Journal of Environmental Chemical Engineering 10 (2022) 107575

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Journal of Environmental Chemical Engineering

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Preparation of rice husk hydrochar as an atrazine adsorbent: Optimization,

characterization, and adsorption mechanisms
Kim Anh Phan a, b, Doungkamon Phihusut c, Nattapong Tuntiwiwattanapun a, b, c, *
a
International Program in Hazardous Substance and Environmental Management, Graduate School, Chulalongkorn University, Bangkok 10330, Thailand
b
Center of Excellence on Hazardous Substance Management (HSM), Chulalongkorn University, Bangkok 10330, Thailand
c
Environmental Research Institute Chulalongkorn University, Chulalongkorn University, Bangkok 10330, Thailand

A R T I C L E I N F O A B S T R A C T

Editor: Dong-Yeun Koh This study aims to develop rice husk hydrochar as an alternative adsorbent for application in atrazine removal.
Hydrochar was obtained by microwave-assisted hydrothermal carbonization under different conditions: tem­
Keywords: perature (150 – 200◦ C), residence time (20 – 60 min), and liquid to solid ratio (5:1 – 15:1 mL g-1). Surface
Atrazine activation of hydrochar was conducted using various concentrations of KOH and H2O2. The results indicated that
Hydrochar
hydrochar prepared at higher temperatures, lower liquid to solid ratios, and longer residence times had signif­
Adsorption
icantly higher atrazine adsorption capacities. Atrazine adsorption by pristine and activated hydrochars could be
Surface properties
best fitted to the pseudo-second-order and Freundlich models. The adsorption capacity of KOH-activated
hydrochar was the highest (4.06 mg g-1), which is even greater than that of biochar with higher surface areas.
The results of FTIR and XPS demonstrated that activated rice husk hydrochars contained abundant oxygen
functional groups, which played a dominant role in atrazine adsorption via hydrogen-bonding interaction.

1. Introduction pre-treatment process that may solve the aforementioned limitation

Agricultural intensification to ensure global food security has led to
extensive use of pesticides and herbicides, which in turn has impacted
human health and environmental quality. Atrazine, a commonly used
herbicide, is applied to control broadleaf weeds and grasses in various
crops such as corn, sugarcane, pineapple, and sorghum [18,41,9]. It is
classified as Group 2B, which means that atrazine is possibly carcino­
genic to humans [11]. Atrazine residues have been detected in agricul­
tural areas where this herbicide was applied as far back as 20 years [25],
indicating that it is persistent in the environment, especially in soil.
Reduction and removal of atrazine through adsorption is considered
one of the most practical methods because of its economic efficiency,
ease of operation, simplicity of design, and avoidance of harmful by-
product formation [2,35]. For instance, peanut husk biochar [29], soy­
bean biochar [18], and rice husk biochar [23] were reported as potential
materials for atrazine adsorption. The adsorption capacities of these
materials were 0.42, 3.05, and 8.2 mg g-1, respectively. However, the
high moisture content in such biomass is a problem as it necessitates a
slow pyrolysis process with high energy consumption to dry the
feedstock.
Hydrothermal carbonization (HTC) is an alternative thermochemical
associated with pyrolysis of wet feedstock. HTC can utilize feedstock
with high or low moisture content by submerging it in water and con­
trolling sub-critical temperature and pressure [26,30,31]. Accordingly,
from a green chemistry perspective, the HTC technique is more suitable
because it (1) utilizes low cost and abundantly available renewable
feedstocks, (2) consumes less energy as it operates at significantly lower
temperatures (150 – 375 ◦ C) and does not require feedstock pre-drying,
(3) reduces air pollutant generation, and (4) is a sustainable technique as
the liquid fraction can be reutilized or recirculated into the process [14,
26,3].
Hydrochar is a carbon-rich solid product of HTC. Recently, its po­
tential for application in multidisciplinary approaches such as carbon
sequestration, energy production, and contaminated soil remediation
has been studied [15,30,31]. In addition, hydrochar surfaces exhibit a
porous structure and a notable abundance of oxygen-containing func­
tional groups (e.g., ─OH, ─C═O, and ─COOH groups), thereby facili­
tating the development of hydrochar as an alternative adsorbent for
application in both inorganic [38,39] and organic [19,20] adsorption. In
previous research, hydrochars derived from corn stalk and corn straw
have shown promising removal of atrazine from aqueous solutions [19,
20]. However, only a few studies have investigated atrazine adsorption

* Corresponding author at: Environmental Research Institute Chulalongkorn University, Chulalongkorn University, Bangkok 10330, Thailand.
E-mail address: Nattapong.T@chula.ac.th (N. Tuntiwiwattanapun).

https://doi.org/10.1016/j.jece.2022.107575
Received 14 October 2021; Received in revised form 15 March 2022; Accepted 15 March 2022
Available online 29 March 2022
2213-3437/© 2022 Elsevier Ltd. All rights reserved.
K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

