Ecotoxicology and Environmental Safety 98 (2013) 352–360

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Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Biosorption of Cd(II) from aqueous solution using xanthated nano

banana cellulose: Equilibrium and kinetic studies
Saumya S. Pillai a,n, B. Deepa a,b, Eldho Abraham a,b, N. Girija c, P. Geetha c,
Laly Jacob d, Mathew Koshy a
a
Department of Chemistry, Bishop Moore College, Alappuzha 690110, India
b
Department of Chemistry, C.M.S College, Kottayam 686001, India
c
Department of Chemistry, D.B. Pampa College, Parumala, Pathanamthitta, India
d
Department of Zoology, Bishop Moore College, Alappuzha 690110, India

art ic l e i nf o a b s t r a c t

Article history: Present study explored the biosorption capacity of xanthated nano banana cellulose (XNBC) for Cd(II)
Received 3 May 2013 from aqueous solution. The biosorbent containing sulfur-bearing groups have a high affinity for heavy
Received in revised form metals. Sulfur can be considered as a soft ligand group having strong affinity for cadmium. In the present
23 August 2013
study, the influence of various important parameters such as pH, time, biosorbent dose and initial Cd(II)
Accepted 2 September 2013
Available online 3 October 2013
concentration on the biosorption capacity were investigated. The maximum biosorption capacity of
XNBC for Cd(II) was found to be 154.26 mg g
1 at 298 K. The Cd(II) sorption of XNBC was confirmed by
Keywords: SEM-EDS and XRF analysis. The isotherms such as Langmuir, Freundlich, Redlich–Peterson and Tempkin
Biosorption were studied. The Langmuir and the Redlich–Peterson isotherms had been well fitted the biosorption of
Xanthated nano banana cellulose
Cd(II) with xanthated nano banana cellulose. The kinetics of Cd(II) removal using XNBC was well
Cd(II)
explained by second-order kinetic model. The thermodynamic parameters were also evaluated from the
Kinetics
Thermodynamic parameters biosorption measurements. Among the various desorbing agents tested, the desorbing efficiency was
found to be maximum with 0.1 mol L
1 HCl. It was found that XNBC is also suitable to be used under
column operation.
& 2013 Elsevier Inc. All rights reserved.

1. Introduction as precipitation, adsorption, membrane processes, ionic exchange

Cadmium is one of the most toxic pollutants in wastewater that
is introduced into water from metal mining, melting, plating,
batteries, pesticides, oil paint, pigments, and alloys (Xiaomin
et al., 2007; Guiqiu et al., 2008). Cadmium is considered to be
particularly toxic and responsible for serious decrease in biological
activity (Bruins et al., 2000; Smit et al., 1997). The World Health
Organization has set a maximum guideline concentration of
0.003 mg L
1 for Cd in drinking water (WHO, 2008). Cadmium is
effectively bound by high molecular weight proteins such as
albumin and by non-protein sulfhydryl groups in the human body.
Cd is accumulated in the kidneys and liver (Doshi et al., 2007).
Cadmium could also be shown to be associated with occurrences
of Itai-Itai, a disease under which patients show a wide range of
symptoms such as low grade of bone mineralization, high rate of
fractures, increased rate of osteoporosis and intense bone asso-
ciated pain (Fridberg et al., 1974; Nogawa et al., 2004). There are
several conventional methods for treatment of heavy metals such
n
Corresponding author. Fax: þ91 479 2303230.
E-mail address: saumyaspillai@gmail.com (S.S. Pillai).
and flotation (Selatnia et al., 2004; Jacques et al., 2007). Among the
numerous techniques of pollutant removal, biosorption is found to
be superior to other techniques in terms of initial cost, simplicity
of design and ease of operation.
Biosorption is a process where certain types of biomass are able
to bind and concentrate metals from even very dilute aqueous
solutions. The main advantages of biosorption are low operating
costs, minimization of the volume of chemical and biological
sludge to be handled, and high efficiency in detoxifying effluents
(Marques et al., 1999; Cho and Kim, 2003). The mechanisms of
biosorption are generally based on physico-chemical interactions
between metal ions and the functional groups present on the cell
surface, such as electrostatic interactions, ion exchange, and metal
ion chelation or complexation (Ozer et al., 2004).
Cellulose nanofibers have tremendous unique characteristics
such as very high surface area to volume ratio, high surface area,
thermal stability and contain 96 percent cellulose (Cherian et al.,
2008). Banana fiber was used for the production of nano fibrils by
steam explosion. The advantages of steam explosion include low
energy consumption, eco-friendly and less hazardous chemicals.
Sulfur group can be introduced into this nano cellulose by
xanthation. The biosorbent containing sulfur-bearing groups have

