Journal of Environmental Chemical Engineering 8 (2020) 104198

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Optimization of preparation conditions for biochar derived from water T

hyacinth by using response surface methodology (RSM) and its application
in Pb2+ removal
Runjuan Zhou*, Ming Zhang, Jiyuan Li, Wei Zhao
College of Electrical Engineering, Anhui Polytechnic University, Wuhu, 241000, Anhui, PR China

A R T I C LE I N FO A B S T R A C T

Editor: Xiwang Zhang In this study, response surface method (RSM) was adopted to optimize the preparation conditions of water
Keywords: hyacinth biochar. The interaction on Pb2+ adsorption performance between the three basic preparation con-
Water hyacinth ditions of heating time (X1), heating temperature (X2) and heating rate (X3) were designed by Box-Behnken
Biochar Design (BBD). The results showed that the mathematical model can fit the experimental data well. The sig-
Adsorption nificance of a single factor affecting followed by X2 > X3 > X1, and the interactive items as follows:
RSM X1X2 > X2X3 > X3X1. Through the analysis of variance and the numerical expectation function method, the
BBD optimal heating time is 2.65 h, heating temperature is 433 ℃, and heating rate is 19.96 ℃/min. The water
hyacinth biochar was prepared under optimized conditions (OWHBC) to adsorb 50 mg/L Pb2+ solution. The
actual experiment value of adsorption capacity (q) for Pb2+ was 24.94 mg/g, the predicted value of the model
was 24.95 mg/g, and the error was only 0.02%. The maximum theoretical adsorption capacity (Qm) obtained
with the Langmuir model were 195.24 mg/g for WHBC (prepared at center values of preparation conditions from
single-factor experiments: 3 h, 400 ℃, and 20 ℃/min) and 251.39 mg/g for OWHBC, respectively. Through the
determination of pH and specific surface area of biochar before and after optimization, it is proved that the RSM
is feasible to optimize the preparation conditions of biochar. The results showed that RSM could optimize the
preparation conditions of water hyacinth biochar and improve the adsorption ability of OWHBC to Pb2+.

1. Introduction
Water hyacinth (Eichhornia crassipes) is a kind of floating perennial
herbaceous plants, native to South America Amazon river basin and
found throughout the world. Water hyacinth has very strong re-
production ability. Under appropriate conditions (generally at the
ambient temperature of 25-35℃), the biomass of water hyacinth can be
doubled within 6 days. If not timely salvage treatment, its rotten roots,
stems, leaves will cause water quality deterioration, affecting the
growth of other aquatic organisms. Water hyacinth has been introduced
to China in 1930s, and caused serious harm to many waters of China
due to its rapid asexual reproduction [1]. Water hyacinth has strong
tolerance and absorption ability to heavy metals, nutrients such as N, P
and other pollutants, and has certain application value in environ-
mental pollution control [2,3], especially for heavy metals. So more and
more water hyacinth materials are widely used in the treatment of
heavy metal pollution in water, such as water hyacinth powder [4],
water hyacinth cellulose extract and water hyacinth biochar [5].
Among these materials, the water hyacinth biochar is widely used.
Using water hyacinth as the precursor of biochar to adsorb heavy me-
tals in waste water, it turns an environmental pollution problem into a
clean technology, which with the goal of "treating waste with waste"
and is worth popularizing.
Lead (Pb) is a highly toxic heavy metal, which enters the body
through the food chain and causes damage to various organs. The Lead
pollution has become an increasingly serious global environmental
problem [6–10]. Therefore, it is urgent to develop a simple and efficient
method to remove lead from water. Adsorption method is considered as
a promising treatment method for heavy metals due to its advantages
such as low cost, high efficiency and great metal recovery potential
[11].
Currently, biochars are widely used in adsorption method, and there
are many factors affecting the adsorption performance of biochar, such
as the raw materials, the preparation conditions of biochar, and ad-
sorption conditions have great effect on the adsorption ability. Many
scholars have studied focus on the composition and structural

⁎
Corresponding author at: College of Electrical Engineering, Anhui Polytechnic University, 8 Middle Beijing Road, Wuhu, 241000, Anhui, PR China.
E-mail address: rjzhou@126.com (R. Zhou).

https://doi.org/10.1016/j.jece.2020.104198
Received 1 April 2020; Received in revised form 6 June 2020; Accepted 16 June 2020
Available online 17 June 2020
2213-3437/ © 2020 Published by Elsevier Ltd.
R. Zhou, et al.
characteristics of biochar under different pyrolysis conditions. The re-
sults showed that heating temperature, heating time and heating rate
are the three most important factors in the preparation conditions of
biochar [12–14,5]. For example, the yield, surface area, pore volume,
elements composition, and calorific value vary with heating tempera-
ture [15,16]. Many studies have shown that, with the increase of
heating temperature, biochar functional groups and production rate
decline [17–24]. The heating time has effect on the composition, sur-
face areas, porosity of biochar [23], and so on. The heating rate mainly
affects the yields, fixation and operation cost of biochar [17,18,25,26].
Nevertheless, many studies have focused on the influence of three
factors on biochar adsorption ability, but rarely considered the influ-
ence of the interaction of these three factors [19,20,27–29], and for
different heavy metals, biochar with different preparation conditions is
required.
In order to study effect of the interaction of three preparation
conditions on the adsorption performance of biochar, the response
surface method (RSM) was used to optimize and improve the pre-
paration conditions of biochar [30–32,5]. This study using the RSM to
optimize the preparation conditions of water hyacinth biochar: heating
time, heating temperature and heating rate. The main purpose was to
obtain the optimal preparation conditions of water hyacinth biochar
with the removal of Pb2+. The BBD under RSM was used to search for
the best preparation conditions of water hyacinth biochar and explore
the interaction between the preparation conditions. The characteriza-
tion of OWHBC, equilibrium of Pb2+ adsorption and the adsorption
mechanisms were also studied. Moreover, these results will also provide
valuable information for the development of efficient, green adsorption
materials that remove other heavy metals from the water environment.
2. Materials and methods
2.1. Materials
Water hyacinth plants were collected from a pond in Anhui
Polytechnic University in Wuhu, Anhui province (long 118°24′19″E, lat
30°20′18″N). 1.5986 g Pb(NO3)2 was dissolved in ultrapure water to
prepare 1000 mg/L of Pb2+, and ultrapure water was used all in this
experiment. All lead solutions in this study were obtained by simulated
solution dilution, and the pH value of all solutions was adjusted with
0.1 mol/L NaOH or 0.1 mol/L HNO3 solutions. All chemical reagents
are analytically pure and purchased from Sinopharm Chemical Reagent
Co., Ltd., Shanghai, China.
2.2. Preparation of water hyacinth biochar
The preparation method is shown in the previous study [5]. A
crucible cup in a muffle furnace was used for production of the water
hyacinth biochar. The heating time, heating temperature and heating
rate could be controlled by the muffle furnace. During the production
process, the crucible cup with a lid was wrapped with tin foil to isolate
the oxygen. The achieved water hyacinth biochar was kept in airtight
bottle for subsequent experiments.
2.3. Response surface methodology (RSM): the Box-Behnken experimental
design
The heating time, heating temperature and heating rate were opti-
mized by Box-Behnken Design (BBD). The central values of the three
preparation conditions were obtained by single factor experiment. On
the basis of BBD experiment design, 17 samples of water hyacinth
biochar were prepared and used for 50 mg/L of Pb2+ solution adsorp-
tion experiment. In the RSM method, in order to predict the optimal
conditions for preparation and the interaction between the preparation
conditions, the mathematical quadratic model shown in Eq. (1)
[5,33,34].
2
Journal of Environmental Chemical Engineering 8 (2020) 104198
3 3 3 3
Y = β0 + ∑ βj Xj + ∑ βjj Xj2 + ∑ ∑ βij Xi Xj + ε
j=1 j=1 i=1 j=1 (1)
Where Y is the predicted response value; β0 is the constant; where βj, βjj,
and βij are linear effect, quadratic effect and interaction effect of the
reference coefficient, respectively; ε is a random error; Xi and Xj are
dimensionless coded predictors of independent factors. Analysis of
variance (ANOVA) was used to predict the applicability of the quadratic
model and the significance of the items in the equation. The experi-
mental scheme and data were analyzed by using the Design-Expert
10.0. The water hyacinth biochar prepared under optimized conditions
is called OWHBC.
2.4. Adsorption experiments
The adsorption properties of all prepared water hyacinth biochar
were studied in batch experiments. In the batch experiment, 0.2 g ab-
sorbent and 100 ml of 50 mg/L Pb2+ solution were added in a 250 ml
conical flask. The solution was oscillated for 3 h at temperature of 298 K
and speed of 150 rpm/min. The pH of the lead solution was adjusted
with 0.1 mol/L HNO3 and NaOH solutions. After the adsorption ex-
periment, a syringe filter (0.45 nm) was used to filter the solution, and
the residual Pb2+ concentration in the solution was determined by
Shimadzu AA-7000 G atomic absorption spectrophotometer (Shimadzu,
Japan). The adsorption capacity (qt) of Pb2+ was calculated by Eq. (2)
[35]:
(C0 − Ct ) V
qt =
m (2)
2+
Where, C0 and Ct are the initial and t time concentrations of Pb (mg/
L), respectively; m means the weight of the adsorbent (g); v is the vo-
lume of the adsorbent solution (L).
2.5. Adsorption kinetics and isotherms
To study the adsorption mechanism of two materials (WHBC and
OWHBC), the adsorption kinetics study and the isothermal adsorption
study were researched.
1.0 g adsorbent was carried into 1000 mL corked conical flask and
added 500 mL Pb2+ solution with initial concentration of 50 mg/L
(other experimental conditions were: temperature at 298 K, rotate
speed at 150 rpm/min). Samples were taken at 30, 60, 90, 120, 150,
180, 210 and 240 min, respectively, and determined the concentration
of Pb2+ in filtrate. The pseudo-first and second-order models were used
to analyze the adsorption kinetic data, two models listed followed in
Eqs. (3) and (4) [36]:
Pseudo-first-order model:
qt = qe (1 − exp (−k1 t )) (3)
Pseudo-second-order model:
qe2 k2 t
qt =
1 + qe k2 t (4)
2+
Where qe and qt (mg/g) are adsorption capacity of Pb at equilibrium
and t time (h), respectively, k1 (min−1) and k2 (g/mg·min) are constants
for pseudo-first-order and pseudo-second-order models, respectively.
The isothermal adsorption results of WHBC and OWHBC at different
initial concentrations of Pb2+ (1–1000 mg/L) were studied under the
conditions of adsorbent dosage of 2.0 g/L, pH value of the solution itself
and contact time of 300 min (other experimental conditions: tempera-
ture of 298 K and rotation speed of 150 rpm/min). Based on the
Langmuir nonlinear model and Freundlich nonlinear model, the equi-
librium data were analyzed, and two mathematical models were listed
in Eqs. (5) and (6), respectively [37]:
Langmuir model:
R. Zhou, et al. Journal of Environmental Chemical Engineering 8 (2020) 104198

