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

Industrial effluents are the major sources for contamination of
water resources by heavy metals. Ni(II) belongs to the so-called
‘‘essential’’ metals and is identified as a component in a number of
enzymes, participating in important metabolic reactions, such as
ureolysis, hydrogen metabolism, methane biogenesis, and acid-
ogenesis [1]. But, nickel(II) ion intake over the permissible levels
results in different types of disease such as pulmonary fibrosis,
renal edema, skin dermatitis, and gastrointestinal distress (e.g.,
nausea, vomiting, diarrhea) [1]. It is therefore, essential to remove
Ni(II) from wastewater before disposal. Mining and metallurgy of
nickel, stainless steel, aircraft industries, nickel electroplating,
battery and manufacturing, pigments and ceramic industries
wastewaters contain high amounts of nickel ions [2].
The commonly used techniques for removing metal ions from
effluents include ion exchange, adsorption, chemical precipitation,
reverse osmosis and solvent extraction [3–5]. These techniques are
* Corresponding author. Tel.: +34 958 243311; fax: +34 958 248992.
E-mail addresses: inesav@uclv.edu.cu (I. Alomá), marianml@ugr.es
(M.A. Martı́n-Lara), ivanl@uclv.edu.cu (I.L. Rodrı́guez), gblazque@ugr.es
(G. Blázquez), mcaleroh@ugr.es (M. Calero).
1
Tel.: +53 42 226768.
2
Tel.: +53 42 211825.
3
Tel.: +34 958 240770; fax: +34 958 248992.
4
Tel.: +34 958 243311; fax: +34 958 248992.
metal removal, generation of toxic sludge and other disposable
waste products. Biosorption utilizes the ability of dead/inactive
biomass to remove heavy metals from solutions. The use of dead/
inactive biomass is preferred over active/live biomass because
living biomass cells often require the addition of fermentation
media which increases the biological oxygen demand (BOD) or
chemical oxygen demand (COD) in the effluent [6]. In addition,
nonliving biomass is not affected by the toxicity of the metal ions,
and they can be subjected to different chemical and physical
treatment techniques to enhance their performance. Furthermore,
adsorbed metals can be easily recovered from the biomass by many
chemical and physical methods, leading to repeated use of the
biomass and better process economy [7,8]. The major advantages
of the biosorption technology are its effectiveness in reducing the
concentration of heavy metal ions to very low levels and the use of
inexpensive biosorbent materials [9].
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],
wheat bran [12], grape stalks waste [13], cork biomass [14],
pomace fibres [15], papaya wood [16], neem leaf [17] and chitosan
[18] have been used.
The utilization of agro-wastes as adsorbent is currently
receiving wide attention because of their abundant availability
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
various agro-wastes, sugarcane bagasse seems to be an important
aspirant. The presence of compounds such as cellulose, hemicel-
lulose, lignin and silica in this material, with binding sites capable
to take up metals, suggests the use of sugarcane bagasse as a low
cost natural biosorbent for heavy metals.
The main objectives of the present study include (1) to study the
sorption potential of sugarcane bagasse for Ni(II) removal from
water, (2) to understand the kinetic mechanism, and (3) to model
the sorption process.
2. Materials and methods
2.1. Preparation of the sorbent material
Sugarcane bagasse (SCB) is a waste byproduct from sugar
industry. The sugarcane bagasse used in this work was supplied by
the pilot plant ‘‘José Marti’’ from Central University ‘‘Marta Abreu’’
of Las Villas, Cuba.
It was washed with distilled water many times and dried at
room temperature. No other chemical or physical treatments were
used prior to biosorption experiments. Then it was grinded with
strong grinder, and sieved to <1 mm particle size.
2.2. Preparation of Ni(II) solutions
A stock solution of 500 mg/L of Ni(II) was prepared by
dissolving an accurate quantity of NiSO46H2O in deionized water.
Other concentrations varying between 10 and 200 mg/L were
prepared from stock solution by dilution.
