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548 © IWA Publishing 2018 Water Science & Technology | 77.

2 | 2018

Adsorption of nitrate onto biochar derived from


agricultural residuals
Haihua Zhao, Yingwen Xue, Li Long and Xiaolan Hu

ABSTRACT

To develop low-cost adsorbents for aqueous nitrate, biochars were prepared from three types of Haihua Zhao
School of Civil Engineering,
agricultural residuals at different pyrolysis temperatures (300  C, 450  C, and 600  C). The corncob Hubei Engineering University,
Xiaogan, Hubei,
biochar produced at 600  C (CC600) was the best nitrate adsorbent of all the tested biochars. China

Characterization results showed that CC600 had good thermal stability, porous structure, and Yingwen Xue (corresponding author)
abundant surface functional groups. Findings from batch adsorption experiments demonstrated that Li Long
Xiaolan Hu
CC600 showed relatively fast adsorption kinetics to nitrate in aqueous solutions. In addition, the School of Civil Engineering,
Wuhan University,
Langmuir adsorption capacity of CC600 to nitrate was 14.46 mg/g, comparable to that of other Wuhan,
China
biochar-based adsorbents. Therefore, CC600 showed promising potential to be used as a low-cost E-mail: ywxue@whu.edu.cn
adsorbent for the treatment of nitrate in water.
Key words | carbon sorbents, modeling, nitrogen, sorption, water treatment

INTRODUCTION

With the rapid population growth and economy develop- the environment. However, it also has too many restrictions
ment, a large amount of nitrate has been released into and often fails to achieve the ideal removal efficiency of
surface water and groundwater through various ways nitrate. In particular, biological methods have limitations
(Burow et al. ; Archna et al. ; Kim et al. ). for the treatment of high concentration nitrate wastewater
This has resulted in a number of environment problems, at low temperatures (Demiral & Gunduzoglu ).
especially water eutrophication (Liu et al. ; Archna Compared with biological methods, physicochemical
et al. ). Nitrate polluted water can also pose a threat to methods, such as ion exchange, electro dialysis, reverse
public health, such as causing cancer (Camargo & Alonso osmosis, and adsorption, are more flexible and effective
; Song et al. ), infant methemoglobinemia (Camargo (Chatterjee & Woo ). Among the different physico-
& Alonso ; Wongsanit et al. ), and nervous tissues chemical methods, adsorption has received extensive
and cognition damage (Lefferts et al. ). The develop- attention because its low cost and easy maintenance. Adsor-
ment of effective treatment technologies that can reduce bents with large specific surface area and pore volume thus
nitrate from wastewater discharges thus has attracted have been developed for the removal of impurity ions from
much attention recently (Liu et al. ). water. Recently, the development of novel, high efficiency,
Due to the good stability and high water solubility of and environmentally friendly adsorbents has become one
nitrate, how to effectively and economically remove aqu- of hot topics in the field of water treatment. As an emerging
eous nitrate nitrogen becomes an issue (Archna et al. engineered carbon material, biochar has been gradually
). To resolve it, many researchers have carried out exper- applied as a low-cost adsorbent in water treatment to
iments to test different biological and physicochemical remove contaminants from wastewater (Yao et al. b;
methods for the removal of nitrate from aqueous solutions. Lou et al. ).
The main principle of biological nitrate removal is using Previous studies have examined the sorption of nitrate
anaerobic denitrifying bacteria to reduce nitrate and nitrite onto biochars made from various agricultural and forest
under anaerobic conditions. This biological treatment has residuals including pine wood, bamboo, wheat straw, mus-
several advantages, such as wide sources of denitrifying bac- tard straw, corn stover, and sugarcane bagasse (Mizuta
teria, low cost of the process, and no secondary pollution to et al. ; Mishra & Patel ; Yao et al. b; Zhang
doi: 10.2166/wst.2017.568

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549 H. Zhao et al. | Adsorption of nitrate onto biochar Water Science & Technology | 77.2 | 2018