0147-6513/$ - see front matter & 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.ecoenv.2013.09.003
 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360
a high affinity for heavy metals but a low affinity for light metals.
The most important sulfur-bearing compounds include sulfides,
thiols, dithiocarbamates, dithiophosphates and xanthates.
Xanthates are most prominent because they are easy to prepare
with relatively inexpensive reagents, highly insoluble and have
high stability constant values of the metal complex formed (Rao,
1971; Wing et al., 1975; Tare et al., 1992). According to HSAB (hard
and soft acids and bases) classification system (Winter, 1994), soft
ligands have strong affinity with soft acids. Sulfur can be con-
sidered as a soft ligand group having strong affinity for cadmium,
that are classed as soft acids. Xanthates are formed by the reaction
of an organic hydroxyl-containing substrate with carbon disulfide
under caustic condition (Bailey et al., 1999).
The objective of the present work was to investigate the biosorp-
tion potential of xanthated nano banana cellulose for the removal
of Cd(II) ions from aqueous solution. The effects of pH, adsorbent
dosage, contact time and temperature on the adsorption capacity
of XNBC were studied. The Langmuir, Freundlich, Redlich–Peterson
and Tempkin isotherm models were used to describe equilibrium
data. The biosorption mechanisms of Cd(II) ions onto XNBC was
also evaluated in terms of thermodynamics and kinetics.
2. Materials and methods
2.1. Reagents
All the chemicals used in the adsorption were of analytical grade. The stock
solution Cd2 þ solution was prepared from in distilled water. The experiment was
conducted over a range of pH from 1.0 to 7.0 using 0.1 mol L
1 HCl and
0.1 mol L
1 NaOH.
2.2. Equipments and methods of characterization
The pH and potential measurements were made using a digital microprocessor
pH meter (Systronics model μ 362). Accurate weight of chemicals and biosorbent
used in the study was taken on an electronic balance, Citizen CX 220, Germany. The
FTIR spectra of the biosorbents were obtained using a Schimadzu FTIR model 1801.
Surface morphology of the biosorbentsand EDS were probed using a Philips XL 30
CP Scanning Electron Microscope. XRF analysis by SKYRAY-REDLANDS (USA), model
EDX3600. The concentration of Cd2 þ ions in the solution was determined by AAS
[Perkin Elmer AA analyst 100(USA)]. For kinetic and isotherm studies, a Labline
temperature controlled water bath shaker with a temperature variation of 7 1.0 1C
was used. The zero point charge of biosorbent was determined by titration method
using ZEN 3600 model zeta potential analyzer. All the glasswares used in the study
were of A-type Borosil glass.
2.3. Biosorbent preparation
The nano banana cellulose (NBC) was prepared by the steam explosion of
banana fiber followed by acid hydrolysis (Cherian et al., 2008). The prepared NBC
was then xanthated (Wing et al., 1975). About 15 gm of NBC was treated with
200 ml 4 M NaOH in Erlenmeyer flak. The sample was well stirred at room
temperature for 3 h and another 3 h after the addition of 10 ml CS2. Allowed to
stand for 1 h and excess alkali was removed by washing with double distilled
water. Finally the mixture was washed with acetone and stored at low temperature
(6–8) abbreviated as XNBC.
353
2.4. Preparation of Cd(II) solution
A stock solution of 1000 mg L
1 of Cd(II) was prepared by dissolving 2.03 g of
CdCl2  2 1/2 H2O in 1000 ml of solution. This solution was diluted as required to
obtain the standard solutions containing 50–300 mg L
1 of Cd(II). pH adjustment
was carried out by using 0.1 N HCl and 0.1 N NaOH solutions.
2.5. Experimental procedure
The batch experiments are carried out in 100 ml borosil conical flask. A specific
amount of adsorbent was added in 50 ml of 50 mg L
1 Cd(II) solutions, and then
stirred for a predetermined period at 25 1C in water bath-cum-mechanical stirrer.
Afterwards, the resultant solution is filtered using a filter paper. The concentration
of Cd(II) ions in the solution is determined by AAS. Biosorption isotherm study was
carried out with different initial Cd2 þ concentrations ranging from 50 to
300 mg L
1 while maintaining the adsorbent amount of 2 g L
1.
The amount of biosorption was calculated as follows:
Co
Ce
qe ¼ V ð1Þ
m
where Co and Ce are the initial and equilibrium Cd2 þ concentrations respectively.
V is the volume of the solution and m is the amount of biosorbent used. All the
experiments were carried out in triplicate and the mean values are presented. The
maximum variation with batch biosorption data among triplicate values was
4.4 percent.
2.6. Statistical analysis
Statistical analysis was done (Bennet and Franklin, 1967) and the results were
analyzed using statistical program SPSS/PC þ, version 11.5. A one way ANOVA was
employed for the comparison among groups. Duncan's post hoc multiple compar-
ison test of significant differences among groups were determined. All the values
are expressed as mean value7 SD (n ¼3).
3. Results and discussions
3.1. Characterization of adsorbent
3.1.1. FTIR
The FTIR spectra of NBC, XNBC and Cd–XNBC are shown in Fig. 1
(A). In NBC spectrum, the broad and intense absorption peak at
3421 cm
1 corresponds to O–H stretching vibrations of hydrogen
bonded hydroxyl group (Gnanasambandam and Protor, 2000;
Cherian et al., 2008). The peak at 2921 cm
1 is due to the aliphatic
saturated C–H stretching vibration in cellulose and hemicellulose.
The peak at 1630 cm
1 is the bending mode of the absorbed water
with some contribution from carboxylate groups (Sun et al., 2005).
The peak at 1430 cm
1 is due to symmetric stretching vibration
of CQO in ionic carboxylic group (Farnella et al., 2007). The bands
in the region 1250–1056 cm
1 involve the C–O stretching vibra-
tions of aliphatic primary and secondary alcohols in cellulose,
hemicellulose and lignin (El-Zawawy, 2006). The broad peak
observed at 1050 cm
1 are assigned to ether linkage (C–O–C)
from lignin or hemicellulose, while the peak at 898 cm
1 is due to
β-glycosidic linkages of glucose ring of cellulose (Gañán et al.,
2004). The other peak at 559 cm
1 is due to the torsional vibration
354 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360

