Ecological Engineering 95 (2016) 101–111

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Ecological Engineering
journal homepage: www.elsevier.com/locate/ecoleng

Removal of nitrate from aqueous solution by modified sugarcane

bagasse biochar
Laleh Divband Hafshejani a,∗ , Abdolrahim Hooshmand a , Abd Ali Naseri a ,
Amir Soltani Mohammadi a , Fariborz Abbasi b , Amit Bhatnagar c,∗
a
Department of Irrigation and Drainage Engineering, Faculty of Water Sciences Engineering, Shahid Chamran University of Ahvaz, Khuzestan, Iran
b
Agricultural Engineering Research Institute (AERI), Agricultural Research, Education and Extension Organization (AREEO), Karaj, Iran
c
Department of Environmental and Biological Sciences, University of Eastern Finland, P.O. Box 1627, FI-70211 Kuopio, Finland

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

Article history: In the present study, chemically modified biochar (developed from sugarcane bagasse) was used for
Received 17 March 2016 the nitrate removal from aqueous solution. The physico-chemical properties of modified biochar such as
Received in revised form 9 May 2016 morphology, surface functional groups, elemental composition, cation exchange capacity, anion exchange
Accepted 15 June 2016
capacity and surface area were analyzed. The effects of various operational parameters such as solution
pH, adsorbent dosage, contact time, initial concentration of nitrate, co-existing anions and temperature
Keywords:
were examined on nitrate adsorption by modified biochar. The experimental data were fitted to dif-
Adsorption
ferent adsorption kinetic models (pseudo-first-order, pseudo-second-order, intraparticle diffusion and
Modification
Biochar
Avrami models) and adsorption isotherms models (Langmuir, Freundlich, Sips and Dubinin–Raduskovich
Nitrate removal models). The obtained results showed that the maximum percentage of nitrate adsorption attained at
Sugarcane bagasse equilibrium pH 4.64, after 60 min of contact time and with an adsorbent dose of 2 g L−1 . In competing
anions experiments, carbonate and chloride ions have shown maximum and minimum influence on
the adsorption of nitrate by modified biochar sugarcane bagasse. Pseudo-second-order kinetic model
and Langmuir isotherm model showed the best fit to the experimental adsorption data. The maximum
adsorption capacity of modified biochar for nitrate removal was found to be 28.21 mg g−1 . The values of
H◦ , G◦ and S◦ indicated that the nature of adsorption was endothermic, spontaneous and feasible.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction sis, ion exchange, biological denitrification, chemical denitrification

Contamination of water resources by nitrate has become an
important problem globally in recent decades. The wide use of
fertilizers in agriculture is one of the major sources of nitrate pol-
lution. Nitrate ion is highly soluble in water and cannot bind well
with the soil particles and as a result, nitrate ions can easily enter
into the groundwater and surface water (Bhatnagar et al., 2010).
Increasing concentration of nitrate in drinking water can cause
harmful effect on human health especially in infant, such as blue-
baby syndrome (Bhatnagar et al., 2010; Moradzadeh et al., 2014).
The U.S. Environmental protection Agency (U.S. EPA) has set the
allowable concentration for nitrate as 10 mg L−1 in drinking water.
Different processes have been applied for the removal of nitrate
from water and wastewater, such as reverse osmosis, electrodialy-
∗ Corresponding authors.
E-mail addresses: mdivband@gmail.com (L. Divband Hafshejani),
amit.bhatnagar@uef.fi (A. Bhatnagar).
and adsorption (Bhatnagar and Sillanpää, 2011). However, some
disadvantages in these methods have been reported in the liter-
ature, for example, ion exchange requires disposal of waste brine
and renewal of costly ion exchange resins, the electrodes are eas-
ily inactive in electrochemical reduction, reverse osmosis has high
operational cost, catalytic reduction could produce the hazardous
by-products such as nitrite and ammonia and biological processes
are in need of addition of carbon source and disposal of large
amounts of biomass waste (Hu et al., 2015; Mukherjee and De,
2014). Among several methods, adsorption has been suggested as
one of the most effective methods (Olgun et al., 2013; Xu et al.,
2013). The adsorption process may be even more encouraging
when natural or agro-industrial wastes are utilized as adsorbents
because these are renewable, low cost, highly available, and in
many cases, their disposal pose a serious environmental problem.
In addition, these materials can be converted into high value-
added adsorbents e.g., biochar or activated carbons, making them
a cleaner source and a highly effective material for environmen-
tal applications (removal of pollutants from air, soil and water)