K a Qm Ce Table 1
qe =
1 + K a Ce (5) Experimental design and results for BBD.

Freundlich model: Run Coded levels Preparation conditions Adsorption

capacity/
1 Heating Heating Heating (mg/g)
Qe = KF Cen (6)
time temperature rate (X3)
(X1)/h (X2)/℃ /(℃/min)
Among them, Ce (mg/L) is the concentration of adsorbent solution
at equilibrium, Ka is the Langmuir constant, KF is Freundlich constant, 1 −1 0 1 2 400 25 24.86
and n (Freundlich index) is the index of strength change in the ad- 2 −1 −1 0 2 300 20 24.59
sorption process and the index of adsorption deviation. Qm represents 3 −1 0 −1 2 400 15 24.86
the Langmuir maximum adsorption capacity (mg/g). Qe is the adsorp- 4 0 1 −1 3 500 15 24.82
5 0 0 0 3 400 20 24.93
tion amount at adsorption equilibrium (mg/g). All experiments were 6 1 −1 0 4 300 20 24.74
repeated three times and the experimental data were averaged. 7 1 0 1 4 400 25 24.87
8 0 0 0 3 400 20 24.92
2.6. pH and point of zero charge measurement (pHpzc) 9 −1 1 0 2 500 20 24.90
10 1 1 0 4 500 20 24.88
11 0 0 0 3 400 20 24.93
The pH of WHBC and OWHBC were determined by pH meter (PHS- 12 0 1 1 3 500 25 24.88
25, LEICI, Shanghai, China). The adsorbent material and ultrapure 13 0 −1 −1 3 300 15 24.60
water were mixed at a mass ratio of 1:10, after oscillating at a speed of 14 0 0 0 3 400 20 24.93
15 0 0 0 3 400 20 24.92
150 r/min at 25℃ for 24 h, filtered and measured the pH of the filtrate
16 1 0 −1 4 400 15 24.89
[38]. The pHpzc of WHBC and OWHBC were determined by (Zetasizer 17 0 −1 1 3 300 25 24.65
Nano ZEN3690, Malvern, England), measured using 0.01 M NaCl aqu-
eous solutions in the pH range from 2.0-11.0. These pH values were
fixed with 0.1 mol/L HCl and NaOH aqueous solution. The suspension terms, X1X2, X1X3, X2X3 are interactive terms and X12, X22, X32 are
was injected into the sample tank with a syringe, and then the Zeta quadratic terms. In the above expression, the positive sign before the
potential was measured in the sample tank, and the curve of Zeta po- coefficient indicates the synergistic effect between factors, while the
tential changing with pH was drawn. When Zeta potential is 0, the negative sign indicates the antagonistic effect. It can be seen from the
corresponding pH is the point of zero charge of the material (pHpzc) Eq. (7), the heating time and heating temperature, the heating time and
[39]. heating rate had antagonistic effects on each other, while the heating
temperature and heating rate had synergistic effects [40].
2.7. Characterization of biochar
3.1.2. Analysis of variance (ANOVA)
The methods of characterization were the same as the previous re- The quadratic regression model was used to analyze the variance of
search [5]. The methods were as follows: Hitachi S-4800 scanning the experimental results, as shown in Table 2. The p-value < 0.05 and
electron microscopy (SEM) and energy dispersive X-Ray (EDX) spec- higher F-value indicated the applicability of the model [41]. As can be
troscopy (Hitachi, Japan) were applied to characterize and determined seen from Table 2, p < 0.0001, F-value = 47.58, indicating that the
the Surface morphology and element composition of OWHBC. Specific model is very suitable for this experiment. The correlation coefficient of
surface area and pore characteristics of OWHBC and WHBC were tested model fitting R2 = 0.9839, R2adj = 0.9632, and the SNR (Signal to Noise
by the surface area and porosity analyzer (Quantachrome, United Ratio) of the model 19.825 is much higher than 4, indicating that the
States). The functional groups on the surface of the adsorbent were quadratic regression model was in good agreement with the experi-
analyzed by IRPrestige-21 transform infrared spectrometer (Shimadzu, mental results. According to the p-value values in Table 2, X1, X2, X1X2,
Japan). The structural characteristics of OWHBC were characterized by X22 and X32 are significant items (p < 0.05), while X3, X1X3, X2X3 and
X-ray diffraction (XRD) with Bruck-D8 series X-ray (powder) dif- X12 are non-significant items (p > 0.1) [32]. In the regression models,
fractometer (Bruck, German). the F values of X1, X2 and X3 are 6.95, 201.3 and 2.01, respectively. The
influence of three factors on the adsorbed performance of water hya-
3. Results and discussions cinth biochar are: X2 > X3 > X1, and the influence of interaction terms
are: X1X2 > X2X3 > X1X3 [42].
3.1. Regression model analysis and optimization
Table 2
3.1.1. Regression model analysis ANOVA for BBD for adsorption capacity (q) of Pb2+ by water hyacinth biochar.
The central value of each preparation condition was obtained from Sources Sum of df Mean F-value p-value
the single-factor experiment [5]. The experimental design of response Squares Square
surface analysis adopts Design-Expert10.0 for regression analysis and
Adsorption capacity 0.21 9 0.02 47.58 < 0.0001
equation fitting. The Box-Behnken design (BBD) was used to optimize
Model
the experiments, the response value is the adsorption capacity of Pb2+, X1 3.424E-003 1 3.424E-003 6.95 0.0336
and the results are shown in Table 1. The codes -1, 0, and 1 in the table X2 0.10 1 0.10 201.30 < 0.0001
represent the low, medium, and high levels of each factor, respectively. X3 9.901E-004 1 9.901E-004 2.01 0.1993
According to the experimental results, the range of adsorption ca- X1X2 8.055E-003 1 8.055E-003 16.35 0.0049
X1X3 2.178E-005 1 2.178E-005 0.04 0.8395
pacity is 24.59–24.93 mg/g. Quadratic regression model equation for
X2X3 4.669E-005 1 4.669E-005 0.09 0.7672
Yq is given as Eq. (7). X12 5.572E-004 1 5.572E-004 1.13 0.3229
X22 0.08 1 0.08 167.28 < 0.0001
Yq = 24.9296 + 0.0207X1 + 0.1114X2 + 0.0111X3 − 0.0449X1 X2 X32 0.01 1 0.01 22.92 0.0020
Residual 3.449E-003 7 4.928E-004 – –
− 2.3333 × 10−3X1 X3 + 3.4167 × 10−3X2 X3 − 0.0115X12 − 0.1399X22
Lack of fit 3.394E-004 3 1.131E-003 81.92 0.0005
− 0.0518X32 (7) Pure error 5.524E-005 4 1.381E-005 – –
Cor total 0.21 16 – – –
In the quadratic regression model equation, X1, X2, X3 are linear