Table 1 carbonized solid, referred to as hydrochar (HC), was separated by vac­

Box-Behnken experimental design matrix and atrazine adsorption capacities. uum filtration and rinsed with DI water until a stable pH was achieved.
Run Variable level Adsorption capacity, q (mg g- The filtered hydrochar was dried in an oven at 105 ◦ C for 12 h and then
order 1
) stored in a desiccator.
Temperature Time L-S ratio Observed Predicted Box-Behnken design including three operating variables (i.e., tem­
(◦ C) (min) (mL g-1) response response perature, residence time, and L-S ratio) was applied to determine the
1 150 20 10 0.41 ± 0.02 0.41
effects of these variables on a response variable (i.e., atrazine adsorption
2 150 40 5 0.39 ± 0.01 0.39 capacity). The experimental matrix was produced using STATISTICA
3 150 40 15 0.43 ± 0.02 0.43 software (version 10) and is listed in Table 1. The preliminary experi­
4 150 60 10 0.53 ± 0.01 0.53 mental set-up for atrazine adsorption onto prepared hydrochar samples
5 175 20 5 1.40 ± 0.01 1.40
is presented in Supplementary Information (SI).
6 175 20 15 0.19 ± 0.01 0.19
7 175 40 10 0.95 ± 0.00 0.76 Amount of atrazine adsorbed per unit mass of the adsorbent (qe, mg
8 175 40 10 0.60 ± 0.01 0.76 g-1) was calculated using Eq. (1):
9 175 40 10 0.74 ± 0.00 0.76
10 175 60 5 1.85 ± 0.04 1.85 (Co -Ce )V
qe = (1)
11 175 60 15 0.55 ± 0.01 0.55 m
12 200 20 10 1.23 ± 0.01 1.23
13 200 40 5 1.07 ± 0.00 1.07 where Co and Ce are the initial and equilibrium concentrations of atra­
14 200 40 15 0.95 ± 0.02 0.95 zine (mg L-1), respectively, V is the volume of aqueous solution (L), and
15 200 60 10 1.37 ± 0.01 1.37
m is the mass of hydrochar used (g).

by biomass-derived hydrochar. Therefore, it is still challenging to study 2.3. Hydrochar activation

the atrazine adsorption potential of hydrochar derived from various
feedstocks and the effects of HTC conditions on adsorption capacity.
However, hydrochars, such as canola straw hydrochar (4.36 m2 g-1)
[26] and corn stalk hydrochar (3.8 m2 g-1) [20], typically have low
specific surface area and poor microporosity. Chemical activation is a
well-recognized approach for enhancing physicochemical properties,
such as specific surface areas, pore sizes, and functional groups of ma­
terials [34]. Thus, potassium hydroxide (KOH) and hydrogen peroxide
(H2O2) solutions were used to enhance the atrazine adsorption perfor­
mance of hydrochar.
The objectives of this study are to (1) investigate the effects of HTC
conditions (i.e., temperature, residence time, and L-S ratio) on the
atrazine adsorption capacity of hydrochar, (2) examine the effects of
activation by KOH and H2O2, (3) determine the effects of contact time
and initial atrazine concentration on the adsorption performance of
hydrochar, (4) characterize the physicochemical properties of pristine
and activated hydrochars, and (5) understand atrazine adsorption
mechanisms.
2. Materials and methods
2.1. Feedstock and chemicals
Rice husk was obtained from a rice mill in Nan province, Thailand
and then washed with deionized (DI) water several times to remove
impurities. The washed rice husk was dried at 105 ◦ C in an oven for 12 h,
and ground and fractionated using a sieve with a 35 mesh (0.5 mm). The
rice husk sample was stored in polypropylene plastic bags for further
use.
Atrazine (analytical grade, ≥ 97% purity) was bought from TCI
America (Japan). Atrazine stock solution (1 g L-1) was prepared by
dissolving 0.10 g of atrazine in 100 mL of methanol (CH3OH) and stored
at 5 ◦ C. Analytical grade potassium hydroxide (KOH), hydrogen
peroxide (H2O2, 30%), and acetonitrile (CH3CN) were used without
further purification.
2.2. Microwave-assisted hydrothermal carbonization (MHTC)
Rice husk was submerged in DI water at the different liquid to solid
(L-S) ratios of 5:1, 10:1, and 15:1 (mL g-1) in reaction vessels. These
vessels were tightly sealed and placed in a microwave oven (Milestone,
Italy) operated at a power of 980 W. The samples were heated to 150,
175, and 200 ◦ C and held at the specified temperature for 20 - 60 min.
The system was subsequently fan-cooled to 25 ± 0.5 ◦ C for 30 min. The
Rice husk hydrochar (HC), which had the highest atrazine adsorption
capacity, was selected for use in the activation process. KOH-activated
rice husk hydrochar was generated by adding 1 g of HC to 25 mL of
KOH solution (5%, 10%, and 20% w/w) and shaking for 1 h at room
temperature. The solid residue was filtered under vacuum and then
rinsed with DI water until stabilization of pH. The wet KOH-activated
hydrochar was dried in an oven at 105 ◦ C for 12 h and then stored in
the desiccator. The hydrochar samples activated with 5%, 10%, or 20%
KOH were labelled 5KHC, 10KHC, or 20KHC, respectively. This activa­
tion procedure was repeated using H2O2 solution instead of KOH solu­
tion. The H2O2-activated hydrochar samples prepared using 5%, 10%, or
20% H2O2 were labelled 5HHC, 10HHC, or 20HHC, respectively.
2.4. Adsorption kinetics
The kinetic adsorption experiment was conducted as follows: 0.1 g of
each adsorbent was added to 25 mL atrazine solution (20 mg L-1) in
40 mL glass vials, which was tightly closed and shaken at 200 rpm and
room temperature. Supernatants were collected at 1, 3, 5, 7, 15, 30, 45,
90, 150, 300, and 1440 min.
The kinetics of atrazine adsorption were calculated as follows [21,
36]:
Pseudo − first − order model log (qe − qt ) = logqe −
k1 t
(2)
2.303
t 1 t
Pseudo − second − order model = − (3)
qt k2 q2e qe
Intraparticle diffusion by Weber and Morris qt = k3 t0.5 + C (4)
where qt and qe (mg g-1) are the amounts of atrazine adsorbed at time t
(min) and at equilibrium, respectively; k1 (min-1), k2 (g mg-1 min-1), and
k3 (mg/(g min0.5)) are the pseudo-first-order, pseudo-second-order, and
intraparticle diffusion rate constants, respectively; and C is a constant
representing the thickness of the boundary layer (mg g-1).
2.5. Adsorption isotherms
The adsorption isotherm study was conducted by adding 0.1 g of
each type of hydrochar to a 25 mL aqueous solution with varying con­
centrations of atrazine (2 - 30 mg L-1). All samples were shaken for 24 h
at 200 rpm and room temperature. The supernatants were collected
using 0.45 µm syringe filters.