http://dx.doi.org/10.1016/j.ecoleng.2016.06.035
0925-8574/© 2016 Elsevier B.V. All rights reserved.
102 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
(Mohamad Nor et al., 2013). Numerous materials have been used
for the adsorption of nitrate from water such as sugarcane bagasse,
rice hull, zeolite, chitosan, clays, slag and fly ash (Bhatnagar and
Sillanpää, 2011).
In recent years, the use of biochar in many environmental appli-
cations has gained wide attention (Cheng et al., 2016; Li et al.,
2016; Miller-Robbie et al., 2015; Mohammadi et al., 2016; Peng
et al., 2016; Trakal et al., 2016; Zhang and Wang, 2016). Agricultural
wastes have been preferred for the production of biochar because
these are available abundantly, free of cost and are non-toxic.
Use of agricultural wastes as feedstocks for biochar production
can improve the waste management and protect the environment
(Ding et al., 2016; Tan et al., 2015). Biochar is produced from the
biomass pyrolysis under limited or in absence of oxygen conditions
(Chintala et al., 2013). Due to its porous structure, biochar has been
used in many studies as an impressive adsorbent to remove differ-
ent pollutants from aqueous solution. The production of biochar,
in comparison with activated carbon, is fast, cheaper and simple
(Ahmad et al., 2012; Tan et al., 2015). Furthermore, some biochars
have shown better adsorption capacity than commercial activated
carbons for the removal of toxic pollutants (Tan et al., 2015). Some
researchers have reported that biochar after adsorption may con-
tain a lot of nutrients such as, nitrate, ammonium and phosphate.
Therefore, it can also be used as fertilizer for increasing the soil
fertility (Yao et al., 2013; Yao et al., 2011). Also, biochar is rich in
carbon and after adsorption, it can be applied to soil for carbon
sequestration (Fornes et al., 2015; Xiang et al., 2015).
It has been reported by various researchers that adsorption
capacity of unmodified adsorbents is low for different pollutants
as compared to the modified adsorbents (Bhatnagar et al., 2013;
Chintala et al., 2013; Xu et al., 2010). Various physical or chemical
modification methods have been found to improve the perfor-
mance of adsorbents (Bhatnagar and Sillanpää, 2011; Chintala et al.,
2013). Also, results of a previous study showed that unmodified
adsorbents were converted into anion exchangers after reaction
with epichlorohydrin and dimethylamine in the presence of N,N-
dimethylformamide (DMF) and pyridine as catalyst (Orlando et al.,
2002). The results of previous studies have also shown that adsorp-
tion rate of modified adsorbents is higher than unmodified ones
(Iakovleva et al., 2015; Rangabhashiyam and Selvaraju, 2015).
In the present work, the potential of modified sugarcane bagasse
biochar has been examined for the removal of nitrate from aque-
ous solution under batch conditions. One of the positive aspects of
the study is the possibility of using a residue of agribusiness, gen-
erated in large quantities worldwide, with little or no use, for the
removal of nitrate from aqueous solution. The aim of this study
was to assess the parameters that influence the nitrate adsorp-
tion process using modified biochar as an adsorbent, obtained
from sugar cane bagasse. Physico-chemical properties of modi-
fied biochar were determined using different analytical techniques
such as scanning electron microscope (SEM), Fourier transform
infrared (FTIR) and CHNSO analyzer. The effects of different param-
eters such as solution pH, adsorbent dosage, contact time, initial
concentration of nitrate, co-existing (competing) anions and tem-
perature on adsorption capacity of modified biochar toward nitrate
removal were investigated. The equilibrium and kinetic data of
nitrate adsorption were evaluated using adsorption kinetic models
(pseudo-first-order, pseudo-second-order, intraparticle diffusion
and Avrami) and the adsorption isotherm models (Langmuir, Fre-
undlich, Sips and Dubinin–Raduskovich).
2. Materials and methods
2.1. Preparation of modified biochar
The sugarcane bagasse was collected from Amir Kabir sugar fac-
tory of Khuzestan in Iran. Sugarcane bagasse was chosen for this
study because it is produced in large quantities as a waste in sugar
industries. Sugarcane bagasse was air dried and was converted to
small size with electric mills. Air dried material was heated in
a carbonization furnace at five different pyrolysis temperatures
(200–600 ◦ C), with a fixed residence time of 4 h. Biochar yield was
calculated by comparing the weight of obtained biochar to the
weight of sugarcane bagasse (dry basis) used for pyrolysis. Oxidis-
able organic carbon content (OC) was determined by the method of
potassium dichromate oxidation. Loss on ignition (LOI) of resultant
biochar was obtained by heating of produced biochar in a muffle
furnace at 750 ◦ C for 6 h (ASTM method, D-1762-84) (Masto et al.,
2013). Stable organic matter (SOM) was determined by (Eq. (1))
(Masto et al., 2013).
SOM = LOI − (OC × 1.724) (1)
where 1.724 is the factor for converting organic carbon to organic
matter. Stable organic matter yield index (SOMYI) was calculated
by the following equation:
 BY 
SOMYI = × SOM (2)
100
In this study, chemical modification method was selected to
improve the adsorption capacity of biochar according to the
method of Xu et al. (2010). Ten grams of biochar was added
in 6 ml of epichlorohydrin (Merck, Germany) and 5 ml of N, N-
dimethylformamide (Merck, Germany) was further added to it. The
mixture was keep at 85 ◦ C. After 60 min, 2 ml of ethylenediamine
(Merck, Germany) was combined with it and the solution was agi-
tated for 45 min at 85 ◦ C. After this time, 5 ml of 40% trimethylamine
(Merck, Germany) was added and the suspension was shaken for
120 min at 85 ◦ C. For elimination of residual chemicals, the solid
part was washed with 500 ml of distilled water and dried at 60 ◦ C
for 12 h (Xu et al., 2010).
2.2. Characterization of the adsorbent
The morphology of modified biochar was investigated using
a scanning electron microscopy (SEM, Leo 1455 VP model, made
in Germany). The functional groups in unmodified and modified
biochar were analyzed with a Fourier transform infrared spec-
troscopy (FTIR, Spectrum GX, and Perkin-Elmer). The concentration
of different elements (C, H, N, S, O) in modified biochar was deter-
mined by the CHNSO analyzer (vario ELIII- elementar- made in
Germany). Surface area was obtained using methylene blue method
(Kaewprasit et al., 1998). The cation exchange capacity (CEC) and
anion exchange capacity (ACE) were measured by the method
reported elsewhere (Chintala et al., 2013).
2.2.1. Determination of pHpzc of modified biochar
For the determination of pH value at the point of zero charge of
modified biochar, 50 ml 0.1 M NaCl solution was added into a series
of 100 ml capped glass tubes. The initial pH (pHi ) of solutions was
adjusted between 2 and 11 by the addition of 0.1 M HCl or 0.1 M
NaOH. After pH adjustment, 0.05 g modified biochar was added to
