Environment International 126 (2019) 69–75

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Environment International
journal homepage: www.elsevier.com/locate/envint

Wheat straw biochar reduces environmental cadmium bioavailability T

a,c b b c,⁎
Liqiang Cui , Matt R. Noerpel , Kirk G. Scheckel , James A. Ippolito
a
School of Environmental Science and Engineering, Yancheng Institute of Technology, No. 211 Jianjun Road, Yancheng 224003, China
b
US Environmental Protection Agency, National Risk Management Research Laboratory, Land and Materials Management Division, 5995 Center Hill Avenue, Cincinnati,
OH 45224-1701, USA
c
Department of Soil and Crop Sciences, Colorado State University, Fort Collins 80523-1170, USA

ARTICLE INFO ABSTRACT

Keywords: Cadmium contamination in waters and soils can lead to food chain accumulation and ultimately deterioration in
BCR method human health; means for reducing bioavailable Cd are desperately required, and biochars may play a role. Long-
Biochar (BC) term (240 d) lab incubation experiments were utilized to explain wheat straw-derived biochar effects on Cd
Cadmium sorption and decreasing Cd bioavailability in soils and solutions (0, 5, and 15% biochar as wt:wt or wt:vol,
Contaminated paddy soil
respectively), and to identify Cd forms present using both the European Community Bureau of Reference (BCR)
Synchrotron
X-ray absorption spectroscopy
chemical sequential extraction procedure and synchrotron-based X-ray absorption spectroscopy (XAS). Biochar
Cd removal was up to ~90% from Cd-containing solutions and contaminated soil as compared to the control.
Based on the wet chemical sequential extraction procedure in conjunction with XAS, biochar application pro-
moted the formation of (oxy)hydroxide, carbonate, and organically bound Cd phases. As a material, biochar may
be promoted as a tool for reducing and removing bioavailable Cd from contaminated waters and soils. Thus,
biochar may play a role in reducing Cd bioaccumulation, trophic transfer, and improving environmental quality
and human health.

1. Introduction contamination. In China and other locations where Cd pollution is an

issue, human exposure to Cd is most often through the consumption of
Soil heavy metal pollution is a serious problem globally, leading to contaminated food (Zhao et al., 2013). In order to reduce the risk of Cd
food chain accumulation and ultimately human health risk. In China accumulation from soils to plants, and ultimately humans, soil Cd
specifically, soil heavy metal pollution can be linked to recent rapid bioavailability needs to be reduced. One such novel approach for re-
industrialization, urbanization, and subsequently widespread solid, li- ducing soil bioavailable Cd is the use of biochar.
quid, and gaseous metal emissions (Wang, 1998; Zhao et al., 2015). Biochar (BC), a carbon enriched material, is produced via pyrolysis
China's Ministry of Environmental Protection (MEP, 2014) has esti- of biomass at moderate temperature (~500 °C) under limited oxygen
mated that over 16% of all agricultural soils are contaminated with concentrations (Lehmann et al., 2006). Because of its unique physical-
heavy metals. Of those heavy metals present, soil cadmium (Cd) con- chemical characteristics, BC is recognized as a multifunctional material
centrations exceed China's environmental standards in 7% of all arable for treating heavy metal polluted soils and water (Lehmann et al.,
lands (98,000 km2) based on limits that protect agricultural production, 2011). Many studies (e.g., Devi and Saroha, 2014; Ippolito et al., 2017;
heavy metal accumulation in the food chain, and consequently human Uchimiya et al., 2011) have reported that BC can significantly sorb
health. When ingested by animals and humans, Cd may lead to kidney heavy metals, leading to reduced heavy metal bioavailability and
dysfunction, skeletal damage, and cancers (Satarug and Moore, 2004). leaching. Multiple studies have focused sole attention on biochar's use
According to the World Health Organization (2011), oral ingestion of as for removing and reducing Cd bioavailability in the environment.
little as 0.125 mg Cd kg−1 body weight can cause health issues. Given Bian et al. (2014) utilized a paddy soil contaminated with Cd due to
the amount of arable land contaminated with Cd, the potential for nearby smelter emissions, adding wheat straw biochar up to
human health issues is exacerbated in China. 40 Mg ha−1. Using a combination of simple extraction techniques,
Almost 250 locations with major human health issues in China have Fourier transform infrared spectroscopy, laser ablation inductively
been identified (China.org.cn, 2013), likely associated with man-in- coupled plasma mass spectrometry, and scanning electron microscopy-
duced pollution; many of these locations are affected by Cd energy dispersive spectroscopy, findings suggested that Cd formed