2.3. Biosorption experiments
Batch biosorption studies were performed by taking 100 ml of
Ni(II) solution with known pH in a 250 ml flask contained 1 g of
SCB. The flask was placed in a shaking reactor at a speed of 300 rpm
and temperature of 25 8C. After 2 h, biosorbent was separated and
the concentration of metal ion in solution was analyzed using a
atomic absorption spectrophotometer, SpectrAA 220 SS.
The effect of contact time on batch experiments was examined
by varying the contact time of suspensions from 3 to 120 min. For
the adsorption isotherm studies, the initial metal ion concentration
was varied over a range of 10–200 mg/L.
Biosorption capacity (qe) i.e., amount of metallic ion (mg)
biosorbed by gram of the biomass and the efficiency of biosorption
(%) were calculated using Eqs. (1) and (2), respectively:
ðC i  C f Þ
qe ¼ V (1)
m
ðC i  C f Þ
%¼  100
Ci
where Ci and Cf are the initial and final (equilibrium) concentra-
tions of Ni(II) in solution whereas V and m are solution volume and
mass of biosorbent, respectively.
All biosorption experiments were carried out in duplicate.
3. Result and discussion
3.1. Characterization of the biosorbent
Characterization of biosorbent surface and structure hold keys
to understanding the metal binding mechanism onto biomass. The
physical and chemical properties of the SCB were determined in
our earlier publication [19]. Elemental analysis results showed that
SCB is composed of 43.0% carbon, 6.4% hydrogen, 0.6% nitrogen,
<0.1% sulphur and 49.9% oxygen.
The Infrared spectrum revealed biosorbent heterogeneity,
evidenced by different characteristic peaks with the possible
presence of carboxylic, hydroxyl and carbonyl groups [19].
The potentiometric titrations results confirmed the presence of
–OH (0.11 mmol/g) and –COOH (0.12 mmol/g) functional groups in
the lignocellulosic moiety of the SCB biomass, and probably these
groups are the major binding groups responsible for metal
biosorption [19]. The value of the point of zero charge, pHpzc
was also calculated from potentiometric titrations. The surface of
SCB becomes negatively charged at pH values higher than 5.9 and
acquires a net positive charge at pH value less than 5.9.
Also, the morphological characters of SCB were qualitatively
studied using SEM [19]. The morphology of this material can
facilitate the adsorption of metals, due to its irregular surface and
porosity.
3.2. Effect of pH
One of the most important factors affecting biosorption of metal
ions is acidity of solution. The metal ion adsorption is affected by
the pH of the solution thereby changing the surface charge of the
sorbent and metal speciation [20–24].
Fig. 1 shows the speciation diagram for nickel species built for
2  104 M and 3  103 M concentrations, approximately the
equivalent concentrations for the experiments carried out in this
work. At pH 5, the predominant species is still Ni2+ which is the
selected pH value for the biosorption experiments. At higher
concentrations, soluble specie NiSO4 also begins to appear but Ni2+
still is predominant. Higher values of pH were avoided in later
biosorption tests to prevent metal ion precipitation as hydroxide
[25,26], and lower values of pH also were avoided due to at lower
pH values the surface charge of the solid could be too positive and
nickel cation adsorption be unfavorable, additionally, at low pH
values, hydrogen ions could compete strongly with nickel ions for
the active sites of SCB and biosorption could be small [19,27]. In
fact, the effect of pH on adsorption of Ni2+ was studied at 25 8C
varying the pH from 1 to 6 (Fig. 2). In pH range of 1–2, there is little
or no biosorption and with the increase of pH, the amount of nickel
uptake by SCB tended to increase and a sharp increase in qe was
observed in the pH ranging from 3 to 5. At about pH 5 a plateau was
reached, e.g., there was no significant difference between pH 5 and
6 in the maximum Ni2+ biosorption capacity. These seemed to
indicate that the optimum pH value for Ni2+ biosorption by SCB
would be around 5.
3.3. Biosorption kinetics
For practical applications, the process design and operation
control, the sorption kinetics were very important. Sorption
(2) kinetics in wastewater treatment was significant, as it provides
valuable insights into the reaction pathways and the mechanism of
the sorption reactions. Since biosorption is a metabolism-
independent process, it would be expected to be a very fast
reaction.
