Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281

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Journal of the Taiwan Institute of Chemical Engineers

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Removal of nickel (II) ions from aqueous solutions by biosorption

on sugarcane bagasse
I. Alomá a,1, M.A. Martı́n-Lara b,*, I.L. Rodrı́guez a,2, G. Blázquez b,3, M. Calero b,4
a
Central University ‘‘Marta Abreu’’ of Las Villas, Carretera a Camajuanı´ Km 5 1/2, Santa Clara, Villa Clara, Cuba
b
Department of Chemical Engineering, University of Granada, Avda. Fuentenueva, s/n 18071 Granada, Spain

A R T I C L E I N F O A B S T R A C T

Article history: The present study was undertaken to evaluate the feasibility of sugarcane bagasse for the removal of
Received 30 May 2011 nickel from aqueous solution. Batch experiments were performed to study the biosorption of nickel on
Received in revised form 5 September 2011 sugarcane bagasse sorbent considering the effect of contact time, initial concentration of nickel ions, pH
Accepted 18 October 2011
of the solution and temperature. The sorption process was well explained with pseudo second-order
Available online 17 November 2011
kinetic model. The experimental maximum sorption capacity of sugarcane bagasse for nickel removal
was approximately 2 mg/g at 25 8C and at pH 5. The biosorption data was fitted to Langmuir, Freundlich
Keywords:
and Sips isotherm models. The Langmuir model showed better representation of data, with correlation
Biosorption
coefficient greater than 0.99. The thermodynamics parameters were evaluated from the experimental
Heavy metals
Sugarcane bagasse data. The Gibbs free energy was determined to be negative, indicating the spontaneous nature of the
Water treatment sorption process. The results of the present study suggest that sugarcane bagasse waste can be used
beneficially for nickel removal from aqueous solution.
ß 2011 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction economically expensive and have disadvantages like incomplete

metal removal, generation of toxic sludge and other disposable
Industrial effluents are the major sources for contamination of waste products. Biosorption utilizes the ability of dead/inactive
water resources by heavy metals. Ni(II) belongs to the so-called biomass to remove heavy metals from solutions. The use of dead/
‘‘essential’’ metals and is identified as a component in a number of inactive biomass is preferred over active/live biomass because
enzymes, participating in important metabolic reactions, such as living biomass cells often require the addition of fermentation
ureolysis, hydrogen metabolism, methane biogenesis, and acid- media which increases the biological oxygen demand (BOD) or
ogenesis [1]. But, nickel(II) ion intake over the permissible levels chemical oxygen demand (COD) in the effluent [6]. In addition,
results in different types of disease such as pulmonary fibrosis, nonliving biomass is not affected by the toxicity of the metal ions,
renal edema, skin dermatitis, and gastrointestinal distress (e.g., and they can be subjected to different chemical and physical
nausea, vomiting, diarrhea) [1]. It is therefore, essential to remove treatment techniques to enhance their performance. Furthermore,
Ni(II) from wastewater before disposal. Mining and metallurgy of adsorbed metals can be easily recovered from the biomass by many
nickel, stainless steel, aircraft industries, nickel electroplating, chemical and physical methods, leading to repeated use of the
battery and manufacturing, pigments and ceramic industries biomass and better process economy [7,8]. The major advantages
wastewaters contain high amounts of nickel ions [2]. of the biosorption technology are its effectiveness in reducing the
The commonly used techniques for removing metal ions from concentration of heavy metal ions to very low levels and the use of
effluents include ion exchange, adsorption, chemical precipitation, inexpensive biosorbent materials [9].
reverse osmosis and solvent extraction [3–5]. These techniques are In this perspective, development of natural based viable,
valuable and cheap biosorbent for removal of heavy metal from
aqueous solutions would be crucial. Recently potential biosorbents
for heavy metal removal such as cactus leaves [10], bark [11],
* Corresponding author. Tel.: +34 958 243311; fax: +34 958 248992.
E-mail addresses: inesav@uclv.edu.cu (I. Alomá), marianml@ugr.es wheat bran [12], grape stalks waste [13], cork biomass [14],
(M.A. Martı́n-Lara), ivanl@uclv.edu.cu (I.L. Rodrı́guez), gblazque@ugr.es pomace fibres [15], papaya wood [16], neem leaf [17] and chitosan
(G. Blázquez), mcaleroh@ugr.es (M. Calero). [18] have been used.
1
Tel.: +53 42 226768. The utilization of agro-wastes as adsorbent is currently
2
Tel.: +53 42 211825.
3
Tel.: +34 958 240770; fax: +34 958 248992.
receiving wide attention because of their abundant availability
4
Tel.: +34 958 243311; fax: +34 958 248992. and low-cost. Furthermore, they have relatively high fixed carbon

