Bioresource Technology 101 (2010) 2067–2069

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Bioresource Technology
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Short Communication

Adsorption behavior of heavy metals onto chemically modified sugarcane bagasse

Puspa Lal Homagai a, Kedar Nath Ghimire a,*, Katsutoshi Inoue b
a
Central Department of Chemistry, Tribhuvan University, Kirtipur, Kathmandu, Nepal
b
Department of Applied Chemistry, Saga University, Saga 840-8502, Japan

a r t i c l e i n f o a b s t r a c t

Article history: A new process for the xanthation of sugarcane (Saccharum officinarum) bagasse was investigated for the
Received 9 September 2009 separation of cadmium, lead, nickel, zinc and copper from their aqueous solutions. Adsorption capacity of
Received in revised form 17 November 2009 the charred xanthated sugarcane bagasse (CXSB) was found to be significantly more than the several bio-
Accepted 17 November 2009
sorbents reported in the literatures. The modified material was characterized by FTIR and elemental anal-
ysis. The kinetics of sorption of the tested metals was fast, reaching equilibrium within 20–40 min. The
maximum adsorption capacities evaluated in terms of mol/kg dry gel were 1.95 for Cd(II), 1.58 for Pb(II),
Keywords:
2.52 for Ni(II), 2.40 for Zn(II) and 2.91 for Cu(II), respectively. The high adsorption capacity and the kinet-
Charred sugarcane bagasse
Adsorption
ics results indicated that CXSB can be used as the selective adsorbent for the removal of these respective
Xanthation metal ions from wastewater.
Adsorbent Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
Heavy metal pollution in water and soil is a matter of great pub-
lic concern these days. Recently, much attention is given to prepare
adsorbents from various wastes generated from forestry (Horsfall
et al., 2006), fishery (Inoue and Yoshizuka, 1999) and by-products
of agriculture (Ghimire et al., 2008; Lokesh and Tare, 1989). In Ne-
pal, sugarcane industries produce a large amount of sugarcane ba-
gasse (SB) that requires little processing to increase its sorptive
capacity and its cost is supposed to be low even after chemical
modification. The SB contains cellulose (46.0%), hemicellulose
(24.5%), lignin (19.95%), fat and waxes (3.5%), ash (2.4%), silica
(2.0%) and other element (1.7%) (Sene et al., 2002). The polysaccha-
rides found in sugarcane bagasse are biopolymers having many hy-
droxyl and/or phenolic groups that can be chemically modified to
form new compounds with changed properties (Navarro et al.,
1996). Although there are some reports of raw sugarcane bagasse
as the adsorbent (Bassso et al., 2002), however, owing to its low
adsorption capacity, we have explored a simple means of chemical
modification to enhance its metal adsorption properties in the
present study. The choice of xanthate group is due to the presence
of sulfur atom and it is well known that sulfur group has a very
strong affinity for most of the heavy metals, and the metal sulfur
complex is very stable in basic medium (Chauhan and Sankararam-
krishnan, 2008; Kumar et al., 2000; Sankararamakrishnan et al.,
2006; Tare and Chaudhari, 1987). In view of this regard, xanthation
of sugarcane bagasse was investigated in the present study. In
* Corresponding author. Tel.: +977 1 4333945, +977 9841830466 (mobile).
E-mail address: knghimire@yahoo.com (K.N. Ghimire).
contrast to the ion exchange chelating resins made of plastic, this
adsorbent is free from any refractory post treatment after its use
since the main component of the adsorbents are natural polysac-
charides, that is very easy to be incinerated.
2. Methods
2.1. Chemicals
Standard stock solutions of 1000 mg/L were prepared appropri-
ately Cd+2 and Pb+2 from their nitrate salts, Ni+2, Zn+2 and Cu+2 from
their chloride salts (Wako Chem. Ltd. Japan), respectively. The pH
of working solution was adjusted using 0.1 M NaOH and 0.1 M
HCl and 0.1 M 2-[4-(2-hydroxymethyl)-1-piperazinyl] ethanesul-
fonic acid (HEPES) was also used as a buffer reagent. All the re-
quired experimental solutions were diluted using 0.1 M HNO3.
2.2. Preparation of adsorbent materials
Sugarcane bagasse (SB) was collected from local juice centre sit-
uated in Kathmandu Metropolitan city. It was dried in air oven at
70 °C for 24 h and grounded into fine particles with the help of
an electric grinder. It was sieved to pass uniform size of 212 lm.
Then 100 g of SB was treated with 200 ml concentrated H2SO4
and stirred for 30 min and left for overnight. It is well known that
acid treatment with such biopolymer creates a suitable environ-
ment for its ring opening (Morrison and Boyd, 1994). It was
washed with deionized water to remove excess acid and any other
soluble substances until neutrality and then dried. This material is
referred as charred sugarcane bagasse (CSB). 25 g of the CSB was

