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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
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.
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.
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.
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