Desalination 268 (2011) 150–157

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Biosorption of Ni(II) from aqueous phase by Moringa oleifera bark, a low

cost biosorbent
D. Harikishore Kumar Reddy a, D.K.V. Ramana a, K. Seshaiah a,⁎, A.V.R. Reddy b
a
Analytical & Environmental Chemistry Division, Department of Chemistry, Sri Venkateswara University, Tirupati 517 502, India
b
Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India

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

Article history: Moringa oleifera bark (MOB), an agricultural solid waste by-product has been developed into an effective and
Received 23 July 2010 efficient biosorbent for the removal of Ni(II) from aqua solutions. The biosorbent was characterized by X-ray
Received in revised form 27 September 2010 diffraction (XRD), scanning electron microscopy (SEM), elemental analysis and FTIR analyses. The
Accepted 2 October 2010
experimental equilibrium adsorption data were analyzed by four widely used two-parameter equations –
Available online 30 October 2010
Langmuir, Freundlich, Dubinin–Radushkevich (D–R), and Temkin isotherms. Among the four isotherm
Keywords:
models Langmuir model provided a better fit with the experimental data than others as revealed by high
Moringa oleifera bark correlation coefficients, low chi-square values. The kinetics data fitted well into the pseudo-second-order
Biosorption model with correlation coefficient greater than 0.99. Desorption experiments were carried out to explore the
Nickel feasibility of regenerating the biosorbent and the biosorbed Ni(II) from MOB was desorbed using 0.2 M HCl
Kinetics with an efficiency of 98.02% recovery. The thermodynamic parameters (ΔH, ΔS and ΔG) of the nickel ion
Isotherms uptake onto MOB indicated that, the process is endothermic and proceeds spontaneously. The findings of the
Thermodynamics present study indicates that MOB can be successfully used for separation of Ni(II) from aqueous solutions.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction cally viable sources of biosorbents; this makes biosorption an

Industrial effluents are the major sources for contamination of
water resources by heavy metals. 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 [1]. Nickel is known as one of the most
common toxic metals, and the US Environmental Protection Agency
(EPA) has established 0.5 mg L−1 as the permissible concentration for
nickel in drinking water [2]. In view of this, it is necessary to remove
nickel from wastewater before they are discharged into natural water
bodies. The current technologies for the removal of nickel include
chemical precipitation, ion exchange, or electrochemical processes.
Many of these methods are neither effective nor economical,
especially when used for the reduction of heavy metal ions to low
concentrations. Hence, there is a need to develop cost-effective
technologies for treating the wastewater that reduce metal ion
concentrations to environmentally acceptable levels.
Biosorption has the potential to contribute to the achievement of
this goal. Biosorption is a process that uses inexpensive biomaterials
to sequester metals from aqueous solutions [3] and the biomaterials
used in this process are termed as biosorbents. The by-products from
agricultural, food and pharmaceutical industries provide economi-
⁎ Corresponding author. Tel.: +91 877 2289303.
E-mail address: seshaiahsvu@yahoo.co.in (K. Seshaiah).
inexpensive alternative treatment method. Several workers have
reported on the potential use of agricultural by-products as good
substances for the removal of metal ions from aqueous solutions and
wastewaters [4–11].
Moringa oleifera belongs to the family Moringaceae, which is native
to the sub-himalayan tracts of India. M. oleifera bark is abundantly
available in India with no commercial use. Since its fruits and leaves
are edible and consumed in all the seasons, these trees are widely
cultivated species in India. Due to this, massive amount of bark is
produced, which is being disposed off as waste. The plant contains
various amino acids, fatty acids, vitamins and nutrients [12]
glucosinolates and phenolics (flavonoids, anthocyanins, proanthocya-
nides and cinnamates) which are the functional groups that are
capable of anchoring metals. The bark tissue of M. oleifera contains 4-
(α-L-rhamnopyranosyloxy)-benzylglucosinolate [13]. Every glucosi-
nolate contains a central carbon atom which is bonded to the
thioglucose group (making a sulfated ketoxime) via a sulfur atom and
to a sulfate group via a nitrogen atom. These functional groups
containing sulfur and nitrogen are good metal sequesters from the
aqueous solution. Because of the composition of M. oleifera bark and
its availability, it was chosen as a biosorbent for the removal of Ni(II)
from aqueous solutions.
In the present study, a simple and economic preparation of the
biosorbent was performed and biosorption experiments have been
conducted to determine the metal biosorption mechanism. The main
objectives of the present study include (1) characterizing the