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.11.073
2068 P.L. Homagai et al. / Bioresource Technology 101 (2010) 2067–2069
added into 200 ml of 4 M NaOH solution and shaken for 1 h. Fur-
ther 25 ml of CS2 was added and stirred for 3 h then left for over-
night. It was filtered and washed repeatedly until the pH of the
suspension became neutral. This material is ready for the experi-
ments and called as charred xanthated sugarcane bagasse (CXSB).
2.3. Adsorption experiments
The test solutions of cadmium (II), lead (II), nickel (II), zinc (II)
and copper (II) were prepared from corresponding standard stock
solution by diluting with 0.1 M nitric acid and 0.1 M of HEPES as
a buffering agent, respectively. The optimum pH of the solution
was maintained by adding small amount of nitric acid or sodium
hydroxide. In the batch-wise tests, 20 mg of dried adsorbent was
taken into 50 ml conical flask with 15 ml of corresponding pre-
pared diluted solution. The flasks were shaken vigorously in a
thermostated shaker at 303 K at 150 rpm for 24 h to ensure the
equilibrium to be attained. The initial and equilibrium concentra-
tions of the metal ions were measured by using Shimadzu AA-
6650 atomic absorption spectrophotometer. All experiments were
performed in duplicate at least and mean values were presented in
all the cases studied. The sorption capacity of metal ions is the con-
centration of the metal ions on the adsorbent and can calculated
based on the mass balance principle where
ci  c e L The main objective of isotherm is to evaluate the capacity of the
q¼  ð1Þ
W 1000
In the above equations, q represents the amount of metal up ta-
ken per unit mass of the adsorbent (mol kg1), L is the volume of
the test solution (mL), W is the dry mass of the adsorbent (kg), Ci
and Ce the initial and final concentrations (mol dm3), respectively.
3. Results and discussion
3.1. Characterization of the adsorbents
The FTIR spectra of the CXSB were recorded on a FTIR/IR-410
(JASCO, Japan) with KBr dispersion method. The peak observed at
3434 cm1 is due to the stretching vibration of the –OH groups.
The bands around 1186 and 3045 cm1 are assigned to C@O
stretching and C–H stretching vibration, respectively. Absorption
peaks appeared at 1556 cm1 corresponding to the C@S stretching
vibration of the xanthate unit and it may be attributed to the –
CS2H deformation suggesting that CXSB has been successfully
xanthated. The peaks at 1176, 1022 and 460 cm1 in the spectrum
of charred bagasse represents the C@S, S@O and S–S stretching
vibration, respectively and were strong indicative of the presence
of xanthate group bonded to the charred materials. Prior to modi-
fication of CSB the band at 1752 cm1 is due to the –CHO group
formed during the charring process. This peak disappears after
modification of CSB into CXSB and an intense broad band is ob-
served at 1556 cm1 revealing that xanthate group had been intro-
duced onto CSB. The major absorption bands characteristic of the
C@S groups lay in the region 1563 700 cm1 (Silverstein et al.,
1981). This region is much more intense for CXSB compared to
CSB. The peak corresponding to C–S–S and C–O–C symmetric
stretching seemed to have merged into a broad band at
1556 cm1.The asymmetric stretching vibration of C–O–C is also
observed at 1176 cm1. The amount of carbon, hydrogen and nitro-
gen in CXSB were found to be 52.35, 2.12, and 0.22% whether raw
sugarcane contained 46.58, 6.11 and 0.11%, respectively. After
xanthation, the percentage of sulfur had been determined to be
as 4.92% which confirmed the proper modification of charred sug-
arcane bagasse by the introduction of xanthate group.
3.2. Effect of pH
The pH of a solution played an important role for adsorption of
metal ions. At low pH, there is high concentration of H+ that has
high mobility as compared to metal ions and competition between
H+ with metal ions decreases their adsorption. On the other hand,
as the pH value of the solution increases, adsorption also increases
due to lesser number of H+ and greater number of surface ligands
with negative charges. The low adsorption of metal ions at low pH
may be due to sorbate lyophobic behavior (Volesky and Schiewer,
1999). The same way, the solubility of metal in solution decreases
with increasing pH and the sorption increases with increasing pH.
The optimum pH for Cd, Pb, Ni, Zn, and Cu biosorption was found
to be 5, 4, 4, 6 and 5, respectively (figure not shown). The selectiv-
ity order in the removal of heavy metals at pH around four follows
the order Pb > Cu > Ni > Cd > Zn. The xanthate group is known to be
unstable in acid solution and to be able to dissociate from the
CXSB. Decomposition is a two step process in which the first is
the protonation of the hydroxyl group and the second is the elim-
ination of carbon disulfide. Since the metal ions are bound to the
sulfur atoms of xanthate groups, any loss of sulfur could lead to
a reduction in the adsorption capacity.
3.3. Adsorption isotherms
modified biomass to sequester heavy metals from an aqueous solu-
tion. It was done by characterizing the equilibrium state of the
functionalized adsorbent that had been allowed to react with
aqueous solution of the metal of interest. Isotherm studies were
performed by batch-wise method using various concentrations of
metal ions ranging from 25 to 1000 mg dm3; and optimum pH
was maintained for all synthetic solutions. Sorption isotherms
were evaluated using linearized Langmuir model represented by
Eq. (2).
ce 1 ce
¼ þ ð2Þ
qe qmb qm
where qe (mol/kg) is the concentration of adsorbed metal ions per
gram of adsorbent; Ce (mol/L) is the concentration of metal ion in
aqueous solution at equilibrium, qm (mol/kg) the ultimate capacity,
b (L/mg) the binding constant. To examine the relationship between
the metal sorption capacity (qe) and the metal ions concentration at
equilibrium (Ce), the sorption equilibrium data for cadmium, lead,
nickel, zinc and copper were compared to Langmuir model. The
experimental qmax and Langmuir adsorption isotherm parameters
evaluated from the isotherm plots for Cd+2, Pb+2, Ni+2, Zn+2 and
Cu+2 are given in Table 1. The maximum adsorption capacity based
on experimental results as shown in Fig. 1 to be was 1.95, 1.58, 2.52,
2.40 and 2.91 mol/kg, respectively. On the other hand, the theoret-
ical monolayer capacity (qmax) of the above respective metal ions
based on Langmuir adsorption equation was determined to be
2.04, 1.69, 2.80, 2.54 and 3.13 mol/kg, respectively. The complexa-
tion mechanism of the metal ions with the xanthate group has ta-
ken place through ion exchange process. This is confirmed by the
fact that the initial pH of the solution after adsorption has been de-
creased due to the release of proton from the CXSB into the aqueous
medium.
3.4. Sorption kinetics
The sorption kinetics of the metal ions onto CXSB was analyzed
as the function of time at an initial concentration of 100 mg/L solu-
tions. The concentrations of the metal ions were analyzed keeping
their optimum pH in a regular and certain interval of time by AAS.
 P.L. Homagai et al. / Bioresource Technology 101 (2010) 2067–2069 2069

