Research Article

Adsorption Science & Technology

2018, Vol. 36(5–6) 1294–1309
Removal of ammonium from ! The Author(s) 2018
DOI: 10.1177/0263617418768944
fish farms by biochar obtained journals.sagepub.com/home/adt

from rice straw: Isotherm

and kinetic studies for
ammonium adsorption

Ahmed Khalil
Don State Technical University, Russian Federation;
Kafrelsheikh University, Egypt

Nikolai Sergeevich
Don State Technical University, Russian Federation

Vita Borisova
Peter the Great St Petersburg Polytechnic University,
Russian Federation

Abstract
Ammonium is a water pollutant that harms the environment, particularly fisheries. Rice straw is
also an economic waste of rice, with millions of tons produced per year around the world. In this
paper, physical and chemical procedures for the modification of rice straw were studied.
The kinetic and isothermal adsorption trends were investigated, including the ammonium
removal efficiency, the contact time of the adsorbent, the amount of adsorbent, and the initial
concentration of NH4þ. The effect of temperature and pH on the adsorption process
was discussed. The removal efficiency of NH4þ recorded 43, 53.7, and 69.5%, with maximum
adsorption values of 2.9, 3.5, and 4.5 mg/g at temperatures of 25  5, 35  5, and 45  5 C,
respectively, at pH 7.5. The biochar obtained from rice follows the pseudo-second-order equa-
tion for ammonium adsorption kinetics (R2 ¼ 0.98). The adsorption isotherm follows Freundlich’s
model (R2 ¼ 0.99) and Langmuir’s model (R2 ¼ 0.98).

Corresponding author:
Ahmed Khalil, Don State Technical University, St. Socialist, 162, Rostov-on-Don 344022, Russian Federation.
Email: ahmed.khalil@eng.kfs.edu.eg

Creative Commons CC BY: This article is distributed under the terms of the Creative Commons Attribution
4.0 License (http://www.creativecommons.org/licenses/by/4.0/) which permits any use, reproduction and
distribution of the work without further permission provided the original work is attributed as specified on the SAGE and
Open Access pages (https://us.sagepub.com/en-us/nam/open-access-at-sage).
Khalil et al. 1295

Keywords
Biochar, ammonium removal, adsorption, kinetic, isotherm, physical and chemical modification
Submission date: 28 August 2017; Acceptance date: 18 February 2018

Introduction
In many nations, eutrophication is a water contamination issue in lakes, rivers, water repos-
itories, and seas. Our study aims to tackle these issues by investigating the nature and reuse
of wastewater, which reduces sewage release and enhances water deficiency conditions.
Investigations of sewage medication have also been performed. The effect of ammonium
was observed in groundwater, aquaculture, and surface water, on the other hand, causing
eutrophication (Huo et al., 2012). The level of ammonium in surface water and groundwater
is lower than 3 mg/l. This level is unacceptable in other areas, which require levels lower
than 0.05 mg/l (e.g. in aquaculture) (Vu et al., 2017). Current treatment methods of water
and wastewater such as coagulation and filtration are not masterful to remove ammonium
effectively (Moradi, 2011). Various methods have been used to remove ammonium from
wastewater, including precipitation, crystallization, biological removal, adsorption, and ion
exchange. The adsorption and ion exchange techniques have a high efficiency to eliminate
ammonium. These techniques need a small area for application and have acceptable effi-
ciency in comparison to other methods (Abdehagh et al., 2013; Ma et al., 2012;
Namasivayam and Sangeetha, 2006; Vargas et al., 2012; Zhu et al., 2005). Identifying
new productive materials that may be used for adsorption and ion exchange is an important
research topic (Li et al., 2016; Liu et al., 2010; Taheran et al., 2016).
However, adsorption onto the surface of activated carbon is the most widely used method
in water treatment (Liu et al., 2013; Zhu et al., 2012). Activated carbon can remove many of
the impurities that occur in water and wastewater (Sarker and Fakhruddin, 2015).
Recently, the use of adsorbents from nature, such as agricultural waste, as alternative
resources to replace traditional adsorbents. These resources are economical and environ-
mentally friendly solutions. The majority of previous studies have investigated the adsorp-
tion of heavy materials and gases, but few studies emphasized nutrients, such as sawdust for
removing phenol (Jadhav and Vanjara, 2004), textile sludge biochars for removing oil
(Sohaimi et al., 2017), sewage sludge for removing methylene blue from aqueous solutions
(Fan et al., 2017), the removal of cadmium (II) (Guo et al., 2017; Wang et al., 2017; Zama
et al., 2017), and atrazine and imidacloprid removal (Mandal et al., 2017). This method has
been applied to many natural materials, such as wheat straw (Ma et al., 2011); activated
carbon (Bj€ orklund and Li, 2017; Gierak and Łazarska, 2017); clinoptilolite (Martins et al.,
2017); light-expanded clay aggregate (Sharifnia et al., 2016); wood and rice husks biochar
(Cope et al., 2014; Kizito et al., 2015); peanut shells, corn cobs, and cotton stalks (Liu et al.,
2016; Vu et al., 2017); six types of wetland plants (i.e. Canna indica, Pennisetum purpureum
Schum, Thalia dealbata, Zizania caduciflora, Phragmites australis and Vetiveria zizanioides)
(Cui et al., 2016); palladium (II) after recrystallization (Mozaffari et al., 2017; Xue et al.,
2017); Al-eggshell for adsorption phosphate (Zhang et al., 2017); and treated ginger waste
(Ahmad and Kumar, 2010). Literature reviews exhibit the possibility to reuse and develop
agricultural wastes as cheap materials for adsorption. However, the conversion of
1296 Adsorption Science & Technology 36(5–6)