Fig. 1. (a) The FTIR spectra of NBC, XNBC and Cd–XNBC. (b) SEM images of NBC and XNBC. (C) TEM image of NBC.

of the pyranose ring (El-Zawawy, 2006). The presence of sulfur (Panda et al., 2008). The peak at 3421 cm
1 was shifted to
groups in the BCX was confirmed by the presence of new peaks at 3307 cm
1 and its reduction in intensity confirmed that hydroxyl
538, 1020 and 1151.5 cm
1 corresponding to γC–S, γCQS and γS–C–S groups have combined with CS2.
 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360
3.1.2. Morphological studies
Scanning electron microscopic analyses of NBC and XNBC were
carried out to assess their surface morphology. The SEM micro-
graphs of NBC and XNBC are shown in Fig. 1(B). The surface
morphology of XNBC was different from that of NBC which
confirmed the chemical changes that took place on the surface
of nano banana fibrils. In NBC, each elementary fiber shows a
compact structure. During chemical treatment with NaOH, swel-
ling of the fibers occurs and hydrophilic groups are strongly
induced on the fiber surface. EDX plot further confirmed the
presence of sulfur on the surface of the biosorbent after treatment
of NBC with CS2.
The nano fiber morphology of the NBC (100 nm) is confirmed
from the TEM micrograph as shown in Fig. 1(C)
3.1.3. Determination of zeta potential
Zeta potential values of the NBC and XNBC were determined
(Abia and Asuquo, 2008) at various pH in deionized water is
shown in Fig. 2. The isoelectric point of the XNBC is less than that
of NBC and also it can be seen that zeta potential of XNBC was
larger than NBC. Above the pH point of zero point charge, the
surface charge of the biosorbent is negative (Krishnan and
Anirudhan, 2003). As the pH was increased, however, the overall
surface charge on biosorbent became negative and the higher
biosorption rate at higher pH was primarily electrostatic in nature.
3.1.4. XRF and EDS analysis of Cd–XNBC
Energy dispersive X-ray spectrometry is a popular method for
the determination of heavy metals in biosorbent. The peak of S in
XNBC indicated the anchoring of xanthate group on the NBC.
Fig. 2. Plot of relation between zeta potential and pH of NBC and XNBC.
Fig. 3. Plot of (A) XRF and (B) EDS of Cd–XNBC.
355
Measurement of the discrete energy of the X-rays emitted is used
to identify the metals species present; measurement of the
number of emitted X-ray provides a quantitative indication of
the concentration of the metal present in sample (Ulmanu et al.,
2011). In the present study, qualitative interpretation of Cd was
done using XRF analysis. The EDS and XRF image of XNBC clearly
show a strong peak of Cd. The XRF and EDS images of Cd treated
XNBC is shown in Fig. 3(A and B) respectively.
3.2. Effect of parameters on biosorption
3.2.1. pH
pH is one of the most important variable affecting metal ion
biosorption. Fig. 4(A) shows the biosorption of Cd2 þ ions onto
XNBC in different pH. From the figure, it was observed that
biosorption rate was found to increase from pH 2 to 7. The low
biosorption rate at low pH was due to increase in positive charge
density (protons) on surface sites and thus electrostatic repulsion
is possible between the positive charges on the metal ion with
surface charge. From the literature on Cd(II) speciation diagram
(Ramos et al., 1997), the dominant Cd(II) species at pH 4 8.0 is Cd
(OH)2 and at pH o8.0 is Cd2 þ and Cd(OH) þ . The maximum
sorption efficiency in the pH range of 5.0–8.0 may be due to the
interaction of Cd2 þ and Cd(OH) þ with surface sulfur groups
present in the biosorbent. In addition to sulfur groups, the carbon
containing carboxyl and hydroxyl groups are also responsible for