1876-1070/$ – see front matter ß 2011 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jtice.2011.10.011
276 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281

content and present a porous structure. In this sense, among the SCB is composed of 43.0% carbon, 6.4% hydrogen, 0.6% nitrogen,
various agro-wastes, sugarcane bagasse seems to be an important <0.1% sulphur and 49.9% oxygen.
aspirant. The presence of compounds such as cellulose, hemicel- The Infrared spectrum revealed biosorbent heterogeneity,
lulose, lignin and silica in this material, with binding sites capable evidenced by different characteristic peaks with the possible
to take up metals, suggests the use of sugarcane bagasse as a low presence of carboxylic, hydroxyl and carbonyl groups [19].
cost natural biosorbent for heavy metals. The potentiometric titrations results confirmed the presence of
The main objectives of the present study include (1) to study the –OH (0.11 mmol/g) and –COOH (0.12 mmol/g) functional groups in
sorption potential of sugarcane bagasse for Ni(II) removal from the lignocellulosic moiety of the SCB biomass, and probably these
water, (2) to understand the kinetic mechanism, and (3) to model groups are the major binding groups responsible for metal
the sorption process. biosorption [19]. The value of the point of zero charge, pHpzc
was also calculated from potentiometric titrations. The surface of
2. Materials and methods SCB becomes negatively charged at pH values higher than 5.9 and
acquires a net positive charge at pH value less than 5.9.
2.1. Preparation of the sorbent material Also, the morphological characters of SCB were qualitatively
studied using SEM [19]. The morphology of this material can
Sugarcane bagasse (SCB) is a waste byproduct from sugar facilitate the adsorption of metals, due to its irregular surface and
industry. The sugarcane bagasse used in this work was supplied by porosity.
the pilot plant ‘‘José Marti’’ from Central University ‘‘Marta Abreu’’
of Las Villas, Cuba. 3.2. Effect of pH
It was washed with distilled water many times and dried at
room temperature. No other chemical or physical treatments were One of the most important factors affecting biosorption of metal
used prior to biosorption experiments. Then it was grinded with ions is acidity of solution. The metal ion adsorption is affected by
strong grinder, and sieved to <1 mm particle size. the pH of the solution thereby changing the surface charge of the
sorbent and metal speciation [20–24].
2.2. Preparation of Ni(II) solutions Fig. 1 shows the speciation diagram for nickel species built for
2  104 M and 3  103 M concentrations, approximately the
A stock solution of 500 mg/L of Ni(II) was prepared by equivalent concentrations for the experiments carried out in this
dissolving an accurate quantity of NiSO46H2O in deionized water. work. At pH 5, the predominant species is still Ni2+ which is the
Other concentrations varying between 10 and 200 mg/L were selected pH value for the biosorption experiments. At higher
prepared from stock solution by dilution. concentrations, soluble specie NiSO4 also begins to appear but Ni2+
still is predominant. Higher values of pH were avoided in later
2.3. Biosorption experiments biosorption tests to prevent metal ion precipitation as hydroxide
[25,26], and lower values of pH also were avoided due to at lower
Batch biosorption studies were performed by taking 100 ml of pH values the surface charge of the solid could be too positive and
Ni(II) solution with known pH in a 250 ml flask contained 1 g of nickel cation adsorption be unfavorable, additionally, at low pH
SCB. The flask was placed in a shaking reactor at a speed of 300 rpm values, hydrogen ions could compete strongly with nickel ions for
and temperature of 25 8C. After 2 h, biosorbent was separated and the active sites of SCB and biosorption could be small [19,27]. In
the concentration of metal ion in solution was analyzed using a fact, the effect of pH on adsorption of Ni2+ was studied at 25 8C
atomic absorption spectrophotometer, SpectrAA 220 SS. varying the pH from 1 to 6 (Fig. 2). In pH range of 1–2, there is little
The effect of contact time on batch experiments was examined or no biosorption and with the increase of pH, the amount of nickel
by varying the contact time of suspensions from 3 to 120 min. For uptake by SCB tended to increase and a sharp increase in qe was
the adsorption isotherm studies, the initial metal ion concentration observed in the pH ranging from 3 to 5. At about pH 5 a plateau was
was varied over a range of 10–200 mg/L. reached, e.g., there was no significant difference between pH 5 and
Biosorption capacity (qe) i.e., amount of metallic ion (mg) 6 in the maximum Ni2+ biosorption capacity. These seemed to
biosorbed by gram of the biomass and the efficiency of biosorption indicate that the optimum pH value for Ni2+ biosorption by SCB
(%) were calculated using Eqs. (1) and (2), respectively: would be around 5.

ðC i  C f Þ 3.3. Biosorption kinetics

qe ¼ V (1)
m
For practical applications, the process design and operation
ðC i  C f Þ control, the sorption kinetics were very important. Sorption
%¼  100 (2) kinetics in wastewater treatment was significant, as it provides
Ci
valuable insights into the reaction pathways and the mechanism of
where Ci and Cf are the initial and final (equilibrium) concentra- the sorption reactions. Since biosorption is a metabolism-
tions of Ni(II) in solution whereas V and m are solution volume and independent process, it would be expected to be a very fast
mass of biosorbent, respectively. reaction.
All biosorption experiments were carried out in duplicate.
3.3.1. Effect of initial nickel concentration on kinetics
3. Result and discussion Biosorption of Ni(II) onto SCB at various initial concentrations
had been carried out at different time intervals (3–120 min) and
3.1. Characterization of the biosorbent was shown in Fig. 3.
The initial metal concentration provides an important driving
Characterization of biosorbent surface and structure hold keys force to overcome all mass transfer resistance of Ni(II) between the
to understanding the metal binding mechanism onto biomass. The aqueous and solid phases. The percent of Ni(II) removal is inversely
physical and chemical properties of the SCB were determined in related to the initial metal ion concentrations (Fig. 3(a)). It
our earlier publication [19]. Elemental analysis results showed that decreased as its concentration was increased. However, the
 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281 277

