biosorption has been
widely used to examine the biosorption isotherm. Its linear form is
given by the following equation [36]:
lg q
e
=
1
n
lg C
e
+ lg K
F
8
where q
e
is a sorbate biosorbed at the equilibrium(mg/g); C
e
is the
equilibriumconcentration of the sorbate or the unadsorbed sorbate in
the solution (mg/L); K
F
is a constant of the equilibrium, that is
indicative of biosorption capacity, and 1/n is the intensity of
biosorption, that indicates the relative distribution of energy sites
and depends on the nature and strength of the adsorption process
[36]. The equilibrium constants of K
F
and 1/n are calculated from the
plot of lgq
e
versus lgC
e
, where K
F
is 10
intercept
, and 1/n is slope.
Fig. 6 shows the Freundlich equation obtained for the biosorption
of BO onto the dried A. liculoides using Eq. (8). Calculated Freundlich
biosorption constants of 1/n and K
F
are 0.854 and 3.577 respectively.
The 1/n value within 0 and 1 indicates that the biosorption of BO on
the dried A. liculoides is favourable [30]. The correlation coefcient
(R
2
) is 0.984, compared to the R
2
value obtained from the Langmuir
equation (0.996). It can be concluded that the Langmuir isotherm
model is better tted to the equilibrium data obtained in this study.
The results suggest that the biosorption of BO onto the dried A.
liculoides may be due to biosorption of monolayers to functional
groups on the surface of the biomass [13].
To calculate the mean free energy of biosorption, that would give
indication of possible mechanisms involved in the biosorption (e.g.,
physical or chemical), the Dubinin-Radushkevich (D-R) equation, that
does not assume a homogeneous surface or a constant biosorption
potential as described by the Langmuir equation [37], was employed.
The linear form of the D-R isotherm equation and the formula for
mean biosorption energy (E) can be expressed as below:
ln q
e
= ln q
m

2
9
E =
1

2
p 10
where q
e
is the amount of a sorbate adsorbed on an adsorbent (mol/
g); q
m
is the maximum biosorption capacity (mol/g); is the activity
coefcient related to mean energy of biosorption (mol
2
/J
2
) and can be
obtained from the slope of lnq
e
versus
2
linear plot; is the Polanyi
potential (=R T ln(1+1/C
e
)), and E is the mean energy of the
biosorption (kJ/mol), that gives an indication of the mechanism
involved in the biosorption. If E value falls in the range from8 to 16 kJ/
mol, the biosorption is a chemisorption, and if Eb8 kJ/mol, the
biosorption process is a physical adsorption [37].
Fig. 7 shows that the D-R isotherm equation can accurately
describe the equilibrium data since the value of the correlation
coefcient is found to be 0.994 at 303 K. The biosorption energy (E)
calculated is 8.69 kJ/mol, indicating that the biosorption of BO onto
the dried A. liculoides may be involved in chemisorption via valence
forces by sharing or exchanging the electrons between sorbent and
sorbate [38]. Therefore, the biosorption of BO onto the dried A.
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0.0
0.1
0.2
0.3
0.4
0.5
0.6
1
/
q
e
1/C
e
Fig. 5. Langmuir isotherm of BO on the dried A. liculoides. Conditions: initial pH of 7,
dosage of 5 g/L, T=303 K, contact time of 4, C
o
varies from 10 to 1000 mg/L.
-0.4 0.0 0.4 0.8 1.2 1.6 2.0 2.4
0.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
l
g

q
e
lgC
e
Fig. 6. Freundlich isotherm of BO on the dried A. liculoides. Conditions: initial pH of 7,
dosage of 5 g/L, T=303 K, contact time of 4 h, C
o
varies from 10 to 1000 mg/L.
3 4 5 6 7 8 9 10 11
-13
-12
-11
-10
-9
-8
-7
-6
l
n
q
e