the solutions and suspension was shaken with a speed of 120 rpm
at 22 ± 1 ◦ C. After 24 h, the solutions were filtered by 0.45 ␮m cel-
lulose acetate membrane filters (Sartorius AG) and final pH (pHf ) of
the filtrates were measured. The difference between the initial and
final pH values (pH = pHi − pHf ) was plotted versus pHi . The pH at
 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
which pH = 0 is as pH value at the point of zero charge (Hafshejani
et al., 2015; Tangsir et al., 2016).
2.3. Batch adsorption studies
2.3.1. Effect of solution pH
The pH of the solution is an important factor in adsorption
studies as it not only affects surface charges and dissociation of
functional groups of the adsorbent, but also chemical speciation
and diffusion rate of solute (Rahmani et al., 2010). For determi-
nation of the pH effect on the nitrate adsorption by modified
sugarcane bagasse biochar, initial pH of nitrate solutions with
concentration of 50 mg L−1 were adjusted at different pH values
(2–11) by using 0.1 M HCl and 0.1 M NaOH. Then desired amount of
modified sugarcane bagasse biochar (1 g L−1 ) was added to 50 ml
solution. The mixture was shaken at 120 rpm at 22 ± 1 ◦ C. After
24 h, solid phase was separated by using centrifugation (4000 rpm)
for 20 min and then solutions were filtered by 0.45 ␮m cellu-
lose acetate membrane filters (Sartorius AG). Nitrate concentration
in the filtered solution was analyzed immediately by UV spec-
trophotometer (model Hach, DR5000) at wavelength of 220 nm (UV
Screening Method 10049). The amount of nitrate adsorbed per unit
weight of adsorbent (qe in mg g−1 ) was calculated as follows:
(Ci − Ce )V
qe =
m
where Ci and Ce are initial and equilibrium concentrations of nitrate
in solution (mg L−1 ), V is the volume of solution (L) and m is mass
of the modified biochar (g). Reproducibility of the measurements
was determined in triplicate and the average values are reported.
2.3.2. Effect of adsorbent dosage
The effect of adsorbent dosage on nitrate adsorption was stud-
ied by adjusting the solution pH at optimum (pH 4.64) with an
initial nitrate concentration of 50 mg L−1 and by adding the vary-
ing adsorbent dosage ranging from 1 to 40 g L−1 . The mixtures
were shaken with a speed of 120 rpm using a shaking assembly at
22 ± 1 ◦ C for 24 h. Then solid phase was separated by using centrifu-
gation (4000 rpm) for 20 min and then solutions were filtered by
0.45 ␮m cellulose acetate membrane filters (Sartorius AG). Resid-
ual nitrate concentration in the filtered solution was determined
by spectrophotometer. The amount of nitrate adsorbed per unit
weight of adsorbent (qe in mg g−1 ) was calculated by Eq. (3).
2.3.3. Adsorption kinetic studies
Kinetic adsorption experiments were conducted by a series of
solutions with initial nitrate concentration of 50 mg L−1 , optimum
equilibrium pH of 4.64, optimum adsorbent dosage of 2 g L−1 , at
22 ± 1 ◦ C by varying the contact time between 5–180 min with
agitation speed of 120 rpm. After completing predetermined time
interval, solids phase was removed from the solutions by filtration
using 0.45 ␮m cellulose acetate membrane filters (Sartorius AG)
and nitrate concentrations were analyzed by spectrophotometer.
The amount of nitrate adsorbed per unit weight of adsorbent (qe
in mg g−1 ) was calculated by Eq. (3). Rate of adsorption can be pre-
dicted by adsorption kinetic parameters. This factor is important
and useful in predicting the adsorption mechanism (Rahmani et al.,
2010). The dynamics of the nitrate adsorption process by modi-
fied biochar was evaluated with the pseudo-first-order (Eq. (4))
(Lagergren, 1898), pseudo-second-order (Eq. (5)) (Ho and McKay,
1999), intraparticle diffusion (Eq. (6)) (Weber and Morris, 1963)
and Avrami (Eq. (7)) (Avrami, 1939) kinetic models. The non-linear
forms of these models are given below:
qt = qe (1 − e−k1 t )
103
q2e k2 t
qt = (5)
1 + qe k2 t
qt = Kp t ⁄2 + I
1
(6)
 nAV 
qt = qe 1 − e(−kAV t) (7)
where qt and qe and are the amounts of nitrate ions adsorbed on the
modified biochar (mg g−1 ) at time t and equilibrium time, respec-
tively; k1 is the rate constant of the pseudo-first-order (min−1 ), k2
is the rate constant of the pseudo-second-order (g mg−1 min−1 ); Kp
is the intraparticle diffusion rate constant (mg g−1 min1/2 ) and I
(mg g−1 ) is the intercept of intraparticle diffusion model and kAV
(min−1 ) and nAV are the exponential of the Avrami model.
2.3.4. Effect of co-existing (competing) anions
The adsorption capacity of modified biochar for the nitrate
adsorption in the presence of co-existing (competing) anions (e.g.,
phosphate, carbonate, sulfate and chloride), which are commonly
present in real ground water, was also investigated. Experiments
were conducted by adding varying concentrations of co-existing
anions (10, 50 and 100 and 200 mg L−1 ) in nitrate solution (fixed
nitrate concentration of 50 mg L−1 ), optimum pH, and an optimum
adsorbent dosage of 2 g L−1 . The mixtures were shaken with a speed
of 120 rpm at 22 ± 1 ◦ C for 60 min. Then solid phase was separated
(3) from solution by filtration using 0.45 ␮m cellulose acetate mem-
brane filters (Sartorius AG) and residual nitrate concentration in
the filtered solution was analyzed. The amount of nitrate adsorbed
per unit weight of adsorbent (qe in mg g−1 ) was calculated by Eq.
(3).
2.3.5. Adsorption equilibrium studies
Equilibrium adsorption experiments were conducted by tak-
ing a series of solutions with initial nitrate concentrations of
1–100 mg L−1 , optimum adsorbent dosage of 2 g L−1 , at 22 ± 1 ◦ C
with an optimum solution pH (equilibrium pH 4.64). The mix-
tures were shaken at 120 rpm and after equilibration, samples were
filtered by 0.45 ␮m cellulose acetate membrane filters (Sartorius
AG) and were analyzed by spectrophotometer for the determi-
nation of residual nitrate concentration. Equilibrium data are the
important requirements for the successful modeling of adsorption
systems. There are different theoretical and empirical relation-
ships for the modeling of adsorption process (Rahmani et al.,
2010). In this study, Langmuir (Eq. (8)) (Langmuir, 1916), Fre-
undlich (Eq. (9)) (Freundlich, 1909), Sips (Eq. (10)) (Sips, 1948) and
Dubinin–Radushkevich (Eq. (11)) (McEnaney, 1987) models were
applied to describe the adsorption process.
(bCe qm )
qe = (8)
(1 + bCe )
1
qe = KF Cen (9)
1/n
(qm Ks Ce )
qe = (10)
1/n
(1 + Ks Ce )
   2 
1
qe = qm exp −ˇ RTln 1 + (11)
ce
where qe (mg g−1 ) is the equilibrium adsorption capacity of modi-
fied biochar, Ce (mg L−1 ) is the equilibrium concentration of nitrate
in solution, qm (mg g−1 ) is the maximum adsorption capacity of
modified biochar; K (mg g−1 ) (L mg−1 )1/n and n (g L−1 ) are the
Freundlich equilibrium constant and exponent, respectively; b
(L mg−1 ) in Langmuir model is related to the energy of adsorption
(L mg−1 ), Ks in Sips model is the affinity constant for adsorption; R
(4) is the universal gas constant (8.314 kJ K−1 mol−1 ), T is the absolute
104 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111