3
R. Zhou, et al.
Fig. 1. The relationship between the actual data of the model and the predicted
data.
3.1.3. Model data adequacy check
Through the experiment of BBD design, the variance analysis of
experimental data was carried out. The actual data were obtained ex-
perimentally, and the predicted response (adsorption capacity) was
provided by the RSM model.
Fig. 1 shows that all the points were on the diagonal between the
predicted value and the actual value, and relevant studies showed that
variable data points on the line indicate the sufficiency of the model
[43]. As shown in Fig. 1, the actual data fit well with the predicted
values.
3.1.4. Interaction effects between factors
Through the quadratic regression model, the three-dimensional
(3D) response surface diagram of the interaction of preparation con-
ditions for the adsorption capacity (q) are shown in Fig. 2 (a), (b) and
(c).
Fig. 2 (a), (b) and (c) showed the 3D response surface of heating
time (X1) and heating temperature (X2), heating time (X1) and heating
rate (X2), and heating temperature (X2) and heating rate (X3) to ad-
sorption performance of water hyacinth biochar, respectively. As can be
seen from Fig. 2 (a), with the increase of heating time and heating
temperature, the adsorption capacity first significantly increased and
then decreased, and the highest q values appeared around X1 of 2.65 h
and X2 was about 430 ℃. According to Fig. 2 (b), with the increase of
pyrolysis time and heating rate, the adsorption capacity of water hya-
cinth biochar to Pb2+ did not change significantly, which was
Fig. 2. Three-dimensional (3D) response surface diagram of the interaction of preparation conditions between q: (a) Effects of X1 and X2; (b) Effects of X1 and X3; (c)
Effects of X2 and X3.
4
Journal of Environmental Chemical Engineering 8 (2020) 104198
consistent with the results of ANOVA. It can be seen from Fig. 2 (c) that
the heating temperature has a significant influence on the adsorption
ability of Pb2+ by water hyacinth biochar, while the heating rate has no
significant influence on the adsorption ability of Pb2+. It can be seen
from the figure that the optimal adsorption capacity occurs when the
heating temperature and heating rate are about 400 ℃ and 20 ℃/min,
respectively.
3.1.5. Response surface optimization
Based on the analysis of experimental data by design-expert10.0
software, the optimal combination of the three factors for the ability of
water hyacinth biochar to absorb Pb2+ is X1, X2 and X3 was 2.654 h,
433.827 ℃ and 19.961 ℃/min, respectively, which is different from the
optimal preparation conditions for the adsorption of Cd2+ [5]. This
further indicates that for different pollutants, biochar under different
preparation conditions is required.
In order to verify the accuracy of the predicted value, experiments
were carried out under the optimal combination condition: X1 at 2.65 h,
X2 at 433 ℃, and X3 of 19.96 ℃/min. The results of verification ex-
periments are shown in Table 3. From the Table 3, it can see that the
actual q was 24.94 mg/g, and the predicted adsorption capacity (q) of
Pb2+ by OWHBC was 24.95 mg/g. Gharbani used response surface
method to optimize the preparation of synthesized nano Zn
(OH)8Cl2H2O, which is used to remove Reactive Yellow 145(RY145)
from the solution. The predicted removal rate by the model and the
experimental removal rate were 48.71% and 52.11% respectively, with
an error of only 0.19% [44]. Similarly, Yu et al. used response surface
method to optimize the preparation of tomato stem activated carbon
and adsorb water vapor. The model predicted that the adsorption ca-
pacity under the optimal combination was 563.4 mg/g, and the actual
experimental value was 576.7 mg/g, with an error of 2.36% [45]. While
in this study, the deviation between the experimental value and the
predicted value is only 0.02%, and the error between the predicted
value and the actual experimental value is very small. Therefore, RSM
model can well predict the q of Pb2+ by OWHBC.
3.2. Adsorption kinetics and isotherms of WHBC and OWHBC
3.2.1. Adsorption kinetics
In order to study the adsorption rate and mechanism of Pb2+ by
biochars, the pseudo-first-order and second-order models are employed.
The fitting results were displayed in Fig. 3(a) and Table 4. As shown in
Fig. 3(a) and Table 4, the experimental data were fitted by the pseudo-
second-order model (R2 were 0.7348 and 0.6977 for OWHBC and
WHBC, respectively) was better than the pseudo-first-order model (R2
were 0.3639 and 0.2821 for OWHBC and WHBC, respectively).
Therefore, Pb2+adsorption by biochars are well fitted by pseudo-
second-order model. The result showed that adsorption of Pb2+ by
water hyacinth biochar was dominated by chemical adsorption,
R. Zhou, et al. Journal of Environmental Chemical Engineering 8 (2020) 104198

Table 3
Optimization verification of adsorption model.
Response value (Y) Predicted value Experimental Value1 Experimental Value2 Experimental Value3 Average experimental value

