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Chemosphere 235 (2019) 825e831

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Removal of lead by rice husk biochars produced at different


temperatures and implications for their environmental utilizations
Junxian Shi a, Xiaoliang Fan a, Daniel C.W. Tsang b, Fei Wang c, Zhengtao Shen d, e, *,
Deyi Hou d, **, Daniel S. Alessi e
a
School of Ecology and Environment, Inner Mongolia University, Hohhot, 010021, China
b
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China
c
Institute of Geotechnical Engineering, School of Transportation, Southeast University, Nanjing, 210096, China
d
School of Environment, Tsinghua University, Beijing, 100084, China
e
Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, T6G 2E3, Canada

h i g h l i g h t s

 The adsorption capacity for lead is in the order of RH300 < RH500 < RH700.
 The exchangeable Pb amount on biochar is in the order of RH300 > RH500 > RH700.
 Hydrocerussite and pyromorphite formed on biochars particularly for RH500 and RH700.
 Rice husk biochar produced at 300  C is suitable for water treatment.
 Rice husk biochars produced at 500  C and 700  C are suitable for soil remediation.

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

Article history: Rice husk is a common agricultural waste. The utilization of rice husk biochar depends on the charac-
Received 17 May 2019 teristics of biochar and its interaction mechanisms with heavy metals. In the present study, rice husk
Received in revised form biochars at three different temperatures 300, 500, and 700  C were produced (RH300, RH500, and
19 June 2019
RH700). The characteristics of these rice husk biochars and their interaction mechanisms with lead (Pb)
Accepted 29 June 2019
Available online 2 July 2019
were investigated, in order to reveal the potential environmental applications of the biochars. It was
observed that the surface area (from 0.632 to 193.149 m2/g) and pH (from 7.13 to 9.80) of the rice husk
Handling Editor: J. Rinklebe biochars significantly increased as production temperature rose from 300 to 700  C, while the number of
functional groups (e.g., carboxyl) decreased. The Langmuir maximum removal capacity (Qmax) values for
Keywords: Pb are in the order of RH300 < RH500 < RH700 (14.1, 21.7, and 26.7 mg/g respectively). Although RH300
Biochar has the smallest Qmax value, its exchangeable Pb amount is the largest (2.61 versus 0.223e0.377 mg/g),
Production temperature suggesting RH300 may be suitable for water treatment due to the easy separation of immobilized Pb and
Exchangeable lead better recycling usage. The Pb immobilized on RH500 and RH700 was mainly acidic soluble and generally
Environmental application
stable. Hydrocerussite is one important form within the acidic soluble fraction. Within the generally
Water treatment
stable formation, pyromorphite is a form for the immobilized Pb on the rice husk biochars, particularly
Soil remediation
for RH500 and RH700. These findings suggest RH500 and RH700 are of promising potential to be applied
in soil remediation to immobilize Pb and reduce its environmental risks.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction

Biochar is the solid and carbon-rich product of heating biomass


(typically agricultural and industrial wastes) under air-limited
* Corresponding author. School of Environment, Tsinghua University, Beijing,
100084, China. conditions in a process called pyrolysis. It was originally regarded
** Corresponding author. as a material to store carbon and consequently help mitigating
E-mail addresses: ztshennju@gmail.com (Z. Shen), houdeyi@tsinghua.edu.cn climate warming (Lehmann et al., 2008). Later on, biochar was
(D. Hou).

https://doi.org/10.1016/j.chemosphere.2019.06.237
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
826 J. Shi et al. / Chemosphere 235 (2019) 825e831