temperature (K), ␤ is activity coefficient related to mean adsorp- Table 1

Effect of different temperatures on the properties of sugarcane bagasse biochar.
tion energy per mole. Modeling calculations were conducted using
Microsoft Office Excel 2007. Isotherm parameters were determined Temperature (◦ C) 200 300 400 500 600
by minimizing the Sum of the Squares of the Errors (ERRSQ) func- Biochar yield (%) 29.3 26.1 17.1 15.2 12
tion across the concentration range studied: Oxidizable organic carbon content (%) 41.4 34 29.5 28.9 21
Loss on ignition (%) 89.1 86 77.3 74.8 59.3

n
Stable organic matters (%) 17.7 27.4 26.5 24.9 23
2
ERRSQ = (Oi − Pi ) (12) Stable organic matter yield index 5.2 7.2 4.6 3.8 2.8
i=1

where: Table 2
n: number of observations. Elemental contents of sugarcane bagasse biochar produced at 300 ◦ C after modifi-
Oi : ith value of the observed measurement. cation (percentage).
Pi : ith value of the predicted measurement. Elemental C H N S O

Sugarcane bagasse biochar 56.2 3.8 4.1 0.8 21.1

2.3.6. Thermodynamic studies Sugarcane bagasse 43.1 6.2 0.3 0.2 39.4
The effect of temperature on nitrate adsorption by modified
biochar was studied at different temperatures (viz., 10 ◦ C, room
temperature (22 ◦ C) and 30 ◦ C). Thermodynamics parameters were high amounts by decomposing the biomass (Mašek et al., 2013).
calculated using the following equations: Oxidizable organic carbon content (OC) and loss on ignition (LOI)
decreased with increasing pyrolysis temperature, which is due to
G0 = −RTlnK (13)
increase in ash content in the biochar at high pyrolysis tempera-
K1 H 0
1 1

tures. A comparison between the stable organic matters (SOM) at
ln = − (14)
K2 R T1 T2 different temperatures showed that SOM increased with increase
in pyrolysis temperature up to 300 ◦ C, thereafter it decreased which
G0 = H 0 − TS 0 (15)
might be due to the increase in the ash content. The results of the
where G◦
is standard free energy change R is the(kJ mol−1 ), present study showed that maximum stable organic matter yield
universal gas constant (8.314 J K−1 mol−1 ), T is the absolute tem- index (SOMYI) occurred at 300 ◦ C (Table 1). Biochar is a carbon rich
◦
perature (in Kelvin), H is standard enthalpy (kJ mol−1 ), S◦ is material and carbon content can significantly influence the adsorp-
standard entropy (J mol K−1 ), and K is the equilibrium constant,
−1 tion capacity. Thus, the stable organic matter yield index of biochar
related to the Langmuir constant ‘b’ (Eq. (16)). is an important parameter (Chintala et al., 2013; Kumar et al., 2013).
Therefore, biochar produced at 300 ◦ C was selected for the chemi-
K = b × 55.5 (16)
cal modification and nitrate adsorption experiments. The elemental
where the value 55.5 corresponds to the molar concentration of the analyses (CHNSO) of modified sugarcane bagasse biochar are given
solvent (water, in this study). in Table 2.
It was found that carbon was present in higher amounts as
2.4. Error analysis compared to other elements which might be due to the pres-
ence of carbon containing functional groups such as carboxylic.
Two Error functions were used to evaluate the goodness of fit The biochar has been graded into three classes according to car-
of the applied adsorption models (kinetics and isotherms) to the bon content. The class 1 contains 60% carbon or more, class 2
experimental data. possesses between 30 and 60% carbon in biochar and class 3
1. The coefficient of determination (R2 ) contains between 10% and 30% carbon in biochar (Mohan et al.,
n 2 2014). Carbon content (56.2%) in modified sugarcane bagasse
(Oi − Oave ) . (Pi − Pave ) biochar shows that produced biochar is in the upper range of
2
R = n i=1
n (17) class 2. The surface area of modified biochar was determined as
i=1 (Oi
− Oave )2 . i=1 (Pi
− Pave )2
41.67 m2 g−1 using methylene blue method. Also, cation exchange
2. Average relative error (ARE) capacity (CEC) and anion exchange capacity (ACE) were obtained
 as 12.90 cmol kg−1 and 10.21 cmol kg−1 , respectively. SEM pho-
100