agricultural waste into charcoal is not simple, as this process depends on several factors to
activate the above materials.
Adsorption is a cheap and effective process for removing ammonium. The adsorption of
ammonium has been studied through the wastewater treatment process by various adsorb-
ents like activated carbon, biochar, zeolite, and corncob-biochar (Gupta et al., 2015;
Ivanova et al., 2010; Lebedynets et al., 2004; Vassileva et al., 2009).
A previous research approved that the surface chemistry plays a more important
role than the Brunauer–Emmett–Teller surface area of adsorbents and the pore structure
in adsorbing inorganic compounds from water. The modification strategy is a current
method to change the surface chemistry and promote the adsorption efficiency of adsorb-
ents. The oxidation process with H2O2, KMnO4, H3PO4, or HNO3 has been used
for modifying the surface characteristics (Abou El-Maaty, 2014; Halim et al., 2013;
Moreno-Castilla et al., 2000).
Rice straw (RS) is an environmental burden in many countries. Thus, in this paper, we
examine methods of RS activation for work in the adsorption environment. The internal
composition of RS is similar to that of wood, which qualifies RS for conversion to good
charcoal. We are interested in the adsorption of ammonium by RS for use as a cheap
material to recycle water in fish farms with ammonium; it is also worth mentioning that
most of these fish farms are near rice farms due to their common necessity of water, as in
Egypt. Therefore, the activation of RS for adsorption has been studied using kinetic and
isothermal models; on the other hand, the influence of various factors, such as temperature
and pH, on the adsorption process was examined to obtain optimum conditions based on
laboratory results and mathematical models (e.g. Lineweaver–Burk, Elovich, pseudo-
second-order and pseudo-first-order models for kinetic studies and Freundlich and
Langmuir models for isothermal studies).
The overall aim of this study was to determine adsorption characteristics of ammonium
with a concentration beginning from 2 mg/l (to simulate wastewater of fish farming in
Egypt) on biochars obtained from RS in different environmental conditions (including
contact time, pH, ammonium concentrations, and adsorbent dose) to determine the kinetics
and equilibrium adsorption parameter. These help to achieve insights in the utilization of
biochar obtained from RS to adsorb ammonium and improve water quality in fish farms,
which operate through water recycling by simple and easy technique.

Methods and materials

Activation of the material (adsorbents)
Biochar synthesis and activation. The biochar was produced from RS that was collected from
Kafr El Sheikh city, Egypt and transported to Don State Technical University in Rostov-on-
Don city, Russia. The RS material was washed to remove dust by tab water. The sample was
dried at a temperature of 105 C until weight stabilization was achieved. The RS was cut to a
size range of 1–1.5 cm and then soaked with 1.0 M of NaOH solution at a solid-to-liquid ratio
of 1.0 g to 2.5 ml for 2 h. The following procedures were used by Gao et al. (2015) and Liu et al.
(2016). The RS after soaking with NaOH was washed four times with tap water, then adjusted
pH to 7–8 for the sample by washing with distilled water for three times (Jindo et al., 2014;
K€orner et al., 2001), and subsequently dried along with storage RSI (chemical activation).
Khalil et al. 1297

Thermal analysis and thermal activation. Thermal analysis of the rice straw (RSI) has been
performed using a NETZSCH-SAT-449 system under the following conditions: raising
the temperature of a sample to 600 C with heating rate 30 /min under a static air atmo-
sphere and crucible DSC/TG pan Al2O3. Furthermore, thermal activation was applied on
the RSI by heating under slow pyrolysis at 500–600 C in the oven for 1 h and obtaining the
RSII in 0.16 mm particles.

Adsorbate
Ammonium chloride was obtained from Aquatest company in Rostov-on-Don city, Russia
(M= 53.5 g/mol). Five solutions with different concentrations of ammonium (3, 8, 12, 18,
and 25 ppm) were prepared by dissolving 0.0446, 0.1188, 0.1783, 0.2673, and 0.371 g of
ammonium chloride (NH4Cl), respectively, in 5 l of distilled water.

