Chemical Engineering Journal xxx (xxxx) xxxx

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Chemical Engineering Journal

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

Simulated solar light driven roxarsone degradation and arsenic

immobilization with hematite and oxalate
⁎
Na Chen, Yichao Wan, Guangming Zhan, Xiaobing Wang, Meiqi Li, Lizhi Zhang
Key Laboratory of Pesticide & Chemical Biology of Ministry of Education, Institute of Environmental & Applied Chemistry, College of Chemistry, Central China Normal
University, Wuhan 430079, People’s Republic of China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Oxalate could enhance the photo-

catalytic molecular oxygen activation
of hematite.
• Suface Fe(III)/Fe(II) cycle was in-
volved in molecular oxygen activation
process.
• Ausedsolar/hematite/oxalate system was
to degrade roxarsone into ar-
senate.
• The generated arenate could be si-
multaneously immobilized on hema-
tite surface.
• This solar/hematite/oxalate system
was reusable for roxarsone treatment.

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

Keywords: Solar light driven organoarsenicals degradation and simultaneous inorganic arsenic immobilization with natu-
Roxarsone degradation rally abundant hematite is very promising for organoarsenicals remediation, but suffers from the fast electron-
Arsenic immobilization hole charge recombination of hematite. Herein, we report that oxalate, widely existed in soil and water en-
Iron oxides vironments, can greatly enhance the photocatalytic molecular oxygen activation of hematite to degrade a typical
Oxalate
organoarsenical roxarsone and immobilize the resulted inorganic arsenic. It was found that oxalate could chelate
Solar light
with surface Fe(III) of hematite to generate plenty of •OH via a surface Fe(III)/Fe(II) cycle mediated oxygen
molecular activation process under a simulated solar light, and thus induced 85.1% of roxarsone transformation
into inorganic arsenic species, mainly As(V), within 6 h. The generated As(V) could be further adsorbed on
hematite surface with prolonging the reaction time to 24 h in dark, avoiding secondary pollution. More im-
portantly, hematite was reusable for the simulated solar light driven roxarsone degradation and As(V) im-
mobilization in the presence of oxalate. This study offers a green and effective strategy for organoarsenicals
remediation, and also sheds light on the environmental effects of iron oxides and oxalate.

1. Introduction control coccidial intestinal parasites [1–3]. In view of their poor me-
tabolism in animal bodies, approximately 90% of organoarsenicals are
Organoarsenicals has been widely used as feed supplement in an- directly extracted in the poultry litter without any chemical structure
imal agriculture to improve feed efficiency, promote growth, and change, resulting in the organoarsenicals pollution of the soil and even

⁎
Corresponding author.
E-mail address: zhanglz@mail.ccnu.edu.cn (L. Zhang).