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.10.011
 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157
biosorbent through FTIR, XRD, SEM and Elemental analysis to know
the physico-chemical properties of the biosorbent, (2) to study the
sorption potential of MOB for Ni(II) removal from water under
equilibrium conditions and (3) to understand the kinetic mechanism.
The data from the experiments were fitted with different kinetic
models to identify the adsorption mechanism.
2. Materials and methods
2.1. Preparation of the biosorbent
Samples of M. oleifera bark were collected from Punganur (Andhra
Pradesh, India) in December 2007, air dried and ground in a mill to get
fine powder. The powder was washed twice with deionized water and
dried at 60 °C for 24 h, then boiled in double distilled water by
changing the water repeatedly until water becomes colorless, which
indicates the removal of water soluble color compounds. The washed
and boiled bark was oven dried at 80 °C for 24 h and stored in
desiccator to prevent moisture adsorption before its use. This treated
M. oleifera bark powder is called as MOB.
2.2. Chemicals and equipment
All reagents used were of AR grade. Deionized double distilled
water was used throughout the experimental studies. Stock solution
(1000 mg L−1) was prepared by dissolving NiSO4·6H2O. This was
further diluted to obtain the desired concentration for practical use.
ACS reagent grade HCl, NaOH and buffer solutions (E. Merck) were
used to adjust the solution pH. An Elico (LI-129) pH meter was used
for pH measurements. The pH meter was calibrated using buffer
standard solutions of pH 4.0, 7.0 and 9.2. Fourier transform infrared
spectrophotometer (Thermo-Nicolet FT-IR, Nicolet IR-200, USA) was
used to analyze the organic functional groups of the biosorbent. Vario
EL, Elementar, Germany was used for elemental analysis of the MOB.
The metal concentrations in the samples were determined using
atomic absorption spectrophotometer (AAS, Varian spectra AA, 55
Australia). Wide angle X-ray diffraction (WAXD) patterns of powder
MOB sample was recorded on an X-ray diffractometer (XRD-6000,
Shimadzu), by using Cu Kα radiation (λ = 1.5406A) at 40 kV and
30 mA with a scan rate of 5°/min in the range of 2θ from 8 to 50°.
Scanning Electron Microscopy (Model Evo15, Carl Zeiss, England) was
used to study the surface morphology of the biosorbent.
2.3. Biosorption experiments
Batch biosorption studies were performed by taking 50 mL of Ni
(II) solution with known pH in a 250 mL flask and by adding 200 mg
of MOB. The sealed flask was placed in a shaking incubator at a speed
of 300 rpm and temperature of 25 °C. After 3 h, biosorbent was
separated using an ashless filter paper and the concentration of metal
ion in solution was analyzed by AAS.
The influence of pH on Ni(II) biosorption was determined by
equilibrating the suspensions in solutions of different pH ranging
from 2.0 to 8.0. The effect of contact time on batch experiments was
examined by varying the contact time of suspensions from 5 to
100 min. For the adsorption isotherm studies, the initial metal ion
concentration was varied over a range of 20 to 200 mg L−1. The
concentration of MOB was varied between 100 and 800 mg to
determine the ratio required for optimum biosorption. The interfer-
ence caused by the presence of other cations that are normally
present in water was checked by the addition of monovalent Na+ and
K+, and divalent Mg2+ and Ca2+ metal solution ranging from 0 to
300 μg mL−1.
151
The amount of metal ion sorbed onto the MOB, Qe, was computed
by the following equation:
v
Qe = ðC −Ce Þ ð1Þ
m 0
Where, C0 and Ce are the initial and equilibrium concentrations of
Ni(II) in solution whereas v and m are solution volume and mass of
biosorbent, respectively.
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
proximate and ultimate analysis of MOB is presented in Table 1.
Percent ash content, moisture content, fixed carbon, and bulk density
are also given in Table 1. Elemental analysis results showed that MOB
is composed of 44.8 ± 1.50% carbon, 5.9 ± 0.18% hydrogen, 0.8 ± 0.01%
nitrogen, 0.9 ± 0.01% sulphur and 47.6 ± 1.82% oxygen. Sulphur
groups, which are soft bases, have chemical affinity towards metal
ions and presence of sulphur in MOB qualifies it as a potential
biosorbent.
3.2. Scanning electron microscopy
Scanning electron microscope has been widely used to study the
morphological features of the biosorbent. Study of the SEM micro-
graphs of MOB showed in Fig. 1(a) and (b) indicated the presence of
asymmetric pores and open pore structure, which may provide high
internal surface area and a rough structure on the surface of MOB,
which is favorable for biosorption of Ni(II) from aqua solutions.
3.3. X-ray diffraction
XRD pattern of the MOB shown in Fig. 2 illustrates the presence of
a significant amount of amorphous material due to lignin and tannin
in the sample.
3.4. Infrared spectroscopy
The FTIR spectra of MOB (Fig. 3a), showed the presence of many
functional groups, indicating the complex nature of MOB biosorbent.
A strong band at 3418 cm−1 indicated the presence of hydroxyl
groups. A peak at 2920 cm−1 is due to the C–H stretching frequency
and the peak at 1644 cm−1 is due to C=O stretching mode of the
primary and secondary amides (NH2CO). The peaks at 1510 cm−1 and
1375 cm−1 are indicative of the N–H stretching of the primary and
secondary amides, and the presence of amide (III) or sulfamide band,
respectively. Bands at 1320 and 1246 cm−1 indicate presence of
carboxylic acids [14].Weak bands at 1462 and 1510 cm−1 are
attributed to aromatic C=C and two sharp peaks at 1733 and
1644 cm−1 characteristic of carbonyl group stretching were also
observed. The strong C–O band at 1054 cm−1 confirms the lignin
structure of the MOB [15]. The asymmetrical stretching vibration at
3418 cm− 1 was shifted to 3342 cm−1 after the biosorption of Ni(II).
The change in hydroxyl group after biosorption shown in Fig. 3b,
indicated that it had been changed from multimer to monopolymer or
even dissociative state [16] which showed that the degree of hydroxyl
polymerization in lignocellulose was decreased by binding of Ni(II).
The spectrum after interaction with Ni(II) showed increased intensity
and shifted to asymmetrical stretching bands at 1732, 1644 and
1054 cm− 1 when compared with those observed in the spectra of
MOB. These results indicated that the biosorption of Ni(II) occurs at
152 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157