observed to have high immobilization/removal abilities for heavy the influence of feedstock type. The influence of production tem-
metals in soil/water due to its unique surface chemistry such as perature on the surface chemistry was investigated. The in-
high surface area, high alkalinity, high aromaticity and various teractions between the biochars and Pb were studied. Rice husk is
functional groups (Beiyuan et al., 2017; Shen et al., 2017b; O'Connor an agricultural waste with abundant availability: it accounts for one
et al., 2018b). Biochar application in soil/water treatment has huge fifth of the annual rice production globally (Battegazzore et al.,
potential, for the reason of multiple additional benefits including 2014). Pb has high health risks (especially to children) and is one
reuse of wastes, low carbon footfrint, and cost-effectiveness of the most problematic heavy metals worldwide (Trakal et al.,
(Beiyuan et al., 2016; El-Naggar et al., 2018, 2019). 2016; O'Connor et al., 2018a). The hypothesis of this research is
The interactions between heavy metals and biochar involve that the rice husk biochars produced at different temperatures may
adsorption (cation exchange, cation-p interaction and surface have different properties relating to their performance in Pb
complexation) and precipitation (Ahmad et al., 2014; Qi et al., 2017; removal/immobilization. Biochars produced at a certain tempera-
Elbana et al., 2018). Cation exchange is the replacement of the Hþ ture range may be more suitable for water treatment, and other
(e.g., from carboxylic and phenolic groups) and other cations (from biochars produced at another temperature range may be more
mineral phase: e.g., Kþ, Naþ and Caþ) from biochar by heavy metal suitable for soil remediation. This study aims to direct the practical
cations. Cation-p interaction refers to the electrostatic interaction applications of rice husk biochars produced at different tempera-
between heavy metal cations and the p electrons from biochar's tures, and shed lights on the optimum environmental utilization of
aromatic benzene rings (Keiluweit and Kleber, 2009). Surface biochar.
complexation means the binding between heavy metals and
organic functional groups (e.g., carboxylic and phenolic groups) 2. Materials and methods
through complexation. In addition to these adsorptive mechanisms,
heavy metals can also be immobilized by biochar through precip- 2.1. Production and characterization of biochar
itation (Shen et al., 2019). Biochar typically has high pH values due
to the presence of alkaline minerals in it. When added to water or The rice husks were obtained from Hengjing, Suzhou, Jiangsu,
soil, biochar may increase the environmental pH due to the disso- China. It is located within China's main rice production areas due to
lution of the alkaline minerals and therefore aid the precipitation of local fertile soil and abundant sunshine and rainfall. Upon recep-
many heavy metals. The alkaline minerals on biochar's surface also tion, the rice husks were dried in an oven at 60  C for 48 h and then
become local hot spots for the surface precipitation of heavy smashed to small particles. Rice husk biochars (RH) were produced
metals. In addition, P-containing biochar was shown to be at 300, 500 and 700  C (RH300, RH500 and RH700). Briefly, the
extremely effective to immobilize Pb due to the formation of stable small particles of rice husks were heated at 10  C/min and main-
pyromorphite (Cao and Harris, 2010; Cao et al., 2011). tained for 1 h at the highest temperature in a furnace without
The environmental applications of biochar highly depend on its protection gas. After production, a mesh sieve (#40) was used to
interaction mechanisms with heavy metals. For water treatment, sieve the produced biochars to particle sizes < 0.42 mm. Then the
biochar is expected to be repeatedly used for many times. There- rice husk biochars were characterized as detailed in supporting
fore, weak binding (e.g., physical adsorption and cation exchange) information (SI). Briefly, the pH, BET surface area and elemental
between heavy metals and biochar is preferred for an easy composition were determined. Biochar's surface functional groups
desorption and separation. In contrast, for soil treatment, relatively was tested by Fourier-transform infrared spectroscopy (FT-IR)
strong binding (e.g., precipitation and complexation) is preferred spectrometer. The mineral composition of the biochar was tested
for a low bioavailability/leachability of heavy metals in soil and a by X-ray diffractometer (XRD). Biochar's surface morphology was
long-term stability. It is therefore crucial to identify the interaction revealed by Scanning Electron Microscope (SEM).
mechanisms between biochar and heavy metals for its practical
applications. 2.2. Batch removal experiments and mechanistic analysis
The interaction between biochar and heavy metals is closely
related to the surface chemistry of biochar. Production temperature Removal kinetics, equilibrium study, and pH-dependence study
is a key factor determining biochar's properties and surface were conducted to reflect the characteristics of biochars’ removal
chemistry (Zhang et al., 2017; Zhao et al., 2018). A range of studies for Pb. The kinetics and equilibrium data were fitted by existing
found that, for a certain feedstock, increasing temperature results models to reveal the removal mechanisms. The details of the
in the increase of biochar pH (due to the formation of alkaline removal tests and data fitting are shown in SI.
minerals) and aromaticity, and the decrease of the number of After Pb removal, the biochar samples were dried in an oven at
functional groups (Zhao et al., 2018). However, there are also con- 60  C for 48 h. FT-IR, XRD, and SEM tests were performed to help
tradictory results from the literature. Lehmann (2007) observed reflect the interaction mechanisms between the biochars and Pb. A
that the cation exchange capacity of a wood biochar generally in- modified sequential extraction test was conducted to indicate the
crease with production temperature within 350e800  C. Mean- different fractions of Pb: 1) exchangeable, 2) acid soluble, and 3)
while, the surface area increased with production temperature generally stable (Shen et al., 2019). The details of the mechanistic
within 350e500  C, but decreased within 500e800  C. In contrast, analysis are shown in SI. The experiments were carried out in du-
Shen et al. (2019) observed that the cation exchange capacity of a plicates. For each experiment, mean and standard deviation were
rice straw biochar decreased with production temperature within calculated and reported.
300e700  C. Zhao et al. (2018) observed that the surface area of a
rapeseed stem biochar increased with production temperature 3. Results and discussion
within 200e700  C. Therefore, the relationship between biochar's
production temperature and properties remains unclear and may 3.1. Biochar characterization
vary among different feedstocks. Consequently, the interaction
mechanisms between heavy metals and biochars produced at The properties of the rice husk biochars are shown in Table 1.
different temperatures were not comprehensively understood. The yield of biochar decreased from 46.5% to 31.6% as production
In view of these considerations, rice husk biochars at different temperature increased from 300 to 700  C. This coincides with
temperatures were produced; only one feedstock was used to avoid previous findings that increasing production temperature
J. Shi et al. / Chemosphere 235 (2019) 825e831 827