3.3.1. Effect of initial nickel concentration on kinetics
Biosorption of Ni(II) onto SCB at various initial concentrations
had been carried out at different time intervals (3–120 min) and
was shown in Fig. 3.
The initial metal concentration provides an important driving
force to overcome all mass transfer resistance of Ni(II) between the
aqueous and solid phases. The percent of Ni(II) removal is inversely
related to the initial metal ion concentrations (Fig. 3(a)). It
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
The effect of temperature (Fig. 4 and Table 2) was studied in the
temperature range 25–65 8C at pH 5, for a solid concentration of
10 g/L and an initial concentration of Ni(II) of 10 mg/L.
Analysis of data showed that the biosorption of Ni(II) followed
again pseudo-second order kinetic model for all temperatures
tested. Also, the temperature effect on biosorption capacity is less
significant than the effect of nickel concentration although a
decrease on kinetic constant and initial sorption rate is produced as
temperature rises.
3.4. Biosorption isotherms. Effect of temperature
Biosorption isotherms of Ni(II) onto SCB had been carried out at
different temperatures (from 25 8C to 65 8C) and shown in Fig. 5.
The analysis of adsorption data is important for developing an
equation which accurately represents the results and could be used
for design purposes. Out of several isotherm equations, the
Langmuir, Freundlich and Sips isotherms were used to fit the
experimental data.
2.5
an empirical parameter relating the biosorption intensity, which
varies with the heterogeneity of the material. From Table 3, KF
values were found to be 0.414, 0.222 and 0.161 and the n values
were found as 2.94, 2.65 and 2.44. The 1/n values were between 0
and 1, indicating that the biosorption of Ni(II) onto the SCB was
favorable at studied conditions. The low values of R2 indicated that
Freundlich model was not altogether properly describing the
relationship between the amounts of sorbed metal ions and their
equilibrium concentrations in the solution.
The Sips model incorporates the features of the Langmuir and
Freundlich models into a single equation as follows [39]:
qm bC e 1=n
qe ¼ (11)
1 þ bC e 1=n
where qm, b and n are the Sips constants. The constant n has two
limiting behaviours: Langmuir form for n = 1 and Freundlich form
for very high n values.
The Sips isotherm constants and correlation coefficient (R2) are
also given in Table 3. On comparing the linear regression values it is
concluded that the Langmuir and Sips isotherms are capable of
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
Maximum capacity for biosorption of Ni2+ by various biosorbents.
Biosorbent qm (mg/g)
Black carrot residues 6.51
Cashew nut shell 18.87
Cassava peel 57.07
Dye groundnut shells 7.49
Orange peel 9.82
Rice husk 5.52
Saw dust (oak tree) 3.37
Sawdust-phosphate treated 0.70
Wallnut sawdust 6.43
Sugarcane bagasse 2.23
In Table 4 the nickel biosorption capacities of SCB were
compared with those obtained by other biosorbents.
On the other hand, the temperature of the sorption medium
could be important for energy-dependent mechanisms in metal
biosorption. The effect of temperature on the adsorption of
nickel(II) is investigated at three different temperatures (25 8C,
50 8C and 65 8C) for SCB and is given in Fig. 5. For an increase in
temperature from 25 to 50 8C, the biosorption capacities of the SCB
for Ni(II) showed a decrease from 2.234 to 1.304 mg/g (Langmuir
model), thus indicating the exothermic nature of the biosorption
process.
A similar exothermic nature of the adsorption process has been
reported for other adsorbent systems [49]. This could be due to
either the damage of active binding sites in the biomass [50] or the
increasing tendency to desorb metal ions from the interface to the
solution [51]. The optimum solution temperature was selected as
25 8C.