⁎
Corresponding author.
E-mail address: [email protected] (J.A. Ippolito).

https://doi.org/10.1016/j.envint.2019.02.022
Received 29 November 2018; Received in revised form 16 January 2019; Accepted 6 February 2019
Available online 16 February 2019
0160-4120/ © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
L. Cui, et al. Environment International 126 (2019) 69–75

associations with surface functional groups, Fe oxyhydroxide phases, Table 1

and Ca and P present in biochar. Subsequently, Cd bioavailability de- Wheat straw biochar (BC) and paddy soil (0 to 15 cm depth) basic properties
creased as noted in a 69% reduction in rice uptake of Cd. In a batch and total elemental analyses.
experiment coupled with the use of a modified European Community pH CECa C N P K Ca Mg Cd
Bureau of Reference (BCR) sequential extraction procedure, Cui et al.
(2014) used peanut hull biochar to remove Cd from solution cmolc kg−1 g kg−1 mg kg−1
(6.74 mg Cd g−1 biochar), with > 50% of Cd bound in the carbonate
BC 10.4 21.7 467 5.90 14.4 11.5 10.4 6.49 0.03
form. Cui et al. (2016) also used the BCR procedure to ascertain long- Soil 6.1 18.0 20.7 3.19 0.82 11.4 1.46 5.38 22.6
term (5 years) changes in soil Cd bioavailability following wheat straw
biochar application (up to 40 Mg ha−1) in a Cd contaminated paddy a
CEC = Cation Exchange Capacity.
soil. The authors noted that biochar was able to convert Cd to more
stable forms (e.g., residual forms), subsequently reducing Cd uptake by analyzed using the molybdate blue method, total K via
rice. Ippolito et al. (2017) also used simple extraction techniques in HClO4–HNO3–HF digestion and analyzed by atomic absorption spec-
combination with the BCR procedure following lodgepole pine or ta- trometry (FAAS; TAS-986, Persee, China), and total Ca, Mg and Cd
marisk biochar addition to four different Cd contaminated soils. The using a HClO4–HNO3–HF digestion and analyzed using inductively
authors noted that bioavailable Cd concentrations could be significantly coupled plasma–optical emission spectroscopy (ICP-OES, Perkin Elmer
reduced simply by raising soil pH and subsequently forming carbonate Optima 7300 DV, Shelton, USA).
and oxyhydroxide metal precipitates.
The above studies illustrate that biochars can reduce heavy metal 2.2. Experimental design
bioavailability via a number of processes. However, the above studies
also utilized various combinations of either relatively short batch 2.2.1. Biochar dose and sorption of Cd from solution
shaking periods (< 24 h), relatively long field studies (e.g., 5 years), In triplicate, 0.00, 0.10, or 0.30 g BC were weighed into 50 mL
simple extraction techniques, or the BCR procedure. Although several centrifuge tubes (identical rates used in the biochar-soil Cd sorption
publications exist regarding synchrotron-based analyses of Cd sorption study below). Next, 40 mL of a Cd solution containing either 0, 5, or
onto organic materials (e.g., Karlsson et al., 2005), to our knowledge 15 mg Cd L−1, in 0.01 M KCl, was added to each tube; the solution pH
only one published study has focused attention on biochar-Cd sorption was not buffered. The tubes were shaken at 120 rpm for 1 h, 2 h, 4 h,
using X-ray adsorption spectroscopy (XAS); Rechberger et al. (2019) 7 d, 14 d, 30 d, 60 d, 12 0d, and 240 d. After each shaking period, the
studied Cd sorption onto woodchip biochar using X-ray adsorption tubes were centrifuged (40g) and solution pH was measured. The su-
near-edge spectroscopy. The authors noted that CdCO3 precipitation pernatant was filtered through a 0.45 μm membrane filter, three drops
initially occurred on biochar surfaces, yet after 15 months of aging, Cd of concentrated HNO3 were added, and the solutions analyzed for Cd
sorption onto biochar-borne organic functional groups dominated. concentrations using ICP–OES. The biochar solid fraction was air-dried,
The novelty of our study is that we coupled simple batch experi- crushed using a mortar and pestle, and then saved for XAS analysis.
ments to the relatively more complex BCR procedure to highly complex