https://doi.org/10.1016/j.cej.2019.123254
Received 8 July 2019; Received in revised form 15 October 2019; Accepted 20 October 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Na Chen, et al., Chemical Engineering Journal, https://doi.org/10.1016/j.cej.2019.123254
N. Chen, et al.
water environment via fertilization and leaching [4–8]. It was reported
that the roxarsone concentration could reach 1.07 μg/L in runoff from a
field amended with poultry manure [9]. Even if organoarsenicals has
been strictly restricted in European Union in 1999 and gradually phased
out from the market in many developing countries, its residual ex-
istence in soil or water environment still remains a lingering serious
problem [2,10]. Despite the low toxicity of organoarsenicals, they could
be readily transformed into arsenite (As(III)) or arsenate (As(V)) with
much higher toxicity and mobility via abiotic or biotic process [11–15].
Therefore, it is urgent to remove organoarsenicals and simultaneously
immobilize inorganic arsenic for further prevention of potential en-
vironmental risks.
Iron-based materials, widely distributed in soils, natural waters and
atmospheric aerosols, are regarded as cost-effective materials for or-
ganoarsenicals transformation and simultaneous inorganic arsenic im-
mobilization for the sake of their excellent redox and adsorption ability
[16–20]. For instance, Cheng’s group reported that a Fe2+/H2O2 Fenton
system could completely oxidize p-arsanilic acid into As(V) in 30 min
with the final content of residual inorganic arsenic less than 70 μg L−1,
meeting the limit of the arsenic content in reclaimed water for the long-
term irrigation (100 μg L−1) [17]. Zhang and his co-workers found that
FeOOH/H2O2 Fenton-like system exhibited a much better capacity for
both roxarsone degradation and arsenic adsorption than Fe2O3/H2O2
and Fe3O4/H2O2 counterparts, and more than 90% of released in-
organic arsenic species were immobilized on the FeOOH surface to
reduce the secondary pollution [16]. Despite these advances, the high
cost of these Fenton systems owing to the addition of H2O2 largely
limits their practical applications. Therefore, it is vital to develop more
inexpensive iron based strategies for organoarsenicals remediation.
Using abundant and renewable solar light energy, photocatalytic
molecular oxygen activation by semiconductors has received attention
due to its high performance in generating various reactive oxygen
species (ROS) for organic pollutants degradation [21,22]. Iron oxides
with semiconductor property could directly activate molecular oxygen
to generate %OH under solar light irradiation without adding H2O2
[23–26]. Since organoarsenicals and iron oxides co-existed in water
environment, solar light driven organoarsenicals degradation and si-
multaneous arsenic immobilization with naturally abundant iron oxides
are very promising for organoarsenicals remediation. Among iron
oxides, hematite is most attractive for its abundance as well as excellent
catalytic and adsorption properties [27,28]. Unfortunately, solar light
driven molecular oxygen activation efficiency of hematite is largely
inhibited by its fast electron-hole charge recombination [24]. It is
therefore of great environmental significance to enhance solar light
driven photocatalytic molecular activation performance of hematite for
green organoarsenicals remediation.
Oxalate, a conjugate base for oxalic acid, is also abundant in natural
environments as a result of microbial decomposition of organic matter
and plant root exudates [29,30]. It was reported that oxalate is able to
form metal-organic complex with Fe(III) of hematite, which could ef-
ficiently enhance its photocatalytic molecular oxygen activation per-
formance associated with a ligand-to-metal charge transfer (LMCT)
process [30–37]. Although the synergistic photocatalytic effect of ox-
alate and hematite has been widely used to treat various kinds of or-
ganic pollutants [30–34], the fundamental surface reaction mechanisms
between surface Fe(III) and oxalate are still remain mystery, and its
potential in organoarsenicals remediation has never been explored. In
the light of this fact, we evaluated the ability of hematite and oxalate to
degrade roxarsone (ROX) in water environment and immobilize the
generated inorganic arsenic under the simulated solar light irradiation
(solar/hematite/oxalate). The roles of surface Fe(III) and oxalate were
systematically checked to explore the molecular oxygen activation
mechanism. The ROS generation and the influence of environmental
factors on ROX degradation were carefully investigated to deeply un-
derstand its degradation pathway. The residual inorganic arsenic con-
centration in the solution was determined and the hematite surface
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adsorbed inorganic arsenic was characterized to evaluate the ability of
this solar/hematite/oxalate system for inorganic arsenic immobiliza-
tion.
2. Experimental
2.1. Chemicals and materials
Roxarsone (ROX, 4-hydroxy-3-nitrophenylarsonic, 98%) was pur-
chased form J&K Scientific Ltd. 2-nitrohydroquinone was purchased
from Fluorochem Ltd (UK). Hematite used in this study was commercial
product purchased from Aladdin Reagent Co., Ltd. The morphology and