n O − P 
i i
ARE =
n Oi
i=1
where Oi and Pi are ith of the observed and predicted value, respec-
tively. Oave and Pave are average of the observed and predicted value
and n is number of observations.
3. Results and discussion
3.1. Characterization of the adsorbent
The properties of biochars produced under different tempera-
tures in this study are listed in Table 1.
It can be seen that the biochar yield decreased as the pyroly-
sis temperature increased. Similar results have also been found by
other researchers where a decrease in biochar yield was observed
at increased pyrolysis temperature (Kumar et al., 2013; Masto et al.,
2013). It can be explained due to the fact that high pyrolysis tem-
perature increases the release of water and volatile compounds in
tographs of modified biochar before and after nitrate adsorption
(18)
are presented in Fig. 1a–b.
SEM image of biochar (before nitrate adsorption) shows
that modified biochar has a porous structure (honeycomb like
structure), which indicates that modified biochar consists a car-
bonaceous skeleton (Ghani et al., 2013). Some tiny fine pores are
also visible in the SEM image of modified biochar (Fig. 1a). After
nitrate adsorption, carbonaceous skeleton was broken and pores
were blocked. Fourier transform infrared spectroscopy is often used
to examine the surface functional groups available on the surface of
adsorbents. Fig. 2 shows FTIR spectrums of modified biochar before
and after nitrate adsorption. The comparison between results of
FTIR spectrum before and after nitrate adsorption shows that wave
numbers and the intensity of some peaks were shifted or sub-
stantially lowered than those before adsorption suggesting the
involvement of some functional groups of biochar in nitrate adsorp-
tion. An absorption band around 3262.48 cm−1 corresponding to
N H groups is shifted to 3331.79 cm−1 after adsorption of nitrate.
This group (N H) has positive charge, which may increase the
 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
Fig. 1. SEM images of modified sugarcane bagasse biochar. (a) Before nitrate adsorp-
tion. (b) After nitrate adsorption.
Fig. 2. FTIR spectra of modified sugarcane bagasse biochar before and after nitrate
adsorption.
105
Fig. 3. pHpzc of modified sugarcane bagasse biochar.
ability of nitrate adsorption with negative charge. The peaks at
1743.52 cm−1 may be attributed to C O stretching vibration, thus
confirms the presence of carbon in biochar structure (Ghani et al.,
2013). The peak at 1505.92 cm−1 in the spectrum shows C C groups
(Kim et al., 2014). The peak at 1306.48 cm−1 may be attributed to
C N groups with positive charge, therefore, it might involve in the
adsorption of nitrate and has shifted to 1270.84 cm−1 after adsorp-
tion (Luo et al., 2014). Peaks at 856.48 cm−1 should correspond to
C H stretching (Chen et al., 2015).
3.2. Point of zero charge (pHpzc)
pHPZC represents the pH at which the net surface charge of the
adsorbent is zero and cation exchange capacity and anion exchange
capacity are equal on adsorbent’s surface (Chintala et al., 2013).
Results of this study (Fig. 3) shows that the pHpzc of biochar is about
5.35. When pH of the solution is lower than the pHpzc, net sur-
face charge of modified biochar is positive due to the adsorption
of excess H+ . In this situation, modified biochar has high ability for
the adsorption of anionic species. Also, when pH of the solution is
higher than the pHpzc, the net surface charge on surface modified
biochar is negative due to desorption of H+ . In this situation, surface
of biochar becomes suitable for desorption of cations.
3.3. Effect of solution pH
Fig. 4 shows the effect of solution pH (initial and final pH) on
adsorption capacity of modified sugarcane bagasse biochar towards
nitrate in the solution with initial concentration of 50 mg L−1 ,
adsorbent dosage of 1 g L−1 and contact time of 24 h. It was observed
that at initial pH 2, nitrate adsorption capacity is 28.3 mg g−1
and with change of initial pH from 3 to 11, final (equilibrium)
pH changes from 4.64 to 9.11 and the adsorption capacity of
modified sugarcane bagasse biochar decreased from 30.7 mg g−1
to 10.3 mg g−1 . Thus, maximum adsorption capacity for nitrate
(30.7 mg g−1 ) was obtained at initial pH 3 (final pH 4.64). It is clear
that by increasing the pH, the adsorption of nitrate decreased. It can
be due to higher competition between nitrate and hydroxide ions
for same sites on adsorbent’s surface (Cengeloglu et al., 2006). Also
at low pH, surface of modified biochar has positive charge due to
protonation reactions, which increased the electrostatic attraction
between modified biochar surface and negatively charged nitrate
ions (Chintala et al., 2013; Demiral and Gündüzoğlu, 2010; Olgun
et al., 2013). Similar results have been reported by other researchers
who reported that adsorption of nitrate by other adsorbents was
106 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
Fig. 4. Effect of solution pH on adsorption capacity of modified sugarcane bagasse
biochar for nitrate adsorption (adsorbent dosage = 1 g L−1 , initial nitrate concentra-
tion = 50 mg L−1 , contact time = 24 h, temperature = 22 ± 1 ◦ C, initial pH = 2-11).
Fig. 5. Effect of adsorbent dosage on adsorption capacity of modified sugar-
cane bagasse biochar for nitrate adsorption (adsorbent dosage = 1–40 g L−1 , initial
nitrate concentration = 50 mg L−1 , contact time = 24 h, temperature = 22 ± 1 ◦ C, initial
pH = 3).
high at acidic pH and decreased at higher pH values (Chintala et al.,
2013; Ganesan et al., 2013; Olgun et al., 2013). Results of this study
(Fig. 3) show that the pHpzc of biochar is about 5.35. Thus, it is rea-
sonable that maximum adsorption of nitrate onto biochar occurred
at final pH 4.64. At pH < 5.35, surface of biochar is positively charged
and due to coulombic attraction, biochar could adsorb negative
charge species like nitrate.
3.4. Effect of adsorbent dosage
Adsorbent dosage is an important factor that determines the
optimum adsorbent dose which is required to remove a definite
amount of pollutants from the solution (Du et al., 2012). In gen-
eral, increase in adsorbent dosage increases adsorption of adsorbate
from the solution which is due to the availability of more active sites
and increase in surface area at higher dosage (Hu et al., 2015; Öztürk
and Bektaş, 2004). Fig. 5 shows the results of nitrate adsorption
efficiency and adsorption capacity of modified sugarcane bagasse
biochar versus different adsorbent dosage in the solution with
initial concentration of 50 mg L−1 , optimum pH (initial pH 3 and
final pH 4.64) and contact time of 24 h. It was evident that with
the increase in adsorbent dosage from 1 to 40 g L−1 , the nitrate
Fig. 6. Effect of contact time on adsorption capacity of modified sugarcane bagasse
biochar for nitrate adsorption (adsorbent dosage = 2 g L−1 , initial nitrate concentra-
tion = 50 mg L−1 , contact time = 5–180 min, temperature = 22 ± 1 ◦ C, initial pH = 3).
adsorption efficiency increased upto 90% and adsorption capac-
ity of modified sugarcane bagasse biochar was decreased. Further
increase in adsorbent dosage beyond 20 g L−1 did not significantly
effect the nitrate adsorption capacity. Similar results were also
reported by other researchers where nitrate adsorption efficiency
from aqueous solution was found to increase up to the optimum
dosage and with further increase in adsorbent dose, the adsorp-
tion efficiency remained constant (Katal et al., 2012; Öztürk and
Bektaş, 2004). Therefore, based on the results of this study, adsor-
bent dosage of 2 g L−1 was selected for further experiments. With
adsorbent dosage of 2 g L−1 , there was a balance between adsorp-
tion capacity and adsorption efficiency and adsorption capacity of
modified sugarcane bagasse biochar towards nitrate was found to
be 18.40 mg g−1 .
3.5. Effect of contact time
The effect of contact time on nitrate adsorption capacity by mod-
ified biochar was conducted with the initial nitrate concentration of
50 mg L−1 , adsorbent dosage 2 g L−1 and at optimum pH. The results
are shown in Fig. 6. It was found that the adsorption capacity of
modified sugarcane bagasse biochar for removing nitrate was rapid
in the beginning stages of contact time. After 15 min, the rate of
adsorption decreases with the time and adsorption process reached
to equilibrium within 60 min. This phenomenon might be due to
the presence of greater number of active sites on modified biochar
for the adsorption of nitrate ions during the initial stages. Similar
results were also reported by other researchers where the nitrate
adsorption was found to increase with increase in contact time
and after reaching to equilibrium time, adsorption remained con-
stant (Ganesan et al., 2013; Olgun et al., 2013; Öztürk and Bektaş,
2004). According to the obtained results, a contact time of 60 min
was chosen for further experiments. The results show that the pro-
cess of nitrate adsorption by modified biochar in this study is faster
than other adsorbents reported/studied by other researchers which
might be due to modification of biochar in this work (Bhatnagar
et al., 2008; Chatterjee et al., 2009).
3.6. Effect of initial nitrate concentration
The effect of initial nitrate concentrations on adsorption capac-
ity of modified sugarcane bagasse biochar was studied by varying
different initial nitrate concentrations in the range of 1–100 mg L−1 ,
 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111 107