Q(mg/g) 24.95 24.94 24.95 24.94 24.94 ± 0.01

involving exchange or sharing of electrons between metal ions and Table 4

surface groups [46]. The parameters of adsorption kinetics.
The adsorption capacity (qe) obtained from the pseudo-second-order Models OWHBC WHBC
was in the order of OWHBC (24.99 mg/g) > WHBC (24.91 mg/g). This
indicates that the ability of biochar to absorb Pb2+ can be improved by Pseudo-first-order Kt (min−1) 0.1397 0.1414
optimizing the preparation conditions. And from the Fig. 3(a), in the qe (mg/g) 24.82 24.75
R2 0.3639 0.2821
initial 1 h, the adsorption rate of OWHBC was faster than the WHBC. Pseudo-second-order K2 (g/mg·min) 0.0512 0.0552
However, in the low concentration range, compared with WHBC, the qe (mg/g) 24.99 24.91
adsorption capacity of OWHBC to Pb2+ was not improved significantly. R2 0.7348 0.6977
Therefore, the adsorption isothermal model was used to further explore
the improvement of the adsorption performance of OWHBC.
Table 5
Langmuir and Freundlich model parameters.
3.2.2. Adsorption isotherms
To further prove that the adsorption performance of the OWHBC is Models OWHBC WHBC
better than that of the WHBC, the adsorption isotherms of Pb2+ by
Nonlinear-Langmuir Ka 0.0272 1.2844
OWHBC and WHBC were fitted by nonlinear-Langmuir model and Qmax (mg/g) 251.39 195.24
nonlinear-Freundlich model. The fitting results of the two models are R2 0.9644 0.9692
shown in Fig. 3 (b) and Table 5. Nonlinear-Freundlich KF 39.2423 58.1253
As shown in Fig. 3(b), with the increase of Pb2+ concentration, it n 3.3490 4.8496
R2 0.9895 0.9155
can be observed that the adsorption behavior of Pb2+ on WHBC and
OWHBC is slightly different. When the initial concentration of Pb2+
solution was higher than 200 mg/L−1, the adsorption capacity of
SEM-EDX, FTIR (Fourier transform infrared spectroscopy) and XRD.
OWHBC on Pb2+ was superior to that of WHBC. Under the condition of
The results showed that the adsorption mechanism of Pb2+ by OWHBC
high initial concentration, the adsorption capacity of OWHBC to Pb2+
mainly included precipitation, electrostatic adsorption, surface physical
is better than that of WHBC, indicating that the OWHBC can provide
adsorption, ion exchange and complexation of functional groups.
more adsorption sites for Pb2+. According to the values of R2, the
Langmuir isotherm was more suitable for WHBC, which may means
monolayer adsorption of Pb2+ on the surface of WHBC [47], while the 3.3.1. pH and Zeta potential of WHBC and OWHBC
Freundlich isotherm model better fitted the OWHBC, which may im- The pH of WHBC and OWHBC are 9.33 and 9.87, respectively. At
plies the multi-molecular adsorption process of Pb2+ by the OWHBC the temperature of 298 K, the solubility product constant (Ksp) of Pb
[48]. Additionally, the Freundlich constant n is between 1 and 10, (OH)2 is 1.2 × 10−15, the concentration of Pb2+ solution used in the
implying favorable Pb2+sorption onto biochar [49]. The maximum experiment was 50 mg/L, it can be calculated that the pH of Pb(OH) 2
theoretical adsorption capacity (Qm) of Pb2+ by OWHBC reached precipitation is 8.30. The initial and equilibrium pH of the solution
251.39 mg/g, which is significantly higher than the theoretical ad- were determined, and the initial solution pH was 5.42 ± 0.03, while
sorption capacity (Qm) of Pb2+ by WHBC (195.24 mg/g). the equilibrium pH of the solution for WHBC and OWHBC were
8.13 ± 0.05 and 8.32 ± 0.06, respectively. Therefore, precipitation is
3.3. Characterization of OWHBC and adsorption mechanisms of Pb2+ by one of the mechanisms by which OWHBC adsorbs Pb2+, and from the
OWHBC pH of adsorption equilibrium, it can be seen that the precipitation of
OWHBC is stronger than that of the WHBC in the process of Pb2+ ad-
In order to study the adsorption mechanism of OWHBC to Pb2+, sorption.
Zeta and pH values of OWHBC and WHBC were measured, and the The Zeta potential of WHBC and OWHBC were displayed in Fig. 4.
characteristics of OWHBC before and after adsorption were analyzed by When the Zeta potential is 0, it is called the point of zero charge, and

Fig. 3. (a) The adsorption kinetics of WHBC and OWHBC; (b) The adsorption isotherms of WHBC and OWHBC.

5
R. Zhou, et al.
Fig. 4. Zeta potential of WHBC and OWHBC.
the pH is pHpzc. From Fig. 4, The point of zero charge of WHBC and
OWHBC were 2.43 and 2.52, respectively, indicating that when the pH
value of solution > 2.55, the surface of WHBC and OWHBC are nega-
tively charged, while the surface of heavy metal ions is positively
charged. Therefore, strong electrostatic adsorption exists between
OWHBC and Pb2+ [50].
3.3.2. BET (specific surface area) and pore size distribution of WHBC and
OWHBC
The BET and pore size distribution analysis of WHBC and OWHBC
are shown in Table 6 and Fig. 5, the average pore size of OWHBC and
WHBC are 3.099 nm and 14.505 nm, respectively, which are belong to
mesoporous materials and are suitable for adsorption materials [51].
The BET and the BJH adsorption pores volume of OWHBC
(337.167 m2/g and 0.219 cm3/g) is 35.14 times and 19.91 times that of
WHBC (9.595 m2/g and 0.011 cm3/g), respectively. The above results
show that the pyrolysis temperature has a great influence on the spe-
cific surface area of biochar, which is consistent with the previous re-
search results [15,16]. So the OWHBC can provide a larger contact area
to adsorb more Pb2+ than the WHBC. It can also be seen from the
specific surface area that, for high concentration Pb2+, the adsorption
capacity of OWHBC is stronger than the WHBC, which is consistent with
the results obtained by isothermal adsorption fitting, and it shows that
the OWHBC can provide more adsorption sites for Pb2+ than the
WHBC.
3.3.3. SEM-EDS spectra of OWHBC and OWHBC + Pb (OWHBC after
adsorption of Pb2+)
SEM images of OWHBC and OWHBC + Pb are shown in Fig. 6. The
SEM image of OWHBC shows a large amount of debris, which will form
pores for heavy metal ions to enter the pores of biochar. The SEM
images of OWHBC + Pb were observed to show that many crystal
particles appeared on the surface of biochar, and EDX analysis showed
that these particles contained Pb element. The results showed that Pb2+
in solution could be absorbed into OWHBC by surface physical ad-
sorption.
The EDX spectra and element analysis of OWHBC and OWHBC + Pb
are displayed in Fig. 7 and Table 7. As can be seen from Fig. 7, OWHBC
contains K, Ca, Mg, P, Cl and other elements, while in the spectra of
OWHBC + Pb, there is a large number of Pb element. The analysis of
Table 6
Specific surface area and pore structure parameters of WHBC and OWHBC.
Samples Surface area (m2/g) Pore volume (cm3/g) Pore diameter (nm)
WHBC 9.595 0.011 14.505
OWHBC 337.167 0.219 3.099
6
Journal of Environmental Chemical Engineering 8 (2020) 104198
element content is shown in Table 7. After adsorption, the content of K
element decreased from 9.49% in OWHBC to 0.12% in OWHBC + Pb,
the content of Ca element decreased from 2.72% to 1.58%, and the
content of Pb element increased from 0 to 4.03%, which indicated that
during the adsorption process, K and Ca had ion exchange reaction with
Pb and transferred Pb elements from water to biochar [9,52].
3.3.4. XRD and FTIR spectra of OWHBC and OWHBC + Pb
X-ray diffraction analysis (XRD) is used to identify the phases of
crystalline substances according to the X-ray diffraction characteristics
of crystals, including the position, intensity and quantity of the dif-
fraction lines. It is often used to determine the morphology of new
substances and to elaborate the precipitation mechanism and adsorp-
tion mechanism of heavy metal ions caused by different fixed sub-
stances [53,54].The XRD spectra of OWHBC and OWHBC + Pb were
showed in Fig. 8. According to EDX energy spectrum analysis, the
OWHBC contains K, Ca, P and Cl, while the content of these elements in
OWHBC + Pb decreases. As can see from Fig. 8, after adsorption, the
peak of OWHBC + Pb at 2θ = 20.18°, 27.26°, 34.22°, 40.3° showed the
formation of Pb(CO3)2(OH)2, and the peak of OWHBC + Pb at
2θ = 24.82°, 43.22°, 47.46°, 48.42° showed the formation of Pb(CO3)2,
while the new peak at 2θ = 29.68° of OWHBC + Pb spectrum is
Pb5(PO4)3Cl, and the Pb5(PO4)3Cl has very low solubility and is prone
to precipitation [55,56], indicating that during the adsorption of Pb by
OWHBC, Pb reacts with P and Cl in OWHBC to form a more stable
precipitation of P and Cl, thus removing Pb [9].
The surface functional groups in the adsorbent materials are one of
the main factors affecting the adsorption of heavy metals [57]. Fourier
transform infrared spectroscopy (FTIR) was used to analyze OWHBC
and OWHBC + Pb, and the obtained spectra were shown in Fig. 9. As
can be seen from Fig. 9, the bands around 3500-3200 cm−1, 2800-
2900 cm−1, 2400-2500 cm−1, 1759 cm−1, 1656 cm−1, 1100-
1200 cm−1 and 800 cm−1 belong to the strecthing vibration of eOH,
eCH2e, eC]C–, PeH, eCHOe, eCOOe, eOH and Si–O–Si functional
groups [58,59], but in the spectrum of OWHBC + Pb, the width and
location of these peaks changed. These changes indicate that the above
functional groups can react with Pb2+. After reaction with Pb2+, the
peak at 3458 cm−1 (OeH stretching vibration) migrated to 3410 cm−1
and weakened significantly, and the 1136 cm−1 peak (OeH bending
vibration) weakened and shifted to 1143 cm−1 [60]. The change of
OeH absorption bands indicates that OeH groups plays an important
role in the adsorption of Pb2+ by OWHBC.
3.4. Comparison with other adsorbents for adsorption of Pb2+
The adsorption capacity of biochar materials to Pb2+ is different
with different raw materials and preparation methods. The Pb2+ ad-
sorption capacities of adsorbents have been published in previous stu-
dies are summarized in Table 8. As can be seen from Table 8, when the
preparation conditions were not optimized, the theoretical adsorption
capacity (Qm) of WHBC for Pb2+ (195.24 mg/g) was worse than that of
rice straw biochar prepared at 700 ℃ (198.18 mg/g) [61]. However,
after the preparation conditions were optimized by response surface
method, the adsorption capacity of OWHBC (251.93 mg/g) was greatly
improved, and the pyrolysis temperature was only increased by 33 ℃.
By comparing the adsorption performance of different biochar to
Pb2+ in Table 8, it can be concluded that the theoretical adsorption
capacity of Pb2+ by OWHBC is relatively larger than others, except the
KMnO4 modified rape straw biochar [10]. In this study, RSM was used
to optimize the basic conditions of biochar preparation, such as the
heating time, heating temperature and heating rate, and select the
optimal combination conditions to improve the adsorption performance
of biochar. However, the KMnO4 modified rape straw biochar needs to
be modified by KMnO4, its production process is more complicated than
that of OWHBC, and the production cost is higher than that of OWHBC.
Therefore, the response surface method is used to optimize the
R. Zhou, et al. Journal of Environmental Chemical Engineering 8 (2020) 104198