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K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

The experimental isotherms were fitted using two isotherm models

given by Eqs. (5) and (6):

Freundlich model : qe = KF C1/n

e (5)

q m KL Ce
Langmuir model : qe = (6)
1 + KL Ce

where qe (mg g-1) represents the sorption number of pollutants at

equilibrium, qm (mg g-1) is the maximum sorption capacity, KL (L mg-1)
is the Langmuir constant, KF is the Freundlich constant, and n is an
empirical parameter that depends on the degree of heterogeneity of
adsorbing sites.

2.6. Quantification of atrazine concentration by HPLC-UV

To ascertain accuracy of the results, all atrazine adsorption experi­

ments were conducted in triplicates. Atrazine concentration in the fil­
trates was analyzed by high-performance liquid chromatography with
ultraviolet detection (HPLC-UV, Agilent) [41]. The filtrate (2 mL) ob­
tained after adsorption was injected into an HPLC ready vial for analysis.
A C18 hypersil column (5 µm, 250 × 4 mm) was used, and operating
conditions were as follows: acetonitrile to DI water ratio of 60:40 (v/v),
flow rate of 1 mL min-1, column temperature of 25 ◦ C, injection volume
of 20 µL, and detection at 220 nm. The retention time for atrazine was
4.5 min.

2.7. Hydrochar characterization

Specific surface area (SSA) was measured by N2 adsorption using the

Brunauer-Emmett-Teller (BET) method (Thermo Finnigan, USA). The
functional groups present on hydrochar surfaces were determined by
Fourier Transform Infrared (FTIR) Spectroscopy (Perkin Elmer, USA)
within the spectral region of 4000 to 400 cm-1 and analyzed by X-ray
photoelectron spectroscopy (XPS) (Kratos, USA). The surface
morphology of pristine and activated rice husk hydrochar was charac­
terized using Scanning Electron Microscopy (SEM) (JEOL Ltd., Japan).

3. Results and discussion

3.1. Optimization of MHTC condition

The effects of MHTC conditions on the atrazine adsorption capacity

Fig. 1. Surface plots showing the effects of temperature and L-S ratio with the
residence time of (a) 20, (b) 40, and (c) 60 min on the atrazine adsorption
capacity of hydrochar.
of each hydrochar are presented in Table 1. The atrazine adsorption
capacities of these prepared hydrochars were in the range of 0.19 –
1.85 mg g-1 for a contact time of 24 h. Rice husk hydrochar obtained via
heating at 175 ◦ C for 60 min and using L-S ratio of 5:1 mL g-1 had the
highest atrazine adsorption capacity. Fang et al. [6] observed a decrease
in specific surface areas of bagasse and peanut hull hydrochar when the
synthesis temperature was over 200 ◦ C. Similarly, hydrochar prepared
from canola and sawdust showed a decrease in specific surface areas and
amounts of oxygen-containing functional groups when the HTC tem­
perature was increased from 180 to 300 ◦ C [26]. It can be deduced that
the processing temperature plays a crucial role in developing the
physicochemical properties of hydrochar, which could in turn influence
the atrazine adsorption capacity of hydrochar.
The results of regression analysis of atrazine adsorption capacity on
different rice husk hydrochars are presented in Table S1. The observed
atrazine adsorption capacities of each hydrochar obtained under
different MHTC conditions were used to generate the predicted equation
(Eq.7) based on a quadratic polynomial model as follows:

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K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

adsorption capacities of each hydrochar type are close to the observed

Fig. 2. Atrazine adsorption capacity on pristine and activated rice husk
hydrochars. Means in each bar graph followed by the different letters are
significantly different (p<0.05).
results. This suggests a good correlation between the observed and
predicted data and provides validation of this model. The predicted
values under different MHTC conditions were used to generate 3D
graphs as illustrated in Fig. 1.
The results of ANOVA analysis (Table S2) indicates that the effect of
temperature on the atrazine adsorption capacity of hydrochar is statis­
tically significant (p<0.05), while those of residence time and L-S ratio
were not (p>0.05). However, the combined effect of temperature and L-
S ratio on the atrazine adsorption capacity of hydrochar was of statistical
significance (p<0.05). This means that L-S ratio affected the atrazine
adsorption performance of hydrochar, which varied with variations in
operating temperature. According to a review by Jain et al. [12], a lower
L-S ratio could facilitate the formation of more oxygen-containing
functional groups on hydrochar surfaces as it allows easy occurrence
of hydrolysis reactions.
As evidenced in Fig. 1, the atrazine adsorption capacity of rice husk
hydrochar increased with an increase in residence time from 20 to
60 min. The residence time governs the degree of carbonization, so a
longer residence time leads to improve surface properties (i.e., porosities
and functional groups) of hydrochar [12,8]. Subsequently, rice husk
hydrochar that adsorbed the highest amount of atrazine (produced by
heating at 175 ◦ C for 60 min and using an L-S ratio of 5:1 mL g-1) was
selected for the activation process.

3.2. Atrazine adsorption on activated rice husk hydrochar

The selected hydrochar was surface activated using H2O2 and KOH
solutions. The adsorption capacities of pristine and activated hydrochar
were experimentally examined with atrazine as shown in Fig. 2. Varying
H2O2 concentration (5 – 20%) did not have a statistically significant
(p>0.05) effect on the atrazine adsorption capacity of H2O2-activated
hydrochars. 20KHC showed a significantly greater atrazine adsorption
capacity at 1.68 ± 0.08 mg g-1 than hydrochar activated with 5KHC
Fig. 3. Effects of contact time on the atrazine adsorption capacity of pristine (1.52 ± 0.07 mg g-1). This enhancement of the adsorption capacity after
and activated rice husk hydrochars.
activation with KOH corresponds with the result of Mihajlović et al.
[24], who reported remarkably more oxygen-containing functional
Table 2
groups on the surface of hydrochar from grape pomace after activation
Kinetic parameters of atrazine adsorption on pristine and activated hydrochars. using a 2 M KOH solution.
In contrast, Liu et al. [20] reported that activation of corn stalk
Absorbents qe, exp. Pseudo- Pseudo-second-order model
(mg g- first-order
hydrochar with H2O2 enhanced atrazine adsorption capacity from 2.6 to
1
) model 3.9 mg g-1 due to an increase in C─OR bonds. This indicates that H2O2
activation only affected the surface of the adsorbent, with minimal effect
qe, cal. (mg k1 R2 qe, cal. k2 (g R2
g-1) (min- (mg g- mg- on physical properties such as pore sizes or specific surface areas [10]. It
1
) 1
) 1
min- can be deduced that oxygen-containing functional groups on hydrochar
1
) surfaces were more abundant after activation, which contributed to the
HC 1.40 0.81 0.01 0.87 1.39 0.03 0.99 higher atrazine adsorption capacity of activated hydrochar than that of
± 0.07 pristine hydrochar. Based on the ANOVA result, the effects of contact
10KHC 1.41 0.50 0.01 0.87 1.41 0.09 0.99 time and atrazine initial concentration on the adsorption performance of
± 0.06
the three prepared materials (i.e., HC, 10KHC, and 5HHC) were further
5HHC 1.52 0.93 0.01 0.93 1.54 0.03 0.99
± 0.05 determined.

q (mg g− 1 ) = − 53.6971 + 0.6085A − 0.0016A2 − 0.2029B − 0.0015B2 + 5.8773C + 0.0011C2 + 0.0029AB − 0.0684AC + 0.0002A2 C − 0.0002BC (7)

where A, B, and C denote the coded values of temperature (◦ C), resi­
dence time (min), and L-S ratio (mL g-1), respectively.
The predicted equation passed the goodness-of-fit test (p-value =
0.99 from Chi-Square test), with a coefficient of determination (R2) of
0.98 and adjusted determination coefficient (R2Adj) of 0.87 at the 95%
confidence interval. As indicated in Table 1, the predicted atrazine
3.3. Adsorption kinetic studies
The effects of contact time (0 – 24 h) on the atrazine adsorption
capacities of the selected pristine and activated rice husk hydrochars
were investigated, as presented in Fig. 3. These prepared materials
exhibited rapid atrazine adsorption behavior within the first 45 min,

