Water and Environment Journal.

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Biosorption of nickel ions from aqueous solutions by natural and

modified peanut husks: equilibrium and kinetics
Katerina Atkovska Burevska1, Hamdije Memedi2, Kiril Lisichkov1, Stefan Kuvendziev1, Mirko Marinkovski1,
Gordana Ruseska1 & Anita Grozdanov 1
1
Faculty of Technology and Metallurgy, University “Ss. Cyril and Methodius,” RugjerBoskovic 16, Skopje, Macedonia; and 2Faculty of Natural Sciences
and Mathematics, State University of Tetovo, str. Ilindenn.n, Tetovo, Macedonia

Keywords
adsorption; equilibrium; kinetics; natural and
modified peanut husks; Ni(II) ions.
Correspondence
Anita Grozdanov, Faculty of Technology and
Metallurgy, University “Ss. Cyril and
Methodius,” RugjerBoskovic 16, Skopje,
Macedonia.
Email: anita.grozdanov@yahoo.com
doi:10.1111/wej.12325
Abstract
The toxicity and non-biodegradation of heavy metals, as well as their tendency to
accumulate in the soils, water resources and the living organisms, makes them the
significant environmental pollutants. Therefore, the reduction and elimination of
heavy metal ions from aqueous systems is very important from the ecological,
nutritional and environmental reasons. The aim of this study is to investigate
whether the natural peanut husks, an agricultural waste, and their chemically modi-
fied form are capable to remove Ni(II) ions from aqueous solutions using batch
method and to compare their efficiency. The effects of the mass of the natural pea-
nut husks and the initial pH of the solution were studied to find the optimal condi-
tions for maximal removal of Ni(II) ions. MATLAB/Curve Fitting Toolbox was
implemented to determine the adequate adsorption isotherm as well as to opti-
mise the equilibrium state of the investigated systems.

Introduction Adsorption is the most utilised technique in wastewater puri-

The world’s growing population and the global industry
development led to enormous environmental pollution.
Heavy metals are one of the seriously dangerous environ-
mental contaminants. Unlike organic pollutants, heavy metal
ions, once introduced into the environment, cannot be bio-
degraded. As they are toxic, indefinitely persistent in the
environment and can enter the food chain through the water
channels, the water pollution by heavy metals causes many
disease problems such as renal kidney disease, nervous sys-
tem damages, cancer and mental retardation (Mubarak et al.
2014). That is the reason why the heavy metals remediation
from the contaminated water and wastewater is very impor-
tant for environmental protection and public health.
The removal of the toxic metal ions from water is very dif-
ficult task because of the high cost of treatment methods.
The most widely used methods for removing heavy metals
are adsorption, ion exchange, solvent extraction, electroly-
sis, chemical precipitation and membrane processes
(Bakalar et al. 2009; Fu & Wang 2011; Vinodh et al. 2011;
Thakur & Parmar 2013; Rahul 2013).
These processes have significant disadvantages, which
are high-energy requirements, ineffectiveness of elimination
the heavy metal ions dissolved in a large water amounts
at low concentrations and production of toxic sludge.
fication, and there are various materials that can be used as
an appropriate adsorbents for heavy metals elimination
from wastewaters: clay minerals (Liu & Zhou 2010; Ghormi
et al. 2013), activated carbon (Bernard & Jimoh 2013; Koua-
kou et al. 2013) and natural and synthetic zeolites (Anielak &
Schmidt 2011; Shaheen et al. 2012).
Recently, attention has been diverted towards the bioma-
terials which are byproducts or the wastes from large-scale
industrial operations and agricultural waste materials. Their
high efficiency, low cost and regeneration are advantages of
the biomaterials for their use in the effluents treatment, over
the conventional materials. There are a number of materials
that can be successfully applied in the processes of heavy
metal elimination from wastewater: tea waste (Thakur & Par-
mar 2013), coffee waste (Kyzas 2012), rice husks (Chuah
et al. 2005), eggs shell (Park et al. 2007), citrus peels (Ajmal
et al. 2000; Schiewer & Patil 2008), maize cop and husk (Igwe
et al. 2005).
Apart from the above-mentioned biosorbents, peanut
husks, as agricultural and food industry waste, are widely
used in the processes of elimination of heavy metals from
wastewater. Many authors in their articles investigate the
adsorption abilities of natural or modified peanut shells in
the removal of heavy metal ions. Omar et al. (2011) studied