Experimental adsorption procedures

Adsorption kinetics. The adsorption kinetics of ammonium on biochar obtained from rice
straw (RSII) were investigated by adding different doses of RSII (0.25, 0.5, and 1 g) to
250 ml of an ammonium chloride solution at a rate of 2 g/l (Yao et al., 2012). The initial
concentration of ammonium is 12 ppm was added in different flasks, which placed in a
shaker at 120 r/min at room temperature (25  0.5 C) for a suitable amount of time to
ensure mixing adsorbent with the solution. Samples were removed from the flasks for anal-
ysis at 5, 10, 15, 20, 30, 40, 60, 90, and 120 min. The samples were passed through 0.22 mm
membrane filters to measure residual ammonium concentrations using an Expert 001 pH
meter ionomer. All experimental results were measured in triplicate, by calculating average
values. Pseudo-first-order, pseudo-second-order, Elovich, and Lineweaver–Burk models
were used to analyze and describe the experimental data related to adsorption kinetics.
The equations of kinetic models and their linear forms are given below:

1. 1. Pseudo-first order (Macıas-Garcıa et al., 2016)


qt ¼ qe 1  ek1 t (1)

The linearized form is

lnðqe  qt Þ ¼ lnðqe Þ  K1 t (2)

1. 2. Pseudo-second order

K2 q2e t
qt ¼ (3)
1 þ ðk2 qe tÞ
The linearized form is

t 1 1
¼ þ t (4)
qt K2 q2e qe
1298 Adsorption Science & Technology 36(5–6)

1. 3. Elovich (Thilagan et al., 2013)

1
qt ¼ lnðabt þ 1Þ (5)
b

The linearized form is

qt ¼ a þ blnðtÞ (6)

1. 4. Lineweaver–Burk (Compostela, 1988)

Vmax ½s
V¼ (7)
km þ ½s

The linearized form is

1 km 1
¼ þ (8)
V Vmax ½s vmax

The ammonium removal efficiency (g) was calculated with the following equation

C0  Ct
g¼  100 (9)
C0

where qt and [s] are the amount of ammonium removed at one time t (mg of adsorbed
per g of adsorbent) was calculated with the following equation (Wassie and
Srivastava, 2016)

ðC 0  C t Þ V
qt ¼ (10)
m

where qe is the adsorption capacity in balance (mg/g); k1, k2, and km are the pseudo-first-
order, pseudo-second-order, and Michaelis–Menten for Lineweaver–Burk constants, respec-
tively; a is the initial adsorption rate (mg/g); b is the desorption constant (g/mg); Vmax is the
maximum reaction velocity (mg/g); t is time (min); C0 is the ammonium concentration at the
start of the experiment (mg/l); Ct is the ammonium concentration at t (mg/l); v is the solu-
tion volume (l); and m is the mass of adsorbent (g).

Adsorption isotherm. The same sampling, mixing, filtration, and analysis procedures described
for adsorption kinetics were used to identify the adsorption isotherms of ammonium in the
Khalil et al. 1299

RSII. Instead of different time periods, 0.5 g of sorbents was mixed with 250 ml of ammo-
nium solutions with varying initial concentrations: 3.15, 8, 12.1, 18, and 25 mg/l. The
Langmuir and Freundlich models were used to analyze the experimental data for the
adsorption isotherm (Langmuir, 1918; Yao et al., 2011). The supposition of the Langmuir
isotherm is based on sorption occurring at specific homogeneous sites of adsorbent heat (as
adsorption for all sites is constant); however, the Freundlich isotherm is assumed to be a
heterogeneous surface (multilayer adsorption) with a nonequal distribution of adsorption
heat over the surface (Novak et al., 2010; Wu et al., 2017; Yusof et al., 2010). The Langmuir
and Freundlich equations can be written as shown below:

1. Langmuir model

q m k1 Ce
qe  (11)
1 þ k1 Ce

The linearized form is

Ce 1 1
¼ þ Ce (12)
qe qm k1 qm

2. Freundlich model

1
qe ¼ kf Ce n (13)

The linearized form is

1
lnqe ¼ lnkf þ lnCe (14)
n

where qe is the adsorption capacity at equilibrium on the adsorbent (mg/g) and Ce is the
equilibrium concentration (mg/l); the other parameters are constants of different isotherms,
which were determined based on the experimental data.
During the experiments, the pH was monitored at all steps to create optimal conditions
for ammonium absorption, which depends directly on the pH. The pH in all experiments
was 7.5  0.5, for the reasons mentioned in section effect of pH.

Results and discussion

Raw material characterization
Physicochemical properties of RS waste. The chemical configuration of RS depends on the plant-
ing time, climate, type of rice, source of water, and geographical conditions (Agbagla-
Dohnani et al., 2003). The quality parameters and main characteristics of the initial RS
are presented in Table 1.
1300 Adsorption Science & Technology 36(5–6)

Table 1. Chemical analysis of the raw material.

The internal components of rice straw

Oxides SiO2 Fe2O3 CaO MgO SO3 P2O5 Na2O TiO2 K2O MnO
Content (%) 74.67 0.8 3.1 5.2 1.3 1.0 1.2 0.03 12.3 0.03
Characteristics Wa Ab Stc VRd
(%) (%) (%) (cm3/g)
The result 14.8 0.96 0.19 1.3
a
W is ash content for dry weight.
b
A is moisture.
c
St is total sulfur.
d
VR is total pores.

Figure 1. TG–DTG curve for RS. DTG: Differential thermogravimetry; TG: Thermogravimetry.