4
K.A. Phan et al.
Fig. 4. Adsorption kinetic fitting results of intraparticle diffusion (Weber-
Morris) model onto (a) HC, (b) 10KHC and (c) 5HHC.
Fig. 5. Effects of initial atrazine concentration on the adsorption capacity of
pristine and activated rice husk hydrochars.
5
Journal of Environmental Chemical Engineering 10 (2022) 107575
and then the adsorption rate decreased until equilibrium state was
achieved at 24 h. The atrazine adsorption capacities of pristine and
activated rice husk hydrochars at the equilibrium state were in the range
of 1.40 – 1.52 mg g-1. Moreover, the adsorption capacities of these
studied materials are comparable to those of biochars obtained from
soybean, corn stalks, and rice straw, which exhibited atrazine adsorp­
tion capacities of 1.46, 1.24, and 1.41 mg g-1, respectively, with an
equilibrium time of 196 h [18]. The equilibrium time for pristine and
activated rice husk hydrochar observed in this study (24 h) is shorter
than that observed for biochars derived from soybean, corn stalks, and
rice straw (7 – 8 days) [18]. Meanwhile, the shortest equilibrium time
(240 min) was reported for pristine and cyclodextrin-modified poly­
acrylonitrile nanofiber membranes, but this was counterpoised by the
low atrazine adsorption capacities (0.60 - 0.82 mg g-1) of these mem­
branes [4].
The pseudo-first-order and pseudo-second-order models were
applied to describe the atrazine adsorption capacity of these prepared
materials as shown in Table 2 and Figure S1. The higher determination
coefficient (R2>0.99) and compatibility between the experimental and
calculated data affirmed that the pseudo-second-order model is more
suitable to describe the kinetics of atrazine adsorption by both pristine
and activated rice husk hydrochars. This result suggests that chemi­
sorption is the dominant mechanism of atrazine adsorption by these
materials [19,22,34]. The adsorption rate of atrazine by 10KHC (k2 =
0.09 g mg-1 min-1) was determined to be higher than that by HC and
5HHC (k2 = 0.03 g mg-1 min-1 for each material).
A similar atrazine adsorption mechanism was observed in the study
of biochar-supported reduced graphene oxide composite, in which the
pseudo-second-order model was used to explain the adsorption
behavior. However, the adsorption rate constant (k2 = 0.02 g mg-1 h-1)
of biochar-supported reduced graphene oxide composite [43] is less
than those of the pristine and activated rice husk hydrochars prepared in
this study. This could be attributable to the abundance of
oxygen-containing functional groups on the hydrochar surface.
The adsorption process is generally divided into three consecutive
stages: (1) an instant adsorption stage, (2) a subsequent slower
adsorption stage, and (3) an equilibrium adsorption stage [18,37]. The
atrazine adsorption capacity of pristine and activated rice husk hydro­
chars decreased over time. This could be attributed to the blocking of
micropores and mesopores of hydrochar and the occupation of available
adsorption sites by atrazine. Moreover, slower diffusion of atrazine
molecules into the pore areas was observed after a certain contact time.
To understand the transport of atrazine onto the three types of ad­
sorbents prepared in this study, the intra-particle diffusion model
described by Webb and Morris was employed. Two linearity correlations
were obtained between the atrazine adsorption capacity (qt) and contact
time (t0.5) as shown in Fig. 4, which means that the adsorption process
consists of two consecutive steps. The first straight line corresponds to
external mass diffusion or boundary layer diffusion, wherein the mass of
atrazine moves from the bulk solution to the adsorbent surface. The
second line represents atrazine adsorption onto the adsorbent pores
under the control of intra-particle diffusion [18,21,33].
The intra-particle diffusion parameters were calculated from the
slope and intercept as given in Table S3. A similar pattern was observed
for pristine and activated hydrochars, for which the first line, corre­
sponding to external mass diffusion, has a higher slope than the line
representing intra-particle diffusion. This implies that the external mass
diffusion of atrazine onto the adsorbent surface was faster than intra-
particle diffusion. Moreover, the lines with x-intercepts that did not
pass through the origin (C constants>0) revealed the existence of mul­
tiple rate-limiting steps influencing atrazine adsorption, including intra-
particle diffusion and boundary diffusion [18,33].
3.4. Adsorption isotherm studies
The adsorption capacity of the prepared materials increased with an
K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

Table 3
Fitting parameters of sorption isotherms of atrazine onto pristine and activated hydrochars by Langmuir and Freundlich models.
Sample Linear Langmuir Freundlich
2 -1 -1 2
Slope Intercept R qm (mg g ) KL (L mg ) R n KF (mg g-1)(L mg-1)1/n R2

