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Bioresource Technology 101 (2010) 2067–2069

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

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 contrast to the ion exchange chelating resins made of plastic, this
adsorbent is free from any refractory post treatment after its use
Heavy metal pollution in water and soil is a matter of great pub- since the main component of the adsorbents are natural polysac-
lic concern these days. Recently, much attention is given to prepare charides, that is very easy to be incinerated.
adsorbents from various wastes generated from forestry (Horsfall
et al., 2006), fishery (Inoue and Yoshizuka, 1999) and by-products
2. Methods
of agriculture (Ghimire et al., 2008; Lokesh and Tare, 1989). In Ne-
pal, sugarcane industries produce a large amount of sugarcane ba-
2.1. Chemicals
gasse (SB) that requires little processing to increase its sorptive
capacity and its cost is supposed to be low even after chemical
Standard stock solutions of 1000 mg/L were prepared appropri-
modification. The SB contains cellulose (46.0%), hemicellulose
ately Cd+2 and Pb+2 from their nitrate salts, Ni+2, Zn+2 and Cu+2 from
(24.5%), lignin (19.95%), fat and waxes (3.5%), ash (2.4%), silica
their chloride salts (Wako Chem. Ltd. Japan), respectively. The pH
(2.0%) and other element (1.7%) (Sene et al., 2002). The polysaccha-
of working solution was adjusted using 0.1 M NaOH and 0.1 M
rides found in sugarcane bagasse are biopolymers having many hy-
HCl and 0.1 M 2-[4-(2-hydroxymethyl)-1-piperazinyl] ethanesul-
droxyl and/or phenolic groups that can be chemically modified to
fonic acid (HEPES) was also used as a buffer reagent. All the re-
form new compounds with changed properties (Navarro et al.,
quired experimental solutions were diluted using 0.1 M HNO3.
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 2.2. Preparation of adsorbent materials
modification to enhance its metal adsorption properties in the
present study. The choice of xanthate group is due to the presence Sugarcane bagasse (SB) was collected from local juice centre sit-
of sulfur atom and it is well known that sulfur group has a very uated in Kathmandu Metropolitan city. It was dried in air oven at
strong affinity for most of the heavy metals, and the metal sulfur 70 °C for 24 h and grounded into fine particles with the help of
complex is very stable in basic medium (Chauhan and Sankararam- an electric grinder. It was sieved to pass uniform size of 212 lm.
krishnan, 2008; Kumar et al., 2000; Sankararamakrishnan et al., Then 100 g of SB was treated with 200 ml concentrated H2SO4
2006; Tare and Chaudhari, 1987). In view of this regard, xanthation and stirred for 30 min and left for overnight. It is well known that
of sugarcane bagasse was investigated in the present study. In 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
* Corresponding author. Tel.: +977 1 4333945, +977 9841830466 (mobile). soluble substances until neutrality and then dried. This material is
E-mail address: knghimire@yahoo.com (K.N. Ghimire). 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- 3.2. Effect of pH
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 The pH of a solution played an important role for adsorption of
suspension became neutral. This material is ready for the experi- metal ions. At low pH, there is high concentration of H+ that has
ments and called as charred xanthated sugarcane bagasse (CXSB). 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
2.3. Adsorption experiments due to lesser number of H+ and greater number of surface ligands
with negative charges. The low adsorption of metal ions at low pH
The test solutions of cadmium (II), lead (II), nickel (II), zinc (II) may be due to sorbate lyophobic behavior (Volesky and Schiewer,
and copper (II) were prepared from corresponding standard stock 1999). The same way, the solubility of metal in solution decreases
solution by diluting with 0.1 M nitric acid and 0.1 M of HEPES as with increasing pH and the sorption increases with increasing pH.
a buffering agent, respectively. The optimum pH of the solution The optimum pH for Cd, Pb, Ni, Zn, and Cu biosorption was found
was maintained by adding small amount of nitric acid or sodium to be 5, 4, 4, 6 and 5, respectively (figure not shown). The selectiv-
hydroxide. In the batch-wise tests, 20 mg of dried adsorbent was ity order in the removal of heavy metals at pH around four follows
taken into 50 ml conical flask with 15 ml of corresponding pre- the order Pb > Cu > Ni > Cd > Zn. The xanthate group is known to be
pared diluted solution. The flasks were shaken vigorously in a unstable in acid solution and to be able to dissociate from the
thermostated shaker at 303 K at 150 rpm for 24 h to ensure the CXSB. Decomposition is a two step process in which the first is
equilibrium to be attained. The initial and equilibrium concentra- the protonation of the hydroxyl group and the second is the elim-
tions of the metal ions were measured by using Shimadzu AA- ination of carbon disulfide. Since the metal ions are bound to the
6650 atomic absorption spectrophotometer. All experiments were sulfur atoms of xanthate groups, any loss of sulfur could lead to
performed in duplicate at least and mean values were presented in a reduction in the adsorption capacity.
all the cases studied. The sorption capacity of metal ions is the con-
centration of the metal ions on the adsorbent and can calculated
3.3. Adsorption isotherms
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 modified biomass to sequester heavy metals from an aqueous solu-
W 1000
tion. It was done by characterizing the equilibrium state of the
In the above equations, q represents the amount of metal up ta- functionalized adsorbent that had been allowed to react with
ken per unit mass of the adsorbent (mol kg1), L is the volume of aqueous solution of the metal of interest. Isotherm studies were
the test solution (mL), W is the dry mass of the adsorbent (kg), Ci performed by batch-wise method using various concentrations of
and Ce the initial and final concentrations (mol dm3), respectively. 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
3. Results and discussion Eq. (2).