RS has a high concentration of silica and can be categorized as attractive material that
contains silica. In addition, in the thermal analysis (based on temperature), silica is respon-
sible for the type of ash that is formed (Elwan et al., 2006), with amorphous ash exhibiting
reduced adsorption. Sodium hydroxide was selected to dilute the silica in the raw material,
which uses the first step in the modification of RS. The reaction of sodium hydroxide and
silicon oxide can be written by the following chemical equation

2NaOH þ SiO2 ! Na2 SiO3 þ H2 O (15)

Results of the TG–DTG analysis of RS. Four temperature zones were obtained from the ther-
mogravimetric analysis curve (TG–DTG) of raw RS (from room temperature to 120 C,
from 120 to 370 C, from 370 to 500 C, and from 500 to 600 C), based on weight loss, as
illustrated in Figure 1.
These zones were explained according to a previous study (Mall et al., 2006). The second
zone recorded a high percentage of weight loss in comparison to the other zones. The weight
Khalil et al. 1301

loss was approximately 6.46% during the heating of RS up to 120 C, due to the loss of
moisture in the RS. A significant weight loss of approximately 50.12% was recorded in the
second zone from 120 to 370 C, which was due to the degradation of the cellulose-related
component that forms carbon. Lignin was decomposed in the third zone (370–500 C), with
a mass loss of 13.8%, indicating better stability than cellulose and hemicellulose. The last
zone was from 500 to 600 C, with a slight loss of mass that stopped at 600 C. The final mass
was approximately 29% of the initial weight, indicating that all organic compounds had
been completely converted. Finally, the appropriate temperature to activate RS to RSII is
500–600 C.

Effect of pH
The ammonium adsorption of RSII was investigated by creating three pH groups. The first
group used RSII without adjusting the pH, which was physically and chemically activated
(burn RSI after soaking with NaOH, and without washing to produce RSII1), while pH
ranges were recorded in these groups from 9 to 10.2. The second group is pH 7, which was
obtained by washing RS after soaking it with a solution of NaOH prior to a burning
process. This pH range was achieved after washing RS with tap water and distilled water
for three times. The third group was achieved by adding HCl to generate a pH from 2 to 6.
In Figure 2, with a low pH from 2 to 5.5, the percentage of removed ammonium was low,
while the process achieved the highest percentage of ammonium removal at 12%. We noted
that when the pH increases from 5.5 to 8 the removal efficiency of NH4þ reaches to 57%,
but when the pH increases from 9 to 10.2 the removal efficiency of NH4þ reaches to 15%.
Decreased adsorption at different pH values is caused by ammonium ion effects with free
hydrogen ions (Hþ) in the solution. The low efficiency of the adsorption process at a lower
pH could relate to high protonation of functional groups (C = O, COO) (HA þ B $ A
þ HBþ) on the biochar surfaces, which impart a partial positive charge that repels the polar
attraction of NH4þ ions in aqueous solutions. In the solution, there is competition between

70

60
Removal of NH4+ (%)

50

40

30

20

10

0
0 2 4 6 8 10 12
PH

Figure 2. Effect of pH on ammonium ion removal efficiency (initial concentration of NH4þ (C0) ¼12 ppm,
temperature ¼25  2 C).
1302 Adsorption Science & Technology 36(5–6)

Hþ and NH4þ ions adsorbed on the surface of an adsorbent. This competition is in favor of
H ions when decreasing the pH in the solution.
Here, the ammonium adsorption in water followed the ion exchange mechanism. High
pH values > 10 lead to the conversion of most ammonium ions into ammonia, which cannot
be adsorbed. Therefore, all steps of adsorption processes were carried out with pH values of
7–8 (Huang et al., 2010; Jindo et al., 2014; Novak et al., 2010).

Adsorption studies: Kinetics and isotherm

Adsorption kinetics of RSII. The relationship between the rate of adsorption and the contact
time shows the kinetics of adsorption. The process of NH4þ adsorption by RSII with dif-
ferent contact times and different concentrations is shown in Figure 3. Adsorption kinetics
of RSII occurs in three main stages: fast, slow, and equilibrium. The first stage is the fastest
stage (up to 15 min), the adsorption rate increased quickly, where half of the adsorption
capacity is obtained. The NH4þ adsorption began to slow down in the second stage, which
occurred from 15 min to the equilibrium stage of adsorption at 60 min. We also noticed that
the adsorption rate increased with an increasing initial concentration of the solution at all
stages of the study.
The speed of the reaction can be explained for RSII, where some anionic groups with
negative charges are located on the surface of the adsorbent such as –COO. These groups
rapidly interact with ammonium ions. At the end of this reaction with the anionic groups,
the NH4þ goes into a slow process, which represents adsorption on the internal skeleton
of the RSII. So, the NH4þ adsorption on RSII consisted of two reaction processes.
Also increasing the concentration of ammonium leads to congestion of cations in the solu-
tion, which increases the chances of adsorption as well as its speed.