HC 0.09 0.19 0.98 4.03 0.04 0.9732 1.28 0.19 0.99

10KHC 0.09 0.20 0.98 4.06 0.05 0.9518 1.32 0.22 0.99
5HHC 0.09 0.20 0.98 3.89 0.05 0.9792 1.29 0.19 0.99

The fitting parameters of the linear, Langmuir, and Freundlich

Table 4
models for atrazine adsorption are illustrated in Table 3 and Figure S2.
Physical properties of pristine and activated rice husk hydrochar.
The higher R2 values (R2>0.99) suggests that the Freundlich model
Sample SSA (m2 g- Total pore volume Pore diameter qea(mg g- could better describe atrazine adsorption by pristine and activated rice
1
) (cm3 g-1) (nm) 1
)
husk hydrochar. It assumes that atrazine adsorption on these adsorbents
HC 13.09 0.033 11.43 1.97 occurs via multilayer adsorption onto heterogeneous active sites. This
10KHC 5.16 0.016 12.66 2.18
finding agrees with those of adsorbents reported in many previous
5HHC 11.51 0.037 11.39 2.10
BC 31.15 0.068 8.72 0.41
studies, such as those of P-doped corn straw biochar [33], β-cyclodextrin
a
functionalized rice husk-based cellulose [28], and H2O2-oxidized corn
Adsorption condition: 30 mg L-1 of initial atrazine concentration, 24 h, and stalk biochar [20]. The nonlinearity factor values (n) of these prepared
4 g L-1 of adsorbent dosage
materials were greater than one. It assumes a ready and favorable pro­
cess of atrazine adsorption that comprised of several processes like
increase in initial atrazine concentration as presented in Fig. 5. The surface adsorption, hydrophobic partitioning, and pore-filling [1,20].
positive relation between the atrazine adsorption capacity of the ad­ Due to the relatively high n value of pristine and activated hydrochars,
sorbents and the initial contaminant concentration is attributed to the surface adsorption, including hydrogen (H)-bonding and π-π electron
concentration gradient driving force [28]. The result showed that the donor-acceptor interaction, could play a dominant role in atrazine
atrazine adsorption capacity of these adsorbents did not reach the adsorption [20]. Atrazine and aromatic material can act as electron
plateau stage due to atrazine’s low water solubility (33 mg L-1). The best donor and acceptor, respectively [19,20,9]. Additionally,
atrazine adsorption performance was observed for 10KOH (2.21 ± oxygen-containing functional groups of the adsorbent can bind with
0.15 mg g-1), followed by HC and 5HHC, both of which could adsorb atrazine via H-bonding interaction [20,23].
approximately 2.05 mg g-1 of atrazine.

Fig. 6. SEM images of pristine and activated rice husk hydrochar: (a) HC, (b) 5HHC, and (c) 10KHC.

Fig. 7. FTIR spectra of BC, HC, 10KHC and 5HHC (a) before and (b) after atrazine adsorption.

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K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

Fig. 8. XPS spectra of (a,d) HC, (b,e) 10KHC, and (c,f) 5HHC before and after atrazine adsorption.

Moreover, the linear model also fitted the experimental data for
atrazine adsorption by pristine and activated rice husk hydrochars
(R2>0.98), implying the contribution of atrazine partitioning into the
non-carbonized fractions of hydrochar [20]. As these materials were
produced at a temperature that is inadequate for complete carboniza­
tion, both carbonized and non-carbonized fractions exist on hydrochar
surfaces simultaneously. This result is similar to the studies on atrazine
adsorption by corn cob biochar [9] and corn stalk hydrochar [20].
Therefore, it can be concluded that atrazine adsorption on rice husk
hydrochar occurs in multiple steps and through different mechanisms.
Analysis of the surface properties of such hydrochars could reveal in­
formation that could guide further improvements.

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K.A. Phan et al. Journal of Environmental Chemical Engineering 10 (2022) 107575

Table 5 higher specific surface area than the prepared rice husk hydrochar and
Integrated areas (%) of functional groups on pristine and activated hydrochar has a dominant micropore system. The atrazine adsorption capacity of
before and after atrazine adsorption. the commercial rice husk biochar is much lower than those of the pris­
Functional group Before adsorption After adsorption tine and activated rice husk hydrochars. According to Gao et al. [7], an
HC 10KHC 5HHC HC 10KHC 5HHC
increase in atrazine adsorption capacity is credited to higher specific
surface areas based on a study of the pore structure of corn straw and
C═C 54.6 28.0 53.3 60.2 52.1 50.3
sawdust biochar. This implies that atrazine adsorption is not strongly
C─OR 34.4 56.1 32.2 30.2 35.9 35.3
C═O 7.8 10.7 9.8 6.9 9.0 9.7 associated with the specific surface area of rice husk hydrochar, which is
─COOR 3.3 5.2 4.8 2.6 3.0 4.8 consistent with the results of soybean biochar [18]. The
oxygen-containing functional groups on the hydrochar surface could
play an essential role in atrazine adsorption. Thus, FTIR spectroscopy
3.5. Hydrochar characterization and XPS were conducted to confirm this result.