the sorption of Cd(II) ions (Krishnan and Anirudhan, 2003).
An appreciable increase in the biosorption rate was observed at
pH 6 at all concentrations of Cd2 þ ions. 97.3 percent biosorption
was observed at pH 6 with Cd2 þ ions concentration of 50 mg L
1.
At higher pH values than 6, the formation of anionic hydroxide
complexes decreases the concentration of free cadmium ion, and
thereby the biosorption capacity of cadmium ion decreased.
Cadmium was precipitated after pH 6, thus, precipitated cadmium
were inaccessible for measurement after filtration (Olu-owolabi
et al., 2012). Therefore, pH 6 was selected to be the optimum pH
for further studies.
3.2.2. Initial cadmium (II) concentration
Effect of initial Cd(II) concentration on biosorption of Cd(II)
using XNBC and initial pH 6 is shown in Fig. 4(B). Values represent
mean 7SD (n ¼3). The percentage removal of cadmium (II) ions
showed a decreasing trend as cadmium (II) ions concentration
increased from 50 mg L
1 to 300 mg L
1. The percentage removal
decreased from 97.5 percent to 85.8 percent with an increase of
Cd(II) concentration from 50 mg L
1 to 300mgL
1. This may be
356 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360
Fig. 4. The effect of (A) pH, (B) Concentration, (C) Contact time, (D) Amount of biosorbent on the removal of Cd(II) onto XNBC.
Fig. 5. Non-linear model of Langmuir isotherm, Freundlich isotherm, Redlich–
Peterson isotherm and Tempkin isotherm.
due to limitation of vacant binding sites, thus decreasing the
cadmium (II) removal yields (Tay et al., 2013).
3.2.3. Contact time
The percentage of cadmium (II) removal by XNBC as a function
of contact time is depicted in Fig. 4(C). The sorption of cadmium by
the biosorbent was found to be very fast in the initial stage and
showed a gradual decrease thereafter and reached an equilibrium
value in approximately 30 min for all the initial metal ion
concentrations. This indicated that initially the presence of abun-
dant vacant binding sites becomes saturated after these sites were
occupied. The biosorption of metal ions on the biosorbent surface
depends on the availability of metal ion around the microenviron-
ment of the biosorbent and the electrostatic interaction between
them at the sorption sites (Anirudhan et al., 2012). Remaining
vacant binding sites might also be difficult to occupy due to
repulsive force between the solute molecules of the solid and
bulk phase (Chakravarty et al., 2010; Gupta and Babu, 2009). The
percentage removal decreased from 97.5 percent to 85.8 percent
while increasing the initial concentration of Cd(II) from 50 to
300 mg L
1 for a contact time of 30 min.
3.2.4. Amount of biosorbent
The percentage of Cd(II) removal was found to be increased
with an increase in the biosorbent amount from 2 g L
1 to 8 g L
1
as shown in Fig. 4(D). The increase in cadmium (II) removal with
the biosorbent concentration could be attributing to increase in
surface area and the availability of more binding sites. While the
biosorption capacity decreased. The decrease in biosorption capa-
city was due to the sites remaining unsaturated during the
biosorption process (Gupta and Babu, 2009).
3.3. Biosorption isotherm study
The study of adsorption isotherms provide the specific relation
between the concentration of sorbate and its sorption degree onto
biosorbent surface at a constant temperature. Three important
isotherms are selected in this study, which are, namely the
Langmuir, Freundlich, Redlich–Peterson and Tempkin isotherm
models and the non-linear plots are shown in Fig. 5.
 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360 357