[Ni2+] TOT = 0.20 mM [SO4 2 ] TOT = 0.20 mM amount of Ni(II) ions adsorbed per unit mass of biosorbent
Ni2+ Ni(OH) 2 (c) increased with the increase of the initial ion concentrations
(a) 1.0
(Fig. 3(b)) [28,29]. In Fig. 2, the removal of Ni(II) ions occurred in
two steps [30]; a first step in which the removal increased rapidly
0.8
(about 30 min), and a slower second phase in which the removal
increased slowly (from about 30 min until the end of experimental
period). The fast step is probably due to the abundant availability
0.6 of active sites on the material, and with the gradual occupancy of
Fraction

these sites, the sorption becomes less efficient in the slower step
[31]. On the other hand, equilibrium was achieved within 40–
0.4 60 min, even earlier, depending on the initial nickel concentration,
so an equilibration period of 120 min was selected for all further
experiments.
0.2 Fig. 3 also shows the effect of initial nickel concentration on
nickel removal at equilibrium (120 min). While the initial Ni(II) ion
NiSO 4
0.0 concentration increased from 10 to 140 mg/L, the percent nickel
2 4 6 8 10 12 removal by SCB decreased from 80.6% to 30.6% at equilibrium and
pH the nickel biosorption capacity increased from 0.403 mg/g to
2.086 mg/g.
[Ni2+] TOT = 3.00 mM [SO4 2 ] TOT = 3.00 mM Then, three simplified kinetic models namely pseudo-first-
Ni(OH) 2 (c) order, pseudo-second-order and Elovich models have been
(b) 1.0 Ni2+ discussed to identify the rate and kinetics of sorption of nickel
on SCB.
The pseudo-first-order kinetic model was proposed by Lagergren
0.8
[32]. The general form of the model generally was expressed as

0.6
(a)
Fraction

100
10 mg/L
20 mg/L
0.4
60 mg/L
NiSO 4 80 80 mg/L
140 mg/L
0.2
Removal, (%)

60

0.0
2 4 6 8 10 12
pH 40

Fig. 1. Speciation of nickel in aqueous solutions as a function of solution pH for a

total NiSO4 concentration of: (a) 2  104 M and (b) 3  103 M. The mole fractions
20
were calculated using MEDUSA1.

0
0 20 40 60 80 100 120 140
t, (min)

0.5 (b) 3.0

10 mg/L
20 mg/L
2.5 60 mg/L
0.4 80 mg/L
140 mg/L

2.0
qt, (mg/g)

0.3
qt, (mg/g)

1.5

0.2
1.0

0.1 0.5

0.0
0.0
0 20 40 60 80 100 120 140
1 2 3 4 5 6 7
t, (min)
pH
Fig. 3. Effect of contact time on the biosorption of Ni(II) onto SCB at different nickel
Fig. 2. Effect of pH on the biosorption of Ni(II) onto SCB (biomass dosage: 10 g/L; concentrations (biomass dosage: 10 g/L; pH 5; temperature: 25 8C) (a) Nickel
temperature: 25 8C; initial nickel concentration 10 mg/L). removal (%) versus time, (b) Nickel biosorption capacity versus time.
278 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281

Table 1
Pseudo-first-order, pseudo-second-order and Elovich parameters for the biosorption of Ni(II) onto SCB at different initial nickel concentrations.

Kinetic models Parameters Initial concentration of Ni2+ (mg/L)

10 20 60 80 140

Pseudo-first order k1 (min1) 0.0361 0.0269 0.0187 0.0191 0.0742

qe,cal (mg/g) 0.397 0.710 1.213 1.309 2.085
R2 0.928 0.981 0.914 0.953 0.975
P
½ðqe Þexp  ðqe Þcal 2 0.00166 0.0531 0.161 0.201 0.124
qe,exp (mg/g) 0.403 0.739 1.357 1.455 2.086

Pseudo-second order k2 (g/mg min) 0.132 0.172 0.109 0.101 0.215

qe,cal (mg/g) 0.462 0.770 1.366 1.458 2.110
h (mg/g min) 0.0282 0.102 0.203 0.214 0.955
R2 0.974 0.995 0.993 0.993 0.999
P
½ðqe Þexp  ðqe Þcal 2 0.00456 0.0367 0.0943 0.153 0.0302
qe,exp (mg/g) 0.403 0.739 1.357 1.455 2.086