3ppm 12ppm 25ppm 8ppm 18ppm

5.0

4.5

4.0

3.5

3.0
qt (mg/g)

2.5

2.0

1.5

1.0

0.5

0.0
0 20 40 60 80 100 120 140
Contact time (min)

Figure 3. Adsorption kinetics of NH4þ onto RSII (temperature ¼ 25  2 C, pH ¼ 7.5, C0 ¼ 3, 8, 12, 18, and
25 ppm).
Khalil et al. 1303

The kinetic NH4þ adsorption data were fitted with four kinetic models. Table 2 shows the
model parameters with R2 and experimental values for five initial concentrations of the
NH4Cl solution. As shown in Table 2, the results showed that the Elovich, pseudo-
first-order, and pseudo-second-order models are suitable for describing the adsorption
kinetics, with all R2 values being larger than 0.87. However, the pseudo-second-order
model had the best fit, based on R2 values and decreases of k2 (g/mg min), with an increased
concentration of ammonium in solution and the convergence of equation values with actual
values; moreover, this model has a better chance to calculate the qe value, which worked
with the experimental result. Therefore, the pseudo-second-order model can be used to
predict the kinetic process for NH4þ adsorption. The pseudo-second-order model obtained
high reliability and stability in another mass of RSII, with an R2 value of 0.99 and an
average qe of 2.6 mg/g, as shown in Figure 4. The above results indicate that this model
is the best choice to represent NH4þ absorption on RSII. For that, the parameters of the
pseudo-second-order model, with an initial concentration of NH4þ = 12 ppm at different

Table 2. Coefficient of determination (R2) for the Lineweaver–Burk, Elovich, pseudo-first-order, and
pseudo-second-order kinetic models and model parameters.

Model Pseudo-first order Pseudo-second order Elovich Lineweaver–Burk

Ca qexpb k1 qe k2 qe b a
(mg/l) (mg/g) (min1) (mg/g) R2 (g/mg min) (mg/g) R2 (g/mg) (mg/g) R2 km R2

3.15 1 0.07 1.1 0.97 0.036 1.42 0.99 0.410 0.164 0.97 59.4 0.87
8 2 0.14 4.25 0.97 0.016 3.04 0.98 0.683 0.305 0.99 9.51 0.77
12 2.6 0.03 1.8 0.95 0.027 2.87 0.99 0.589 0.004 0.98 10.7 0.89
18 3.55 0.04 2.67 0.98 0.021 3.9 0.98 0.648 1.354 0.93 15.5 0.96
25 4.5 0.04 4.1 0.87 0.012 5.22 0.98 1.053 0.720 0.92 25.5 0.85
a
Initial concentration of ammonium in aqueous solution.
b
Experimental results for the adsorption capacity at the equilibrium.

70

60

50
t/qt ( min,mg -1,g)

40

30 0.05 g/ 50ml

20 0.2 g/ 50ml

10 0.1g / 50ml

0
0 20 40 60 80 100 120 140
Time ( min)

Figure 4. Pseudo-second-order plot (C0 ¼12 ppm, temperature ¼ 25  2 C, pH ¼ 7.5).

1304 Adsorption Science & Technology 36(5–6)

concentrations of adsorbent RSII were presented in Table 3 with mean absolute percentage
error (MAPE). The MAPE was calculated by an equation which is defined below (Mozaffari
et al., 2017)
!
100 Xk
qexp  qmodel
MAPE ¼ (16)
k i¼1
qexp

where k is the number of data points in each set and qexp and qmodel are the experimental
and model results for the adsorption capacity at the equilibrium.

Adsorption isotherm of RSII. The experimental data for isotherm adsorption were placed in
the Langmuir and Freundlich models and R2 values were extracted for both models.
The adsorption isotherm of RSII for NH4þ is described in Figure 5 using the Langmuir
and Freundlich models. The parameters of these models with correlation coefficient R2 were
presented in Table 4. The results show that the Freundlich and Langmuir models accurately
describe the adsorption of NH4þ, with R2 values larger than 0.98 for all models, but the
Freundlich model coincides with the experimental data better than the Langmuir model,

Table 3. Parameters of the pseudo-second-order model, with an initial concentration of

NH4þ ¼ 12 ppm at different concentrations of adsorbent RSII.

Pseudo-second-order parameters
Concentration of
adsorbent (mg/50 ml) qexp (mg/l) k2 (g/mg min) qe (mg/g) R2 MAPE (%)

0.05 2.1 0.036 2.4 0.993 6.41

0.1 2.6 0.026 2.8 0.996 3.45
0.2 2.8 0.076 2.6 0.991 1.15
MAPE: mean absolute percentage error.

5
4.5
4
3.5
qe (mg/g)

3
2.5
Experimental data
2
1.5 prediction by langmuir

1 prediction by freundlich
0.5
0
0 5 10 15 20
Ce (mg/L)

Figure 5. Ammonium adsorption equilibrium prediction on RSII from the Langmuir and Freundlich models
(contact time ¼ 120 min, temperature ¼ 25  2 C, and pH ¼ 7.5).
Khalil et al. 1305

Table 4. Isothermal parameters for the Langmuir and Freundlich models of adsorbent
NH4þ on RSII.

Langmuir Freundlich

Kl (l/mg) qmax (mg/g) R2 Kf (l/mg) n R2

RSII 0.260 4.251 0.98 0.822 1.623 0.99

40 t=20-30 t = 30-40 t= 40-50

y = 0.3498x + 4.4742 y = 0.2892x + 1.512 y = 0.2233x + 0.9525

35 R² = 0.9997
R² = 0.9917 R² = 0.9997

30
t/qt ( min,mg-1,g)

25

20

15

10

0
0 20 40 60 80 100
Time (min)

Figure 6. The pseudo-second-order equation model at different temperatures (C0 ¼12 ppm and pH ¼ 7.5).

with R2 = 0.99. In addition, the n constant for the Freundlich isotherm measures exchange
intensity or surface heterogeneity and also indicates the ease of adsorption when n > 1.
In this study, the value of n was larger than 1, which suggested that the adsorption con-
ditions fit with the Freundlich model.