crystal structure of the commercial hematite were provided in Fig. S1.
The point of zero charge and surface area of the hematite were 7.3 and
4.43 ( ± 0.38) m2 g−1 (Fig. S2), respectively. Superoxide dismutase
(SOD) and catalase from bovine liver (CAT) were obtained from
Aladdin Reagent Co., Ltd. Oxalate dehydrate, sodium hydroxide
(NaOH), sulfuric acid (H2SO4), tert-butyl alcohol (TBA), 1,10-phenan-
throline, hydrochloric acid (HCl), benzoic acid (BA) and potassium
borohydride (KBH4) were all of analytical grade and obtained from
Sinopharm Chemical Reagent Co., Ltd. Humic acid was purchased from
Sigma-Aldrich. Deionized water was used throughout the experiments.
2.2. Roxarsone degradation procedure
Batch ROX degradation experiments were carried out in 100 mL
containers and magnetic stirred at 250 rpm. The temperature of the
reaction system was controlled at 25 °C by using a circulating water
system (Scheme S1). Generally, 0.025 g of hematite and 0.25 mL of
0.4 mol L−1 oxalate solution (pH = 1.31 and I = 0.1 M) were in-
troduced into 50 mL of ROX stock solution (20 mg L−1 pH = 4.5) to
ensure the dosages of hematite and oxalate were 0.5 g L−1 and
2 mmol L−1, respectively (pH = 2.8 and I = 1 × 10−3 M). A xenon
lamp with the output energy of 300 W (PLS-MW2000, Beijing Perfect
Light Co., Ltd., China) was used to simulate the solar light. The reaction
was initiated by switching on the xenon lamp. At predetermined time
intervals, 0.9 mL of the degraded solution was sampled by filtering
through 0.22 μm nylon syringe filter, followed with 0.1 mL of ethanol
addition to quench the reaction. Control experiments without hematite
or oxalate in dark or under the simulated solar light were also per-
formed for comparison. All of the experiments were conducted in tri-
plicate. Error bars in figures represent ± one standard deviation de-
rived from triplicate experiments.
2.3. Characterizations of hematite samples
The morphology of hematite samples was characterized by scanning
electron microscopy (SEM, 6700-F, JEOL), while the powder X-ray
diffraction (XRD) patterns of hematite samples was recorded by a D/
Max-IIIA X-ray diffractometer equipped with a Cu Kα radiation
(λ = 1.5418 nm). The specific surface area of the commercial hematite
was determined by the BET (Brunauer-Emmett-Teller) nitrogen ad-
sorption isotherm at 77 K (Micrometics ASAP2020). An X-ray photo-
electron spectroscopy (Thermal Scientific, ESCALAB 250Xi) was em-
ployed to obtain the Fe and As binding states on the surface of hematite
samples (Text S1). The hematite samples separated from the different
reaction systems were first dried in vacuum oven at 40 °C for 24 h, and
then preserved in a vacuum bag for characterization.
2.4. Analytical methods
The concentration of oxalate and nitrate (NO3–) was determined by
an ion chromatography (IC, Dionex ICS-900, Thermo). The concentra-
tion of accumulative %OH was quantified by a molecule probe method
with using BA as probe agent (Text S2) [38,39]. A Shimadzu TOC-VCPH
analyzer was employed to determine the total organic carbon (TOC)
N. Chen, et al.
content. The Fe leaching contents during the ROX degradation in dif-
ferent systems were measured by an inductively coupled plasma mass
spectrometry (ICP-MS, 7800, Agilent). The detection limit was
0.1 μg L−1. The free radicals generated during the ROX degradation
were recorded by an electron spin resonance (ESR) spectrometer
(Bruker E500, Germany) at 25 °C.
The concentrations of ROX and 2-nitrohydroquinone were detected
by high-performance liquid chromatography (HPLC, LC-20AT,
Shimadzu) equipped with a Agilent SB-C18 (150 mm × 4.6 mm, 5 μm)
reverse phase column and a diode array detector (SPD-20A). The eluent
consisted of 70% mixture of 0.05 mmol L−1 phosphoric acid and 0.1%
formic acid as well as 30% methanol. The flow rate was 1.0 mL min−1
and the column temperature was controlled at 35 °C. The detection
wavelengths for ROX and 2-nitrohydroquinone were respectively
260 nm and 220 nm.
The concentration of total inorganic arsenic was measured by an
atomic fluorescence spectrometer (AFS 9600, Beijing Kechuang
Haiguang Instrument Co., Ltd). The detection limit was 1 μg L−1. 5%
HCl and 2% KBH4 solutions were added online with using a peristaltic
pump for hydride generation of volatile arsines. The As(III) and As(V)
species were separated and determined by a HPLC coupled with AFS
(HPLC-AFS). The detection limits for As(III) and As(V) were 1.4 μg L−1
and 2.8 μg L−1, respectively. The As(III) and As(V) were separated with
a 250 × 4.1 mm Hamilton PRP X-100 anion-exchange column using an
isocratic elution of 5 mmol L−1 Na2HPO4 and 45 mmol L−1 KH2PO4
buffer at a flow rate of 2.0 mL min−1 [40].
3. Results and discussion
3.1. Roxarsone degradation and reactive oxygen species contribution
We first evaluated the ability of hematite and oxalate to degrade
ROX under the simulated solar light irradiation at a pH value of 4.5, the
Fig. 1. (a) Time profiles of ROX degradation in different systems. (b) Plots of -ln(C/C0) versus time for ROX degradation in comparative systems. Time profiles of ROX
degradation (c) and accumulative %OH generation (d) in solar/hematite/oxalate system with adding different scavengers (TBA for %OH, SOD for %O2– and CAT for
H2O2). The initial concentrations of ROX, hematite, oxalate, and BA were 20 mg L−1, 0.5 g L−1, 2 mmol L−1, and 10 mmol L−1, respectively. The initial pH values