et al. ; Chintala et al. ; Xue et al. ). These exper- Characterizations
iment results show various results of effectiveness of
biochar-based sorbents for the removal of aqueous nitrate. Basic physical and chemical properties of biochars were
Nevertheless, some the biochars showed better nitrate sorp- determined using method reported previously (Inyang
tion ability than commercial activated carbon, indicating the et al. ; Yao et al. a; Wang et al. ). Briefly,
promising potentials of biochar as a low-cost and environ- carbon (C), hydrogen (H), oxygen (O), and nitrogen (N) con-
mentally friendly sorbent for nitrate treatment. tents of the samples were analyzed using a CHN Elemental
The overarching objective of this work was to further Analyzer (Elementar Analysen systeme GmbH). Surface
evaluate the effectiveness of biochar as an adsorbent for morphology of the samples was determined using a scan-
the removal of aqueous nitrate. Various types of biochars ning electron microscopy (SEM). X-ray diffraction (XRD)
were prepared from three types of agricultural residuals analysis was used to detect crystalline minerals on either
through slow pyrolysis at different temperatures. Laboratory pre-or post-sorption samples using a computer controlled
batch sorption and mathematical models were used to deter- X-ray diffract meter. Fourier transform infra-red (FTIR)
mine the sorption characteristics of nitrate onto the analysis was used to verify the presence of surface functional
biochars. The specific objectives of this work were as fol- groups on the samples. In the thermogravimetric analysis
lows: (1) optimize the production conditions of biochars (TGA), the physical and chemical changes in the combus-
from agricultural residuals; (2) determine the adsorption tion process of a microcomputer based thermogravimetric
characteristics of nitrate onto biochars; and (3) explore the differential thermal analyzer (HCT-1).
adsorption mechanism of nitrate onto biochar.
Batch sorption

METHODS About 0.1 g of the selected biochars were mixed with 50 mL


sodium nitrate solutions (Xue et al. ). The mixtures were
Materials then shaken in the mechanical shaker (150 r/min) at 30  C.
After 24 h (predetermined equilibrium time), the mixtures
Dry agriculture residuals were obtained locally from Wuhan were filed through 0.22 μm membrane filters to measure
in Hubei Province in China. Potassium nitrate (KNO3) was the nitrate concentrations in the supernatants. Nitrate con-
purchased from Sinopharm Chemical Reagent Co., Ltd. centrations were determined by ion chromatograph
Reagent in this work were of analytical grades and solutions (Metrohm) using ion chromatographic column (Metrosep
were prepared using deionized water (18.2 MΩ). A Supp 4). Sorbed nitrate concentrations on the biochar
and removal rate were calculated based on the difference
between the initial and final aqueous concentrations. Nitrate
Biochar production adsorption amount of q (mg/g) and adsorption removal rate
of R (%) were calculated by formula (1.1) and formula (1.2):
Three types of agriculture residuals, corncobs (CC), peanut
shell (PS), and cotton stalks (CS), were collected as feed- (C0  Ce )V
q¼ (1:1)
stock materials for biochar production. They were milled, m
washed, and air-dried at 80  C (Gao et al. ). The feed-
stocks were then pyrolyzed in a tube furnace under N2 C0  Ce
flow at a temperature of 300  C, 450  C, or 600  C for 2 h, R¼ × 100 (1:2)
C0
respectively (Yao et al. a). The solid product (biochar)
was collected and ground in a mortar with a pestle, and where V is the volume of solution (mL) and m is the weight
then sieved to a uniform size fraction of 0.9–1.2 mm. After of biochar adsorbent, and C0 and Ce are the initial concen-
further rinsing with deionized (DI) water several times to tration and equilibrium concentration of nitrate ion
remove impurities and drying at 80  C (Creamer et al. solution, respectively (mg/L).
), the final biochar samples were stored for later exper- The biochar sample with the best sorption performance
iments. The samples were named after their feedstock and for nitrate was selected for the rest of the batch sorption
temperature. For example, the biochar prepared from CC experiments to determine the adsorption kinetics and iso-
and pyrolyzed at 600  C was named CC600. therms using similar experimental procedures. The kinetics

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550 H. Zhao et al. | Adsorption of nitrate onto biochar Water Science & Technology | 77.2 | 2018

were measured at different time intervals (0–24 h) and iso- After 24 h shaking in the mechanical shaker, the same pro-
therm was determined using different initial concentration cedures were then used to determine the nitrate
(0–2,000 mg/L). concentrations in the filtrates.