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Biosorption of nickel ions from aqueous solutions
the behaviour of peanut husks in the process of removal of
Cu21 and Zn21 ions. Peanut shells and banana peels as bio-
logical adsorbents for elimination of lead, copper, zinc and
cadmium were analysed by Monisha et al. (2014). Sarifah
et al. (2015) conducted the study to determine the adsorp-
tion ability of peanut shells and tea waste in the removal of
lead (II) ions from aqueous solutions. Xiao-Kun et al. (2014)
proposed green approach using peanut shells as adsorbents
to remove Pb(II) from solutions containing amino acid and
sodium chloride. The adsorption of lead was also examined
by Nordiana & Siti (2013) who used mixture of charcoal and
peanut shell as a low-cost adsorbents. Copper, nickel and
zinc removal by peanut hulls was the main goal of the
research work of Oliveira et al. (2010). Carbon prepared
from peanut husks has been used for the adsorption of
Pb21, Zn21, Ni21 and Cd21 by Ricordel et al. (2001). The
objective of the study of Kermit et al. (2006) was to convert
peanut shells to activated carbon for use in adsorption of
cadmium, copper, lead, nickel and zinc. There are a great
number of studies, which, in order to enhance adsorptive
characteristics of the peanut husks, committed their chemi-
cal, magnetic and thermal modification. Removal of cad-
mium ions from aqueous solutions using chemically
modified peanut shell with ZnCl2 was analysed by Liang &
Zhijun (2014).The results of experiments of Lucia et al. (2016)
show that magnetically modified peanut husks is suitable
material for sorption of Pb21 and Cd21 ions from water solu-
tion. Lucia et al. (2013), also, had investigated the sorption
properties of magnetically modified peanut husks in the
removal of cadmium and zinc ions.
The adsorption properties of natural and chemically modi-
fied peanut husks for removal of nickel ions from water
resources are presented and compared in this study.
Materials and methods
Biomass preparation
The peanut husks, NPH, used as adsorbents for Ni(II) ions,
were collected from local sources. The material was washed
several times with distilled water to remove external dust
particles and dried in an oven at 608C for 24 h. The dried pea-
nut husks were milled in a coffee mill and dried again in an
oven at 608C to constant weight and then stored in a desic-
cator prior to use.
The chemically modified peanut husks, MPH, were pre-
pared by using HNO3 and NaOH. About 20 g of the natural
peanut husks were soaked in 400 mL 0.3M HNO3 at ambient
temperature and stirred at magnetic stirrer, 24 h at 100 rpm.
Then the husks were washed with distilled water several
times and put in an oven for 2 h. After that the material was
soaked in 400 ml 0.1 M NaOH at ambient temperature and
stirred 2 h at 100 rpm. Then they were washed with distilled
2 Water and Environment Journal 00 (2017) 00–00 V
K.A. Burevska et al.
water till the filtrate was neutral, and, at the end, chemically
modified peanut husks were dried at 608C to constant weight
and stored in the desiccator.
Reagents and chemicals
Standard solution of nickel nitrate, Ni(NO3)2 with a concen-
tration of 1000 mg/L was used for preparation of the Ni(II)
solutions with the desired initial concentrations. pH of the
solutions were adjusted using 0.1 M HCl or 0.1 M HNO3 and
0.1 M NaOH. Concentrated HNO3 (65%) was used to prepare
0.3 M HNO3 required for chemical modification. All the
reagents and chemicals used in the experiment were of ana-
lytical grade.
Characterisation methods
A set of standard sieves with the diameter of perforation
from 0.063 mm to 1.00 mm (0.063, 0.125, 0.250, 0.500 and
1.00 mm) were used to determine the particle size distribu-
tion of the investigated materials. Sieve analysis was con-
ducted on 50 g previously dried samples. Scanning electron
microscopy was used for high magnification of the biomate-
rials. The SEM from TESCAN, VEGA3LMU model, was used
for the study of natural and modified peanut husks structure.
For the determination of the point of zero charge, PZC, of
the natural and modified peanut husks, a 0.2 g material was
weight and then transferred to 300-mL Erlenmeyer flasks to
which 100 mL of distilled water, with varying pH (pHinitial)
from 2 to 10 were added. The initial pH was adjusted by add-