XAS in order to fully illustrate the strengths of each technique for 2.2.2. Biochar sorption of Cd from contaminated soil
quantifying biochar-Cd sorption mechanisms. We hypothesized that In quadruplicate, 2.00 g of contaminated soil and either 0.00, 0.10,
maximum biochar heavy metal sorption likely requires > 24 h to attain or 0.30 g BC (equivalent to 0, 5, and 15% BC by weight) were placed
equilibrium, potentially on the order of days or weeks. Furthermore, we into 50 mL centrifuge tubes. Next, 40 mL of 0.01 M KCl (a proxy for
hypothesized that, given time, biochar-heavy metal interactions may metal bioavailability, as compared to Ippolito et al., 2017) was added to
lead from precipitation of heavy metal mineral phases to sorption via each tube; the solution pH was not buffered. The tubes were shaken at
surface functional groups, as noted by Rechberger et al. (2019). Our 120 rpm for 1 h, 2 h, 4 h, 7 d, 14 d, 30 d, 60 d, 120 d, and 240 d. Fol-
objectives were to 1) utilize biochar to reduce bioavailable soil Cd and lowing each shaking period, the tubes were centrifuged, the solution pH
solution Cd, 2) investigate biochar-metal sorption and 3) identify form determined, and then the supernatant was filtered through a 0.45 μm
(s) present as affected by biochar application rate and time using both membrane filter. Three drops of concentrated HNO3 were added, and
the BCR procedure and XAS. the solutions analyzed for equilibrium Cd concentrations using ICP-
OES. The biochar-soil solid fraction from 1 h, 1 d, 14 d, and 120 d were
2. Materials and methods air-dried, crushed using a mortar and pestle, and saved for wet che-
mical-heavy metal sequential extraction and XAS analysis.
2.1. Biochar and soil
2.2.3. Biochar effects on soil Cd fractionation (BCR sequential extraction)
Biochar was made from wheat straw pyrolyzed at ~450 °C in a The air-dried, crushed soil-BC composite samples from 1 h, 1 d, 14 d,
continuous vertical kiln at the Sanli New Energy Company (Henan and 120 d, were extracted using the four-step European Community
Province, China). Approximately 30–35% of the feedstock was con- Bureau of Reference (BCR) sequential extraction procedure according
verted to BC. Additional pyrolysis information is proprietary to Sanli to Ure et al. (1993). Briefly, Step 1 (B1; soluble, carbonates, ex-
New Energy. After collection, BC was ground to pass through a 2-mm changeable fraction): 40 mL of 0.11 M acetic acid was added to 1 g of
sieve. the soil-BC samples in a 50 mL centrifuge tube and shaken for 16 h at
The experimental soil was collected from nine random locations, at room temperature. The extract was then separated from the solid re-
a depth of 0 to 15 cm, in a rice paddy field (31°24.434′N and sidue by centrifugation, decantation, and filtration through a 0.45 μm
119°41.605′E) where atmospheric fallout and effluent discharges from a membrane filter. Step 2 (B2; iron and manganese oxyhydroxides frac-
local smelter had contaminated the soil with Cd over several years. The tion): 40 mL of a freshly prepared 0.1 M hydroxylamine hydrochloride
paddy soil was air-dried and then passed through a 2-mm sieve. Basic was added to the residue from step 1 and the residue was re-suspended
BC and soil properties are listed in Table 1 and were determined using by shaking for 16 h at room temperature. The extract was separated
methods described by Lu (2000). Briefly, pH was determined using a from the solid phase as described above. Step 3 (B3; organically bound
soil:water ratio of 1:2.5, cation exchange capacity (CEC) was de- and sulfides fraction): 10 mL of 30% H2O2 was added to the residue
termined via the ammonium acetate exchange method, total C using the from step 2 and occasionally shaken over a 1 h period at room tem-
potassium dichromate method, total N via Kjeldahl digestion and ana- perature, followed by digestion at 85 °C until the volume was reduced
lyzed colorimetrically, total P via HClO4—H2SO4 digestion and to about 3 mL. An additional 10 mL of 30% H2O2 was added and the