Mathematical models
RESULTS AND DISCUSSION
Pseudo-first-order, pseudo-second-order, and Elovich
models were used to simulate the adsorption kinetics data.
Effects of pyrolysis conditions on nitrate adsorption
Governing equations for these models can be written as
onto biochar
(Yao et al. b):
The C, H, and N contents of the biochars showed variations
Pseudo-first-order: qt ¼ qe (1  ek1 t ) (2:1)
among different feedstocks and temperatures (Table 1). For
k2 q2e t the same feedstocks, biochars produced at higher tempera-
Pseudo-second-order: qt ¼ (2:2)
1 þ k2 q2e t tures had higher C content, which is consistent with
findings of previous studies (Sun et al. ). The H content
1
Elovich: qt ¼ ln (αβt þ 1) (2:3) of the biochars increased first and then decreased with
β
temperature, which is also consistent with the conclusions
where qt and qe are the amount of sorbate removed at time t of previous studies (Xue et al. ; Zhang et al. ; Liu
and at equilibrium (mg/g), respectively. k1 and k2 are the et al. ). Both feedstock type and pyrolysis temperature
first-order and second-order sorption rate constants (h1), showed strong effects on biochars’ sorption ability to NO 3
respectively. α is the initial sorption rate (mg/g) and β is in aqueous solutions (Figure 1). The CC and crop waste
the desorption constant (g/mg). (CW) biochars showed higher sorption to nitrate than the
The Langmuir and Freundlich models were used to PS biochars, indicating they are better feedstocks for this
simulate the adsorption isotherms. Their governing purpose. In addition, nitrate sorption abilities of the CC
equations can be written as (Tian et al. ): and CW biochars increased with pyrolysis temperature.
The CC600 showed the highest sorption of nitrate from aqu-
KSmax Ce
Langmuir: qe ¼ (3:1) eous solution among all the tested biochars, it was thus
1 þ KCe
selected as an example for further characterization and sorp-
Freundlich: qe ¼ Kf Ce1=n (3:2) tion investigations.

where K and Kf are the Langmuir bonding term related to


Physiochemical properties of CC600
interaction energies(L/mg) and the Freundlich affinity coef-
ficient ((mg/g)(1/mg)1/n), respectively. Smax is the Langmuir
The combustion process of CC600 showed three stages:
maximum capacity(mg/g), Ce is the equilibrium solution
dehydration, weight loss, and burnout (Figure 2(a)). The
concentration(mg/L) of the sorbate, and n is the Freundlich
linearity constant. The Langmuir model assumes monolayer
adsorption onto a homogeneous surface with no inter- Table 1 | CHN contents of the biochars

actions between the adsorbed molecules. The Freundlich


Biochar samples C (%) H (%) N (%)
model is an empirical equation commonly used for hetero-
CW300 68.11 3.079 0.832
geneous surface.
CW450 73.85 5.554 1.135
Effects of sorbent dosage, pH, temperature and CW600 84.19 2.842 0.878
co-existing anions CC300 75.91 3.631 0.285
CC450 81.80 4.013 0.358
The effect of adsorbent dosage was studied by adding differ- CC600 79.69 3.632 0.599
ent amounts of biochar (0.05 g, 0.10 g, 0.15 g, 0.20 g) to PS300 69.27 2.509 1.686
50 mL nitrate solution. At the dosage of 0.10 g to 50 mL sol- PS450 77.12 5.065 1.896
ution, pH (3–11), temperature (20–40  C) and co-existing
PS600 82.44 2.401 1.425
anions (Cl, SO2 3
4 , PO4 ) were determined respectively.

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551 H. Zhao et al. | Adsorption of nitrate onto biochar Water Science & Technology | 77.2 | 2018

CC600 was about 30 μm. The relatively large pores would


be beneficial for the adsorption process. The FTIR spectra
of CC600 showed strong peaks 1,100 cm1 and 3,400 cm1
(Figure 2(c)), corresponding to C-O stretching vibration
(three hydroxyl) and O-H stretching vibration (hydroxyl).
The FTIR results indicated that the main functional group
on the biochar surface was hydroxyl (-OH), which has
strong affinity to polar compounds in water. Compared
with the initial biochar after adsorption there were peak
shifts at 1,100 cm1 and 3,400 cm1 and these shifts indi-
Figure 1 | Removal of nitrate from aqueous solution by different types of biochars.
cated that functional groups involved in the adsorption. The
XRD spectra showed no evidence of diffraction peaks,
first stage was from room temperature to 300  C, where ther- suggesting CC600 might not have any crystal lattice structure
mogravimetric (TG) curve showed small decline and the on its surface.
sample weight loss rate was only about 2%, mainly for the
dehydration process. The second stage accompanied with a
main weightlessness from 300 to 750  C, mainly for volatile Adsorption kinetics and isotherms
and fixed carbon combustion. The third stage was from 750
to 1,000  C, where TG curve became smooth and the quality Nitrate adsorption kinetics onto CC600 showed two distinct
of the sample picked up slightly. This was probably because phases: a rapid initial phase over the first few hours and a
the same chemical composition had different crystal type slow phase to reach maximum (Figure 3(a)). For the nitrate,
with the temperature changing, so there was a crystal nearly all the sorption occurred within the first several
form of inorganic transformation. In other words, a small hours. Pseudo-first-order, pseudo-second-order, and Elovich
amount of stable compound was generated at the high temp- models were used to simulate the sorption kinetics data
erature. SEM image of the CC600 showed porous structures (Figure 3(a)). Nitrate sorption onto CC600 were best fitted
with rough surfaces (Figure 2(b)). The average pore size of by the pseudo-second-order with R2 equal to 0.94

Figure 2 | TGA (a), SEM (b), FTIR (c), and XRD (d) analyses of CC600.