Elovich a (mg/g min) 0.0531 0.902 1.618 0.486 1.727

b (g/mg) 9.597 9.479 5.243 5.294 2.214
qe,cal (mg/g) 0.428 0.731 1.140 1.083 1.729
R2 0.963 0.987 0.966 0.977 0.901
P
½ðqe Þexp  ðqe Þcal 2 0.00909 0.00224 0.0208 0.0138 0.0933
qe,exp (mg/g) 0.428 0.739 1.357 1.455 2.086

follows: for simulating the sorption kinetic in a liquid phase. The Elovich
equation can be written as [34,35],
dqt
¼ k1 ðqe  qt Þ (3)
dt
dqt
in which k1 is the rate constant of pseudo-first order biosorption ¼ a expðbqt Þ (7)
dt
(min1) and qt is the amount of Ni(II) ions biosorbed at time
t (mg/g), qe is its value at equilibrium (mg/g). After definite where a and b are the model parameters. The parameter a is the
integration by applying boundary conditions qt = 0 at t = 0 and initial sorption rate (mg/g min), and the parameter b is related to
qt = qt at t = t, the integrated form becomes: the extent of surface coverage (g/mg).
To simplify the Elovich equation, Chien and Clayton [36]
qt ¼ qe ð1  ek1 t Þ (4)
assumed that abt >> 1, and given that for t = 0, qt = 0 and for t = t,
The constants were determined experimentally by non-linear qt = qt, the final form of the equation is
regression. The results are given in Table 1. The theoretical
amounts of Ni(II) ions biosorbed at equilibrium (qe,cal) were lower 1 1
qt ¼ lnðabÞ þ lnðtÞ (8)
than those experimental data, qe,exp and low correlation coefficient b b
values obtained for the pseudo first-order model indicate that
sorption is not occurring exclusively onto one site per ion. The constants were determined experimentally by non-linear
The pseudo-second-order kinetic model proposed by Ho and regression. The results are given in Table 1. The theoretical
McKay [33] was based on the assumption that the adsorption amounts of Ni(II) ions biosorbed at equilibrium (qe,cal) were, in
follows second order chemisorption. The general form can be most concentrations, lower than those experimental data, qe,exp
written as follows: and low correlation coefficient values obtained for the Elovich
model indicate that sorption is not well reproduced by this model.
dqt
¼ k2 ðqe  qt Þ2 (5)
dt
0.5
in which k2 is the rate constant of the pseudo-second-order
C = 10 mg/L
biosorption (g/mg min) and qt and qe have the same meaning that
is described in pseudo-first order model. For the boundary
0.4
conditions qt = 0 at t = 0 and qt = qt at t = t, the integrated form
becomes:
t 0.3
qt , (mg/g)

qt ¼ (6)
ð1=hÞ þ ðt=qe Þ

where the initial biosorption rate, h (mg/g min) is k2qe2. 0.2

The constants were determined experimentally by non-linear
regression. The values of qe, k2, h and R2 are listed in Table 1. All the
R2 values are closer to 1 and there is only a little difference between 0.1
qe,exp and qe,cal, confirming the applicability of pseudo-second-
order equation. From Table 1, it can be observed that, with an
increase in initial metal concentration, the initial sorption rate (h) 0.0
also increased. In accordance with the pseudo-second reaction 0 20 40 60 80 100 120 140
mechanism, the overall rate of Ni(II) sorption processes appears to
t, (min)
be controlled by the chemical processes.
The Elovich kinetic model has been used for describing reactions Fig. 4. Effect of contact time on the biosorption of Ni(II) onto SCB at different
involving chemisorption of gases on a solid surface [34], but also temperatures (biomass dosage: 10 g/L; pH 5; initial nickel concentration: 10 mg/L).
 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281 279

Table 2 The Langmuir isotherm theory assumes monolayer coverage of

Pseudo-first-order, pseudo-second-order and Elovich parameters for the biosorp- adsorbate over a homogeneous adsorbent surface [37].
tion of Ni(II) onto SCB at different temperatures.

Kinetic models Parameters Temperature (8C) bqm C e

qe ¼ (9)
1 þ bC e
25 50 65

Pseudo-first order k1 (min1) 0.0361 0.0338 0.0240 where qm is the monolayer biosorption capacity of the biosorbent
qe,cal (mg/g) 0.397 0.392 0.332 (mg/g), qe is the equilibrium metal ion concentration on the
R2 0.928 0.981 0.985
P biosorbent (mg/g), Ce is the equilibrium metal ion concentration in
½ðqe Þexp  ðqe Þcal 2 0.00147 0.00207 0.00260
qe,exp (mg/g) 0.403 0.399 0.352
the solution (mg/L), and b is the Langmuir biosorption constant
(L/mg) related to the free energy of biosorption.
Pseudo-second order k2 (g/mg min) 0.132 0.0394 0.0414
The R2 (Table 3) values for SCB sorbent indicated that Langmuir
qe,cal (mg/g) 0.462 0.571 0.501
h (mg/g min) 0.0282 0.0128 0.0104 theory describes the sorption phenomena favorably. With respect
R2 0.974 0.967 0.980 to the effect of temperature on the coefficients of the Langmuir
P
½ðqe Þexp  ðqe Þcal 2 0.00450 0.00751 0.00347 model, qm decreases with the temperature, indicating that the
qe,exp (mg/g) 0.403 0.399 0.352 decrease of adsorption capacity with the increasing temperature
Elovich a (mg/g min) 0.0531 0.0353 0.0251 was probably due to greater energy acquired by the adsorbed
b (g/mg) 9.597 9.009 10.111 molecule to escape from the surface. However, the temperature
qe,cal (mg/g) 0.428 0.404 0.338 has no significant effects on the b values (affinity).
R2 0.963 0.977 0.969
P
½ðqe Þexp  ðqe Þcal 2 0.00911 0.00638 0.00417
The Freundlich model assumes a heterogeneous sorption
qe,exp (mg/g) 0.403 0.399 0.361 surface [38].