Table 1
Rice husk biochar properties.

RH300 RH500 RH700

Yield 46.5% 33.6% 31.6%


pH 7.1 9.5 9.8
BET surface area (m2/g) 0.632 45.274 193.149
Average pore size (nm)b 14.5 11.6 6.80
C (%) 53.1 ± 0.4a 55.6 ± 0.2 57.1 ± 0.1
H (%) 3.69 ± 0.04 2.55 ± 0.06 1.35 ± 0.05
N (%) 2.07 ± 0.02 1.98 ± 0.02 1.58 ± 0.02
O (%) 16.7 ± 0.1 7.42 ± 0.23 4.84 ± 0.06
H/C 0.0695 0.0459 0.0236
O/C 0.3145 0.1334 0.0848
a
Mean ± standard deviation, n ¼ 2.
b
BJH Adsorption average pore width (4V/A).

promoted the formation of bio-oil and syn-gas and reduces solid


yield (Zhang et al., 2017; Zhao et al., 2018). Biochar's pH value
increased as more alkaline minerals formed in biochar at high
temperatures (Dodson, 2011). The overall pH of biochar is a balance
of its acidic functional groups and alkaline minerals. RH300 has a
pH (7.1) of nearly neutral, because a certain amount of acidic
functional groups remain in biochar at this production temperature
(Dodson, 2011). RH500 and RH700 are significantly alkaline (pH of
9.5 and 9.8), suggesting that alkaline minerals dominated the pH
and there may be limited acidic functional groups in these two
biochars. It is also observed that after 500  C, the increase of pro-
duction temperature only slightly raised the pH values of the rice
husk biochars.
The BET surface areas of the rice husk biochars dramatically
increased with the increase of production temperature. RH300 has
a very low surface area (0.632 m2/g), after further heating, the
volatilization of organics in biochar created porous structure,
resulting in a much higher surface area for RH700 (193.149 m2/g).
The average pore size of the rice husk biochars decreased with
production temperature as the large pores were destroyed and
more small pores formed during further heating. In comparison to
rice straw biochar (Shen et al., 2019), the rice husk biochar has a
lower surface area (0.632 versus 6.77 m2/g) at lower temperature
(300  C); however, at higher temperature (500 and 700  C), the rice
husk biochar has significantly higher surface areas (e.g., 193 versus
116 m2/g at 700  C). The SEM images (Fig. 1) also reveal the porous
structure of the rice husk biochars. Although not quantitatively, it
can be observed that RH700 generally shows more active porous
structure, with many small pores existing within or between big
pores. The carbon content were within 53.1e57.1% for all three
biochars. Increasing production temperature from 300 to 700  C
slightly increased the biochars’ carbon content. In comparison, H, N,
and O contents decreased due to the dehydration of volatile or-
ganics (Zhao et al., 2018). Correspondingly, the O/C and H/C values
decreased, indicating lower hydrophilicity and higher aromaticity
for biochar surface (Zhao et al., 2017).
Fig. 2 shows the biochars’ FT-IR spectra. Peaks representing C¼C
were observed at 1549-1607 cm1 for all biochars. These are typical
peaks observed for biochar, representing its aromatic structure
(Keiluweit et al., 2010). The peak at 1703 cm1 from RH300 attri-
butes to C¼O, which is mainly carboxyl (Keiluweit et al., 2010). This
peak was not observed for RH500 or RH700, because further
heating resulted in the decomposition of carboxyl in the biochars.
All biochars show peaks at ~1070 and ~795 cm1. These two peaks
represent Si-O-Si and Si-O respectively, which were typically
observed for rice husk biochars due to its abundant Si (Shen et al.,
2017b). Likewise, XRD patterns of the biochars show the presence Fig. 1. SEM images of the rice husk biochars (a) RH300, (b) RH500, and (c) RH700.
of SiO2 in all biochars (Fig. 3). No other significant peaks were
observed on the XRD patterns for the biochars, suggesting their
828 J. Shi et al. / Chemosphere 235 (2019) 825e831