Table 1 5.21 kg mol1 min1, respectively based on kinetic model as shown

Langmuir adsorption isotherm model parameters and experimental qmax. in Eq. (3).
Metal qmax (mol /kg) Langmuir qmax (mol /kg) b (1/ R2
ions model experimental kg) 4. Conclusion
Cd (II) 2.04 1.95 3.10 0.99
Pb (II) 1.69 1.58 4.44 0.99 A novel adsorbent CXSB was prepared by treating the charred
Ni (II) 2.80 2.52 0.58 0.99
sugarcane bagasse with CS2 under alkaline condition. The equilib-
Zn (II 2.54 2.40 1.36 0.99
Cu (II) 3.13 2.91 0.87 0.99 rium sorption data fitted well with Langmuir adsorption isotherm
and the adsorbent–adsorbate kinetics exhibited pseudo-second or-
der model. The maximum adsorption capacity onto the CXSB was
evaluated to be higher than the reported values in various litera-
tures. This signifies that the introduction of xanthate group onto
charred sugarcane bagasse is of importance in enhancing the
adsorption capacities of raw sugarcane bagasse. Such chemically
modified xanthated sugarcane bagasse might find potential use
as adsorbent in industrial wastewater treatment. The regeneration
and desorption aspect of CXSB needs further studies for its real cost
effectiveness.

Acknowledgements

One of the researchers Mr. Puspa Lal Homagai is grateful to

NAST, Nepal, for bestowing PhD Fellowship to undertake this re-
search work.

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