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digestion was continued at 85 °C until the volume was reduced to 1 mL; Cd loss from biochar itself when placed in solution containing
the samples were then allowed to cool. Finally, 40 mL of 1 M ammo- 0 mg Cd L−1 (Fig. 1B), with Cd concentrations near or below detection.
nium acetate was added and the tubes were shaken for 16 h at room When placed in solution containing either 5 or 15 mg Cd L−1, there was
temperature. The extract was separated from the solid phase as de- always significantly less Cd in solution with the 15% versus 5% biochar
scribed above. Step 4 (B4; residual fraction): the residue from step 3 application rate (p < 0.001). Over time, the 15% biochar application
was allowed to air-dry and then it was digested in a 50 mL digestion sorbed and removed practically all Cd from the 5 mg L−1 solution
tube by first adding 1 mL of deionized water to make a slurry, followed (> 90% removal after 4 h), and removed almost 75% of the Cd from the
by an aqua regia addition (7 mL concentrated HCl: 2 mL of concentrated 15 mg L−1 solution. As with the above pH findings, as well as those
HNO3). The mixtures were allowed to predigest overnight at room from others (e.g., Ippolito et al., 2017; Xu et al., 2013; Kolodyńska
temperature and then digested at 105 °C for 2 h the next day. Then, the et al., 2012), greater biochar application rates likely provided more
mixtures were brought to a 50 mL final volume and filtered through a reactive sites (e.g., organic functional groups, counter ions, (oxy)hy-
0.45 μm membrane filter. Cadmium concentrations in all four steps droxide and/or carbonate mineral phases) for Cd sorption and pre-
were using ICP–OES. cipitation reactions to occur. Other researchers have found similar re-
sults. For example, Bogusz et al. (2017) reported that the biogas residue
2.2.4. Biochar-Cd solution and contaminated soil X-ray absorption biochar (600 °C) effectively removed Cd from solution, with sorption
spectroscopy (XAS) analysis potentially affected by interfering anions (e.g., Cl−, NO3−). However,
Air-dried, crushed biochar from the 1 h, 1 d, 14 d, and 120 d Cd the authors suggested that Cd-(hydr)oxide precipitates blocked active
solution study, and air-dried crushed biochar amended soils from 1 h, sites on biochar surfaces, reducing interfering ion effects. Other in-
1 d, 14 d, and 120 d, were analyzed using XAS spectroscopy to elucidate organic ions (e.g., Ca2+, Mg2+, PO43−, SO42−) from biochar were
solid-phase Cd speciation. The XAS experiments were conducted at the positively correlated to Cd removal from solution, promoting sorption
Materials Research Collaborative Access Team's beamline 10-BM, or precipitation reactions (Park et al., 2011; Clemente et al., 2017).
Sector 10 located at the Advanced Photon Source, Argonne National Usman et al. (2016) also found that palm waste biochar (700 °C) could
Laboratory, Argonne, Illinois (Kropf et al., 2010). The electron storage remove almost 100% of Cd from solution, attributed to biochar func-
ring operated at 7 GeV in top-up mode. A liquid N2-cooled, double tional groups (such as eOH, eCO32−). Similarly, Štefelová et al. (2017)
crystal Si (111) monochromator was used to select incident photon found that spruce sawdust wood biochar could sorb 13.4 mg Cd g−1,
energies, and a platinum-coated mirror was used for harmonic rejec- attributed to biochar surface functional groups (eOH) as pyrolysis
tion. The samples were prepared as thin pellets with a hand-operated IR temperature increased (400–700 °C), promoting Cd precipitation reac-
pellet press, and the samples were secured by Kapton tape in sample tions. Thus, although the aforementioned pH increases may certainly
holders. Five XAS spectra were collected in fluorescence (Si drift de- have played a role in terms of Cd removal/precipitation from solution,
tector) and transmission mode at room temperature from −200 to we cannot discount the role that organic functional groups or other
800 eV relative to the absorption edge position of Cd. Data processing inorganic ions present in biochar may play in terms of solution Cd re-
and linear combination fitting (LCF) of X-ray absorption near-edge moval.
structure (XANES) derivative spectra were done with the program
Athena (Ravel and Newville, 2005). 3.2. Biochar sorption of Cd from contaminated soil