Fig. 2. Rice husk biochars' FT-IR spectra before and after the adsorption of lead. Fig. 4. Kinetics results for the rice husk biochars's removal of lead (1 mM Pb solution
(20 mL) mixed with 0.1 g biohcar).

Table 2
Parameters of kinetics fitting for the removal of lead on the rice husk biochars.

Pseudo first order Pseudo second order


1 2
qe (mg/g) k1 (h ) R qe (mg/g) k2 (g/mg h) R2

RSB300 11.3 0.232 0.784 13.0 0.0220 0.848


RSB500 20.1 0.199 0.798 22.7 0.0121 0.864
RSB700 23.7 0.366 0.931 26.4 0.0179 0.974

played important roles in the removal kinetics (Choy et al., 2004).


The rate constant (K) of both models decreased from RH300 to
RH500 and then increased from RH500 to RH700. The development
of porous structure for RH500 may have resulted in longer intra-
particle diffusion and slower kinetics compared with RH300,
however, RH700 has higher alkalinity and more chemisorption may
have resulted in the shorter adsorption kinetics.
The equilibrium results are shown in Fig. 5 and Table 3.
Fig. 3. Rice husk biochars' XRD patterns before and after the adsorption of lead. Freundlich model generally described the equilibrium data better.

amorphous carbon structure.

3.2. Removal characteristics

Fig. 4 and Table 2 show the kinetics results of Pb removal by the


biochars. Pseudo second order model described the data better
compared to the pseudo first order model, with R2 of 0.848e0.974.
The obtained removal capacity (qe) was in the order
RH300 < RH500 < RH700. At 12 h, 70.0%, 69.6%, 84.5% of the qe
were immobilized on RH300, RH500, and RH700 respectively. In
comparison, for rice straw biochars (RSB), 65%, 73% and 94% of its qe
were immobilized on RSB300, RSB500, and RH700 within 1 h (Shen
et al., 2019). This suggests a much slower kinetics process for the
rice husk biochars to remove Pb. In general, the removal of Pb by all
biochars approximately reached equilibrium within the investi-
gated 24 h.
In general, if the removal of heavy metals by an adsorbent is a
mainly chemical process, the kinetics is typically very fast: e.g.,
reaching equilibrium within several minutes (Hai Nguyen et al.,
2016; Saleh et al., 2016). The relatively slow kinetics suggests that Fig. 5. Isotherms results for the rice husk biochars' removal of lead (20 mL Pb solution
physical process (e.g., film diffusion and intraparticle diffusion) also mixed with 0.1 g biochar).
J. Shi et al. / Chemosphere 235 (2019) 825e831 829

Table 3 rate and pyrolyzer type) etc.