Table 1
Characteristics of Moringa oliefera bark (MOB).

Biosorbent Bulk Moisture Ash Fixed PZC Elemental analysis (%)

density content content carbon (%)
Carbon Hydrogen Nitrogen Sulphur Oxygena
(g/cm3) (%) (%)

MOB 0.5 ± 0.03 2.5 ± 0.08 11.1 ± 0.32 20.1 ± 0.51 4.2 ± 0.67 44.8 ± 1.50 5.9 ± 0.18 0.8 ± 0.01 0.9 ± 0.01 47.6 ± 1.82
a
Estimated by difference.

hydroxyl, carboxyl, and carbonyl functional groups present on the
surface of MOB.
3.5. Influence of pH
It is well known that pH of the medium is most important factors
that influence the biosorption process [17]. The pH level affects the
network of negative charge on the surface of the biosorbing cell walls,
as well as physicochemsitry and hydrolysis of the metal. Therefore,
preliminary experiments have been performed to find out the
optimum pH for maximizing the metal removal. Percentage removal
of the metal ion as a function of pH is shown in Fig. 4. It has been
observed that under highly acidic conditions (pH ≈ 2.0) the amount of
Ni(II) removal was very small, while the sorption had been increased
with the increase in pH from 3.0 to 6.0 and then decreased in the
range 7.0 and 8.0. The lower removal efficiency at low pH is
apparently due to the presence of higher concentration of H+ in the
solution which compete Ni(II) ions for the adsorption sites of the
MOB. With increase in pH, the H+ concentration decreases leading to
increased Ni(II) uptake.
On considering the point of zero charge of MOB another
explanation for Ni(II) has been provided. The point of zero charge
(PZC) of biosorbent was determined according to the procedure
described by Lu et al. [18]. At pH below 4.2 ± 0.67 (PZC), the surface of
MOB would positively charged due to protonation. This protonation
effect was more pronounced at lower pH values due to the presence of
higher concentration of H+ ions in the solution which resulted in
more unfavorable Ni(II) biosorption. At the optimum pH value (pH
6.0) the surface of the MOB is negatively charged and favorable to the
biosorption of Ni(II). Decreased biosorption at higher pH (pH N 6) was
due to the formation of soluble hydroxylated complexes of the metal
ions and their competition with the active sites, and as a consequence,
the retention had been decreased again. Therefore further experi-
ments were carried out with initial pH value of 6. Previous studies also
reported that the maximum biosorption efficiency for Ni(II) metal ion
on biomass was observed at pH 6 [19–21].
3.6. Effect of biosorbent dose
Biosorption of Ni(II) onto MOB was studied by changing the
quantity of sorbent from 0.1 to 0.8 g in the test solution while
maintaining the initial concentration 50 mg mL−1, pH 6 and contact
time 2 h constant. Biosorption of Ni(II) as a function of biomass shown
in Fig. 5, indicates the effect of sorbent dose on the Ni(II) biosorption
by MOB. Obviously, the biosorption efficiency increased as the sorbent
dose increased, but it remained almost constant when the sorbent
dose reached 0.4 g. This may be explained by the following analysis.
When sorbent ratio is small, the active sites for binding metal ions on
the adsorbent surface is less, so the adsorption efficiency is low; when
biosorbent dose increased more metal ions were adsorbed. Thus it