3.3.1. Langmuir isotherm Table 1

The Langmuir model assumes that adsorptions occur at specific Isotherm constants and regression data for biosorption of Cd(II) on XNBC.
homogeneous sites on the adsorbent and is used successfully in
SI. No Biosorption isotherm Isotherm parameters R2
many monolayer adsorption processes. Once a site is filled, no
further sorption takes place at that site (Boparai et al., 2011). The 1 Langmuir Qm 154.26 0.99
Langmuir constant, Qm, was obtained as 154.26 mg g
1. The b 0.11
Langmuir constant, b, which indicates biosorption energy, was 2 Freundlich KF 26.94 0.98
nF 0.42
found to be 0.11 L mg
1. The value of R2 ¼0.99 and the biosorption 3 Redlich–Peterson KR 25.15 0.99
favorability (RL) was found in the range of 0.03 and 0.1 RL values a 0.34
between 0 and 1 indicate favorable biosorption (Mckay et al., g 0.81
1982). 4 Tempkin AT 1.5 0.98
BT 30.14
Non-linear Langmuir equation is given by,
bT 32.2

Q 0 bL C e
qe ¼ ð2Þ
1 þbL C e

Table 2
Calculated kinetic parameters for first and second order kinetic model for the
biosorption of Cd(II) using XNBC.
3.3.2. Freundlich isotherm
The Freundlich isotherm is applicable to both monolayer SI No Co Ce qe First order kinetic Second order kinetic
(mg L
1) (mg L
1) (mg g
1) model model
(chemisorption) and multi-layer adsorption (physisorption) and
is based on the assumption that the adsorbate adsorbs onto the k1 qe R2 k2 qe R2
heterogeneous surface of an adsorbent (Yang, 1998). (mg g
1) (mg g
1)
Freundlich equation is given by,
1 50 1.2 24.4 0.13 15.9 0.96 0.01 25.7 0.99
2 100 4.2 47.9 0.12 32.3 0.94 0.007 50.5 0.99
qe ¼ K F C 1=n
e ð3Þ
3 200 14.8 92.6 0.11 58.7 0.97 0.007 95.2 0.99
4 300 42.6 128.7 0.14 88.1 0.97 0.006 131.5 0.99
The values of n and KF were 0.42 and 26.94 respectively. The
obtained coefficient of determination (R2) was 0.98. The values of
Freundlich coefficient, n ¼0.42 represented the deviation from
3.4. Kinetic studies
linearity of biosorption. The Freundlich constant indicated the
relative biosorption capacity of the biosorbent related to the
3.4.1. Pseudo first-order kinetics
bonding energy.
The pseudo first-order equation (Lagergren's equation) describes
adsorption in solid–liquid systems based on the sorption capacity of
solids (Ho, 2004).
3.3.3. Redlich–Peterson isotherm The linear form of pseudo first order model can be expressed as
The Redlich–Peterson isotherm contains three parameters and
incorporates the features of the Langmuir and the Freundlich K ad t
log ðqe
qt Þ ¼ log qe
ð6Þ
isotherms (Redlich and Peterson, 1959). It can be described as 2:303
follows:
where qe and qt (mg g
1) are the adsorption capacities at equili-
K g Ce brium and at time t respectively. The first order rate constant, Kad
qe ¼ ð4Þ and qe for the initial Cd(II) concentration from 50 mg L
1 to
1 þaR C ge
300 mg L
1 were obtained from the plot of log(qe
qt) versus t
The model has a linear dependence on concentration in the are listed in Table 2. The coefficient of R2 was found to be in the
numerator and an exponential function in the denominator range of 0.94–0.97. But the true value of qe obtained from