Parameters of isotherm fitting. The influence of initial solution pH on the removal of Pb by the
Langmuir Freundlich rice husk biochars and the equilibrium solution pH are shown in
Qmax (mg/g) b (L/mg) R2 Kf (mg/g) 1/n R2
Fig. 6. It can be observed that the amount of immobilized Pb is
closely related to equilibrium solution pH at lower initial pH ranges.
RH300 14.1 0.057 0.843 3.92 0.212 0.954
It dramatically increased for all biochars as equilibrium solution pH
RH500 21.7 0.430 0.550 8.63 0.171 0.610
RH700 26.7 0.739 0.699 10.3 0.184 0.767 rose from 1.0 to 3.3e5.7 at initial pH of 1e3. At higher initial so-
lution pH range (3-6), the amount of immobilized Pb may increase
or remain constant as the equilibrium pH increases.
Freundlich model assumes a heterogeneous adsorption while At low equilibrium pH values (1.0 and 2.0e2.1), the biochars
Langmuir model assumes a homogeneous adsorption (Foo and exhibited very low immobilized Pb amount (1.25e1.91 and
Hameed, 2010). Therefore, the removal of Pb by the rice husk bio- 4.12e4.30 mg/g). This was due to the electrostatic repulsion as the
chars may have different mechanisms. The calculated maximum biochars' surfaces were intensively surrounded by protons under
removal capacity (Qmax) values for RH300, RH500, and RH700 are such low pH conditions, which repelled he positively charged Pb
14.1, 21.7, and 26.7 mg/g respectively. This coincides with the ki- cations (Gao et al., 2013). At initial solution pH 6, although the
netics findings that higher production temperature aided the Pb equilibrium solution pH values were not significantly different from
removal for the rice husk biochars. The Qmax values of plant-derived those at 5, the immobilized Pb amount was significantly enhanced.
biochars for Pb are summarized by Inyang et al. (2015), it can be This was due to the surface precipitation of Pb on the biochars.
found that the Qmax values observed in this study are higher than Although the equilibrium solution pH values were at 5.6e5.8 which
most of the values observed for other plant-derived biochars (e.g., may not aid the precipitation of Pb, there were alkaline minerals on
pine wood, oak wood, pine bark, oak bark, and sugarcane bagasse). the biochars’ surfaces forming local hot spots with high alkalinity.
For rice husk biochars, Samsuri et al. (2014) observed the Qmax Therefore, the Pb in the solution can precipitate on these hot spots.
value of 43.9 mg/g for Pb for a commercial rice husk biochar, but the This phenomenon was not observed for initial solution pH 4 or 5,
production temperature was not mentioned. Shen et al. (2017a) because more alkaline minerals were consumed under these lower
observed the Qmax value of 35.0 mg/g for Pb for a rice husk bio- pH conditions to buffer the solution to the equilibrium pH within
char produced at 700  C in the UK. A range of factors may result in 5e6. In general, the lower Pb removal for the biochars under lower
the differences in the Qmax values for the rice husk biochars solution pH values suggests the limitations of them in treating
including production temperature, rice growing region, detailed acidic wastewater (e.g., acid mine drainage) containing Pb.
production parameter (e.g., with or without protection gas, heating

Fig. 6. Influence of initial solution pH on rice husk biochars' removal of lead (0.1 g of
biochar mixed with 1 mM Pb solution (20 mL)) and the equilibrium solution pH. Fig. 7. Lead fractions (mg/g) immobilized on the rice husk biochars.
830 J. Shi et al. / Chemosphere 235 (2019) 825e831