results in the increment of adsorption efficiency until saturation.

3.7. Effect of contact time and biosorption kinetics

For practical applications, the process design and operation

control, the sorption kinetics were very important. Sorption kinetics
in wastewater treatment was significant, as it provides valuable
insights into the reaction pathways and the mechanism of the
Intensity (CPS)

10 15 20 25 30 35 40 45 50
2θ (deg)

Fig. 1. SEM micrographs of MOB surface: (a) low magnification, (b) high magnification. Fig. 2. XRD spectrum of MOB.
 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157 153

100
(b)

90
Transmittance (%)

% Removal
80

(a)
70

60
Ni(II)

4000 3500 3000 2500 2000 1500 1000 500 50

100 200 300 400 500 600 700 800
Wavenumber (cm-1)
Amount of biosorbent (mg)
Fig. 3. FT-IR spectra of : (a) MOB ; (b) Ni-loaded MOB.
Fig. 5. Effect of sorbent dose on the sorption of Ni(II) by MOB. Error bars represent ± S.D.

sorption reactions. Biosorption of Ni(II) onto MOB at various initial The pseudo-second-order model proposed by Ho and McKay [23]
concentrations had been carried out at different time intervals (5– was based on the assumption that the adsorption follows second-
100 min) and shown in Fig. 6. order chemisorption. The linear form can be written as follows:

3.8. Biosorption kinetics t 1 t

In order to further investigate the biosorption mechanism of Ni(II)
onto MOB and rate-controlling steps, a kinetic investigation was
conducted, Pseudo-first, pseudo-second-order and intra-particle
diffusion kinetic models have been used for testing experimental data.
The pseudo-first-order kinetic model was proposed by Lagergren
[22]. The integral form of the model generally expressed as follows:
k1
logðqe −qÞ = log qe  t ð2Þ
2:303
Where, qe (mg g−1) and qt (mg g−1) are the adsorption amount at
equilibrium and time t (min), respectively. k1 (min−1) is the rate
constant in the pseudo-first-order adsorption process. The constants
were determined experimentally by plotting log(qe − qt) vs t. The
results are given in Table 2. The theoretical values (qe,cal) were far
lower than those experimental data, qe,exp and low correlation
coefficient values obtained for the pseudo first-order model indicate
that sorption is not occurring exclusively onto one site per ion.
= + ð3Þ
q k2 q2e qe
where, k2 (g mg−1 min−1) is the rate constant of adsorption. By
plotting a curve of t/qt against t, qe and k2 can be evaluated. The initial
adsorption rate, h0 (mg g−1 min−1) is defined as
2
h0 = k2 qe ð4Þ
The values of qe, k2, h0 and R2 are listed in Table 2. The dependence
of t/qt vs t gives a linear relation for all the experimental concentra-
tions (Fig. 7.), and all the R2 values are closer to 1 (Table 2), confirming
the applicability of pseudo-second-order equation. In addition, there
is only a little difference between qe,exp and qe,cal (Table 2), reinforcing
the applicability of this model. From Table 2, it can be observed that,
with an increase in initial metal concentration, the initial sorption rate
(h0) also increased. In accordance with the pseudo-second reaction
mechanism, the overall rate of Ni(II) sorption processes appears to be
controlled by the chemical processes, through sharing of electrons