3.5.1. BET analysis 3.5.2. SEM analysis

The H2O2 and KOH activation process had different effects on the
physical properties of rice husk hydrochar, as presented in Table 4. The
specific surface area of rice husk hydrochar produced at moderate
temperature (175 ◦ C) was comparable to those of canola straw hydro­
char (produced at 300 ◦ C, 1.76 m2 g-1) [26], corn stalk hydrochar
(produced at 250 ◦ C, 3.8 m2 g-1) [20], and rice husk biochar (fabricated
at 600 ◦ C, 6.1 m2 g-1) [22]. However, the specific surface areas of the rice
husk hydrochar were much lower than those of commercial activated
carbon because of incomplete pore formation and carbonization [26].
The specific surface areas and total pore volumes of the hydrochar
decreased after activation. This result was consistent with the effects of
H2O2 treatment on corn stalk hydrochar and biochar (produced at 200
and 500 ◦ C, respectively) [20] and activated carbon (obtained at 900 ◦ C)
[13]. In the case of corn stalk biochar obtained at 500 ◦ C, the maximum
atrazine adsorption capacity was declined from 3.57 to 2.02 mg g-1 after
this biochar was oxidized by H2O2. However, despite the decrease in SSA
of corn stalk hydrochar as biochar, the maximum atrazine adsorption
capacity of hydrochar was increased from 2.63 to 3.98 mg g-1 [20].
Additionally, Khalid et al. [16] concluded that inadequate process
temperature caused clogging of pores by alkaline metal carbonates,
which in turn reduced the material surface area. Therefore, improve­
ment in surface area of each material strongly depends on the type of
feedstock and activation conditions.
The average pore diameters of pristine and activated rice husk
hydrochars ranged from 11.39 to 12.66 nm, which can be classified as
mesopores. Due to the molecular diameter of atrazine (0.4 – 0.9 nm), the
mesopores in the adsorbents facilitated atrazine diffusion into the inner
pores. This could enhance the adsorption capacity of the materials [34].
The commercial rice husk biochar (BC) used in this study was bought
from a market, which was produced by a local retort (500 – 600 ◦ C) in
compliance with FAO guidelines [32]. This biochar has a significantly
The SEM images can provide insights into the surface morphology of
pristine and activated rice husk hydrochar, as illustrated in Fig. 6. It can
be seen that the surfaces of 5HHC and 10KHC were rougher than HC.
This is in agreement with the study of Petrović et al. [27] that found
higher surface roughness of KOH-modified grape pomace hydrochar
than unmodified hydrochar. The presence of some broken holes on the
surfaces of 10KHC can explain its lower pore volume compared to HC
and 5HHC. 10KHC appeared with the porous structure, which possibly
facilitates greater atrazine adsorption on its surfaces.
3.5.3. FTIR analysis
The FTIR spectra of pristine and activated rice husk hydrochar before
and after adsorbing atrazine are presented in Fig. 7. Different peaks
representing various functional groups on the adsorbent surface were
observed. The –OH stretching vibration at 3400-3300 cm-1 can be
attributed to alcohol groups in cellulose, hydroxyl groups in water, and
phenol in lignin. The peaks present at 1515 and 1611 cm-1 are assigned
to C═C bonds in aromatic rings of lignin [24], while the peak at
1161 cm-1 represents C–O stretching vibration in cellulose [5]. The
peaks at around 1701, 1382, and 1035 cm-1 are attributed to C═O bonds
in cellulose and lignin, COOR bonds, and SiO2 stretching vibrations,
respectively [20,24,40]. These functional groups were present on pris­
tine rice husk hydrochar and their abundance did not dramatically
change after KOH or H2O2 treatment. However, the intensity 10KHC
peak at 1035 cm-1 was less than that of HC and 5HHC. The presence of
SiO2 in 10KHC can facilitate the hydrolysis of atrazine by releasing
minerals that can catalyse atrazine reactions on the adsorbent’s surface
[23]. Regarding the BC sample, while the peaks of polar groups
(─COOH, C═O, and ─OH) vanished, the intensity of aromatic peak
(C═C) was enhanced compared to pristine and activated HCs (Fig. 7).
The far higher temperature of the pyrolysis process has resulted in a

Fig. 9. Schematic diagram of the atrazine adsorption mechanism on pristine and activated rice husk hydrochars.