Fig. 5. Pore diameter distribution and nitrogen adsorption-desorption isotherm of WHBC and OWHBC: (a) Pore diameter distribution; (b) nitrogen adsorption-
desorption isotherm.

Fig. 6. SEM images of OWHBC and OWHBC + Pb: (a) and (b) OWHBC; (c) and (d) OWHBC + Pb.

Fig. 7. EDX spectra of OWHBC and OWHBC + Pb.

Table 7 4. Conclusions
EDX elemental analysis of OWHBC and OWHBC + Pb.
Element (Wt%) OWHBC OWHBC + Pb (1) The preparation conditions of water hyacinth biochar adsorbed
Pb2+ was optimized by response surface method. According to the
C 66.57 76.42 results, the heating temperature has the greatest influence on the
O 12.14 17.15 adsorption performance of biochar, while the heating time has the
Mg 0.23 0.23
P 0.72 0.29
least influence, which is different from the preparation conditions
Cl 8.12 0.18 of biochar adsorbed to Cd2+. The order of influence of interaction
K 9.49 0.12 terms on water hyacinth biochar adsorption of Pb2+ is: heating
Ca 2.72 1.58 time and heating temperature (X1X2) > heating temperature and
Pb – 4.03
heating rate (X2X3) > heating time and heating rate (X1X3). The
Totals 100 100
optimal conditions for the preparation of water hyacinth biochar
adsorbed with Pb2+ were optimized and analyzed as follows:
preparation conditions of biochar, improve the adsorption performance heating time of 2.65 h, heating temperature of 433 ℃ and heating
of biochar is feasible. Moreover, for different pollutants, the optimal rate of 19.96 ℃/min, and these conditions were different from
preparation conditions obtained by the optimization are also different, those of OWHBC adsorbed with Cd2+. The OWHBC was used to
so as to avoid the problem of using biochar prepared under the same adsorb Pb2+, the actual q was 24.94 mg/g, and the error with the
conditions to absorb and remove different pollutants, resulting in poor predicted value (24.95 mg/g) was only 0.02%.
adsorption effect on certain pollutants. (2) Adsorption kinetics results show that adsorption of Pb2+ by water
hyacinth biochar was dominated by chemical adsorption, involving

7
R. Zhou, et al. Journal of Environmental Chemical Engineering 8 (2020) 104198

distribution of the OWHBC and WHBC were analyzed, and the

difference of adsorption capacity before and after modification was
preliminarily discussed. SEM-EDX, FTIR and XRD analysis before
and after Pb2+ adsorption by OWHBC showed that the adsorption
mechanisms of Pb2+ by OWHBC are mainly including: precipita-
tion, ion exchange, surface physical adsorption and complexation.

CRediT authorship contribution statement

Runjuan Zhou: Conceptualization, Methodology, Software, Writing

- original draft, Writing - review & editing. Ming Zhang: Formal ana-
lysis, Funding acquisition, Investigation, Supervision. Jiyuan Li:
Validation, Visualization, Data curation. Wei Zhao: Funding acquisi-
tion, Resources, Project administration.
Fig. 8. XRD patterns of OWHBC and OWHBC + Pb.

Declaration of Competing Interest

We declare that we have no financial and personal relationships

with other people or organizations that can inappropriately influence
our work, there is no professional or other personal interest of any
nature or kind in any product, service and/or company that could be
construed as influencing the position presented in, or the review of the
manuscript entitled” Optimization of preparation conditions for biochar
derived from water hyacinth by using response surface methodology
(RSM) and its application in Pb2+ removal”

Acknowledgements

This work was supported by National Nature Science Foundation of

Fig. 9. Infrared spectra of OWHBC and OWHBC + Pb.
exchange or sharing of electrons between metal ions and surface
groups. Isothermal adsorption studies show that the maximum
theoretical adsorption capacity of Pb2+ by OWHBC and WHBC
were 251.39 mg/g and 195.24 mg/g, respectively. The results
showed that the adsorption ability of the optimized biochar to Pb2+
was higher than that of the unoptimized biochar.
(3) The pH, Zeta potential, BET specific surface area and pore size
China under Grant No. 51808001 and No. 51409001, Anhui Provincial
Natural Science Foundation (2008085ME159, 1808085QE146 and
1708085QB45), Anhui Provincial Higher Education promotion pro-
gram Humanities and Social Sciences General Project (TSSK2016B14).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jece.2020.104198.