3.1. Characterization of the adsorbents ce 1 ce


¼ þ ð2Þ
qe qmb qm
The FTIR spectra of the CXSB were recorded on a FTIR/IR-410
(JASCO, Japan) with KBr dispersion method. The peak observed at where qe (mol/kg) is the concentration of adsorbed metal ions per
3434 cm1 is due to the stretching vibration of the –OH groups. gram of adsorbent; Ce (mol/L) is the concentration of metal ion in
The bands around 1186 and 3045 cm1 are assigned to C@O aqueous solution at equilibrium, qm (mol/kg) the ultimate capacity,
stretching and C–H stretching vibration, respectively. Absorption b (L/mg) the binding constant. To examine the relationship between
peaks appeared at 1556 cm1 corresponding to the C@S stretching the metal sorption capacity (qe) and the metal ions concentration at
vibration of the xanthate unit and it may be attributed to the – equilibrium (Ce), the sorption equilibrium data for cadmium, lead,
CS2H deformation suggesting that CXSB has been successfully nickel, zinc and copper were compared to Langmuir model. The
xanthated. The peaks at 1176, 1022 and 460 cm1 in the spectrum experimental qmax and Langmuir adsorption isotherm parameters
of charred bagasse represents the C@S, S@O and S–S stretching evaluated from the isotherm plots for Cd+2, Pb+2, Ni+2, Zn+2 and
vibration, respectively and were strong indicative of the presence Cu+2 are given in Table 1. The maximum adsorption capacity based
of xanthate group bonded to the charred materials. Prior to modi- on experimental results as shown in Fig. 1 to be was 1.95, 1.58, 2.52,
fication of CSB the band at 1752 cm1 is due to the –CHO group 2.40 and 2.91 mol/kg, respectively. On the other hand, the theoret-
formed during the charring process. This peak disappears after ical monolayer capacity (qmax) of the above respective metal ions
modification of CSB into CXSB and an intense broad band is ob- based on Langmuir adsorption equation was determined to be
served at 1556 cm1 revealing that xanthate group had been intro- 2.04, 1.69, 2.80, 2.54 and 3.13 mol/kg, respectively. The complexa-
duced onto CSB. The major absorption bands characteristic of the tion mechanism of the metal ions with the xanthate group has ta-
C@S groups lay in the region 1563 700 cm1 (Silverstein et al., ken place through ion exchange process. This is confirmed by the
1981). This region is much more intense for CXSB compared to fact that the initial pH of the solution after adsorption has been de-
CSB. The peak corresponding to C–S–S and C–O–C symmetric creased due to the release of proton from the CXSB into the aqueous
stretching seemed to have merged into a broad band at medium.
1556 cm1.The asymmetric stretching vibration of C–O–C is also
observed at 1176 cm1. The amount of carbon, hydrogen and nitro- 3.4. Sorption kinetics
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 The sorption kinetics of the metal ions onto CXSB was analyzed
xanthation, the percentage of sulfur had been determined to be as the function of time at an initial concentration of 100 mg/L solu-
as 4.92% which confirmed the proper modification of charred sug- tions. The concentrations of the metal ions were analyzed keeping
arcane bagasse by the introduction of xanthate group. 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.