3.3. Mechanistic analysis biochar required relatively high volume of adsorption bed. There-
fore, care should be taken before large-scale application of this
Fig. 7 and Fig. S1 show the fractions of immobilized Pb. RH300 biochar in water treatment.
has significantly higher amount of exchangeable Pb (2.61 mg/g) RH500 and RH700 have little exchangeable Pb and therefore
compared with RH500 and RH700 (0.377 and 0.223 mg/g respec- may not be suitable for the application in water treatment. They
tively). In contrast, RH500 and RH700 have much higher amounts have large amount of acid soluble and generally stable Pb. Under
of acid soluble (11.9 and 14.9 mg/g) and generally stable (8.60 and normal conditions, these two fractions of heavy metals are immo-
8.70 mg/g) Pb than RH300 (7.64 mg/g acid soluble Pb and 1.69 mg/g bile and of low risks in soil (Filgueiras et al., 2002). Hydrocerussite
generally stable Pb). It can be therefore concluded that, for the rice has very low solubility (Ksp of 1047) (Mohammadzadeh et al.,
husk biochars, the increase of production temperature from 300 to 2015), and is relatively stable. Therefore, RH500 and RH700 have
700  C decreased the exchangeable Pb while increase the acid the potential to be applied in soil to immobilize Pb and reduce its
soluble and generally stable Pb on biochar. As suggested by the FT- environmental risks.
IR results, RH300 contains carboxyl, which may provide Pyromorphite has extremely low solubility (Ksp ~1070-1080)
exchangeable Hþ and contribute to its higher cation exchange ca- (Park and Bolan, 2013; Shen et al., 2018) and is superiorly stable.
pacity (CEC). The carboxyl disappeared for RH500 and RH700, From the view of soil remediation or soil stabilization, the forma-
therefore their CEC decreased and exchanged less Pb. tion of pyromorphite is the most ideal condition for Pb immobili-
The FT-IR (Fig. 2) and XRD (Fig. 3) results suggest the formation zation. P-containing manure biochar was observed to immobilize
of hydrocerussite (Pb3(CO3)2(OH)2) on RH500 and RH700 after Pb Pb in the form of pyromorphite (Cao and Harris, 2010). This study
removal. The peaks from the XRD patterns representing hydro- also observed the formation of pyromorphite on rice husk biochars,
cerussite on RH700 were significantly stronger than RH500, sug- especially for RH500 and RH700. This further suggests these two
gesting that more hydrocerussite formed on RH700. This is in line biochars may be of great potential to be applied in soil remediation
with the fractions findings (Fig. 7) that these two biochars have a of Pb.
high amount of acid soluble Pb and that of RH700 was higher. The
relatively high pH values of the two biochars aided the formation of 4. Conclusions
hydrocerussite. RH300 did not reveal the presence of hydro-
cerussite, because its pH was nearly neural and it was not able to Production temperature significantly affects the properties of
precipitate Pb to hydrocerussite. Rice husk biochar typically con- rice husk biochars. The surface area and alkalinity of rice husk
tains less organic carbon compared to other biomass-derived bio- biochars significantly increased as production temperature rose
chars. Therefore, the cation-p interaction may not be a from 300 to 700  C., while the number of functional groups (e.g.,
predominant mechanism for the removal of Pb. The acid soluble carboxyl) decreased. The Qmax values for Pb are in the order of
fraction may be dominated by precipitation. RH300 < RH500 < RH700 (14.1, 21.7, and 26.7 mg/g respectively).
The XRD patterns (Fig. 3) show that all biochars show the Although RH300 has the smallest Qmax value, its exchangeable Pb
presence of pyromorphite (Pb5(PO4)3X (X ¼ Cl, F, OH)) after Pb amount is the largest. This suggests RH300 may be suitable to be