Effect of temperature on ammonium removal efficiency

The influence of three different temperatures on the adsorption of ammonium on RSII was
investigated. In the experimental study, the concentration of adsorbent of RSII was 0.1 g/50
ml with the initial concentration of ammonium (C0) = 12 mg/l; a pH value was 7.5  5;
and the same conditions of shaking, extraction, and measurement as previously mentioned
for calculating the adsorption isotherm and kinetics. The first temperature is room temper-
ature, which was 25  2 C. The second and third temperatures were applied by heating the
samples in electric furnaces with the following temperatures 35  5 and 45  5 C.
The removal of ammonium was high at high temperatures, with values of 43, 53.7, and
69.5% at temperatures of 25  2, 35  5, and 45  5 C, respectively. In Figure 6 based on
the pseudo-second-order equation, the reason for the increased removal efficiency of ammo-
nium is the fact that the ammonium ion acquires greater kinetic energy at high temperatures,
allowing rapid adsorption on the surface, with complete adsorption including adsorption
1306 Adsorption Science & Technology 36(5–6)

into the internal pores of RSII. The adsorption capacity at equilibrium (qe) is 2.858, 3.457,
and 4.478 mg/g at these temperatures, respectively.

Conclusions
This study examined the potential use of biochar obtained from RS for NH4þ adsorption
from aqueous solution. We investigated the factors that influence the process of adsorption:
physical and chemical methods of modifying RS, contact time, adsorbent dose, initial con-
centration of adsorbate, and pH solution. The rice straw RSII achieved a removal efficiency
of 43% of ammonium at room temperature (25 C), with an initial concentration of NH4Cl
of 12 mg/l and a pH of 7.5  0.5. The adsorption equilibrium of NH4þ was achieved after a
contact time 90 min, with the best range of pH 7–8 yielding an improved adsorption per-
formance. The kinetic data for the adsorption of NH4þ fit with the pseudo-second-order
kinetic model. The isothermal data coincided with Freundlich’s model, which achieved R2
= 0.99 and Langmuir’s model (R2 = 0.98).
Overall, these results suggest that biochar obtained from rice straw (RSII) can be used
effectively for ammonium removal from aqueous solutions.

Acknowledgements
Authors are thankful to Kafrelsheikh University and Don State Technical University for supporting
our work.

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of
this article.

References
Abdehagh N, Tezel FH and Thibault J (2013) Adsorbent screening for biobutanol separation by
adsorption: Kinetics, isotherms and competitive effect of other compounds. Adsorption
19: 1263–1272.
Agbagla-Dohnani A, Nozire P, Gaillard-Martinie B, et al. (2003) Effect of silica content on rice straw
ruminal degradation. The Journal of Agricultural Science 140(2): 183–192.
Ahmad R and Kumar R (2010) Adsorption studies of hazardous malachite green onto treated ginger
waste. Journal of Environmental Management 91(4): 1032–1038.
Bj€
orklund K and Li LY (2017) Adsorption of organic stormwater pollutants onto activated carbon
from sewage sludge. Journal of Environmental Management 197: 490–497.
Compostela SD (1988) Kinetics of acid phosphatase activity various soils of Galicia (NW Spain). Soil
Biology and Biochemistry 20(3): 275–280.
Cope CO, Webster DS and Sabatini DA (2014) Arsenate adsorption onto iron oxide amended rice
husk char. Science of the Total Environment 488–489(1): 554–561.
Cui X, Hao H, Zhang C, He Z and Yang X (2016) Capacity and mechanisms of ammonium and
cadmium sorption on different wetland-plant derived biochars. Science of The Total Environment
539: 566–575. DOI: 10.1016/j.scitotenv.2015.09.022.
Khalil et al. 1307