15
100
50 mg L-1
25 mg L-1
80
10 mg L-1
10
% Removal

qe (mg g-1)

60
Ni(II)

40
5

20

0 0
0 2 4 6 8 0 20 40 60 80 100
Initial pH Contact time (min)

Fig. 4. Effect of pH on the sorption of Ni(II) by MOB. Error bars represent ± S.D. Fig. 6. Effect of contact time on the sorption of Ni(II) by MOB. Error bars represent ± S.D.
154 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157

Table 2
The pseudo-first-order and pseudo-second-order and Weber and Morris constants.

Initial Ni(II) Experimental Pseudo-first-order Pseduo-second-order Weber and Morris

concentration value qe,exp
qe,cal k1 × 10−2 R2 qe,cal k2 × 10−2 h0 R2 qe,cal Kid R2
(mg L−1) (mg g−1)
(mg g−1) (min–1) (mg g−1) (g mg–1 min–1) (mg g−1 min−1) (mg g−1) (mg g−1 min−1/2)

50 9.70 8.00 7.02 0.9888 10.29 1.91 2.03 0.9971 1.5 0.20 0.9353
25 6.74 4.72 5.61 0.9344 7.14 2.70 1.38 0.9964 2.88 0.44 0.9213
10 3.27 2.16 5.73 0.9233 3.43 12.74 1.05 0.996 4.03 0.67 0.9243

between biosorbent and sorbate, or covalent forces, through the
exchange of electrons between the particles involved.
An empirically found functional relationship, common to the most
adsorption processes, is that the uptake varies almost proportionally
with t1/2, as per the Weber–Morris plot, rather than with the contact
time, t [24]
1=2
q = Ki t
where q (mg g−1) is the adsorbed metal amount, Ki intraparticle
diffusion rate constant (mg g−1 min−1/2). According to this model, the
plot of uptake (q) vs the square root of time should be linear if
intraparticle diffusion is involved in the adsorption process and if
these lines pass through the origin then intraparticle diffusion is the
rate-controlling step. The low correlation coefficient values obtained
(Table 2) for the intraparticle diffusion model indicated that
adsorption is not occurring in the pores of biosorbent accordance
with surface adsorption.
3.9. Biosorption isotherm
The successful representation of the dynamic adsorptive separa-
tion of solute from solution onto an adsorbent depends upon an
appropriate description of the equilibrium separation between two
phases [25]. In order to determine the mechanism of Ni(II)
biosorption onto MOB and to evaluate the relationship between
biosorption temperatures, the experimental data was applied to the
two-parameter non-linear isotherm models, i.e. Langmuir, Freundlich,
Dubinin–Radushkevich (D–R) and Temkin. The Chi-square (χ2) test
was also carried out to find out the best fit adsorption isotherm model.
The equation for evaluating the best fit model is
 2
2
qe −qe;m
χ =∑
qe;m
35
30
50 mg L-1
25
25 mg L-1
t/qt (min g mg-1)
where, qe,m is equilibrium capacity obtained by calculating from
model (mg g−1), qe is the experimental data of equilibrium capacity
(mg g−1).
The isotherm constants, correlation coefficient (R2) of these
models for sorption of Ni(II) onto MOB for three different tempera-
tures are presented in Tables 3 and 4.
The Langmuir isotherm theory assumes monolayer coverage of
adsorbate over a homogeneous adsorbent surface [26].
ð5Þ
qm KL ce
qe = ð7Þ
1 + KL ce
In Eq. (7) qm is the monolayer biosorption capacity of the
biosorbent (mg g−1), qe is the equilibrium metal ion concentration
on the biosorbent (mg g−1), Ce is the equilibrium metal ion
concentration in the solution (mg L−1), and KL is the Langmuir
biosorption constant (L mg−1) related to the free energy of biosorp-
tion. The constants qm and KL increased with increase in temperature.
The R2 and χ2 (Table 4) values for MOB sorbent indicated that
Langmuir theory describes the sorption phenomena more favorably.
The essential features of the Langmuir biosorption isotherm can be
expressed in terms of a dimensionless constant separation factor (RL),
which is defined in Eq. (8).
1
RL = ð8Þ
ð1 + KL C0 Þ
where KL is the Langmuir constant (L mg−1) and C0 is the initial
adsorbate concentration (mg L−1). The value of RL indicates the type
of isotherm [27,28]. The values of RL are all in the range of 0–1, which
indicate the favorable biosorption of Ni(II) onto MOB.
The Freundlich model assumes a heterogeneous sorption surface
[29].
1=n
qe = KF Ce ð9Þ
ð6Þ
In Eq. (9) Kf is a constant relating the biosorption capacity and 1/n
is an empirical parameter relating the biosorption intensity, which
varies with the heterogeneity of the material. From the graphs, Kf
values were found to be 7.62 ± 0.78, 8.59 ± 0.90 and 10.41 ± 1.00 and
the n values were found as 3.01 ± 0.30, 3.07 ± 0.33 and 3.41 ± 0.38.
The 1/n values were between 0 and 1 indicating that the biosorption