3.4.1. Thermodynamic study
The thermodynamics parameters were evaluated from the
experimental data. Both energy and entropy factors must be
considered in thermodynamics, in order to determine whether a
process will occur spontaneously or not. The process of nickel(II)
ion biosorption can be assumed by the following reversible
process, which represents a heterogeneous equilibrium
NiðIIÞ ion in solution $ NiðIIÞ  sugarcane bagasse
For such equilibrium reactions, the Gibbs free energy (DG8) was
determined by the following equation:
DG ¼ RT ln K0C
where, R is the universal gas constant, 8.314 J/mol/K and T is the
absolute temperature in K and K0C is the equilibrium constant. The
Gibbs free energy indicates the degree of spontaneity of the
adsorption process, where more negative values reflect a more
energetically favorable adsorption process. The relationship
between the equilibrium constant, K0C and the temperature is
given by the Van’t Hoff equation
DS DH
ln K0C ¼  (13)
R RT
The entropy change of biosorption, DS8, and the enthalpy
change of biosorption, DH8 can be obtained from the slope and
intercept of a Van’t Hoff plot of ln K0C versus 1/T [52–54]. In this
study, the thermodynamic parameters have been calculated using
the Langmuir isotherm, i.e., by replacing the equilibrium constant,
K0C from Eqs. (12) and (13) by the Langmuir isotherm constant, b
(L/mol) [55] and are given in Table 5.
The negative values of DG8 indicate the feasibility of the process
and the spontaneous nature of sorption with a high affinity for
Table 5
Thermodynamic parameters for the biosorption of Ni(II) onto SCB at different
temperatures.
Reference
T (8C) DG (kJ/mol) DH (kJ/mol) DS (J/mol K)
[40]
[41] 25 20.78 74.32 332.29
[42] 50 22.07
[43] 65 22.30
[44]
[45]
[46]
[47] nickel (II) ion onto SCB. The standard enthalpy and entropy
[48] changes of biosorption were 74.32 kJ/mol and 332.29 J/mol/K,
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.
3.5. Mechanism of Ni(II) biosorption by SCB
Mechanisms involved in the biosorption process by agro-based
biomasses include ion exchange, chelation, precipitation, sorption
by physical forces, and ion entrapment in inter and intrafibrillar
capillaries and spaces of the structural lignin and polysaccharide
networks as a result of diffusion through cell wall and membrane
[56].
Some information about the surface chemistry characterization
of the SCB, for example the alteration of functional groups, can be
used as evidences in proposing the biosorption mechanism. Also
biosorption kinetics and equilibrium can be used to explain the
biosorption mechanism.
In this work, the release of calcium, magnesium and potassium
ions was measured in relation to the nickel biosorption. The release
of calcium, magnesium and potassium was followed in the same
time of nickel biosorption. It was found a equivalent ratio of the
released light metals to the biosorbed nickel ions, which indicated
that the ion exchange would be a mechanism involved in
biosorption of Ni2+ by SCB. Also, to verify the release of protons
during the biosorption process, pH variation was recorded. A
decrease of pH values was appreciated, probably due to the
exchange of protons during the nickel biosorption.
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
governing the biosorption process. It was also possible that Ni(II)
ions were bound into carboxylate groups in the lignocellulosic
structure of SCB by creating ionic forces with carboxylic oxygen
atoms. These oxygen atoms exhibited negative charge in their
(12) structure as a result of the dissociation of carboxylic groups. The
negatively charged oxygen atom in carboxylate anions will
coordinate with nickel cations, resulting in the formation of
metal–carboxylate complexes (COO–Ni) on the SCB surface.
These conclusions support the mechanism previously
explained in other papers [42] based on the interaction of metal
ions with acidic functional groups in the biomass surface.
4. Conclusions
The experimental investigations conclude the capacity of SCB to
biosorb the nickel ions. The biosorption of toxic Ni2+ by SCB was
influenced by contact time, initial concentration of the metal ions
and temperature. The experimental data turn out good fits with
Langmuir isotherm (R2 > 0.99). The kinetic studies proved that
pseudo-second-order kinetic was a suitable model. The thermo-
dynamic calculations indicated the feasibility, exothermic and
spontaneous nature of the biosorption of Ni(II) ion onto SCB
biomass at 25–65 8C. It can be also concluded that the SCB is an
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
wastewaters in terms of natural and abundant availability and low
cost.
Acknowledgements
The authors are grateful to the alfa BIOPROAM Program
Contract No. AML/190901/06/18414/II-0548-FC-FA, Metropolitan
Autonomous University Ixtapalapa, Mexico, D.F., and the Depart-
ment of Chemical Engineering of Central University ‘‘Marta Abreu’’
of Las Villas for the financial support.
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