8
K.A. Phan et al.
lower abundance of polar groups and elevated aromatic groups [20].
Atrazine adsorption by pristine and activated hydrochars changed
the intensity of some vibration peaks. The C═O peak became less intense
and flatter for hydrochar and H2O2-activated hydrochar after atrazine
adsorption. This result is in accordance with those of atrazine-adsorbed
biochar produced from different feedstocks such as soybeans, corn
stalks, and rice stalks [18]. As atrazine is likely to act as both H-bond
donor and H-bond acceptor, it can undergo H-bonding interaction with
the polar groups (─COOH, C═O, and ─OH) present on hydrochar surface
[42]. Unlike the prepared HC samples, a decrease in intensities of aro­
matic peaks at 1611 and 1515 cm-1 was observed in the BC sample after
atrazine adsorption, which suggests adsorption process involving π-π
electron donor-acceptors [42,44]. These findings combined with the
adsorption capacities of these adsorbents in Table 4 can confirm the
importance of oxygen-containing functional groups to atrazine
adsorption.
3.5.4. XPS analysis
The XPS spectra of HC, 10KHC, and 5HHC before and after atrazine
adsorption are illustrated in Fig. 8. The C1s spectra could be deconvo­
luted into four different peaks: (1) peak I with a binding energy of 284.7
± 0.2 eV attributable to aromatic carbon (C═C, CHx, and C─C), (2) peak
II with a binding energy of 285.7 ± 0.2 eV corresponding to alcohol
group (C─OR), (3) peak III with a binding energy of 288.0 ± 0.2 eV
ascribable to carbonyl groups (C═O, (O═C─O)), and (4) peak III with a
binding energy of 289.2 ± 0.2 eV attributable to carboxyl group
(─COOR) [17–20,38]. There was a remarkable increase in the abun­
dance of oxygen-containing functional groups after KOH treatment as
presented in Table 5. The total abundance of C─OR, C═O (C═O─O) and
─COOR bonds increased from 34.4, 7.8, and 3.3% in HC to 56.1, 10.7,
and 5.2% in 10KHC, respectively. Similarly, there was a slight increase
in ─COOR bonds from 3.3% in HC to 4.8% in 5HHC.
After atrazine adsorption for 24 h, there was a significant decrease in
the abundance of oxygen-containing functional groups on HC, from 34.4
to 30.2% for C─OR groups, 7.8 to 6.9% for C═O groups, and 3.3 to 2.6%
for ─COOR groups, as presented in Table 5. A similar reduction of these
functional groups was observed for 10KHC, in which the contents of
C─OR, C═O, and ─COOR groups decreased from 56.1 to 35.9%, 10.7 to
9.0%, and 5.2 to 3.0%, respectively. This affirms that oxygen-containing
functional groups play a crucial role in atrazine adsorption by HC and
10KHC. Meanwhile, a decrease in carbon compounds (C═C, CHx, and
C─C) and C═O from 53.3 to 50.3% and 9.8 to 9.7%, respectively, was
presented in 5HHC. Based on these results, it can be concluded that
oxygen-containing functional groups and aromatic compounds may
significantly influence atrazine adsorption performance.
3.6. Implication of atrazine adsorption mechanisms
The suggested mechanisms of atrazine adsorption by pristine and
activated rice husk hydrochars are illustrated in Fig. 9. As indicated by
the results of the kinetic studies, atrazine adsorption on the prepared
hydrochar was dominant via chemical reactions. Additionally, the XPS
results revealed a notable decrease in the proportion of oxygen-
containing functional groups (e.g., C─OR and C═O (C═O─O)) on HC
and 10KHC after adsorption of atrazine. This is suggestive of H-bond
formation between atrazine and these functional groups on the adsor­
bent surface. Meanwhile, the proportions of aromatic compounds,
especially C═C, CHx, and C─C, on 5HHC dropped after atrazine
adsorption. These aromatic compounds could act as π-electron accep­
tors, while atrazine acts as π-electron donors [20]. Furthermore, atrazine
partitioning could occur owing to the existence of non-carbonized
fractions in these adsorbent materials. The atrazine adsorption capac­
ity of 10KHC was generally higher than those of the other two studied
materials, suggesting a crucial role of oxygen-containing functional
groups and aromatic groups in atrazine adsorption. This finding agrees
with those of not only corn stalk hydrochar but also
9
Journal of Environmental Chemical Engineering 10 (2022) 107575
cyclodextrin-modified polyacrylonitrile nanofiber membrane in terms of
atrazine removal [20,4].
4. Conclusions
The higher atrazine adsorption capacity of rice husk hydrochar is
attributable to the higher MHTC temperature, lower L-S ratio, and
longer residence time. Due to the significant increase in oxygen-
containing functional groups on hydrochar surfaces after activation,
the atrazine adsorption capacity of rice husk hydrochar is superior to
that of conventional biochar, although it exhibited higher specific sur­
face areas. Furthermore, H-bonding interaction plays a dominant role in
atrazine adsorption by the studied adsorbents. This chemical adsorption
mechanism could ensure slow atrazine desorption from such adsorbent
materials. Therefore, rice husk hydrochar has great potential as a low-
cost adsorbent for environmental applications.
CRediT authorship contribution statement
Kim Anh Phan: Conceptualization, Methodology, Formal Analysis,
Investigation, Writing – original draft, Writing – review & editing.
Doungkamon Phihusut: Validation, Resources, Writing – review &
editing, Supervision. Nattapong Tuntiwiwattanapun: Conceptualiza­
tion, Validation, Resources, Writing – review & editing, Supervision,
Project Administration, Funding acquisition
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
The authors would like to acknowledge the Center of Excellence on
Hazardous Substance Management (HSM) and Graduate School Thesis
Grant (GCUGR1225641003M), Graduate School, Chulalongkorn Uni­
versity for providing financial support for this research work.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2022.107575.
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