Table 8
Comparison of Pb2+ adsorption capacity (Qm) with other reported adsorbents.
Adsorbents Adsorption conditions Pb2+ adsorption capacity (mg/g) Reference

Orange peel biochar T = 298 K, pH = 5.0 27.86 [62]

Sugar cane bagasse biochar 86.96
Cinnamomum camphora leaves biochar T = 308 K, pH = 5.8 39.06 [11]
NaOH modified cinnamomum camphora leaves biochar 98.33
Rice straw biochar (300 ℃) – 100.27 [61]
Rice straw biochar (500 ℃) – 164.62
Rice straw biochar (700 ℃) – 198.18
Ginkgo leaves biochar T = 298 K, pH = 5.0 138.89 [63]
Peanut shells biochar 30.67
Metasequoia leaves biochar 34.01
Ginkgo leaves 117.64
Peanut shells 33.33
Metasequoia leaves 108.69
Rice husk biochar (300 ℃) – 14.10 [64]
Rice husk biochar (500 ℃) – 21.70
Rice husk biochar (700 ℃) – 26.70
Rape straw biochar T = 298 K ± 2, pH = 5.0 ± 0.1 36.26 [10]
HNO3 modified rape straw biochar 108.99
H2O2 modified rape straw biochar 190.00
KMnO4 modified rape straw biochar 278.27
WHBC T = 298 K, pH = 5.5 195.24 This study
OWHBC T = 298 K, pH = 5.5 251.39 This study