Fig. 7. Effect of initial nitrate concentration on adsorption capacity of modi- Fig. 8. Effect of solution temperature on adsorption capacity of modified sugar-
fied sugarcane bagasse biochar for nitrate adsorption (adsorbent dosage = 2 g L−1 , cane bagasse biochar for nitrate adsorption (adsorbent dosage = 2 g L−1 , initial nitrate
initial nitrate concentration = 1–100 mg L−1 , contact time = 60 min, tempera- concentration = 50 mg L−1 , contact time = 60 min, temperature = 10, 22 and 30 ± 1 ◦ C,
ture = 22 ± 1 ◦ C, initial pH = 3). initial pH = 3).

adsorbent dosage of 2 g L−1 , contact time of 60 min and at opti-

mum pH. The results are presented in Fig. 7. It was evident from the
results that with the increase in initial nitrate concentrations from
1 to 80 mg L−1 , adsorption capacity of modified biochar increased
from 0.5 mg g−1 to 23.7 mg g−1 and further increase in initial nitrate
concentration (more than 80 mg L−1 ) did not effect on adsorption
capacity of modified biochar towards nitrate. This phenomenon can
be attributed to the number of available active adsorption sites on
modified biochar for the nitrate adsorption (Milmile et al., 2011;
Olgun et al., 2013). Similar results were also reported by other
researchers where adsorption capacity of adsorbents increased
with increasing initial concentration of nitrate (Milmile et al., 2011;
Olgun et al., 2013).

3.7. Effect of temperature

The adsorption experiments were conducted at different tem-

peratures viz. 10 ◦ C, room temperature (22 ◦ C) and 30 ◦ C to
investigate the effect of temperature on the adsorption capac-
ity of modified biochar for the removal of nitrate with an initial
nitrate concentration of 50 mg L−1 , contact time of 60 min, with
optimum pH and an optimum adsorbent dosage of 2 g L−1 . It is
observed in Fig. 8 that with increase in temperature from 10 ◦ C
to 30 ◦ C, nitrate adsorption capacity increases from 10.9 mg g−1
to 20.1 mg g−1 , which might be due to the increased interaction
between nitrate ions and active site on surface of modified biochar.
Also, these results (increasing adsorption capacity with increasing
temperature) indicate that the adsorption process is endothermic
in nature. Similar results were also reported by other researchers
where the nitrate adsorption capacity was found to increase with
an increase in temperature (Ganesan et al., 2013).
3.8. Effect of co-existing (competing) anions
The effect of co-existing (competing) anions on the nitrate
removal by modified biochar was studied by varying initial con-
centrations of co-existing anions (10, 50, 100 and 200 mg L−1 ) in a
nitrate solution with a constant nitrate concentration of 50 mg L−1 ,
at optimum pH, an optimum adsorbent dosage of 2 g L−1 , contact
time of 60 min at room temperature (22 ◦ C). The results are shown
in Fig. 9. It was found that the adsorption capacity of modified sug-
arcane bagasse biochar towards nitrate was reduced due to the
Fig. 9. Effect of co-existing anions on adsorption capacity of modified sugarcane
bagasse biochar for nitrate adsorption (adsorbent dosage = 2 g L−1 , initial nitrate con-
centration = 50 mg L−1 , initial concentrations of co-existing anions = 0–200 mg L−1 ,
contact time = 60 min, temperature = 22 ± 1 ◦ C, initial pH = 3).
presence of co-existing (phosphate, carbonate, sulfate and chlo-
ride) in the water. The carbonate and chloride ions have shown
maximum and minimum effects on the adsorption of nitrate. It
could be explained by the fact that in the multi element solution,
the electrostatic interaction of co-existing anions with adsorption
sites of modified biochar was much stronger than nitrate ions
species. It has been reported that multivalent anion with higher
charge density was adsorbed more readily than monovalent anion
(Rezaei Kalantary et al., 2015). Similar results have been reported
by other researchers where multivalent and mono charge anions
have shown more and less adsorption trend, respectively (Rezaei
Kalantary et al., 2015; Yang et al., 2015).
3.9. Adsorption kinetics
Study of adsorption kinetics is one of the important parameters
because it provides good information about the reaction path-
way and mechanism of the adsorption process (Xu et al., 2013).
In this study, adsorption kinetics of nitrate ions onto modified
108 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111

Table 3
Kinetic parameters of nitrate adsorption by modified sugarcane bagasse biochar.

Pseudo-first-order qe(exp) (mg g−1 ) k1 (min−1 ) qe(cal) (mg g−1 ) ARE R2

18.44 0.14 17.90 4.61 0.99

Pseudo-second-order qe(exp) (mg g−1 ) k2 (g mg−1 min−1 ) qe(cal) (mg g−1 ) ARE R2
18.44 0.01 19.07 1.15 0.99

Intraparticle diffusion I (mg g−1 ) kP (mg g−1 min−0.5 ) – ARE R2

7.68 1.05 – 12.01 0.81

Avrami qe(exp) (mg g−1 ) kAV (min−1 ) nav qe(cal) (mg g−1 ) ARE R2
18.44 0.09 1.45 17.90 4.76 0.99

Table 4
Isotherm parameters of nitrate adsorption by modified sugarcane bagasse biochar.