ing either HCl or NaOH solution. The Erlenmeyer flasks were
continuously shaken in an atomic shaker with 140 rpm for
24 h at room temperature. Then the suspensions were fil-
tered and pH (pHfinal) of each filtrate was measured.
Adsorption experiment
Adsorption studies were done using the batch adsorption
technique to obtain equilibrium data for different initial Ni(II)
ions concentrations of 0.3, 0.5, 0.6 and 0.7 mg/L for natural
and modified peanut husks. The effect of the amount of natu-
ral peanut husks (0.5, 1.5, 2.5, 3.5, 4.5 and 5.5 g/L) and the
influence of pH (4.5, 5.5, 6.5 and 7.5) were investigated. The
mixtures of biosorbent and Ni(II) solutions were added at lab-
oratory glass reactor with volume of 2 L and stirred using
magnetic stirrer at 400 rpm, at room temperature, for 3 h,
sufficient time to reach equilibrium. The samples were
taken at particular time (5, 10, 20, 30, 60, 90, 120 and 180
min), filtered and the remaining concentrations of Ni(II) ions
in the filtrate were determined using atomic absorption spec-
trophotometer, AAS Perkin Elmer model AA700Exp and UV/
VIS Spectrophotometer Prove 600 (Perkin Elmer, Norwalk,
CT, USA). Experimental data were processed by Langmuir,
Freundlich, Langmuir–Freundlich and Redlich–Peterson
C 2017 CIWEM.
K.A. Burevska et al.
isotherms, by using MATLAB/Curve Fitting Toolbox. To evalu-
ate the kinetics of the adsorption process, the pseudo first-
order and pseudo second-order models were tested to inter-
pret the experimental data.
Results and discussion
Characterisation of the biosorbents
The majority of the composition of peanut husks is fibre (60–
65%) including cellulose and lignin. The composition of the
natural peanut husks is given in Table 1. The results obtained
by sieve analysis are listed in Table 2. The both biosorbents
have the highest percentage of particles with size from
0.500 to 1.000 mm.
Morphological analysis of the natural and modified peanut
husks was done by scanning electron microscopy (SEM) and
characteristic pictures are presented in Figs 1 and 2. Figure 1
shows the structure with surface rough texture and a large
number of pores and cavities. Peanut husks have prolonged slit
and slightly longitudinal shape. Figure 2 shows that after chemi-
cal modification of the peanut husks, new pores and cavities are
opened which will contribute to increase the specific surface
area and will enable improving of the adsorption capacity.
The point of zero charge of an adsorbent surface corre-
sponds to the pH (pHpzc) at which the surface has a net natu-
ral charge. The point of zero charge of the sample is defined
as the pH value of the plateau on the graph of dependence
pHfinal 5f(pHinitial). pHPZC for natural and modified peanut
husks were obtained and are 6.3 and 7.5, respectively. Addi-
tional examination of the impact of pH on the adsorption
effectiveness of the natural peanut husks was conducted, in
order to determine the optimal pH value.
Adsorption studies
The influence of the initial pH of the solution and the effect of
the mass of natural peanut huskson the adsorption of Ni(II)
ions were investigated. In order to perform comparison of
the adsorption properties between natural and modified
peanut husks, the obtained optimal pH value and the dosage
Table 1 Chemical composition of natural peanut husks
Total Total
Component proteins Lignin Cellulose Fibre fats
wt% 7–8 30–35 35–40 60–65 1–2
Table 2 Particle size distribution of natural and modified peanut husks
Fraction (mm)
Biosorbent > 1.000 0.500–1.000
NPH (wt%) 18.95 41.65
MPH (wt%) 17.68 57.80
Water and Environment Journal 00 (2017) 00–00 V
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Biosorption of nickel ions from aqueous solutions
of natural peanut husks will be used for both biosorbents in
further adsorption experiments.
The percentage of removal, %R, of Ni(II) ions was calcu-
lated using the following equation:
%R5
C0 2Ce
 100 (1)
C0
where C0 is the initial metal ion concentration (mg/L) and Ce
is the equilibrium concentration (mg/L).
The adsorbed amount of metal ion, qt [mg/g], was calcu-
lated using the following equation:
ðC0 2Ct ÞV
qt 5 (2)
m
where Ct (mg/L) is the metal concentration at time t, V is the
volume of the solution (L) and m is the mass of the biosorb-
ent (g).
Effect of pH
The pH of the solution is an important variable which con-