2.2.5. Statistics Increasing biochar application rate caused significant upward shifts
All data were expressed as means plus or minus one standard de- in soil pH (p < 0.001) (Fig. 2A), likely due to the wheat straw biochar
viation. Differences between the treatments were examined using a pH being 10.4 (Table 1). Additionally, when biochar is used as
Student's t-test in a two-way analysis of variance (ANOVA), and con- amendment, elements such as Ca, Mg, and K (Table 1) found on biochar
sidered significant when p < 0.05. All statistical analyses were carried sorption sites can be dissociated and replaced with heavy metals such as
out using SPSS (version 20.0, USA) and are presented within the text Cd, causing a rise in soil pH (Huggins et al., 2016; Zambon et al., 2016).
below. As suggested in the biochar-solution pH results above, biochar appli-
cation likely supplied (oxy)hydroxides and carbonate phases to the soil
3. Results and discussion and caused the pH to increase (Ippolito et al., 2017).
Biochar addition of 5 and 15% (by wt.) to the Cd contaminated soil
3.1. Biochar sorption of Cd from Cd-containing solution reduced bioavailable Cd concentration by 53.4%–87.9% over the 240 d
experiment as compared to the control soil (p < 0.001; Fig. 2B), likely
As compared to the control, solution pH was significantly elevated due to processes similar to those as suggested in the above biochar-Cd
over time (by ~1 to 4 pH units) with both 5 and 15% biochar appli- solution study. Supporting this contention, Beesley et al. (2010) showed
cations in either 0 or 5 mg Cd L−1 (all p < 0.001) (Fig. 1A). When that an 8% biochar application rate (wt/wt) reduced the water-soluble
placed into the Cd solution containing 15 mg L−1, the 15% biochar Cd concentration in a multi-heavy metal contaminated soil in 56 days
application rate maintained about a 2 to 5 unit pH increase over the incubation pot experiment, due to increasing pH and the creation of
control over time (all p < 0.001); lesser increases were observed with insoluble Cd precipitates. In a subsequent study, Beesley and Marmiroli
the 5% biochar application rate. The biochar pH was 10.4 (Table 1), (2011) found a significant negative correlation between pH and Cd
likely elevated due to the presence of oxides, hydroxides, and carbonate sorption by biochar. A Chinese herb biochar immobilized 81% Cd in
phases in the biochar (as shown by Ippolito et al., 2017). A fraction contaminated soil following a 28 day incubation, with shifts from ex-
(i.e., likely not all) of solution Cd removal may have occurred due to changeable (i.e., bioavailable) to residual and organically bound phases
precipitation of Cd (oxy)hydroxides and carbonate mineral phases. (i.e., less bioavailable) occurring (Qiao et al., 2017). Yuan et al. (2011)
Greater biochar application rates would have introduced greater (oxy) and Li et al. (2016) proposed that reduction in soil heavy metal bioa-
hydroxides and carbonate phases into solution, thus helping maintain vailability (e.g., Cd) was not only a function of metal precipitate for-
an elevated pH over the control or lower biochar application rates (Li mation, but metal reactions with biochar surface organic functional
et al., 2016; Ippolito et al., 2017; Zhang et al., 2018). Concomitantly, groups.
increasing Cd solution concentrations would potentially allow for solid Thus, up to this point our data suggests that increasing pH played a
phase Cd precipitation reactions to occur, lowering solution pH as role in Cd bioavailability reduction likely due to precipitation reactions.
sorption sites and precipitation reactions occurred. However, we still cannot rule out Cd-organic function group associa-
Furthermore, neither biochar application rate caused appreciable tions promoting reductions in Cd bioavailability. Thus, we followed the