References
Fig. 1. Adsorption isotherm plot for adsorption of several metal ions onto CXSB.
Bassso, M.C., Cerrella, E.G., Cukierman, A.L., 2002. Lignocellulosic materials as
potential biosorbents of trace metals from wastewater. Ind. Eng. Chem. Res. 41
(15), 3580–3585.
Chauhan, D., Sankararamkrishnan, N., 2008. Highly enhanced adsorption for
Table 2
decontamination of lead ions from battery wastewaters using chitosan
Sorption kinetics of pseudo-second order for several metal ions onto CXSB.
functionalized with xanthate. Bioresour. Technol. 99, 9021–9024.
Metal ions R2 K2 (kg/mol/min) Ghimire, K.N., Inoue, J.I., Inoue, K., Kawakita, H., Ohto, K., 2008. Adsorptive
separation of metal ions onto phosphorylated orange waste. Sep. Sci. Technol.
Cd (II) 0.99 4.14 43, 362–375.
Pb (II) 0.99 6.59 Horsfall Jr., M., Abia, A.A., Spiff, A.I., 2006. Kinetic studies on the adsorption of Cd+2,
Ni (II) 0.99 7.90 Cu+2 and Zn+2 ions from aqueous solutions by cassava (Manihot sculenta Cranz)
Zn (II) 0.99 1.09 tuber bark waste. Bioresour. Technol. 97, 283–291.
Cu (II) 0.99 5.20 Inoue, K., Yoshizuka, K., 1999. Adsorptive separation of some metal ions by
complexing agent types of chemically modified chitosan. Anal. Chim. Acta 388,
209–218.
Kumar, A., Rao, N.N., Kau, S.N., 2000. Alkali treated straw and insoluble straw
xanthate as low cost adsorbent for heavy metal removal-preparation,
From the experimental data, it is observed that the percentage of characterization and application. Bioresour. Technol. 71, 133–142.
adsorption increased with the increase in time from 5 to 40 min Lokesh, K.S., Tare, V., 1989. Cadmium starch- xanthate interaction in aqueous
and then it became constant in the range 20–240 min. The pseu- system under varied environmental conditions. Indian J. Environ. Health 31 (2),
145–155.
do-second order kinetics model has often been used to fit the
Morrison, R.T., Boyd, R.N., 1994. Organic Chemistry. sixth ed. Printice Hall of India
experimental kinetic adsorption data. The linearized pseudo-sec- Private Ltd, New Delhi. pp. 1200–1201.
ond order kinetic equation is used as the following form: Navarro, R.R., Sump, K., Fujii, N., Matsumura, M., 1996. Mercury removal from
wastewater using porous cellulose carrier modified with polyethyleneimine.
Water Res. 30 (10), 2488–2494.
t 1 t Sankararamakrishnan, N., Dixit, A., Iyengar, L., Sanghi, R., 2006. Removal of
¼ þ ð3Þ
qt k2 q2e qe hexavalent chromium using a novel cross linked xanthated chitosan.
Bioresour. Technol. 97, 2377–2382.
Sene, L., Converti, A., Felipi, M.G.A., Zilli, M., 2002. Sugarcane bagasse as alternative
where qt (mol kg1) is the amount of adsorption at time t (min), K2 packing material for bio-filtration of benzene polluted gaseous streams: A
(kg mol1 min1) is the rate constant of the pseudo-second order ki- preliminary study. Bioresour. Technol. 83, 153–157.
netic adsorption. The values of K2 and qe can be obtained from the Silverstein, R.M., Bassler, G.C., Morril, T.C., 1981. Spectrometric Identification of
Organic Compounds, fourth ed. John Wiley and Sons, New York. pp. 95–180.
intercept and slope of the plot of the experimental t/qt versus t. The Tare, V., Chaudhari, S., 1987. Evaluation of soluble and insoluble xanthate process
experimental data are shown in Table 2, which can be explained by for the removal of heavy metals from wastewaters. Water Res. 21, 1109–1118.
the pseudo-second order kinetic model with the correlation coeffi- Volesky, B., Schiewer, S., 1999. In: Flickinger, M.C., Drew, S.W. (Eds.), Biosorption of
metals in encyclopedia of bioprocess technology: fermentation, biocatalysis,
cient R2 being almost unity (0.99) for all the metal ions. The exper- and bioseparation. Wiley, New York, pp. 433–453.
imental value of K2 was found to be 4.14, 6.60, 7.91, 1.09 and