2
(10
8
)
Fig. 7. D-R model isotherm of BO on the dried A. liculoides. Conditions: initial pH of 7,
dosage of 5 g/L, T=303 K, contact time of 4, C
o
varies from 10 to 1000 mg/L.
60 C. Tan et al. / Desalination 266 (2011) 5662
liculoides in this study is inuenced by chemisorption. Since BO
molecule biosorption onto the surface of biosorbent appeared to be a
quick process [8], amino, carboxyl, thiol and phosphate groups
presented on the surface wall of the dried A. liculoides are responsible
for binding the dye molecules [7].
3.4. Biosorption thermodynamics
Thermodynamic parameters, including the Gibbs' free energy
(G), enthalpy (H) and entropy (S) change, were calculated in
order to describe thermodynamic behaviour of the biosorption of BO
onto the dried A. liculoides. The Gibbs' free energy Gibbs' (G) of the
biosorption can be calculated from the following equation:
G = R T lnK
d
11
where R is the universal gas constant (8.314 J/mol K); T is the
absolute temperature (K); and K
d
is the distribution coefcient
(K
d
=q
e
/C
e
) [39], which is temperature dependent. Both enthalpy
(H) and entropy (S) change associated can be estimated from the
following equation:
lnK
d
=
G
RT
=
H
RT
+
S
R
: 12
The enthalpy (H) and entropy (S) change of biosorption were
calculated fromthe slope and intercept derived fromthe linear plot of
lnK
d
versus 1/T (Fig. 8) respectively.
Values for the change in Gibbs' free energy (G) are 18.658,
19.891, 21.186 and 22.805 kJ/mol for the biosorption of BO
onto the dried A. liculoides at temperatures of 293, 303, 313 and
323 K respectively. The negative G values indicate the thermody-
namically feasible and spontaneous nature of the biosorption of BO.
An increase in G absolute values with increasing temperatures
shows an increase in feasibility of biosorption at a higher temperature,
suggesting that higher temperatures play a positive role in the
biosorption. The plot of lnK
d
versus 1/T is presented in Fig. 8, where
the H and S values are estimated to be 21.52 kJ/mol and 136.88 J/
mol K respectively. The positive value of the enthalpy (21.53 kJ/mol)
shows that the adsorption process of the BO on the dried A. liculoides
is endothermic and may involve chemisorption since it falls into the
range of 20.9418.4 kJ/mol [40].
3.5. Characterization of surface by FT-IR
To understand any possible interaction between the function
groups on the surface of the dried A. liculoides and BO cations, dried
A. liculoides was examined using FT-IR spectroscopy both before and
after use. As shown in Fig. 9(a) and (b), both the dried A. liculoides
before and after use show a similar pattern with a number of peaks
observed in the spectra. The broad peak at 3427.0 cm
1
is likely to be
due to the overlap of OH and NH stretching vibrations, indicating
the presence of both surface free hydroxyl groups and chemisorbed
water [38]. The peaks at 2920.6 cm
1
and 1384.3 cm
1
correspond to
the CH symmetric stretch of the methylene groups (CH
2
) and
deformation vibration of methyl groups (CH
3
). The peak at
1631.7 cm
1
can be attributed to C=O stretching vibration of
carboxylate (COO

) or mode with NH deformation vibration of

amide I groups. The peaks at 1254.6 and 1033.5 cm
1
are due to the
COstretching vibration of ketones, aldehydes and lactones or carboxyl
groups [41]. Some shifts in wave numbers from 1631.7 cm
1
to
1633.0 cm
1
, 1254.6 cm
1
to 1259.7 cm
1
, and 1033.5 cm
1
to
1039.1 cm
1
were however noticed in the spectra of dried A. liculoides
before and after use. This suggests that amide, hydroxy, carboxylate and
CO groups could participate in BO biosorption on the surface of dried
A. liculoides because of the shifts in wave numbers, which results from
change in bonding energy in these corresponding functional groups
[42].
4. Conclusions
This study showed that the dried A. liculoides biomass can be used
as a biosorbent to remove BO from aqueous solutions since the
biomass has a high maximum biosorption capacity of BO (833.33 mg/
g at a temperature of 303 K, an initial pHof 7.0, a biosorbent dosage of
5 g/L and a contact time of 4 h) as estimated using the Langmuir
equation. Kinetic examination of the equilibrium data showed that
the biosorption of BO onto the dried A. liculoides was a multi-step
process, including external biosorption of BO ions onto the surface
sites of the dried A. liculoides, intraparticle diffusion, and the
chemical biosorption on the external surface sites as a rate-controlling
step. Biosorption equilibrium was better described by the Langmuir
isotherm than the Freundlich equation. The mean free energy
calculated from the D-R equation was 8.69 kJ/mol, conrming that
the biosorption of BO onto the dried A. liculoides biomass involves
chemisorption. In addition, the thermodynamic calculations indicated
feasibility, endothermic and spontaneous nature of the biosorption at
the temperatures from 293 to 323 K. Based on the results obtained in
this study, it can be concluded that the biosorption of BO onto the
3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45
7.6
7.8
8.0
8.2
8.4
8.6
l
n

K
d
1 / T
Fig. 8. The estimation of thermodynamic parameters for the biosorption of BO on the
dried A. liculoides. Conditions: C
o
=100 mg/L, initial pH of 7, dosage of 5 g/L, and
contact time of 4 h.
4000 3500 3000 2500 2000 1500 1000 500
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
Wavenumber (cm
-1
)
(a)
(b)
3423.7
2920.5
1633.0
1039.1
564.1
3427.0
2920.6
1631.7 1033.5
565.9
1254.6
1259.7
1384.3
1384.3
(a) Before use
(b) After use
Fig. 9. FT-IR spectra of the dried A. liculoides: (a) before use; (b) after use.
61 C. Tan et al. / Desalination 266 (2011) 5662
dried A. liculoides mainly is an endothermic chemisorption via
external surface sit binding.
Acknowledgements
The authors sincerely thank Fujian Normal University, PR China for
providing the research funding under the program of MinJiang
Fellowship.
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