qe ¼ K F C e 1=n (10)

where KF is a constant relating the biosorption capacity and 1/n is

3.3.2. Effect of temperature on kinetics an empirical parameter relating the biosorption intensity, which
The effect of temperature (Fig. 4 and Table 2) was studied in the varies with the heterogeneity of the material. From Table 3, KF
temperature range 25–65 8C at pH 5, for a solid concentration of values were found to be 0.414, 0.222 and 0.161 and the n values
10 g/L and an initial concentration of Ni(II) of 10 mg/L. were found as 2.94, 2.65 and 2.44. The 1/n values were between 0
Analysis of data showed that the biosorption of Ni(II) followed and 1, indicating that the biosorption of Ni(II) onto the SCB was
again pseudo-second order kinetic model for all temperatures favorable at studied conditions. The low values of R2 indicated that
tested. Also, the temperature effect on biosorption capacity is less Freundlich model was not altogether properly describing the
significant than the effect of nickel concentration although a relationship between the amounts of sorbed metal ions and their
decrease on kinetic constant and initial sorption rate is produced as equilibrium concentrations in the solution.
temperature rises. The Sips model incorporates the features of the Langmuir and
Freundlich models into a single equation as follows [39]:
3.4. Biosorption isotherms. Effect of temperature
qm bC e 1=n
Biosorption isotherms of Ni(II) onto SCB had been carried out at qe ¼ (11)
1 þ bC e 1=n
different temperatures (from 25 8C to 65 8C) and shown in Fig. 5.
The analysis of adsorption data is important for developing an where qm, b and n are the Sips constants. The constant n has two
equation which accurately represents the results and could be used limiting behaviours: Langmuir form for n = 1 and Freundlich form
for design purposes. Out of several isotherm equations, the for very high n values.
Langmuir, Freundlich and Sips isotherms were used to fit the The Sips isotherm constants and correlation coefficient (R2) are
experimental data. also given in Table 3. On comparing the linear regression values it is
concluded that the Langmuir and Sips isotherms are capable of
2.5 representing the data more satisfactorily (R2 > 0.98) than the
Freundlich isotherm (R2 < 0.94).

Table 3
2.0
Langmuir, Freundlich and Sips parameters for the biosorption isotherms of nickel
by SCB.

Temperature (8C)
1.5
qe, (mg/g)

25 50 65

Langmuir qm (mg/g) 2.234 1.304 1.339

1.0 b (L/mg) 0.0745 0.0629 0.0474
R2 0.990 0.994 0.993
P
½ðqe Þexp  ðqe Þcal 2 0.210 0.0267 0.0239

0.5 Freundlich KF (L/g) 0.414 0.222 0.161

n 2.94 2.65 2.44
R2 0.941 0.888 0.901
P
½ðqe Þexp  ðqe Þcal 2 0.0658 0.139 0.120
0.0
0 20 40 60 80 100 120 140 160 180 Sips qm (mg/g) 2.281 1.401 1.245
b (L/mg) 0.108 0.0433 0.0208
Ce, (mg/L)
n 1.189 0.871 0.850
R2 0.988 0.987 0.991
Fig. 5. Biosorption isotherms of Ni(II) onto SCB at different temperatures (contact P
½ðqe Þexp  ðqe Þcal 2 0.138 0.0240 0.0144
time: 120 min; biomass dosage: 10 g/L; pH 5).
280 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281