trols the adsorption of the metal ions at the solid–water
interface. The influence of pH on the adsorption of Ni(II) ions
onto natural peanut husks was examined at pH 4.5, 5.5, 6.5
and 7.5, conducting the experiment at room temperature,
with constant value of initial metal concentration of 0.5 mg/
L, constant amount of peanut husks of 2.5 g/L, at 400 rpm.
The effect of the pH on the percentage of removal is given in
Fig. 3. It is observed that the percentage of removal
increases with an increase in the pH value of Ni(II) solution
up to 6.5 and then decreased at pH 7.5. These results are in
correlation with the value of the point of zero charge of natu-
ral peanut husks that was determined to be 6.3.
It has been generally reported that in highly acidic
medium, the removal of metal ions is almost negligible and it
increases by increasing the solution pH up to a certain limit
(Nour & Ghadir 2014). The minimum biosorption at low pH is
because of the fact that high concentration and high mobility
of H1 ions lead to preferentially adsorbing hydrogen ions
rather than the metal ions. At higher pH values, the lower
number of H1 and greater number of ligands with negative
charges results in greater metal ions biosorption (Feng et al.
Moisture
2011). Decreased biosorption at higher pH (pH > 6.5 in our
3–5
study) occurs because of the formation of soluble
0.250–0.500 0.125–0.250 0.063–0.125 <0.063
21.18 9.45 4.38 4.00
19.18 4.66 0.70 0.14
3
Biosorption of nickel ions from aqueous solutions
Fig. 1. SEM of natural peanut husk.
Fig. 2. SEM of modified peanut husks.
hydroxylated complexes of the metal ions and their competi-
tion with the active sites, and as a consequence, the reten-
tion decreased (Reddy et al. 2011).
Effect of adsorbent dose
The amount of biosorbent used for the adsorption studies is
an important parameter, which determines the potential of
biosorbent to remove metal ions at a given initial
4 Water and Environment Journal 00 (2017) 00–00 V
K.A. Burevska et al.
Fig. 3. Effect of pH on adsorption of Ni(II) on natural peanut husks.
concentration. The effect of the amount of natural peanut
husks (0.5, 1.5, 2.5, 3.5, 4.5 and 5.5 g/L) on the removal of
Ni(II) was investigated at constant value of initial metal con-
centration of 0.5 mg/L, at room temperature, pH 6.5, at
400 rpm and is given in Fig. 4. It can be observed that on
increasing the adsorbent dose, the percentage of removal of
Ni(II) increases up to a natural peanut husks of 2.5 g/L.
Increasing the adsorbent dose provides greater surface area
and availability of more active sites, thus leading to the
enhancement of metal ions uptake (Kumar & Gaur 2011). At
an amount of adsorbent higher than 2.5 g/l, the incremental
Ni(II) removal becomes very low as the surface Ni(II) concen-
tration and the solution Ni(II) concentration come to equilib-
rium with each other. The percentage of removal of Ni(II)
increases from 38% to 52% with an increase of the adsorbent
dose from 0.5 to 5.5 g/L, respectively. A similar trend of pea-
nut husks dosage effect on metal ions biosorption was
reported by many authors (Nordiana & Siti 2013; Ossman
et al. 2014; Sarifah et al. 2015).
Effect of initial metal ion concentration
Further adsorption experiments, for natural and modified
peanut husks, were conducted at constant room tempera-
ture, pH of the solution 6.5, with an amount of biosorbents
of 2.5 g/L and different initial metal ion concentrations of 0.3,
0.5, 0.6 and 0.7 mg/L. The effects of the initial concentration
on the percentage of removal for natural and modified pea-
nut husks, as well as their comparison, are shown in Fig. 5. It
can be seen from the figure that the removal percentage
decreases with the increase in initial Ni(II) ions concentra-
tion. At lowest initial metal ion concentration of 0.3 mg/L,
the percentage of removal is 57% after which it decreases
gradually to 53%, 40% and 38% as the initial concentration of
Ni(II) increases at 0.5, 0.6 and 0.7 mg/L, for natural peanut
husks and for modified adsorbent the removal percentage
decreases from 77% to 68%, 57% and 53% as the initial con-
centration of Ni(II) ions increases. This happens because at
lower initial metal ion concentrations, sufficient adsorption
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K.A. Burevska et al. Biosorption of nickel ions from aqueous solutions