removal. In addition, the peaks representing pyromorphite became applied in water treatment due to the easy separation of immobi-
stronger for higher temperature rice husk biochars. Rice husk lized Pb and better recycling usage. The Pb immobilized on RH500
biochar was reported to contain 0.1e0.16% content of phosphorus and RH700 was mainly acidic soluble and generally stable.
(P) (Shen et al., 2017b), which may have aided the formation of Hydrocerussite (Pb3(CO3)2(OH)2) is one important form within the
pyromorphite. Higher temperature rice husk biochars contain more acidic soluble fraction. Within the generally stable formation, it was
pyromorphite, because higher pH values aided the formation of observed that pyromorphite (Pb5(PO4)3X (X ¼ Cl, F, OH)) is a form
Pb5(PO4)3(OH). Dairy-manure derived biochar was observe to for the immobilized Pb on the rice husk biochars, particularly for
immobilize Pb through the formation of pyromorphite (Cao and RH500 and RH700. These findings suggest RH500 and RH700 are of
Harris, 2010; Cao et al., 2011) due to the presence of P (0.86%). huge potential to be applied in soil remediation to immobilize Pb
However, rice husk contains much less P compared with diary and reduce its environmental risks.
manure. One recent research applied biochar produced from 70 wt
% rice husk and 30 wt% pig manure, and claimed the formation of Appendix A. Supplementary data
pyromorphite after Pb removal (Chen et al., 2019). However, the P
to form pyromorphite may come from the pig manure. It was the Supplementary data to this article can be found online at
first time to observe the formation of pyromorphite for pure rice https://doi.org/10.1016/j.chemosphere.2019.06.237.
husk biochar to immobilize Pb in this study.
References
3.4. Environmental implications
Ahmad, M., Rajapaksha, A.U., Lim, J.E., Zhang, M., Bolan, N., Mohan, D.,
The Qmax for RH300, RH500, and RH700 are 14.1, 21.7, and Vithanage, M., Lee, S.S., Ok, Y.S., 2014. Biochar as a sorbent for contaminant
management in soil and water: a review. Chemosphere 99, 19e33.
26.7 mg/g respectively. Although RH300 shows the smallest Battegazzore, D., Bocchini, S., Alongi, J., Frache, A., 2014. Rice husk as bio-source of
removal capacity. It has the highest amount of exchangeable Pb. silica: preparation and characterization of PLAesilica bio-composites. RSC Adv.
These Pb was weakly immobilized on RH300 and can be easily 4, 54703e54712.
Beiyuan, J., Awad, Y.M., Beckers, F., Tsang, D.C., Ok, Y.S., Rinklebe, J., 2017. Mobility
separated from the biochar (e.g., by slightly lowering solution pH). and phytoavailability of as and Pb in a contaminated soil using pine sawdust
Therefore, RH300 may be suitable to be applied in water treatment biochar under systematic change of redox conditions. Chemosphere 178,
due to the easy recycling usage. However, it is of note that lower 110e118.
Beiyuan, J., Tsang, D.C.W., Ok, Y.S., Zhang, W., Yang, X., Baek, K., Li, X.D., 2016.
pyrolysis temperature may result in the biochars with more labile
Integrating EDDS-enhanced washing with low-cost stabilization of metal-
carbon and less resistant to ageing (Zhang et al., 2017; Zhao et al., contaminated soil from an e-waste recycling site. Chemosphere 159, 426e432.
2018), and it is possible that the structure of biochar may be Cao, X., Harris, W., 2010. Properties of dairy-manure-derived biochar pertinent to its
instable after a few cycles, diminishing its removal capacity. The potential use in remediation. Bioresour. Technol. 101, 5222e5228.
Cao, X., Ma, L., Liang, Y., Gao, B., Harris, W., 2011. Simultaneous immobilization of
relatively slow removal kinetics may also limit the practical appli- lead and atrazine in contaminated soils using dairy-manure biochar. Environ.
cation of RH300 in water treatment, because it means that the Sci. Technol. 45, 4884e4889.
J. Shi et al. / Chemosphere 235 (2019) 825e831 831