10 mg L-1 of Ni(II) onto the MOB was favorable at studied conditions. The low
value of R2 and high χ2 values indicated that Freundlich model was
20
not altogether properly describing the relationship between the
amounts of sorbed metal ions and their equilibrium concentrations in
15
the solution.
The Dubinin–Radushkevich (D–R) model, which does not assume
10
a homogeneous surface or a constant biosorption potential as the
Langmuir model, was also used to test the experimental data [30].
5
    2 
1
qe = Qm exp −K RT ln 1 + ð10Þ
0 Ce
0 20 40 60 80 100
t (min)
 
2
qe = Qm exp −kε ð11Þ
Fig. 7. Pseudo-second-order kinetics plots for the sorption of Ni(II) onto the MOB.
 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157 155

Table 3
Langmuir, Freundlich, Temkin and Dubinin–Radushkevich constants for Ni(II) biosorption by MOB.

Metal Temp. Langmuir Freundlich Dubinin–Radushkevich Temkin

ion (K)
qm (mg/g) KL (L/mg) Kf (mg/g) n Qm K b KT

Ni(II) 303 26.84 ± 0.91 0.26 ± 0.02 7.62 ± 0.78 3.01 ± 0.30 21.82 ± 2.02 0.06 ± 0.01 7.76 ± 0.56 5.26 ± 1.24
313 29.46 ± 0.99 0.27 ± 0.03 8.59 ± 0.90 3.07 ± 0.33 24.12 ± 2.20 0.05 ± 0.01 6.33 ± 0.48 5.56 ± 1.42
323 30.38 ± 0.82 0.31 ± 0.03 10.41 ± 1.00 3.41 ± 0.38 25.13 ± 1.86 0.02 ± 0.01 6.09 ± 0.35 7.43 ± 1.51