Fig. 4. Effect of adsorbent dose on adsorption of Ni(II) on natural

peanut husks.
Fig. 6. Dependence of adsorbed amount of Ni(II) from time of
adsorption for natural peanut husks.

Fig. 5. Effect of initial concentration on adsorption of Ni(II) on natural

and modified peanut husks.
sites are available for adsorption, whereas at higher concen-
trations, more ions are left un-adsorbed in the solution
because of the saturation of the adsorption sites. Other
researchers obtained the similar results on the impact of ini-
tial metal ion concentration on the percentage of removal,
using peanut husks as biosorbents (Omar et al. 2011; Ugwe-
kar & Lakhawat 2012). Figure 5 also shows that the modified
peanut husks, as expected, are more effective in the Ni(II)
removal than natural peanut husks, at the same operating
conditions.
Effect of contact time
The dependence of adsorbed amount of Ni(II) ions from time
of adsorption for natural and modified peanut husks for vari-
ous initial concentrations of metal ions are given in Figs 6
and 7, respectively. The experiment was conducted using
2.5 g/L natural or modified peanut husks, at 2 L of Ni(II) solu-
tions with different initial concentration, at pH 6.5, room
Fig. 7. Dependence of adsorbed amount of Ni(II) from time of
adsorption for modified peanut husks.
temperature and 400 rpm. The samples were taken at partic-
ular time (5, 10, 20, 30, 60, 90, 120, 150 and 180 min), filtered
and filtrates were collected for analysis and the remaining
Ni(II) concentration was determined. As shown in figures,
biosorption of Ni(II) ions on the adsorbents increased with
an increase of contact time. It can be seen that the adsorp-
tion equilibriums were attained after 60–90 min of magnetic
stirring for Ni(II) concentrations of 0.5, 0.6 and 0.7 mg/L and
it took 120 min to achieve equilibrium at the lowest initial
concentration for natural peanut husks, while the shorter
time was required, 30–60 min, to reach steady state for all
concentrations, using modified peanut husks.
Adsorption isotherm studies
Equilibrium studies that give the capacity of the adsorbent
and the equilibrium relationships between adsorbent and

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Biosorption of nickel ions from aqueous solutions K.A. Burevska et al.

adsorbate are described by adsorption isotherms. The

adsorption isotherms are essential data source to design,
understand and optimise the biosorption process.
Experimental data were processed by the four most com-
monly used isotherms: Langmuir Freundlich, Langmuir–
Freundlich and Redlich–Peterson, by using the MATLAB/
Curve Fitting Toolbox. The correct choice of the equilibrium
isotherm is an important segment for determining the maxi-
mum capacity of the adsorbent for the investigated adsorb-
ate and for modelling the kinetics and dynamics of
adsorption (Shaban et al. 2016)

Langmuir isotherm
The Langmuir adsorption isotherm is valid for monolayer
sorption onto a surface with a finite number of identical sites Fig. 8. Modelling of the experimental data for the system Ni(II) –
natural peanut husks
(Melichiva & Hromada 2013) and it can be defined according
to the following equation:
qm  KL  Ce
qe 5 (3)
11KL  Ce
where qe (mg/g) is the adsorbed amount of metal ion at equi-
librium, Ce (mg/L) is the equilibrium metal ion concentration,
qm (mg/g) is the maximum adsorption capacity and KL (L/mg)
is the Langmuir equilibrium constant related to the affinity to
the binding site.