Table 4 Table 5
Maximum capacity for biosorption of Ni2+ by various biosorbents. Thermodynamic parameters for the biosorption of Ni(II) onto SCB at different
temperatures.
Biosorbent qm (mg/g) Reference
T (8C) DG (kJ/mol) DH (kJ/mol) DS (J/mol K)
Black carrot residues 6.51 [40]
Cashew nut shell 18.87 [41] 25 20.78 74.32 332.29
Cassava peel 57.07 [42] 50 22.07
Dye groundnut shells 7.49 [43] 65 22.30
Orange peel 9.82 [44]
Rice husk 5.52 [45]
Saw dust (oak tree) 3.37 [46]
Sawdust-phosphate treated 0.70 [47] nickel (II) ion onto SCB. The standard enthalpy and entropy
Wallnut sawdust 6.43 [48] changes of biosorption were 74.32 kJ/mol and 332.29 J/mol/K,
Sugarcane bagasse 2.23 In this work
respectively. The negative value of DH8 confirms the exothermic
nature of the process and the positive value of entropy, DS8,
indicating the affinity of the adsorbent for nickel.
In Table 4 the nickel biosorption capacities of SCB were
compared with those obtained by other biosorbents. 3.5. Mechanism of Ni(II) biosorption by SCB
On the other hand, the temperature of the sorption medium
could be important for energy-dependent mechanisms in metal Mechanisms involved in the biosorption process by agro-based
biosorption. The effect of temperature on the adsorption of biomasses include ion exchange, chelation, precipitation, sorption
nickel(II) is investigated at three different temperatures (25 8C, by physical forces, and ion entrapment in inter and intrafibrillar
50 8C and 65 8C) for SCB and is given in Fig. 5. For an increase in capillaries and spaces of the structural lignin and polysaccharide
temperature from 25 to 50 8C, the biosorption capacities of the SCB networks as a result of diffusion through cell wall and membrane
for Ni(II) showed a decrease from 2.234 to 1.304 mg/g (Langmuir [56].
model), thus indicating the exothermic nature of the biosorption Some information about the surface chemistry characterization
process. of the SCB, for example the alteration of functional groups, can be
A similar exothermic nature of the adsorption process has been used as evidences in proposing the biosorption mechanism. Also
reported for other adsorbent systems [49]. This could be due to biosorption kinetics and equilibrium can be used to explain the
either the damage of active binding sites in the biomass [50] or the biosorption mechanism.
increasing tendency to desorb metal ions from the interface to the In this work, the release of calcium, magnesium and potassium
solution [51]. The optimum solution temperature was selected as ions was measured in relation to the nickel biosorption. The release
25 8C. of calcium, magnesium and potassium was followed in the same
time of nickel biosorption. It was found a equivalent ratio of the
3.4.1. Thermodynamic study released light metals to the biosorbed nickel ions, which indicated
The thermodynamics parameters were evaluated from the that the ion exchange would be a mechanism involved in
experimental data. Both energy and entropy factors must be biosorption of Ni2+ by SCB. Also, to verify the release of protons
considered in thermodynamics, in order to determine whether a during the biosorption process, pH variation was recorded. A
process will occur spontaneously or not. The process of nickel(II) decrease of pH values was appreciated, probably due to the
ion biosorption can be assumed by the following reversible exchange of protons during the nickel biosorption.
process, which represents a heterogeneous equilibrium On the other hand, chemisorption models fitted well experi-
mental data and low errors were obtained. Therefore a chemisorp-
tion controlled mechanism can be postulated as the mechanism
NiðIIÞ ion in solution $ NiðIIÞ  sugarcane bagasse governing the biosorption process. It was also possible that Ni(II)
ions were bound into carboxylate groups in the lignocellulosic
For such equilibrium reactions, the Gibbs free energy (DG8) was
structure of SCB by creating ionic forces with carboxylic oxygen
determined by the following equation:
atoms. These oxygen atoms exhibited negative charge in their
DG ¼ RT ln K0C (12) structure as a result of the dissociation of carboxylic groups. The
negatively charged oxygen atom in carboxylate anions will
where, R is the universal gas constant, 8.314 J/mol/K and T is the coordinate with nickel cations, resulting in the formation of
absolute temperature in K and K0C is the equilibrium constant. The metal–carboxylate complexes (COO–Ni) on the SCB surface.
Gibbs free energy indicates the degree of spontaneity of the These conclusions support the mechanism previously
adsorption process, where more negative values reflect a more explained in other papers [42] based on the interaction of metal
energetically favorable adsorption process. The relationship ions with acidic functional groups in the biomass surface.
between the equilibrium constant, K0C and the temperature is
given by the Van’t Hoff equation
4. Conclusions
DS DH
ln K0C ¼  (13)
R RT
The experimental investigations conclude the capacity of SCB to
The entropy change of biosorption, DS8, and the enthalpy biosorb the nickel ions. The biosorption of toxic Ni2+ by SCB was
change of biosorption, DH8 can be obtained from the slope and influenced by contact time, initial concentration of the metal ions
intercept of a Van’t Hoff plot of ln K0C versus 1/T [52–54]. In this and temperature. The experimental data turn out good fits with
study, the thermodynamic parameters have been calculated using Langmuir isotherm (R2 > 0.99). The kinetic studies proved that
the Langmuir isotherm, i.e., by replacing the equilibrium constant, pseudo-second-order kinetic was a suitable model. The thermo-
K0C from Eqs. (12) and (13) by the Langmuir isotherm constant, b dynamic calculations indicated the feasibility, exothermic and
(L/mol) [55] and are given in Table 5. spontaneous nature of the biosorption of Ni(II) ion onto SCB
The negative values of DG8 indicate the feasibility of the process biomass at 25–65 8C. It can be also concluded that the SCB is an
and the spontaneous nature of sorption with a high affinity for effective and alternative biomass for the removal of Ni(II) ions from
 I. Alomá et al. / Journal of the Taiwan Institute of Chemical Engineers 43 (2012) 275–281 281