Elwan M, Attriss M, Mahmoud A, et al. (2006) Characterization of rice straw/ash and using in clay
bricks. In: Proceeding of first scientific environmental conference, Zagazig University, pp.79–92.
El-Wakil AM, Abou El-Maaty WM and Awad FS (2014) Removal of lead from aqueous solution on
activated carbon and modified activated carbon prepared from dried water hyacinth plant. Journal
of Analytical & Bioanalytical Techniques 5: 187. DOI: 10.4172/2155-9872.1000187.
Fan S, Wang Y, Wang Z, et al. (2017) Removal of methylene blue from aqueous solution by sewage
sludge-derived biochar: Adsorption kinetics, equilibrium, thermodynamics and mechanism. Journal
of Environmental Chemical Engineering 5(1): 601–611.
Gao F, Xue Y, Deng P, et al. (2015) Removal of aqueous ammonium by biochars derived from
agricultural residuals at different pyrolysis temperatures. Chemical Speciation and Bioavailability
27(2): 92–97.
Gierak A and Łazarska I (2017) Adsorption of nitrate, nitrite, and ammonium ions on carbon
adsorbents. Adsorption Science & Technology 35: 721–727.
Guo X, Tang S, Song Y, et al. (2017) Adsorptive removal of Ni2þ and Cd2þ from wastewater using a
green longan hull adsorbent. Adsorption Science & Technology 36(1-2): 762–773. DOI: 10.1177/
0263617417722254.
Gupta VK, Sadegh H, Yari M, et al. (2015) Removal of ammonium ions from wastewater: A short
review in development of efficient methods. Global Journal of Environmental Science and
Management 1(2): 149–158.
Halim AA, Latif MT and Ithnin A (2013) Ammonia removal from aqueous solution using organic
acid modified activated carbon. World Applied Sciences Journal 24(1): 1–6.
Huang H, Xiao X, Yan B, et al. (2010) Ammonium removal from aqueous solutions by using natural
Chinese (Chende) zeolite as adsorbent. Journal of Hazardous Materials 175(1–3): 247–252.
Huo H, Lin H, Dong Y, et al. (2012) Ammonia-nitrogen and phosphates sorption from
simulated reclaimed waters by modified clinoptilolite. Journal of Hazardous Materials
229–230: 292–297.
Ivanova E, Karsheva M and Koumanova B (2010) Adsorption of ammonium ions onto natural
zeolite. Journal of the University of Chemical Technology and Metallurgy 45(3): 295–302.
Jadhav DN and Vanjara AK (2004) Removal of phenol from wastewater using sawdust, polymerized
sawdust and sawdust carbon. Indian Journal of Chemical Technology 11(1): 35–41.
Jindo K, Mizumoto H, Sawada Y, et al. (2014) Physical and chemical characterization of biochars
derived from different agricultural residues. Biogeosciences 11(23): 6613–6621.
Kizito S, Wu S, Kipkemoi Kirui W, et al. (2015) Evaluation of slow pyrolyzed wood and rice husks
biochar for adsorption of ammonium nitrogen from piggery manure anaerobic digestate slurry.
Science of the Total Environment 505: 102–112.
K€orner S, Das SK, Veenstra S, et al. (2001) The effect of pH variation at the ammonium/ammonia
equilibrium in wastewater and its toxicity to Lemna gibba. Aquatic Botany 71(1): 71–78.
Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of
the American Chemical Society 40(9): 1361–1403.
Lebedynets M, Sprynskyy M, Sakhnyuk I, et al. (2004) Adsorption of ammonium ions onto a natural
zeolite: Transcarpathian clinoptilolite. Adsorption Science & Technology 22(9): 731–741.
Li R, Wang JJ, Zhou B, et al. (2016) Enhancing phosphate adsorption by Mg/Al layered double
hydroxide functionalized biochar with different Mg/Al ratios. Science of the Total Environment
559: 121–129.
Liu H, Dong Y, Liu Y, et al. (2010) Screening of novel low-cost adsorbents from agricultural
residues to remove ammonia nitrogen from aqueous solution. Journal of Hazardous Materials
178(1–3): 1132–1136.
Liu N, Sun ZT, Wu ZC, et al. (2013) Adsorption characteristics of ammonium nitrogen by biochar
from diverse origins in water. Advanced Materials Research 664: 305–312.
Liu Z, Xue Y, Gao F, et al. (2016) Removal of ammonium from aqueous solutions using alkali-
modified biochars. Chemical Speciation and Bioavailability 28(1–4): 26–32.
1308 Adsorption Science & Technology 36(5–6)

Ma J, Si C, Li Y, et al. (2012) CO2 adsorption on zeolite X/activated carbon composites. Adsorption