Where Qm is the maximum amount of the metal ion that could be
sorbed onto unit weight of sorbent (mg g−1), ε is the Polanyi potential
which is equal to RT ln (1 + 1/Ce), where R and T are the universal gas
constant (kJ mol−1 K−1) and the absolute temperature (K), respec-
tively. The D–R isotherm parameters for three different temperatures
have been presented in Table 3. The values of correlation coefficient
were lower than that of other three isotherm values. In all the cases,
the D–R equation represents the least fit to experimental data than
the other isotherms equations.
The Temkin isotherm [31] assumes that the heat of adsorption of
all the molecules in the layer decreases linearly with coverage due to
adsorbent–adsorbate interactions [32], and that the adsorption is
characterized by a uniform distribution of the binding energies, up to
some maximum binding energy.
RT
qe = lnðK T Ce Þ
b
qe = B1 lnðK T Ce Þ
Where constant B1 = RT/b, which is related to the heat of
adsorption, R is the universal gas constant (J mol− 1 K−1), T is the
temperature (K), b is the variation of adsorption energy (J mol−1) and
KT is the equilibrium binding constant (L mg−1) corresponding to the
maximum binding energy. Temkin isotherm parameters are listed in
Table 3.
By comparing the results, the values of χ2 and the correlation
coefficients (Tables 3 and 4), it has been found that the Langmuir
isotherm best represented the equilibrium adsorption of Ni(II) onto
MOB.
3.10. Biosorption thermodynamics
Different thermodynamic parameters, such as the standard Gibbs
free energy ΔG° (kJ mol−1), the standard enthalpy (ΔH°), and the
standard entropy (ΔS°) for biosorption of Ni(II) onto MOB were
calculated using the following equations
Eq. (14) can be written as
ΔSB ΔHB
ln K = − ð16Þ
R RT
The values of ΔG° were calculated from Eq. (14). Reciprocal of
temperature (1/T) was plotted against ln k and a straight line was
obtained as shown in Fig. 8. The values of ΔH° and ΔS° calculated from
the slope and intercept of the straight line were summarized in
Table 5. The negative value of ΔG° indicates the feasibility of the
process and indicated the spontaneous nature of the adsorption. The
values of ΔG° were found to increase as temperature increased,
indicating more driving force and hence resulting in higher biosorp-
tion capacity. The value of ΔH° was positive, indicating the
ð12Þ endothermic nature of the biosorption of Ni(II) onto MOB. In addition,
the positive values of ΔS° shows an affinity of biosorbent and the
ð13Þ increasing randomness at the solid-solution interface during the
biosorption of Ni(II) on the bark [34].
3.11. Biosorption of Ni(II) in presence of other cations
For the determination of interference caused by the presence of
other cations, Na+ K+, Ca2+ and Mg2+ were added to the Ni(II)
solution. These elements are major constituents of saline and hard
waters and are likely to be encountered in most industrial effluents
[10] from which toxic metals are intended to be removed by
biosorption. The presence of Na+ and K+ had no antagonistic effect
on sorption of Ni(II) by MOB biomass as shown in Fig. 9. The effect of
Ca2+ and Mg2+ was only marginal. These observations pointed to a
significant advantage in favor of MOB in an industrial water treatment
plant over the ion exchanger resin system since the binding of Ca2+
and Mg2+ with these limits their application for the sorption of other
metals, since particularly both these divalent cations are present in
high concentrations in wastewaters.

ΔGB = −RT ln K ð14Þ 2.4

−1
where K (L g ) an equilibrium constant obtained by multiplying the
Langmuir constants qm and KL [33], R is the universal gas constant 2.2
(8.314 × 10−3 kJ mol−1 K−1) and T is the absolute temperature (K).
The enthalpy (ΔH°) and entropy (ΔS°) parameters were estimated
ln K

from the following equation: 2.0

ΔGB = ΔH B−TΔSB ð15Þ

1.8

Table 4
Chi-square and correlation coefficient for isotherms at different temperatures.
1.6
T Langmuir Freundlich Dubinin– Temkin
(K) Raduskovich
0.00310 0.00315 0.00320 0.00325 0.00330
R2 χ2 R2 χ2 R2 χ2 R2 χ2
1/T (K-1)
303 0.9972 0.9843 0.9507 3.8117 0.9312 13.0593 0.9650 2.7029
313 0.9970 1.1920 0.9453 5.0504 0.9308 15.6236 0.9607 3.6256
Fig. 8. Plot of ln K vs 1/T for the estimation of thermodynamic parameters for biosorption of
323 0.9994 2.0626 0.9395 6.0889 0.9655 16.5379 0.9775 4.2588
Ni(II) onto MOB.
156 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157

Table 5
Thermodynamic parameters of the Ni(II) biosorption on the MOB at different 100
temperatures.