Freundlich KF (mg g−1 ) (L mg−1 )1/n n (g L−1 ) – ARE R2

5.82 2.59 – 62.35 0.98

Langmuir b (L mg−1 ) qm (mg g−1 ) RL ARE R2

0.13 28.21 0.07 5.90 0.99

Sips KS (L mg−1 ) qm (mg g−1 ) n ARE R2

0.11 25.94 0.82 7.14 0.99

D–R ␤ qm (mg g−1 ) nav E (kJ mol−1 ) ARE R2

1.81 25.84 0.53 18.41 0.99

biochar of sugarcane bagasse was studied by using pseudo-first-
order, pseudo-second-order, intraparticle diffusion and Avrami
models. Pseudo-first order model assumes that the sorption rate
decreases linearly with the increase of adsorption capacity (Zhen
et al., 2015). The pseudo-second order kinetic model assumes that
the rate-limiting step is the interaction between two reagent par-
ticles and it is usually used to describe a chemical adsorption (Ho
and McKay, 1999; Zhen et al., 2015). In the liquid–solid system, the
intraparticle diffusion model has been used to identify an adsorp-
tion controlled process by diffusion mechanism, where the rate of
adsorption process depends on the diffusion speed of adsorbate
towards adsorbent (Xu et al., 2013). Avrami model is the revision
of kinetic thermal decomposition modeling and Avrami exponen-
tial shows probable variations of the adsorption mechanism that
occur throughout the adsorption process. The results of adsorption
kinetic models are shown in Table 3, Fig. 10a–b. The rapid equilib-
rium process (ca. 60 min) in Fig. 10a shows that nitrate interacts
with the outermost surface of modified sugarcane bagasse biochar
layers. Pseudo-second-order kinetic model with the higher values
of R2 and lower values of RAE (R2 = 0.99 and RAE = 1.15) has pro-
vided a better fit as compared to the other models for adsorption of
nitrate ions by modified biochar (Table 3). A good fit of experimen-
tal data with the pseudo-second-order model would indicate the
chemical adsorption is the rate controlling mechanism (Zhen et al.,
2015). Similar results have also been reported by other researchers
where pseudo-second-order kinetic model has shown good agree-
ment with the experimental data for adsorption of nitrate ions
(Demiral and Gündüzoğlu, 2010; Olgun et al., 2013). In addition
to that, qe(cal) value determined from pseudo-second-order model
agreed very well with the experimental value (qe(exp) ).
In this study, intraparticle diffusion model (qt vs. t1/2 plot)
showed three distinct linear portions (Fig. 10b). This would indicate
the existence of more than one kinetic stage in adsorption process
(Olgun et al., 2013). The overall rate of nitrate adsorption by intra-
particle diffusion model can be described by the following three
steps: (1) the first stage can be indicated to the diffusion of nitrate
ions to the external surface of the modified biochar (fluid trans-
port), (2) the second stage explains the gradual adsorption (film

Table 5
Comparison of the efficiencies of various adsorbents for nitrate removal from water.