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552 H. Zhao et al. | Adsorption of nitrate onto biochar Water Science & Technology | 77.2 | 2018

Figure 3 | Adsorption kinetics (a) and isotherms (b) of nitrate onto CC600.


Table 2 | Best-fit kinetic parameters of NO3 adsorption onto CC600

P. first-order kinetic model P. second-order kinetic model Weber-Morris model Elovich kinetic model

1 0.5
Adsorbent qe (mg/g) k1 (h ) R2 qe (mg/g) k2 (g/mg min) R2 K (mg/g/h ) C (mg/g) R2 α (mg/g) β (g/mg) R2

CC600 6.4 0.381 0.886 7.1 0.079 0.940 1.3053 1.4245 0.838 12.933 0.7874 0.926

(Table 2). The experimental value of qe was almost identical confirmed that CC600 was good adsorbent for the removal
to the model-predicted value. The pseudo-second-order of nitrate from water.
model assumes that the adsorption rate is controlled by
the chemical adsorption mechanism that involves the elec- Effects of sorbent dosage, pH, temperature and
tron sharing or electron transfer between the adsorbent co-existing anions
and adsorbate. The model results of this work suggested
that the adsorption kinetics of nitrate onto CC600 might The removal rate increased with increasing biochar dose
be mainly controlled by the chemical adsorption (Ozacar (Figure 4(a)). The adsorption capacity increased from
& Sengil ). According to the Weber-Morris model, C 5.56 mg/g to 7.74 mg/g when the biochar dose went from
was 1.4245 and it indicated that intra particular diffusion 0.05 g to 0.20 g.
played a little role in the adsorption process. Changes of initial solution pH significantly affected
Adsorption isotherms of nitrate onto CC600 showed adsorption effect (Figure 4(b)). When the pH increased, the
relatively high equilibrium concentrations (Figure 3(b)). adsorption capacity decreased. This is probably because
Two commonly used isotherm equations were used to when there were low pH (3–7) and high concentration of
describe the experimental isotherm, which is better fitted Hþ in the solution, a large number of Hþ attached to the bio-
by the Langmuir model with R2 equal to 0.968 (Table 3). char surface that was favorable to electrostatic adsorption. As
The Langmuir maximum sorption capacity of CC600 to the pH is over 7, there was a competition between OH and
nitrate was 14.46 mg/g, comparable to the values reported NO 3 , which led to the reduction of adsorption capacity.
in the literature on other biochar-based adsorbents (Mizuta When the reaction temperature increased from 20  C to
et al. ; Mishra & Patel ; Yao et al. b; Zhang 
40 C, the adsorption increased from 5.83 mg/g to 7.59 mg/g
et al. ; Chintala et al. ; Xue et al. ). This result (Figure 4(c)). This indicates that the adsorption process was
endothermic and the increase of temperature was beneficial
to the reaction. This made a great contribution to actual pro-

Table 3 | Best-fit isotherm parameters NO3 adsorption onto CC600
duction application.
Langmuir isotherm Freundlich isotherm According to the test data (Figure 4(d)), the existence of
three anions showed negative effect on the adsorption and
K qm Kf
Adsorbent (L/mg) (mg/g) R2 (mg/g)(1/mg)1/n n R2
even resulted in desorption (Figure 4(d)). Relatively speak-
ing, the influence of SO2 4 and PO3
4 on adsorption were
CC600 0.0014 14.46 0.968 0.249 0.503 0.917 
higher than that of Cl . It is probably because the adsorption

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553 H. Zhao et al. | Adsorption of nitrate onto biochar Water Science & Technology | 77.2 | 2018

Figure 4 | Effect of sorbent dosage (a), pH (b), temperature (c) and co-existing anions (d) on nitrate adsorption onto CC600.

affinity of the high valence anion was generally higher than [grant number 2014BAL04B04], [grant number
that of the low valence anion. 2015BAL01B02], Scientific Research Fund Project In
Hubei Province Department Of Education (B2016180),
and the Wuhan Water Engineering & Technology Co. Ltd.
CONCLUSIONS The authors also thank the anonymous reviewers for their
invaluable insight and helpful suggestions.
A range of biochars were produced from three types of agri-
cultural residuals at three pyrolysis temperatures. Among
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First received 11 May 2017; accepted in revised form 27 October 2017. Available online 9 November 2017

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on 05 November 2018

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