8
R. Zhou, et al.
References
[1] R. Sindhu, P. Binod, P. Ashok, A. Madhavan, J.A. Alphonsa, N. Vivek,
E. Gnansounou, E. Castro, V. Faraco, Water hyacinth a potential source for value
addition: an overview, Bioresour. Technol. 230 (2017) 152–162, https://doi.org/
10.1016/j.biortech.2017.01.035.
[2] P. Kumar, M.S. Chauhan, Adsorption of chromium(VI) from the synthetic aqueous
solution using chemically modified dried water hyacinth roots, J. Environ. Chem.
Eng. 7 (2019) 103218, , https://doi.org/10.1016/j.jece.2019.103218.
[3] J.B. Neris, F.H.M. Luzardo, P.F. Santos, O.N. Almeida, F.G. Velasco, Evaluation of
single and tri-element adsorption of Pb2+, Ni2+ and Zn2+ ions in aqueous so-
lution on modified water hyacinth (Eichhornia crassipes) fibers, J. Environ. Chem.
Eng. 7 (2019) 102885 https://do-i.org/10.1016/j.jece.2019.102885.
[4] X.S. Li, S.L. Liu, Z.Y. Na, D.N. Lu, Z. Liu, Adsorption, concentration, and recovery of
aqueous heavy metal ions with the root powder of Eichhornia crassipes, Ecol. Eng.
60 (2013) 160–166, https://doi.org/10.1016/j.ecoleng.2013.07.039.
[5] R.J. Zhou, M. Zhang, J.H. Zhou, J.P. Wang, Optimization of biochar preparation
from the stem of Eichhornia crassipes using response surface methodology on ad-
sorption of Cd2+, Sci. Rep. 9 (2019) 17538, https://doi.org/10.1038/s41598-019-
54105-1.
[6] M. Boskabady, N. Marefati, T. Farkhondeh, F. Shakeri, A. Farshbaf,
M.H. Boskabady, Th-e effect of environmental lead exposure on human health and
the contribution of inflamma-tory mechanisms, a review, Environ. Int. 120 (2018)
402–420, https://doi.org/10.1016/j.envint.2018.08.013.
[7] Z. Han, X.Y. Guo, B.M. Zhang, J.G. Liao, L.S. Nie, Blood lead levels of children in
urban and suburban areas in China (1997-2015): temporal and spatial variations
and influencing factors, Sci. Total Environ. 625 (2018) 1659–1666, https://doi.org/
10.1016/j.scitotenv.2017.12.315.
[8] P.K. Rai, S.S. Lee, M. Zhang, Y.F. Tsang, K.H. Kim, Heavy metals in food crops:
health risks, fate, mechanisms, and management, Environ. Int. 125 (2019)
365–385, https://doi.org/10.1016/j.envint.2019.01.067.
[9] R.L. Gao, Q.L. Fu, H.Q. Hu, Q. Wang, Y.H. Liu, J. Zhu, Highly-effective removal of
Pb by co-pyrolysis biochar derived from rape straw and orthophosphate, J. Hazard.
Mater. 371 (2019) 191–197, https://doi.org/10.1016/j.jhazmat.2019.02.079.
[10] R.L. Gao, L. Xiang, H.Q. Hu, Q.L. Fu, J. Zhu, Y.H. Liu, G.Y. Huang, High-efficiency
removal capacities and quantitative sorption mechanisms of Pb by oxidized rape
straw biochars, Sci. Total Environ. 699 (2020) 134262, , https://doi.org/10.1016/j.
scitotenv.2019.134262.
[11] C.Q. Wang, H. Wang, Y.J. Cao, Pb(II) sorption by biochar derived from
Cinnamomum camphora and its improvement with ultrasound-assisted alkali acti-
vation, Colloids Surf. A Physicochem. Eng. Asp. 556 (2018) 177–184, https://doi.
org/10.1016/j.colsurfa.2018.08.036.
[12] J.H. Yuan, R.K. Xu, H. Zhang, The forms of alkalis in the biochar produced from
crop r-esidues at different temperatures, Bioresour. Technol. 102 (3) (2011)
3488–3497, https://doi.org/10.1016/j.biortech.2010.11.018.
[13] Y.J. Chang, S.K. Dodla, J.J. Wang, Fundamental and molecular composition char-
acteristics of biochars produced from sugarcane and rice crop residues and by-
products, Chemosphere 142 (2016) 4–13, https://doi.org/10.1016/j.chemosphere.
2015.05.084.
[14] M.I.S. Gonzaga, C.L. Mackowiak, N.B. Comerford, E.F.V. Moline, J.P. Shirley,
D.V. Guimaraes, Pyrolysis methods impact biosolids-derived biochar composition,
maize growth and nutrition, Soil Till. Res. 165 (2017) 59–65, https://doi.org/10.
1016/j.still.2016.07.009.
[15] B.A. Mohammad, J.L. Zhou, H.H. Ngo, W.S. Guo, Insight into biochar properties and
its cost analysis, Biomass Bioenerg. 84 (2016) 76–86, https://doi.org/10.1016/j.
biombioe.2015.11.002.
[16] Z.T. Shen, D.Y. Hou, F. Jin, J.X. Shi, X.L. Fan, D.C.W. Tsang, D.S. Alessi, Effect of
production temperature on lead removal mechanisms by rice straw biochars, Sci.
Total Environ. 655 (2019) 751–758, https://doi.org/10.1016/j.scitotenv.2018.11.
282.
[17] D. Angın, Effect of pyrolysis temperature and heating rate on biochar obtained from
pyrol-ysis of safflower seed press cake, Bioreour. Technol. 128 (2013) 593–597,
https://doi.org/10.1016/j.biortech.2012.10.150.
[18] I.A.W. Mohammad, A.O. Abdulrasoul, H.E.N. Ahmed, N. Mahmoud, R.A. Usman,
Pyrolysis temperature induced changes in characteristics and chemical composition
of biochar prod-uced from conocarpus wastes, Bioresour. Technol. 131 (2013)
374–379, https://doi.org/10.1016/j.biortech.2012.12.165.
[19] T. Mimmo, P. Panzacchi, M. Baratieri, C.A. Davies, G. Tonon, Effect of pyrolysis
temperature on miscanthus (Miscanthus × giganteus) biochar physical, chemical
and functional properties, Biomass Bioenerg. 62 (2014) 149–157, https://doi.org/
10.1016/j.biombioe.2014.01.004.
[20] H.R. Yuan, T. Lu, Y.Z. Wang, H.Y. Huang, Y. Chen, Influence of pyrolysis tem-
perature and holding time on properties of biochar derived from medicinal herb
(radix isatidis) resi-due and its effect on soil CO2 emission, J. Anal. Appl. Pyrol. 110
(2014) 274–284, https://doi.org/10.1016/j.jaap.2014.09.016.
[21] H. Huang, W.L. Yao, R.H. Li, A. Ali, J. Du, D. Guo, R. Xiao, Z.Y. Guo, Z.Q. Zhang,
M.K. Awasthi, Effect of pyrolysis temperature on chemical form, behavior and en-
vironmental risk of Zn, Pb and Cd in biochar produced from phytoremediation
residue, Bioresour. Technol. 249 (2018) 487–493, https://doi.org/10.1016/j.
biortech.2017.10.020.
[22] C. Zhang, B.Q. Shan, S.X. Jiang, W.Z. Tang, Effects of pyrolysis temperature on the
biotoxicity of Phyllostachys pubescens biochar in the aquatic environment, J.
Hazard. Mater. 376 (2019) 48–57, https://doi.org/10.1016/j.jhazmat.2019.05.
010.
[23] J. Zhang, J. Liu, R.L. Liu, Effects of pyrolysis temperature and heating time on
9
Journal of Environmental Chemical Engineering 8 (2020) 104198
biochar obtained from the pyrolysis of straw and lignosulfonate, Bioresour.
Technol. 176 (2015) 288–291, https://doi.org/10.1016/j.biortech.2014.11.011.
[24] X.X. Zhang, P.Z. Zhang, X.R. Yuan, Y.F. Li, L.J. Han, Effect of pyrolysis temperature
and correlation analysis on the yield and physicochemical properties of crop residue
biochar, Bioresour. Technol. 296 (2020) 122318, , https://doi.org/10.1016/j.
biortech.2019.122318.
[25] E. Hodgson, A.L. James, S.R. Ravella, S.T. Jones, W. Perkins, J. Gallagher,
Optimisation of slow-pyrolysis process conditions to maximize char yield and heavy
metal adsorption of biochar produced from different feedstocks, Bioresour. Technol.
214 (2016) 574–581, https://doi.org/10.1016/j.biortech.2016.05.009.
[26] S. Ghysels, F. Ronsse, D. Dickinson, W. Prints, Production and characterization of
slow pyrolysis biochar from lignin-rich digested stillage from lignocllulosic ethanol
production, Biomass Bioenerg. 122 (2019) 349–360, https://doi.org/10.1016/j.
biombioe.2019.01.040.
[27] Y.W. Lee, J. Park, C. Ryu, K.S. Gang, W. Yang, Y.K. Park, J. June, S. Hyun,
Comparison of biochar properties from biomass residues produced by slow pyrolysis
at 500 ℃, Bioresour. Technol. 148 (2013) 196–201, https://doi.org/10.1016/j.
biortech.2013.08.135.
[28] N.S. Sulaiman, R. Hashim, M.H.M. Amini, M. Danish, O. Sulaiman, Optimization of
activated carbon preparation from cassava stem using response surface metho-
dology on surface area and yield, J. Clean. Prod. 198 (2018) 1422–1430, https://
doi.org/10.1016/j.jclepro.2018.07.061.
[29] B. Zhao, D. O’Connor, J.L. Zhang, T.Y. Peng, Z.T. Shen, D. Tsang, D.Y. Hou, Effect of
pyrolysis temperature, heating rate, and residence time on rape seed stem derived
biochar, J. Clean. Prod. 174 (2018) 977–987, https://doi.org/10.1016/j.jclepro.
2017.11.013.
[30] X.J. Lee, L.Y. Lee, B.Y.Z. Hiew, S. Gan, S.T. Gopakumar, H.K. Ng, Multistage opti-
mizations of slow pyrolysis synthesis of biochar from palm oil sludge for adsorption
of lead, Bioresour. Technol. 245 (2017) 944–953, https://doi.org/10.1016/j.
biortech.2017.08.175.
[31] N. Iberahim, S. Sethupathi, C.L. Goh, M.J.K. Bashir, W. Ahmad, Optimization of
activated palm oil sludge biochar preparation for sulphur dioxide adsorption, J.
Environ. Manage. 248 (2019) 109302, , https://doi.org/10.1016/j.jenvman.2019.
109302.
[32] Y.T. Peng, Y.Q. Sun, R.Z. Sun, Y.Y. Zhou, D.C.W. Tsang, Q. Chen, Optimizing the
synthesis of Fe/Al(Hydr) oxides-Biochars to maximize phosphate removal via re-
sponse surface model, J. Clean. Prod. 237 (2019) 117770, , https://doi.org/10.
1016/j.jclepro.2019.117770.
[33] L. Shi, D. Wei, H.H. Ngo, W.S. Guo, B. Du, Q. Wei, Application of anaerobic granular