wastewaters in terms of natural and abundant availability and low [26] Zhou JL, Kiff RJ. The uptake of copper from aqueous-solution by immobilized
fungal biomass. J Chem Technol Biotechnol 1991;52:317–30.
cost. [27] Hernáinz F, Blázquez G, Calero M, Martı́n-Lara MA, Tenorio G. Comparative
study of the biosorption of cadmium(II), chromium(III) and lead(II) by olive
Acknowledgements stone. Environ Prog 2008;27:469–78.
[28] Lata H, Garg VK, Gupta RK. Sequestration of nickel from aqueous solution onto
activated carbon prepared from Parthenium hysterophorus L. J Hazard Mater
The authors are grateful to the alfa BIOPROAM Program 2008;157:503–9.
Contract No. AML/190901/06/18414/II-0548-FC-FA, Metropolitan [29] Skodras G, Diamantopoulou I, Pantoleontos G, Sakellaropoulos GP. Kinetic
studies of elemental mercury adsorption in activated carbon fixed bed reactor.
Autonomous University Ixtapalapa, Mexico, D.F., and the Depart- J Hazard Mater 2008;158:1–13.
ment of Chemical Engineering of Central University ‘‘Marta Abreu’’ [30] Onal S, HAmarat Baysal S, Ozdemir G. Studies on the applicability of alginate-
of Las Villas for the financial support. entrapped Chryseomonas luteola TEM 05 for heavy metal adsorption. J Hazard
Mater 2007;146:417–20.
[31] Fiol N, Villaescusa I, Martı́nez M, Miralles N, Poch J, Serarols J. Sorption of Pb(II),
References Ni(II), Cu(II) and Cd(II) from aqueous solution by olive stone waste. Sep Purif
Technol 2006;50:132–40.
[1] Akhtar N, Iqbal J, Iqbal M. Removal and recovery of nickel(II) from aqueous [32] Lagergren S. About the theory of so-called adsorption of soluble substances. K
solution by loofa sponge-immobilized biomass of Chlorella sorokiniana: Sven Vetenskapsakad Handl 1898;24:1–39.
characterization studies. J Hazard Mater 2004;108:85–94. [33] Ho YS, McKay G. Pseudo-second order model for sorption processes. Process
[2] Ozer A, Gurbuz G, Calimli A, Korbahti BKJ. Investigation of nickel(II) biosorp- Biochem 1999;34:451–65.
tion on Enteromorpha prolifera: optimization using response surface analysis. J [34] Low MJD. Kinetics of chemisorption of gases on solids. Chem Rev
Hazard Mater 2008;152:778–88. 1960;60:267–312.
[3] Yu Q, Kaewsam P. Adsorption of Ni2+ from aqueous solutions by pre-treated [35] Günay A, Arslankaya E, Tosun I. Lead removal from aqueous solution by
biomass of marine macroalgae Durvillaea potatorum. Sep Sci Technol natural and pretreated clinoptilolite: adsorption equilibrium and kinetics. J
2000;35:689–701. Hazard Mater 2007;146:362–71.
[4] Juang RS, Shiau RC. Metal removal from aqueous solutions using chitosan [36] Chien SH, Clayton WR. Application of Elovich equation to the kinetics of
enhanced membrane filtration. J Membr Sci 2001;165:159–67. phosphate release and sorption in soils. Soil Sci Soc Am J 1980;44:265–8.
[5] Yan G, Viraraghavan T. Heavy metal removal in a biosorption column by [37] Langmuir I. The adsorption of gases on plane surfaces of glass, mica and
immobilized M. rouxii biomass. Bioresour Technol 2001;78:243–9. platinum. J Am Chem Soc 1918;40:1361–403.
[6] Aksu Z, Kutsal T, Gun S, Haciosmano N, Gholaminejad M. Investigation of [38] Freundlich H, Helle W. On adsorption in solution. J Am Chem Soc
biosorption of Cu(II), Ni(II) and Cr(VI) ions to activated sludge bacteria. Environ 1939;61:2228–30.
Technol 1991;12:915–21. [39] Sips R. Structure of a catalyst surface. J Chem Phys 1918;16:490–5.
[7] Dilek FB, Erbay A, Yetis U. Ni(II) biosorption by polyporous versicolor. Process [40] Guzel F, Yakut H, Topal G. Determination of kinetic and equilibrium param-
Biochem 2002;37:723–6. eters of the batch adsorption of Mn(II), Co(II), Ni(II) and Cu(II) from aqueous
[8] Padmavathy V, Vasudevan P, Dhingra SC. Biosorption of nickel(II) ions on solution by black carrot (Daucus carota L) residues. J Hazard Mater
Baker’s yeast. Process Biochem 2003;38:1389–95. 2008;153:1275–87.
[9] Wong JPK, Wong YS, Tam NFY. Nickel biosorption by two chlorella species, C. [41] Kumar PS, Ramalingam S, Kirupha SD, Murugesan A, Vidhyadevi T, Sivanesan
Vulgaris (a commercial species) and C. Miniata (a local isolate). Bioresour S. Adsorption behavior of nickel(II) onto cashew nut shell: equilibrium,
Technol 2000;73:133–7. thermodynamics, kinetics, mechanism and process design. Chem Eng J
[10] Dakiky M, Khamis M, Manassra A, Mereb M. Selective adsorption of chro- 2011;167:122–31.
mium(VI) in industrial wastewater using low-cost abundantly available [42] Kurniawan A, Kosasih AN, Febrianto J, Ju Y-H, Sunarso J, Indraswati N, et al.
adsorbents. Adv Environ Res 2002;6:533–40. Evaluation of cassava peel waste as lowcost biosorbent for Ni-sorption:
[11] Prasad MNV, Freitas H. Removal of toxic metals from solution by leaf, stem and equilibrium, kinetics, thermodynamics and mechanism. Chem Eng J