Freundlich isotherm
Freundlich isotherm is used for modelling the adsorption on
heterogeneous surfaces and is applicable to both monolayer
and multilayer adsorption. The Freundlich equation is
expressed as
qe 5KF  Ce 1=n
where KF (L/g) is the Freundlich constant related to the
adsorption capacity and n is an empirical parameter related
to the intensity of adsorption.
Langmuir–Freundlich isotherm
Langmuir–Freundlich isotherm is derived from the limiting
behaviour of the Langmuir and Freundlich isotherms. At low
adsorbate concentrations, it reduces to Freundlich, while at
high concentrations, it predicts a monolayer adsorption
characteristic of the Langmuir isotherm (Foo & Hameed
2010). The Langmuir–Freundlich equation is given below
qm  KC  Ce 1=n
qe 5
11KC  Ce 1=n
where KC (L/mg) is the Langmuir–Freundlich equilibrium
constant.
Fig. 9. Modelling of the experimental data for the system Ni(II) –
modified peanut husks.
(4)
Redlich–Peterson isotherm
Redlich–Peterson isotherm is a three-parameter empirical
adsorption model, Eq. (6), that incorporates elements from
both Langmuir and Freundlich isotherms (Foo & Hameed 2010)
KRP  Ce
qe 5 (6)
11A  Ce b
where KRP (L/g) is the Redlich–Peterson constant determined
via trails and errors to obtain the maximum regression coeffi-
cient or by using some fitting model, A (L/mg) and b are
parameters of Redlich–Peterson isotherm.
The modelling of the experimental data for the investigated
systems applying these four models is given in Figs 8 and 9.
(5)
Table 3 contains the data of model parameters of the
applied adsorption isotherms as well as the coefficients of
correlation (R2) for the adsorption of Ni(II) ions on natural
and modified peanut husks.

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K.A. Burevska et al. Biosorption of nickel ions from aqueous solutions

The results for maximum adsorption capacities, qm, from and Freundlich parameters can be compared with the results
Langmuir and Langmuir–Freundlich isotherms and Freudlich from a few researchers who have also applied peanut husks
constants, KF, show that modified peanut husks have higher for Ni(II) adsorption (Periasamy & Namasivayam 1995; Ricordel
adsorption capacity than natural peanut husks. This confirms et al. 2001; Kermit et al. 2006). The high values of the coeffi-
the conclusion reached earlier on higher efficiency of the modi- cients of correlation for natural peanut husks (R2>0.99) reveal
fied peanut husks that showed a greater percentage of that experimental results correspond to good to all four uti-
removal of Ni(II) ions than natural peanut husks at the same lised isotherm models. The modified peanut husks have high
experimental conditions. The obtained values for Langmuir values of the correlation coefficients (R2>0.99) for Langmuir,
Langmuir–Freundlich and Redlich–Peterson isotherms, while
Table 3 Parameters and correlation coefficients of equilibrium Freundlich isotherm shows a little bit less corresponding to
isotherm models for Ni(II) adsorption on natural and modified peanut the experimental data with a coefficient of correlation 0.9846.
husks
Parameters and Biosorbent Kinetic studies
correlation
Isotherm coefficients NPH MPH On the purpose of investigating the mechanism of biosorp-
tion and its potential rate-controlling steps that include mass
Langmuir qm (mg/g) 0.1273 0.1729
KL (l/mg) 8.483 17.58 transport and chemical reaction processes, kinetic models
R2 0.9984 0.9921 have been exploited to test the experimental data. To evalu-
Freundlich KF (l/g) 0.1369 0.2026 ate the kinetics of the adsorption process, the pseudo first-
N 2.88 3.69 order and pseudo second-order models were applied to
R2 0.9974 0.9846 interpret the experimental data. The working conditions for
Langmuir–Freundlich qm (mg/g) 0.1287 0.1473
the kinetic experiments are the same as mentioned above.
KC (l/mg) 7.954 519.5
n 1.02 0.46
R2 0.9984 0.9961 Pseudo first-order kinetics
Redlich–Peterson KRP (l/g) 1.161 1.970 The pseudo first-order equation (Lagergren’s equation)
A (l/mg) 8.982 14.540
describes adsorption in solid–liquid systems based on the
b 0.9635 1.282
R2 0.9984 0.9947
sorption capacity of solids (Ho 2004). The linear form of
pseudo first-order model can be expressed as

ln ðqe 2qt Þ5ln qe 2k1 t (7)

where k1 is the pseudo first-order rate constant (per min).