sludge for competitive biosorption of methylene blue and Pb(II): fluorescence and
respons-e surface methodology, Bioresour. Technol. 194 (2015) 297–304, https://
doi.org/10.1016/j.biortech.2015.07.029.
[34] M.H. Dehghani, A. Dehghan, A. Najafpoor, Removing reactive red 120 and 196
using chitosan/zeolite composite from aqueous solutions: kinetics, isotherms, and
process optimization, J. Ind. Eng. Chem. 51 (2017) 185–195, https://doi.org/10.
1016/j.jiec.2017.03.001.
[35] S.J. Mousavi, M. Parvini, M. Ghorbani, Adsorption of heavy metals (Cu2+ and
Zn2+) on novel bifunctional ordered mesoporous silica: optimization by response
surface methodology, J. Taiwan Inst. Chem. E. 84 (2018) 123–141, https://doi.org/
10.1016/j.jtice.2018.01.010.
[36] T.W. Chen, L. Luo, S.H. Deng, G.Z. Shi, S.R. Zhang, Y.Z. Zhang, O.P. Deng,
L.L. Wang, J. Zhang, L.Y. Wei, Sorption of tetracycline on H3PO4 modified biochar
derived from rice straw and swine manure, Bioresour. Technol. 267 (2018)
431–437, https://doi.org/10.1016/j.biortech.2018.07.074.
[37] R.J. Zhou, Y.B. Wang, M. Zhang, P.X. Yu, J.Y. Li, Adsorptive removal of phosphate
from aqueous solutions by thermally modified copper tailings, Environ. Monit.
Assess. 191 (4) (2019) 198–210 https://link.springer.com/article/10.1007/s10661-
019-7336-0.
[38] M.I. Al-Wabel, A. Al-Omran, A.H. El-Naggar, M. Nadeem, A.R.A. Usman, Pyrolysis
temperature induced changes in characteristics and chemical composition of bio-
char produced from conocarpus wastes, Bioresour. Technol. 131 (2013) 374–379,
https://doi.org/10.1016/j.biortech.2012.12.165.
[39] T.R. Bastami, M.H. Entezari, Activated carbon from carrot dross combined with
magnetite nanoparticles for the efficient removal of p-nitrophenol from aqueous
solution, Chem. Eng. J. 210 (2012) 510–519, https://doi.org/10.1016/j.cej.2012.
08.011.
[40] P.C. Wang, J. Mo, N.Z. Xie, W.J. Jiang, Cypress sawdust based activated carbon
preparati-on and its adsorptive capacity towards macromolecule dye(AR88) : op-
timization by surfa-ce methodology, Chinese J. Environ. Eng. 11 (11) (2017)
6109–6116, https://doi.org/10.12030/j.cjee.201608078.
[41] S. Dixit, V.L. Yadav, Optimization of polyethylene/polypropylene/alkali modified
wheat straw composites for packaging application using RSM, J. Clean. Prod. 240
(2019) 118228, , https://doi.org/10.1016/j.jclepro.2019.118228.
[42] Y.H. Jiang, C.H. Ye, M.Y.D. Lin, Y.Q. Wu, Z.Q. Zhu, Y.N. Zhu, Preparation and
characterization of the magnesium-loaded biochar from banana stem, Environ. Sci.
Technol. 41 (10) (2018) 56–61, https://doi.org/10.19672/j.cnki.1003-6504.2018.
10.008.
[43] S.Y. Lu, J.Q. Qian, Z.G. Wu, W.D. Ye, G.F. Wu, Y.B. Pan, K.Y. Zhang, Application of
statistical method to evaluate immobilization variables of trypsin entrapped with
sol-gel method, J. Biochem. Technol. 1 (3) (2009) 79–84.
[44] P. Gharbani, Preparation, characterization and application of synthesized nano Zn
(OH)8Cl2H2O in removing of dye pollutants: modeling of removal process by re-
sponse surface methodology, J. Mol. Liq. 246 (2017) 317–324, https://doi.org/10.
1016/j.molliq.2017.09.036.
[45] Q.F. Yu, H.R. Zhao, H. Zhao, S.N. Sun, X. Ji, M. Li, Y.F. Wang, Preparation of to-
bacco-stem activated carbon from using response surface methodology and its
R. Zhou, et al.
application for water vapor adsorption in solar drying system, Sol. Energy 177
(2019) 324–336, https://doi.org/10.1016/j.solener.2018.11.029.
[46] C. Wang, H. Wang, Carboxyl functionalized Cinnamomum camphora for removal of
heavy metals from synthetic wastewater-contribution to sustainability in agrofor-
estry, J. Clean. Prod. 184 (2018) 921–928, https://doi.org/10.1016/j.jclepro.2018.
03.004.
[47] M.A. Zazycki, M. Godinho, D. Perondi, E.L. Foletto, G.C. Collazzo, G.L. Dotto, New
biochar from pecan nutshells as an alternative adsorbent for removing reactive red
141 from aqueous solutions, J. Clean. Prod. 171 (2018) 57–65, https://doi.org/10.
1016/j.jclepro.2017.10.007.
[48] C. Zhang, Y.Q. Li, F.H. Wang, Z.G. Yu, J.J. Wei, Z.Z. Yang, C. Ma, Z.H. Li, Z.Y. Xu,
G.M. Zeng, Performance of magnetic zirconium-iron oxide nanoparticle in the re-
moval of phosphate from aqueous solution, Appl. Surf. Sci. 396 (2017) 1783–1792,
https://doi.org/10.1016/j.apsusc.2016.11.214.
[49] C. Wang, H. Wang, G. Gu, Ultrasound-assisted xanthation of cellulose from lig-
nocellulosic biomass optimized by response surface methodology for Pb(II) sorp-
tion, Carbohydr. Polym. 182 (2018) 21–28, https://doi.org/10.1016/j.carbpol.
2017.11.004.
[50] X. Huang, D. Wei, X.W. Zhang, D.W. Fan, X. Sun, B. Du, Q. Wei, Synthesis of amino-
functionalized magnetic aerobic granular sludge-biochar for Pb(II) removal: ad-
sorption perf-ormance and mechanism studies, Sci. Total Environ. 685 (2019)
68–689, https://doi.org/10.1016/j.scitotenv.2019.05.429.
[51] Z.A. Ghani, M.S. Yusoff, N.Q. Zaman, M.F.M.A. Zamri, J. Andas, Optimization of
preparation conditions for activated carbon from banana pseudo-stem using re-
sponse surface methodology on removal of color and COD from landfill leachate,
Waste Manage. 62 (2017) 177–187, https://doi.org/10.1016/j.wasman.2017.02.
026.
[52] J.Q. Deng, X.D. Li, Y.G. Liu, G.M. Zeng, J. Liang, B. Song, X. Wei, Alginate-modified
biochar derived from Ca(II)-impregnated biomass: excellent anti-interference
ability for Pb(II) removal, Ecotox. Environ. Safe. 165 (2018) 211–218, https://doi.
org/10.1016/j.ecoenv.2018.09.013.
[53] M. Chen, L.Q. Ma, S.P. Singh, R.X. Cao, R. Melamed, Field demonstration of in situ
immobilization of soil Pb by using P amendments, Adv. Environ. Res. 8 (1) (2003)
93–102, https://doi.org/10.1016/S1093-0191(02)00145-4.
[54] R. Melamed, X. Cao, M. Chen, Q.Y. Ma, Field assessment of lead immobilization in a
contaminated soil after phosphate application, Sci. Total Environ. 305 (2003)
117–127, https://doi.org/10.1016/S0048-9697(02)00469-2.
10
Journal of Environmental Chemical Engineering 8 (2020) 104198
[55] T.T. Yang, L.R. Meng, H. Li, J.Y. Wu, W.Q. Yin, S.S. Wang, J.H. Hou, X.Z. Wang,
Adsorption of Pb by biochars derived from two type of biomass, J. Agro- Environ.
Sci. 36 (8) (2017), https://doi.org/10.11654/jaes.2017-0276 1627-133.
[56] J. Topolska, M. Manecki, T. Bajda, O. Borkiewicz, P. Budzewski, Solubility of
pyromorphite Pb5(PO4)3Cl at 5-65 °C and its experimentally determined thermo-
dynamic parameters, J. Chem. Thermodyn. 98 (2016) 282–287, https://doi.org/10.
1016/j.jct.2016.03.031.
[57] X.D. Yang, Y.S. Wan, Y.L. Zheng, F. He, Z.B. Yu, J. Huang, H.L. Wang, Y.S. Ok,
Y.S. Jiang, B. Gao, Surface functional groups of carbon-based adsorbents and their
roles in the removal of heavy metals from aqueous solutions: a critical review,
Chem. Eng. J. 366 (2019) 608–621, https://doi.org/10.1016/j.cej.2019.02.119.
[58] Y.J. Xue, C. Wang, Z.H. Hu, Y. Zhou, Y. Xiao, T. Wang, Pyrolysis of sewage sludge
byelectromagnetic induction: biochar properties and application in adsorption re-
moval of Pb(I-I), Cd(II) from aqueous solution, Waste Manage. 89 (2019) 48–56,
https://doi.org/10.1016/j.wasman.2019.03.047.
[59] W.Q. Yin, D. Dai, J.H. Hou, S.S. Wang, X.G. Wu, X.Z. Wang, Hierarchical porous
biochar-based functional materials derived from biowaste for Pb(II) removal, Appl.
Surf. Sci. 465 (2019) 297–302, https://doi.org/10.1016/j.apsusc.2018.09.010.
[60] G.Q. Tan, Y. Wu, Y. Liu, D. Xiao, Removal of Pb(II) ions from aqueous solution by
manganese oxide coated rice straw biochar - A low-cost and highly effective sor-
bent, J. Taiwan Inst. Chem. Eng. 84 (2018) 85–92, https://doi.org/10.1016/j.jtice.
2017.12.031.
[61] Z.T. Shen, D.Y. Hou, F. Jin, J.X. Shi, X.L. Fan, D.C.W. Tsang, D.S. Alessi, Effect of
production temperature on lead removal mechanisms by rice straw biochars, Sci.
Total Environ. 655 (2019) (2019) 751–758, https://doi.org/10.1016/j.scitotenv.
2018.11.282.
[62] J.H.Li A.A.Ahmed, Removal of Pb(II) from aqueous solution by using biochars de-
rived from sugar cane bagasse and orange peel, J. Taiwan Inst. Chem. E. 61 (2016)
367–375, https://doi.org/10.1016/j.jtice.2016.01.005.
[63] M.E. Lee, J.H. Park, J.W. Chung, Comparison of the lead and copper adsorption
capacities of plant source materials and their biochars, J. Environ. Manage. 236
(2019) 118–124, https://doi.org/10.1016/j.jenvman.2019.01.100.
[64] J.X. Shi, X.L. Fan, D.C.W. Tsang, F. Wang, Z.T. Shen, D.Y. Hou, D.S. Alessi, Removal
of lead by rice husk biochars produced at different temperatures and implications
for their environmental utilizations, Chemosphere 235 (2019) 825–831, https://
doi.org/10.1016/j.chemosphere.2019.06.237.