roots phytomass of Quercus ilex L. (holly oak). Environ Pollut 2002;110:277– 2011;172:158–66.
83. [43] Shukla SR, Pai RS. Adsorption of Cu(II), nickel(II) and Zn(II) on dye loaded
[12] Wang XS, Li ZZ, Sun C. Removal of Cr(VI) from aqueous solutions by low-cost groundnut shells and sawdust. Sep Purif Technol 2005;43:1–8.
biosorbents: marine microalgae and agricultural by products. J Hazard Mater [44] Feng N, Guo X, Liang S, Zhu Y, Liu J. Biosorption of heavy metals from aqueous
2008;15:1176–84. solutions by chemically modified orange peel. J Hazard Mater 2011;185:49–
[13] Villaescusa I, Fiol N, Martinez M, Miralles N, Poch J, Serarols J. Removal of 54.
copper and nickel ions from aqueous solutions by grape stalks wastes. Water [45] Krishnani KK, Meng X, Christodoulatos C, Boddu VM. Biosorption mechanism
Res 2004;38:992–1002. of nine different heavy metals onto biomatrix from rice husk. J Hazard Mater
[14] Chubar N, Carvalho JR, Correia MJN. Cork biomass as a biosorbent for Cu(II), 2008;153:1222–34.
Zn(II) and Ni(II). Colloids Surf A Physiochem Eng Aspects 2004;230:57–65. [46] Argun ME, Dursun S, Ozdemir C, Karatas M. Heavy metal adsorption by
[15] Nawirska N. Binding of heavy metals to pomace fibers. Food Chem modified oak sawdust, thermodynamics and kinetics. J Hazard Mater
2005;90:395–400. 2007;141:77–85.
[16] Saeed A, Akther MW, Iqbal M. Removal and recovery of heavy metals from [47] Ara Aiddiqui S, Sharma PP, Sultan M. Adsorption studies on phosphate treated
aqueous solution using papaya wood as a new biosorbent. Sep Purif Technol saw dust separation of Cr (VI) from Zn(II), Ni(II) and Cu(II) and their removal
2005;45:25–31. and recovery from electroplating wastes. Ind J Environ Protect 1999;19:846–
[17] Sharma A, Bhattacharyaa KG. Azadirachta indica (Neem) leaf powder as a 52.
biosorbent for removal of Cd(II) from aqueous medium. J Hazard Mater [48] Bulut Y, Tez Z. Removal of heavy metal ions by modified sawdust of walnut,
2005;125:102–12. fresen. Environ Bull 2003;12:499–504.
[18] Gamage A, Shahidi F. Use of chitosan for the removal of metal ion contami- [49] Sari A, Tuzen M, Uluozlu OD, Soylak M. Biosorption of Pb(II) and Ni(II) from
nants and proteins from water. Food Chem 2007;104:989–96. aqueous solution by lichen (Cladonia furcata) biomass. Biochem Eng J
[19] Martı́n-Lara MA, Rodrı́guez IL, Alomá I, Blázquez G, Calero M. Modification of 2007;37:151–8.
the sorptive characteristics of sugarcane bagasse for removing lead from [50] Ozer A, Ozer D. Comparative study of the biosorption of Pb(II), Ni(II) and Cr(VI)
aqueous solutions. Desalination 2010;256:58–63. ions onto S. cerevisiae: determination of biosorption heats. J Hazard Mater
[20] Tiwari DP, Singh DK, Saksena DN. Adsorption from aqueous-solutions using 2003;100:219–29.
rice-husk ash. J Environ Eng 1995;121:479–81. [51] Saltali K, Sari A, Aydin M. Removal of ammonium ion from aqueous solution by
[21] Edyvean GJ, Williams CJ, Wilson MM, Aderhold D. Biosorption using unusual natural Turkish (Yıldızeli) zeolite for environmental quality. J Hazard Mater
biomasses. In: Wase J, Forster C, editors. Biosorbents for metal ions. London: 2007;141:258–63.
Taylor and Francis Ltd.; 1998. [52] Ajmal M, Rao RAK, Ahmad R, Ahmad J. Adsorption studies on Citrus reticulata
[22] Puranik PR, Paknikar KM. Biosorption of lead, cadmium, and zinc by Citro- (fruit peel of orange): removal and recovery of Ni(II) from electroplating
bacter strain MCM B-181: characterization studies. Biotechnol Progr wastewater. J Hazard Mater 2000;79:117–31.
1999;15:228–37. [53] Daniels F, Alberty RA. Physical chemistry. New York: Wiley; 1975.
[23] Sheng PX, Ting YP, Chen JP, Hong L. Sorption of lead, copper, cadmium, zinc, [54] Smith JM, Van Ness HC. Introduction to chemical engineering
and nickel by marine algal biomass: characterization of biosorptive capacity thermodynamics, 4th ed., Singapore: McGraw-Hill; 1987.
and investigation of mechanisms. J Colloid Interf Sci 2004;275:131–41. [55] Gupta VK. Equilibrium uptake, sorption dynamics, process development, and
[24] Deng SB, Bai RB. Removal of trivalent and hexavalent chromium with ami- column operations for the removal of copper and nickel from aqueous solution
nated polyacrylonitrile fibers: performance and mechanisms. Water Res and wastewater using activated slag, a low-cost adsorbent. Ind Eng Chem Res
2004;38:2424–32. 1998;37:192–202.
[25] Harris PO, Ramelow GJ. Binding of metal ions by particulate biomass derived [56] Kumar J, Balomajumder C, Modal P. Application of agro-bases biomasses
from Chlorella vulgaris and Scenedesmus quadricauda. Environ Sci Technol for zinc removal from wastewater—a review. Clean Soil Air Water 2011;39:
1990;24:220–8. 641–52.