T (K) −ΔG° ΔS° ΔH° R2

(KJ mol−1) (J mol−1 K−1)a (KJ mol−1)a 90

desorption rate %
303 4.89
313 5.39 56.27 12.15 0.9916
323 6.02 80
a
Measured between 303 and 323 K.

70

3.12. Desorption and regeneration studies

In order to investigate desorption of metal ion from metal loaded
MOB, the metal-loaded biosorbent was treated with HCl, which has
been reported as an efficient metal desorbent [35–37]. Desorption
studies were performed with different hydrochloric acid concentra-
tions and the results are shown in Fig. 10. From the results of this
study, with the increasing of hydrochloric acid concentration, the
desorption rate also increased initially, and then become almost
stable. The maximum percentage recovery of Ni(II) was 98.02% with
0.2 M HCl solution.
In biosorption process, to keep the processing cost down and to
open the possibility of recovering the metal(s) extracted from the
liquid phase, it is desirable to regenerate the biosorbent material. In
this study 0.2 M HCl was used as a regenerating agent (or eluent). The
regenerated biosorbent was reused for up to six biosorption–
desorption cycles and the results are illustrated in Fig. 11. An
efficiency of 98.02% recovery of Ni(II) was obtained with 0.2 M HCl
in the first cycle and is therefore suitable for regeneration of
biosorbent. There is a gradual decrease in Ni(II) biosorption with an
increase in the number of cycles. After a sequence of six cycles, the Ni
(II) uptake capacity of the biosorbent was reduced from 98.02% to
92.02%. The lost in the biosorption capacity of the biomass for metal
ions was found to be b6%. This might be due to the ignorable amount
of biomass lost during the biosorption–desorption process. These
results indicate that the MOB could be used repeatedly in Ni(II)
biosorption studies without any detectable loss in the total biosorp-
tion capacity.
3.13. Comparison of nickel removal with different biosorbents
The biosorption capacity of the biosorbent MOB for the removal of
nickel has been compared with those of other biosorbents reported in
literature [38–48] and the values of adsorption capacities (qm) have
been presented in Table 6. The values are based on Langmuir
60
Ni(II)
50
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
HCl Concentration (M)
Fig. 10. Effect of HCl concentration on desorption of Ni(II) from the MOB. Error bars
represent ± S.D.
adsorption capacity. The maximum Ni(II) biosorption by MOB at
optimum pH 6.0 in this study (30.38 mg g−1) was comparable and
found to be higher than many other biosorbents. The economical
success of any biosorption process depends largely on the cost of
biosorbent used. The biosorbent that is used in the present
investigation is easily available waste material; hence the cost of the
biosorbent would be very less compared to ion exchange resins. The
easy availability and cost effectiveness of MOB biomass are additional
advantages, which make it better biosorbent for treatment of nickel
waste waters.
4. Conclusion
The experimental investigation concluded that MOB could be used
as potential sorbent, for the removal of Ni(II) from aqueous solution.
The batch study parameters; pH of solution, biomass concentration,
contact time, and temperature were found to be effective on the
biosorption processes. The kinetic studies revealed that the biosorp-
tion process followed the pseudo-second-order kinetic model. The
maximum biosorption capacity of Ni(II) was 30. 38 mg g−1 at an
optimum pH 6.0. The calculated thermodynamic parameters showed
the feasibility, endothermic and spontaneous nature of the biosorp-
tion of Ni(II) onto MOB biomass. The reusability of the biosorbent was

100
Adsorption Desorption
Na+ 100
K+
Adsorption/Desorption (%)

95 Ca2+
Mg2+
Ni(II) Removal (%)

80

60
90

40

85
20

80 0
0 50 100 150 200 250 300 1 2 3 4 5 6
Concentration (μg mL-1) Cycle number

Fig. 9. Effect of other metal ions on the sorption of Ni(II) by MOB. Error bars represent±S.D. Fig. 11. Six cycles of Ni(II) adsorption–desorption with 0.2 M HCl. Error bars represent±S.D.
 D.H.K. Reddy et al. / Desalination 268 (2011) 150–157 157

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