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Fig. 1. Increasing wheat straw biochar (0, 5, and 15% by wt.) in solutions containing 0, 5, or 15 mg Cd L−1, on (A) solution pH and (B) residual solution Cd
concentration after sorption onto biochar over shaking time.

above work with research focused on using operationally defined soil sequential extraction procedure. This approach is justifiable when the
fractions via a sequential extraction procedure, followed by definitive goal is to compare differences in a soil as affected by different treat-
Cd sorption analysis via XAS. ments (Ippolito et al., 2009), or in the current study, by increasing
biochar application rate.
In the current study, Cd increased in the soluble/carbonate/ex-
3.3. Biochar effects on soil Cd fractionation changeable fraction when 5 or 15% biochar was added as compared to
the control (p < 0.001), while the 1 h, 1 d, and 14 d contained greater
Soil Cd fractions were operationally defined using the BCR

Fig. 2. Increasing wheat straw biochar (0, 5, and 15% by wt.) on Cd contaminated soil (A) pH and (B) bioavailable Cd concentration after sorption onto biochar over
shaking time.

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Table 2
Speciation results of biochar sorption of Cd from solution.
Biochar Treatment Cd speciation distribution (%) R-factora
rate (%; time (d)
wt:v) OM/Biochar Cd sulfate Cd thiol Mineral
Bound

5 0.04 69 16 15 0.0021
15 66 18 16 0.0021
5 1 65 19 16 0.0032
15 62 20 18 0.0029
5 14 65 21 14 0.0019
15 66 20 14 0.0029
5 120 67 21 12 0.0078
15 68 20 12 0.0014

a
A measure of mean square sum of the misfit at each data point.