Fig. 10. Pseudo first-order model for Ni(II) adsorption on natural and
modified peanut husks.
k1 and qe, for initial Ni(II) ion concentration of 0.5 mg/L for
both biosorbents were calculated using the slope and inter-
cept of the plots of ln(qe2qt) versus t, Fig. 10. Kinetic parame-
ters for pseudo first-order and pseudo second-order models
and coefficients of correlation, R2, for the Ni(II) biosorption on
the natural and modified peanut husks are listed in Table 4.
As shown in Fig. 10 and Table 4, the correlation coeffi-
cients for the pseudo first-order kinetic model, for natural
and modified peanut husks, were low. Also the calculated qe
values differ a lot from the experimentally observed equilib-
rium adsorptions, for both biosorbents. This suggests that
the pseudo first-order model is not suitable to explain the
kinetic sorption of the Ni(II) ions on natural and modified pea-
nut husks.

Table 4 Adsorption kinetic model rate parameters for Ni(II) adsorption on natural and modified peanut husks
Pseudo first-order Pseudo second-order
2
Biosorbent qe,exp (mg/g) qe,cal. (mg/g) k1 (min 21
) R qe,cal. (mg/g) k2 (g/mgmin) h (mg/gmin) R2
Natural peanut husks 0.116 0.038 0.014 0.632 0.111 46.5 0.573 0.998
Modified peanut husks 0.136 0.043 0.009 0.365 0.123 51.1 0.773 0.996

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Biosorption of nickel ions from aqueous solutions
Fig. 11. Pseudo second-order model for Ni(II) adsorption on natural
and modified peanut husks.
Pseudo second-order kinetics
The pseudo second-order rate expression, which has been
applied for analysing chemisorption kinetics from liquid solu-
tions (Ho 2006), is linearly expressed as
t 1 1 References
5 1 t (8)
qt k2 qe 2 qe
where k2 is the rate constant for pseudo second-order
adsorption (g/mgmin) and k2q2e or h (mg/gmin) is the initial
adsorption rate.
Pseudo second-order adsorption parameters qe, cal. and
k2 in Eq. (8) were determined by plotting t/qt versus t, Fig. 11
and Table 4.
The linearity of the plots, Fig. 11, confirmed by high values
of the coefficients of correlation, Table 4, reveal that experi-
mental results are in good agreement with the pseudo
second-order kinetic model. The calculated qe values also
matched well with the experimental data for both applied
adsorbents. This indicates that nickel adsorption on natural
and modified peanut husks followed pseudo second-order
kinetics and that chemisorption is the rate-limiting step. Simi-
lar trends have been reported for the adsorption of Ni(II)
ions from aqueous solutions using other biosorbents (Hanif
et al. 2007; Zafar et al. 2007; Padmavathy 2008).
Conclusion
(1) In this study, the biosorption of Ni(II) on natural and modi-
fied peanut husks was investigated. The SEM image shows
that modification of peanut husks lead to increase the surface
area and hence improving the adsorption capacity. The effects
of pH and dose of natural peanut husks were examined and it
was found that maximum removal is obtained at pH of the
solution 6.5 and with dosage of biosorbent of 2.5 g/L.
8 Water and Environment Journal 00 (2017) 00–00 V
K.A. Burevska et al.
(2) The percentage of removal, for all initial Ni(II) ions con-
centrations, were higher for modified than natural peanut
husks. The Langmuir, Freundlich, Langmuir–Freundlich and
Redlich–Peterson isotherms were applied to study equilib-
rium data and all models indicate good correspondence to
the experimental results for natural peanut husks, and for
modified peanut husks only Freundlich isotherm does not fit
well to the experimental data.
(3) The sorption kinetics of Ni(II) onto natural and modified
peanut husks could be represented by the pseudo second-
order kinetic model. It can be concluded that natural peanut
husks, an agricultural waste, could be effectively used as
low-cost adsorbent for the removal of nickel ions from aque-
ous solutions, and their chemical modification enhances the
adsorption efficiency. The process of biosorption requires
further investigation in the direction of modelling, regenera-
tion of biosorbents and recovery of metal ions.
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