(Ng et al., 2002) to represent adsorption equilibrium over a wide experiments was not in agreement as expected with pseudo-first
concentration range, that can be applied either in homogeneous or order model.
heterogeneous systems due to its versatility (Gimbert et al., 2008).

3.4.2. Second-order kinetics

3.3.4. Tempkin isotherm
Tempkin model assumes that heat of adsorption (function of
temperature) of all molecules in the layer would decrease linearly
with the coverage of molecules (Aharoni and Ungarish, 1977). The
non-linear form of Tempkin equation is given by
RT
qe ¼ lnðAT C e Þ
bT
where BT ¼ (RT)/bT, T is the absolute temperature in K and R is the
universal gas constant. bT is related to the heat of adsorption, AT is
the equilibrium binding constant corresponding to the maximum
binding energy.
Table 1 shows the Langmuir, Freundlich, Redlich–Peterson and
Tempkin isotherm constants and regression data for biosorption of
Cd(II) onto XNBC.
The pseudo second-order rate expression, which has been
applied for analyzing chemisorption kinetics from liquid solutions
(Ho, 2006; Azizian, 2004) is linearly expressed as
t 1 1
¼ þ t ð7Þ
qt K 2 q2e qe
ð5Þ where K2 is the rate constant for pseudo second-order adsorption
and K 2 q2e or h is the initial adsorption rate. The slopes and
intercepts of plots t/qt versus t was used to calculate the K2 and
qe are included in Table 2. The correlation coefficients (R2) for the
pseudo second-order kinetic model fits were much higher than
the correlation coefficients derived from pseudo first-order model
fits. Furthermore there was a good agreement between experi-
mentally observed equilibrium adsorption capacities; this suggests
that cadmium adsorption followed pseudo second-order kinetics.
358 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360

3.5. Thermodynamic parameters
The thermodynamic parameters such as free energy (ΔG),
enthalpy (ΔH) and entropy (ΔS) were evaluated using equilibrium
constants changing with temperature. The –ve value of ΔG
indicated the feasibility of the process and spontaneous nature
of biosorption. The þve value of ΔH and ΔS indicated the
endothermic nature and irreversibility of Cd(II) biosorption,
respectively (Ertugay and Bayhan, 2008). The Gibbs free energy
changes (ΔG) were found to be negative (i.e. feasible and exergonic)
and was obtained from the following relation:
ΔG ¼
RT ln K C
Hefne et al., 2008). The ΔH and ΔS were obtained from the
relation, the Gibbs free energy change,
ΔG ¼ ΔH–T ΔS ð9Þ
The standard enthalpy and entropy change of biosorption can be
obtained by plotting ΔG versus T (K). The positive nature of the ΔS
values suggesting spontaneous process. This occurs as a result of
redistribution of energy between the biosorbate and the biosor-
bent. This increase in randomness at the solid–solution interface
during the adsorption process leads to the increase in entropy and
hence overall positive ΔS (Ibrahim and Jimoh, 2011). The thermo-
dynamic parameters are shown in Table3.
ð8Þ