Chen, H., Zhang, J., Tang, L., Su, M., Tian, D., Zhang, L., Li, Z., Hu, S., 2019. Enhanced Pb Resour. Prot. 07, 389e397.
immobilization via the combination of biochar and phosphate solubilizing O'Connor, D., Hou, D., Ye, J., Zhang, Y., Ok, Y.S., Song, Y., Coulon, F., Peng, T., Tian, L.,
bacteria. Environ. Int. 127, 395e401. 2018a. Lead-based paint remains a major public health concern: a critical re-
Choy, K.K., Ko, D.C., Cheung, C.W., Porter, J.F., McKay, G., 2004. Film and intraparticle view of global production, trade, use, exposure, health risk, and implications.
mass transfer during the adsorption of metal ions onto bone char. J. Colloid Environ. Int. 121, 85e101.
Interface Sci. 271, 284e295. O'Connor, D., Peng, T., Zhang, J., Tsang, D.C.W., Alessi, D.S., Shen, Z., Bolan, N.S.,
Dodson, J., 2011. Wheat Straw Ash and its Use as a Silica Source. University of York. Hou, D., 2018b. Biochar application for the remediation of heavy metal polluted
El-Naggar, A., Lee, S.S., Rinklebe, J., Farooq, M., Song, H., Sarmah, A.K., land: a review of in situ field trials. Sci. Total Environ. 619e620, 815e826.
Zimmerman, A.R., Ahmad, M., Shaheen, S.M., Ok, Y.S., 2019. Biochar application Park, J.H., Bolan, N., 2013. Lead immobilization and bioavailability in microbial and
to low fertility soils: a review of current status, and future prospects. Geoderma root interface. J. Hazard Mater. 261, 777e783.
337, 536e554. Qi, F., Kuppusamy, S., Naidu, R., Bolan, N.S., Ok, Y.S., Lamb, D., Li, Y., Yu, L.,
El-Naggar, A., Shaheen, S.M., Ok, Y.S., Rinklebe, J., 2018. Biochar affects the dissolved Semple, K.T., Wang, H., 2017. Pyrogenic carbon and its role in contaminant
and colloidal concentrations of Cd, Cu, Ni, and Zn and their phytoavailability immobilization in soils. Crit. Rev. Environ. Sci. Technol. 47, 795e876.
and potential mobility in a mining soil under dynamic redox-conditions. Sci. Saleh, M.E., El-Refaey, A.A., Mahmoud, A.H., 2016. Effectiveness of sunflower seed
Total Environ. 624, 1059e1071. husk biochar for removing copper ions from wastewater: a comparative study.
Elbana, T.A., Selim, H.M., Akrami, N., Newman, A., Shaheen, S.M., Rinklebe, J., 2018. Soil Water Res. 11, 53e63.
Freundlich sorption parameters for cadmium, copper, nickel, lead, and zinc for Samsuri, A.W., Sadegh-Zadeh, F., Seh-Bardan, B.J., 2014. Characterization of biochars
different soils: influence of kinetics. Geoderma 324, 80e88. produced from oil palm and rice husks and their adsorption capacities for heavy
Filgueiras, A.V., Lavilla, I., Bendicho, C., 2002. Chemical sequential extraction for metals. Int. J. Environ. Sci. Technol. 11, 967e976.
metal partitioning in environmental solid samples. J. Environ. Monit. 4, Shen, Z., Tian, D., Zhang, X., Tang, L., Su, M., Zhang, L., Li, Z., Hu, S., Hou, D., 2018.
823e857. Mechanisms of biochar assisted immobilization of Pb(2þ) by bioapatite in
Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm aqueous solution. Chemosphere 190, 260e266.
systems. Chem. Eng. J. 156, 2e10. Shen, Z., Zhang, Y., Jin, F., McMillan, O., Al-Tabbaa, A., 2017a. Qualitative and
Gao, H., Sun, Y., Zhou, J., Xu, R., Duan, H., 2013. Mussel-inspired synthesis of quantitative characterisation of adsorption mechanisms of lead on four bio-
polydopamine-functionalized graphene hydrogel as reusable adsorbents for chars. Sci. Total Environ. 609, 1401e1410.
water purification. ACS Appl. Mater. Interfaces 5, 425e432. Shen, Z., Zhang, Y., McMillan, O., Jin, F., Al-Tabbaa, A., 2017b. Characteristics and
Hai Nguyen, T., You, S.-J., Chao, H.-P., 2016. Effect of pyrolysis temperatures and mechanisms of nickel adsorption on biochars produced from wheat straw
times on the adsorption of cadmium onto orange peel derived biochar. Waste pellets and rice husk. Environ. Sci. Pollut. Res. Int. 24, 12809e12819.
Manag. Res. 34, 129e138. Shen, Z.T., Hou, D.Y., Jin, F., Shi, J.X., Fan, X.L., Tsang, D.C.W., Alessi, D.S., 2019. Effect
Inyang, M.I., Gao, B., Yao, Y., Xue, Y., Zimmerman, A., Mosa, A., Pullammanappallil, P., of production temperature on lead removal mechanisms by rice straw biochars.
Ok, Y.S., Cao, X., 2015. A review of biochar as a low-cost adsorbent for aqueous Sci. Total Environ. 655, 751e758.
heavy metal removal. Crit. Rev. Environ. Sci. Technol. 46, 406e433. Trakal, L., Veselska, V., Safarik, I., Vitkova, M., Cihalova, S., Komarek, M., 2016. Lead
Keiluweit, M., Kleber, M., 2009. Molecular-level interactions in soils and sediments: and cadmium sorption mechanisms on magnetically modified biochars. Bio-
the role of aromatic pi-systems. Environ. Sci. Technol. 43, 3421e3429. resour. Technol. 203, 318e324.
Keiluweit, M., Nico, P.S., Johnson, M.G., Kleber, M., 2010. Dynamic molecular Zhang, H., Chen, C., Gray, E.M., Boyd, S.E., 2017. Effect of feedstock and pyrolysis
structure of plant biomass-derived black carbon (biochar). Environ. Sci. Technol. temperature on properties of biochar governing end use efficacy. Biomass
44, 1247e1253. Bioenergy 105, 136e146.
Lehmann, J., 2007. Bio-energy in the black. Front. Ecol. Environ. 5, 381e387. Zhao, B., O'Connor, D., Zhang, J., Peng, T., Shen, Z., Tsang, D.C.W., Hou, D., 2018. Effect
Lehmann, J., Skjemstad, J., Sohi, S., Carter, J., Barson, M., Falloon, P., Coleman, K., of pyrolysis temperature, heating rate, and residence time on rapeseed stem
Woodbury, P., Krull, E., 2008. Australian climateecarbon cycle feedback reduced derived biochar. J. Clean. Prod. 174, 977e987.
by soil black carbon. Nat. Geosci. 1, 832e835. Zhao, S.X., Ta, N., Wang, X.D., 2017. Effect of temperature on the structural and
Mohammadzadeh, M., Basu, O.D., Herrera, J.E., 2015. Impact of water chemistry on physicochemical properties of biochar with apple tree branches as feedstock.
lead carbonate dissolution in drinking water distribution systems. J. Water Material. Energies 10.

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