18: 503–510.
Ma Z, Li Q, Yue Q, et al. (2011) Adsorption removal of ammonium and phosphate from water by
fertilizer controlled release agent prepared from wheat straw. Chemical Engineering Journal
171(3): 1209–1217.
Macıas-Garcıa A, G omez Corzo M, Alfaro Domınguez M, et al. (2016) Study of the adsorption and
electroadsorption process of Cu (II) ions within thermally and chemically modified activated
carbon. Journal of Hazardous Materials 328: 46–55. DOI: 10.1016/j.jhazmat.2016.11.036.
Mall ID, Srivastava VC and Agarwal NK (2006) Removal of Orange-G and methyl violet dyes by
adsorption onto bagasse fly ash – Kinetic study and equilibrium isotherm analyses. Dyes and
Pigments 69(3): 210–223.
Mandal A, Singh N and Purakayastha TJ (2017) Characterization of pesticide sorption behaviour of
slow pyrolysis biochars as low cost adsorbent for atrazine and imidacloprid removal. Science of the
Total Environment 577: 376–385.
Martins TH, Souza TSO and Foresti E (2017) Ammonium removal from landfill leachate by clinopti-
lolite adsorption followed by bioregeneration. Journal of Environmental Chemical Engineering
5(1): 63–68.
Moradi O (2011) The removal of ions by functionalized carbon nanotube: Equilibrium, isotherms and
thermodynamic studies. Chemical and Biochemical Engineering Quarterly 25(2): 229–240.
Moreno-Castilla C, L opez-Ram on M, Carrasco-Marın F, et al. (2000) Changes in surface chemistry of
activated carbons by wet oxidation. Carbon 38(14): 1995–2001.
Mozaffari S, Li W, Thompson C, et al. (2017) Colloidal nanoparticle size control: Experimental and
kinetic modeling investigation of the ligand-metal binding role in controlling the nucleation and
growth kinetics. Nanoscale 9: 3772–13785.
Namasivayam C and Sangeetha D (2006) Removal and recovery of vanadium (V) by adsorption onto
ZnCl2 activated carbon: Kinetics and isotherms. Adsorption 12: 103–117.
Novak JM, Busscher WJ, Watts DW, et al. (2010) Short-term CO2 mineralization after additions of
biochar and switchgrass to a Typic Kandiudult. Geoderma 154(3–4): 281–288.
Sarker N and Fakhruddin ANM (2015) Removal of phenol from aqueous solution using rice
straw as adsorbent. Applied Water Science 7(3); 1459–1465. Springer Berlin Heidelberg. DOI:
10.1007/s13201-015-0324-9.
Sharifnia S, Khadivi MA, Shojaeimehr T, et al. (2016) Characterization, isotherm and kinetic studies
for ammonium ion adsorption by light expanded clay aggregate (LECA). Journal of Saudi Chemical
Society 20: S342–S351.
Sohaimi KSA, Ngadi N, Mat H, et al. (2017) Synthesis, characterization and application of textile
sludge biochars for oil removal. Journal of Environmental Chemical Engineering 5(2): 1415–1422.
DOI: 10.1016/j.jece.2017.02.002.
Taheran M, Naghdi M, Brar SK, et al. (2016) Adsorption study of environmentally relevant concen-
trations of chlortetracycline on pinewood biochar. Science of the Total Environment 571: 772–777.
Thilagan J, Gopalakrishnan S and Kannadasan T (2013) Adsorption of copper(II) ions in aqueous
solution by chitosan immobilised on red soil: Isotherms, kinetics and mechanism. International
Journal of Pharmaceutical and Chemical Sciences 2(2): 1055–1066.
Vargas DP, Giraldo L and Moreno-Piraján JC (2012) Study of CO2 adsorption in functionalized
carbon. Adsorption 19(2–4): 323–329.
Vassileva P, Tzvetkova P and Nickolov R (2009) Removal of ammonium ions from aqueous solutions
with coal-based activated carbons modified by oxidation. Fuel 88(2): 387–390.
Vu TM, Trinh VT, Doan DP, et al. (2017) Removing ammonium from water using modified corncob-
biochar. Science of the Total Environment 579: 612–619.
Wang H, Wang X, Ma J, et al. (2017) Removal of cadmium (II) from aqueous solution: A comparative
study of raw attapulgite clay and a reusable waste–struvite/attapulgite obtained from nutrient-rich
wastewater. Journal of Hazardous Materials 329(2): 66–76.
Khalil et al. 1309

Wassie AB and Srivastava VC (2016) Teff straw characterization and utilization for chromium remov-
al from wastewater: Kinetics, isotherm and thermodynamic modelling. Journal of Environmental
Chemical Engineering 4(1): 1117–1125.
Wu W, Li J, Lan T, et al. (2017) Unraveling sorption of lead in aqueous solutions by chemically
modified biochar derived from coconut fiber: A microscopic and spectroscopic investigation.
Science of the Total Environment 576: 766–774.
Xue C, Qi P and Liu Y (2017) Adsorption of aquatic Cd2þ using a combination of bacteria and
modified carbon fiber. Adsorption Science & Technology (August 21, 2017): 1–15. DOI: 10.1177/
0263617417724946.
Yao Y, Gao B, Inyang M, et al. (2011) Removal of phosphate from aqueous solution by
biochar derived from anaerobically digested sugar beet tailings. Journal of Hazardous Materials
190(1–3): 501–507.
Yao Y, Gao B, Zhang M, et al. (2012) Effect of biochar amendment on sorption and leaching of
nitrate, ammonium, and phosphate in a sandy soil. Chemosphere 89(11): 1467–1471.
Yusof AM, Keat LK, Ibrahim Z, et al. (2010) Kinetic and equilibrium studies of the removal of
ammonium ions from aqueous solution by rice husk ash-synthesized zeolite Y and powdered
and granulated forms of mordenite. Journal of Hazardous Materials 174(1–3): 380–385.
Zama EF, Zhu Y-G, Reid BJ, et al. (2017) The role of biochar properties in influencing the sorption
and desorption of Pb(II), Cd(II) and As(III) in aqueous solution. Journal of Cleaner Production
148(2): 127–136.
Zhang Y, Li H, Zhang Y, et al. (2017) Statistical optimization and batch studies on adsorption of
phosphate using. Adsorption Science & Technology (November 13, 2017): 1–19. DOI: 10.1177/
0263617417740790.
Zhu K, Fu H, Zhang J, et al. (2012) Studies on removal of NH4þ-N from aqueous solution by using
the activated carbons derived from rice husk. Biomass and Bioenergy 43: 18–25.
Zhu W, Kapteijn F, Groen JC, et al. (2005) Adsorption on Kureha activated carbon: Isotherms and
kinetics. Adsorption 11: 637–641.