Adsorbent qm (mg g−1 ) pH Contact time Reference

Untreated coconut granular activated carbon 1.7 5.5 2h Bhatnagar et al. (2008)
ZnCl2 treated coconut granular activated carbon 10.2 5.5 2h Bhatnagar et al. (2008)
Cross-linked and quaternized chinese reed 7.55 5.8 10 min Namasivayam and Höll (2005)
Chemically modified sugar beet bagasse 9.14–27.55 6.58 – Demiral and Gündüzoğlu (2010)
Commercial activated carbon 1.22 – 10 min Mishra and Patel (2009)
Wheat straw charcoal 1.10 – 10 min Mishra and Patel 2009
Mustard straw charcoal 1.30 – 10 min Mishra and Patel (2009)
Nano-alumina 4 3.1 60 min Bhatnagar et al. (2010)
Modified rice husk 55.55 7 90 min Katal et al. (2012)
Non-activated biochar of corn stover 11.77 4 – Chintala et al. (2013)
Chemically activated biochar of corn stover 13.33 4 – Chintala et al. (2013)
Non-activated biochar of pine wood chips 3.49 4 – Chintala et al. (2013)
Chemically activated biochar of pine wood chips 13.22 4 – Chintala et al. (2013)
Non-activated biochar of switchgrass 11.87 4 – Chintala et al. (2013)
Chemically activated biochar of switchgrass 15.19 4 – Chintala et al. (2013)
Zero-valent iron nanoparticles 20.95 original pH 60 min Wang et al. (2014)
Fe3 O4 nanoparticles 2.435 original pH 10 min Wang et al. (2014)
Poly-o-toluidine zirconium (IV) ethylenediamine 20.09 4.5 90 min Rahman and Khan (2015)
Granular chitosan-Fe3+ complex 8.35 5.9 ± 0.2 90 min Hu et al. (2015)
Sugarcane bagasse 2.13 3 – This study
Biochar of sugarcane bagasse 11.56 3 4h This study
Modified biochar of sugarcane bagasse 28.21 3 60 min This study
 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
Fig. 10. (a) Pseudo-first-order, pseudo-second-order and Avrami kinetic models. (b)
Intraparticle diffusion model for nitrate adsorption by modified sugarcane bagasse
biochar.
Fig. 11. Different isotherm models for nitrate adsorption by modified sugarcane
bagasse biochar.
109
diffusion), (3) the third stage shows the final equilibrium due to
reduction of nitrate concentration in the solution and decrease of
active sites of modified biochar (surface diffusion). As can be seen
from Fig. 10b, the intercept of the plot does not pass through the
origin, which indicates that adsorption kinetics may be controlled
by film diffusion and intra-particle diffusion concurrently. Similar
results have also been reported by other researchers where linear
plots of intra-particle diffusion model do not pass through the ori-
gin for nitrate adsorption (Demiral and Gündüzoğlu, 2010; Olgun
et al., 2013).
3.10. Adsorption isotherms
Adsorption isotherms show the relationship between the
amount adsorbed by a unit weight of adsorbent distribution of
adsorbable solute between the liquid and solid phases at various
equilibrium concentrations and at constant temperature. The main
assumptions for Freundlich adsorption isotherm model are that the
surface containing the adsorption sites is heterogeneous, and each
site can hold several molecule in thickness (multilayer) and the
enthalpy of adsorption decrease with an increase of occupied sites
(Keränen et al., 2015). In other words, Freundlich model expresses
reversible adsorption and is not restricted to the formation of the
monolayer (Zhen et al., 2015). The Langmuir adsorption isotherm
model is based on the assumption that the surface containing
the adsorption sites is homogeneous, and each site can hold at
most one molecule in thickness (monolayer adsorption) (Keränen
et al., 2015). Dubinin–Raduskovich adsorption isotherm model
(D–R isotherm) is based on the assumption that the characteristic
adsorption curve is related to the porous structure of adsorbent (Ho
et al., 2002). This model can be used for determination of nature of
adsorption process (physical or chemical) (Bhatnagar et al., 2010;
Olgun et al., 2013). The Sips adsorption isotherm model is a com-
bination of Langmuir and Freundlich isotherms. At low adsorbate
concentrations, it changes to a Freundlich isotherm and at high
adsorbate concentrations, it reduces to a Langmuir isotherm (Ho
et al., 2002).
The results of Langmuir, Freundlich, Sips and
Dubinin–Raduskovich (D-R) isotherms for the adsorption of
nitrate by modified biochar are presented in Table 4 and Fig. 11.
In this study, Langmuir model with the higher values of coeffi-
cient of determination (R2 ) (0.99) and lower values of average
relative error (ARE) (5.91) presented a better fit for the adsorption
of nitrate as compared to other isotherm models. Therefore, a
good fit of experimental data with the Langmuir model would
indicate monolayer adsorption of nitrate on homogenous surface
of modified biochar of sugarcane bagasse.
Also, it shows that the energy of adsorption for all sites on
surface of modified biochar of sugarcane bagasse is equal. Lang-
muir fitting has been found applicable for nitrate adsorption onto
various adsorbent by other researchers as well (Cengeloglu et al.,
2006; Demiral and Gündüzoğlu, 2010). The value of the maximum
adsorption capacity was found to be 28.21 mg g−1 as calculated by
the Langmuir isotherm model.
The value of separation factor or equilibrium parameter, RL , can
be used to estimate whether adsorption is favorable. It is calculated
from the Langmuir isotherm model parameter as follows:
1
RL = (19)
1 + bc0
According to Table 4, the RL value obtained is 0.07 (between 0
and 1) which indicates that adsorption isotherm is favorable in this
study. The n value in Freundlich model is 2.59 (between 1 and 10)
which indicates favorable adsorption of nitrate by modified sug-
arcane bagasse biochar. The value of mean adsorption energy, E,
is very useful in predicting the type of adsorption and if the value
110 L. Divband Hafshejani et al. / Ecological Engineering 95 (2016) 101–111
Table 6
Thermodynamic parameters for the adsorption of nitrate ions by modified sugarcane
bagasse biochar.
◦ ◦ ◦ onto various materials. J. Hazard. Mater. 112, 155–162.
Temperature (◦ C) G (kJ mol−1 ) H (kJ mol−1 ) S (J mol−1 K−1 )
10 −32.00 54.50 293.09
22
is from 1 to 8 kJ mol−1 , then the adsorption is physical in nature
and if it is from 8 to 16 kJ mol−1 , then the adsorption is chemical in
nature. It can be calculated from Dubinin–Raduskovich parameter
as follows: (Bhatnagar et al., 2010; Olgun et al., 2013):
1 nano-alumina: characterization and sorption studies. Chem. Eng. J. 163,
E=  (20)
2ˇ
The E value obtained in present study is 0.53 kJ mol−1 , indicating
the adsorption of nitrate by modified biochar is physical in nature.
Adsorption capacities of modified sugarcane bagasse biochar
from the present study were compared with other adsorbents stud-
ied by other researchers (Bhatnagar et al., 2008, 2010; Chatterjee
et al., 2009; Chintala et al., 2013; Hassan et al., 2010; Katal et al.,
2012; Mishra and Patel, 2009; Wang et al., 2014) for nitrate removal
(Table 5). The results presented in Table 5 suggest that modified
sugarcane bagasse biochar has comparable adsorption efficiency
for the nitrate removal from aqueous solution.
3.11. Thermodynamic parameters
The knowledge of thermodynamic parameters is of fundamental
importance to test the spontaneous occurrence of a given process
as well as the feasibility of operation at a given temperature (Muthu
Prabhu and Meenakshi, 2014, 2015). In this study, adsorption
experiments were compared at two temperatures (10 ◦ C and 22 ◦ C)
in order to obtain the information on thermodynamic nature of the
adsorption process. The results of thermodynamic parameters are
listed in Table 6. The negative value of G◦ (−32.00 kJ mol−1 ) indi-
cates that the nitrate adsorption process is spontaneous in nature.
The positive value of H◦ (54.50 kJ mol−1 ) shows adsorption of
nitrate by modified biochar bagasse sugarcane is endothermic in
nature. Other researchers have also reported that nitrate adsorp-
tion by different adsorbents is endothermic in nature (Bhatnagar
et al., 2010; Liu and Zhang, 2015). The positive value of S◦
(293.09 J mol−1 K−1 ) indicates the affinity of the modified biochar
for nitrate ions. The G◦ value obtained in this study for nitrate ions
is lower than −10 kJ mol−1 , suggesting that the physical adsorption
occurs during the adsorption process (Liu and Zhang, 2015). These
results are in agreement with the results of Dubinin–Raduskovich
isotherm model.
4. Conclusions
The results of this study suggest that the modified sugarcane
bagasse biochar is an effective adsorbent for the nitrate adsorption
from aqueous solution. Nitrate adsorption efficiency was higher
under acidic pH as compared to basic pH which might be due
to the electrostatic attraction between nitrate ions and the mod-
ified biochar surface. The obtained results showed that adsorption
equilibrium was reached within 60 min. The experimental data fit-
ted well with pseudo-second-order kinetic model and Langmuir
isotherm model. The maximum adsorption capacity of modified
biochar for nitrate ions was obtained as 28.21 mg g−1 .
Acknowledgment
The authors would like to thank Shahid Chamran University of
Ahwaz, Iran, for the financial and other supports.
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