The decrease in ΔG (i.e. increase negative) values indicated 3.6. Mechanism of biosorption
the more efficient biosorption and the ease with which the
ions are desolvated (Qadeer, 2005; Chen and Wang, 2006; Cellulose consists of cellobiose units repeated through
1,4-glycosidic linkages in a polymer. The treatment of strong alkali
Table 3 causes the chemical change of CH2OH group resulting in the
Thermodynamic parameters for the biosorption of Cd(II) on XNBC.
formation of sodium alkoxide groups. The biosorption of Cd2 þ
Temperature (K) ΔG (K J mol
1) ΔH (J/mol) TΔS (K J mol
1) by XNBC is through ion exchange or complexation or by the
combination of both processes. Similar mechanism was also
298
2.99 5.27 reported for the binding of divalent metal ions with xanthates
303
3.07 2.28 5.36
(Liang et al., 2009). The empty orbitals of the cadmium can
308
3.17 5.45
occupied by electrons to form complex, so mechanism (B) is the

Scheme 1. Mechanism of biosorption of Cd2+ by XNBC.

 S.S. Pillai et al. / Ecotoxicology and Environmental Safety 98 (2013) 352–360 359

most possible biosorption process. The proposed mechanism was 4. Conclusion

shown in Scheme 1.
Natural biosorbent like cellulose has the ability of removing
heavy metals from aqueous solutions. The xanthated nano banana
3.7. Column studies cellulose had much potential as an efficient and useful biosorbent
for the removal of Cd(II) from aqueous solutions. The extent of
The fixed bed column with an internal diameter of 2 cm was biosorption dependent on process parameters such as pH, initial
used for the study. A known quantity of biomass was packed in the concentration of Cd(II), biosorbent dosage and contact time. The
column to yield the desired bed height of the sorbent. Cd(II) Cd(II) intake by biosorbent was confirmed by SEM-EDS and XRF
solutions of initial concentration 50 mg L
1 were fed upward analysis. The maximum percentage removal of Cd(II) was obtained
inside the column by a peristaltic pump to get the desired flow at pH 6.0. The percentage removal of Cd(II) increased with the
rate. The pH of the solution was maintained constant at 6. The increase of biosorbent amount and the biosorption capacity of the
temperature was controlled at 25 1C. The flow rate was adjusted to xanthated nano banana cellulose was decreased because of the
5, 10 and 20 ml min
1. The aliquot of the sample at the outlet of availability of more unsaturated biosorption sites. The isotherm
the column was collected at regular time intervals. Column models such as Langmuir, Freundlich, Redlich–Peterson and Tempkin
effluent samples were analyzed by AAS. The removal efficiency were used to analyze the biosorption study. The kinetic data was
was low at high flow rate because the contact time of metal ions found to be applicable to second order kinetic model indicating
with biosorbent was very short at high flow rate. chemisorption. Thermodynamic constants were evaluated using
Total amount of metal ion sent to column is calculated from the equilibrium constants changing with temperature. The –ve value
equation: of ΔG indicated the feasibility of the process and spontaneous
nature of biosorption. The þve value of ΔH and ΔS indicated the
C 0 Q t total
mtotal ¼ ð10Þ endothermic nature and irreversibility of nano banana cellulose.
1000
Among the various desorbing agents tested, the desorbing effi-
Total removal is calculated from the following equation: ciency was found to be maximum with 0.1 mol L
1 HCl. Compar-
qtotal ing the batch and column experiments, batch mode experiment is
mtotal ¼  100 ð11Þ more effective than fixed bed column. Results from the study
mtotal
confirmed that xanthated nano banana cellulose is an effective
Equilibrium metal uptake (qe) in the column is defined as the biosorbent for removing Cd(II) from aqueous solutions.
total amount of metal sorbed per gram of the sorbent (X) at the
end of total flow time (Aksu and Gonen, 2004).
Acknowledgments
qtotal
qeq ¼ ð12Þ
X
The authors would like to thank all the colleagues who helped
The parameters are shown in Table 4. to do the analysis. This research was financially supported by a
Research Grant-in-Aid from the University of Kerala, Thiruva-
nanthapuram, Kerala.
3.8. Regeneration studies
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