sulfate (Cd Sulfate), cadmium bound to thiol (Cd Thiol), and Cd sorbed
to Fe/Mn/Al (oxy)hydroxides or clay minerals (Mineral Bound).
Speciation results for the biochar-Cd solution sorption study were
similar regardless of the biochar or Cd rate or as a function of treatment
time. On average, OM/Biochar accounted for 66% ( ± 2.16%), Cd
Sulfate averaged 19% ( ± 1.76%), and Cd Thiol measured 15%
Fig. 3. The effect of increasing biochar rate (0, 5, or 15% by wt.) over time
( ± 2.20%) (Table 2). Similarly, Rechberger et al. (2019) used X-ray
(0.04 days [1 h], 1, 14, and 120 d) on the ratio of (B1) soluble/exchangeable/
carbonate, (B2) Fe/Mn oxyhydroxide, (B3) organically bound and sulfide
adsorption near-edge spectroscopy to study woodchip biochar sorption
fraction, and (B4) residual fractions of Cd in a Cd-contaminated soil. in a Cd-spiked soil. The authors noted initial sorption phenomenon was
likely due to CdCO3 precipitation, yet as the system aged, Cd sorption
onto organic functional groups dominated (similar to that shown in our
Cd in this phase as compared to 120 d (p < 0.001) (Fig. 3). There were
system). Although XAS was not used, Li et al. (2018) did use XRD to
no statistical treatment differences between Cd in steps 2 (iron/man-
quantify Cd sorption onto biochar, noting both CdCO3 precipitation and
ganese oxyhydroxides fraction; p = 0.069) or 3 (organically bound/
biochar surface organic functional groups could promote Cd com-
sulfide fraction; p = 0.365), while over time the iron/manganese oxy-
plexation reactions during sorption, again, similar to our study's find-
hydroxides fraction increased (p < 0.001). Cadmium content de-
ings.
creased in the residual fraction when 5 or 15% biochar was added as
Speciation results for biochar sorption of Cd from the contaminated
compared to the control (p < 0.001), while no differences over time
soil varied relative to biochar rate and treatment time (Table 3, Fig. 4).
were observed (p = 0.965); this decrease may have contributed to the
The control soil (0% biochar rate) showed consistent results as a
Cd increase in soluble/carbonate/exchangeable and the conversion of
function of treatment time, demonstrating that Cd was associated with
Cd bound in the iron/manganese oxyhydroxides fraction over time.
37 ± 2.02% OM/Biochar, 17 ± 3.15% Cd Sulfate, 20 ± 2.18% Cd
The increase in the soluble/carbonate/exchangeable fraction with
Thiol, and 26 ± 1.68% Mineral Bound. In contrast, upon biochar
biochar application might be attributed to Cd being weakly sorbed onto
amendment into soil there was a modest decrease in Mineral Bound Cd
the biochar surface (Cui et al., 2014). Yet weakly sorbed or unstable
and Cd Thiol at each treatment time interval. Cd Sulfate showed a sharp
forms would not likely not lead to a reduction in Cd bioavailability.
increase at the 0.04-d treatment time relative to the 0% biochar value;
Others (e.g., Egene et al., 2018; Cui et al., 2016) have shown water-
however, Cd Sulfate in both the control and biochar treatments reduced
soluble and exchangeable Cd reductions due to biochar application, but
in percentage over the 120-d reaction period to about 15%. Finally, the
did not specify where Cd eventually resided. Other researchers have
amount of Cd associated with OM/Biochar steadily increased as a
identified Cd transformations from bioavailable to other soil forms. The
function of treatment time, with slightly greater OM/Biochar values for
reduction in Cd bioavailability has been associated with increasing soil
the 15% biochar rate over the 5% rate. These findings are corroborated
pH and the formation of carbonate and oxyhydroxide precipitates when
by those of Harvey et al. (2011) who used flow adsorption
biochars were introduced into Cd-contaminated soil, as shown by
Ippolito et al. (2017) using the BCR technique. Houben and Sonnet
(2015) used an extraction procedure to show that miscanthus straw Table 3
Speciation results of biochar sorption of Cd from contaminated soil.
biochar shifted the Cd exchangeable pool to the carbonate pool pri-
marily due to increasing pH. Moreno-Barriga et al. (2017) showed that Biochar Treatment Cd speciation distribution (%) R-factora
biochar could reduce metal mobility due to increasing soil pH, and shift rate (%; time (d)
wt:wt) OM/Biochar Cd sulfate Cd thiol Mineral
metals toward Fe/Mn oxyhydroxide phases. Shen et al. (2017) showed
Bound
that biochar application could cause heavy metal shifts toward carbo-
nate and carbonate-hydroxide phases. Thus, it appears that increasing 0 0.04 37 21 18 24 0.0031
and maintaining soil pH may help prevent dissolution and release of Cd 5 39 30 14 18 0.0022
15 38 29 19 15 0.0019
back into the soil solution, which would re-promote Cd bioavailability.
0 1 40 15 19 26 0.0011
5 46 20 13 22 0.0013
15 47 22 12 20 0.0017
3.4. Biochar-Cd X-ray absorption spectroscopy (XAS) analysis 0 14 37 16 20 27 0.0019
5 45 19 14 23 0.0023
Cadmium speciation in both the biochar-Cd solution sorption study 15 50 17 11 23 0.0025
0 120 35 15 23 28 0.0015
and Cd in biochar amended soil investigation was determined through
5 48 15 13 25 0.0023
linear combination fitting (LCF) of the derivative XANES spectra. Four 15 55 14 11 20 0.0037
primary Cd species were identified, which include Cd associated with
typical organic matter functional groups (OM/Biochar), cadmium a
A measure of mean square sum of the misfit at each data point.

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article, the research presented was not performed by or funded by EPA

Normalize Absorption Derivative and was not subject to EPA's quality system requirements.
Consequently, the views, interpretations, and conclusions expressed in
this article are solely those of the authors and do not necessarily reflect
0% BC, 0.04d or represent EPA's views or policies.

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