were 4.5.
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initial pH value of the ROX stock solution (20 mg L−1). As shown in
Fig. 1a, the self-degradation of ROX was negligible in dark or under the
simulated solar light irradiation. Less than 10% of ROX could be re-
moved by hematite with or without the simulated solar light irradiation
within 6 h, suggesting its poor photocatalytic performance and weak
ROX adsorption ability, which was lower than those reported adsorp-
tion capacity of p-arsanilic acid on hematite (ranging from 1.9 × 1013
to 2.6 × 1013 molecules/cm2) [41]. This lower adsorption capacity was
mainly arisen from the relatively lower surface area of the commercial
hematite sample. The influence of surface area on hematite adsorption
ability was discussed in the supplementary materials in detail (Text S3,
Fig. S3 and Fig. S4). Although the ROX degradation with oxalate in the
dark was negligible, oxalate could induce 46.0 ( ± 4.8)% of ROX de-
gradation under the simulated solar light because of oxalate’s photo-
decomposition [42,43], generating a small amount of •OH to degrade
ROX. In dark, the combination of hematite and oxalate could not re-
move ROX significantly. Interestingly, 85.1 ( ± 2.0)% of ROX was de-
graded by hematite and oxalate under the simulated solar light irra-
diation. To obtain the apparent ROX degradation rates, these
experimental degradation data were plotted in the liner form of the
pseudo first-order kinetic model, k = −ln(C/C0), where k is the ap-
parent ROX degradation rate, C is the ROX concentration at a given
time, C0 is the initial ROX concentration. The apparent ROX degrada-
tion rate constant in the solar/hematite/oxalate system was calculated
to be 0.361 ( ± 0.027) h−1, about 4 times that (0.099 ( ± 0.007) h−1)
in the solar/oxalate system (Fig. 1b). Meanwhile, the anaerobic ROX
degradation in the solar/hematite/oxalate system was checked by
constantly bubbling high-purity Ar gas with the flow of 1.5 L min−1
during the whole reaction. As expected, the ROX degradation in the
solar/hematite/oxalate system in Ar atmosphere was negligible (Fig.
S5), confirming that a molecular oxygen activation process was in-
volved in the ROX degradation with hematite and oxalate under the
simulated solar light irradiation.
N. Chen, et al.
As various reactive oxygen species (ROS) could be produced during
the oxygen molecular activation process, we thus checked the con-
tributions of different ROS to the ROX degradation in the solar/hema-
tite/oxalate system with adding different scavengers (TBA for %OH,
SOD for %O2–, and CAT for H2O2) [44]. As expected, the ROX de-
gradation efficiencies and rates in the solar/hematite/oxalate system
were all decreased by adding the different scavengers (Fig. 1c and Fig.
S6a). Particularly, the addition of TBA completely inhibited the ROX
degradation, indicating that •OH was the main ROS for the ROX de-
gradation in the solar/hematite/oxalate system. The addition of CAT
suppressed ROX degradation by 40.6 ( ± 1.9)%, suggesting that •OH
generation may be produced by the H2O2 decomposition. Meanwhile,
ROX degradation efficiency was decreased by 58.1 ( ± 2.6)% after
adding SOD, indicating that a successive single-electron transfer route
(O2 → •O2− → H2O2) of molecular oxygen activation might account for
the H2O2 generation [45]. To verify these hypotheses, we thus com-
pared the accumulative %OH generation in this solar/hematite/oxalate
system with or without adding scavengers, and found that the con-
centration of accumulative •OH reached to 247.2 ( ± 19.8) μmol L−1 in
the solar/hematite/oxalate system, then decreased to 38.2 ( ± 5.9),
105.3 ( ± 7.6) and 140.3 ( ± 16.4) μmol L−1 after adding TBA, SOD
and CAT, respectively (Fig. 1d). The %OH generation rate also slowed
down in the presence of these scavengers (Fig. S6b). On the basis of
these results, we concluded that solar/hematite/oxalate system could
activate molecular oxygen via a single-electron transfer route to first
form H2O2, and then produce •OH via the decomposition of in-situ
generated H2O2 for ROX degradation.
3.2. Roles of iron ions and oxalate in solar/hematite/oxalate system
We first checked the role of iron ions in the ROX degradation by
chelating the iron ions of hematite with 1, 10-phenanthroline. It was
found that the chelation of iron ions in hematite with 1, 10-phenan-
throline suppressed ROX degradation by 50 ( ± 2.5)%, confirming the
crucial role of iron ions in the ROX degradation within the solar/he-
matite/oxalate system (Fig. 2a and Fig. S7). To further figure out the
individual contributions of dissolved iron ions and surface iron ions to
the ROX degradation, we thus monitored the Fe leaching contents
during the ROX degradation in different systems using ICP-MS. As
shown in Fig. 2b, the Fe content in the initial solution was about
0.029 mg L−1. After the reaction, the Fe content slightly increased to
0.042 and 0.058 mg L−1 in the solar/hematite and solar/hematite/ox-
alate systems, respectively. Therefore, the Fe leaching contents from
hematite during the ROX degradation were calculated to be 0.013 and
0.029 mg L−1 in the solar/hematite and solar/hematite/oxalate sys-
tems, respectively, which were lower than the limitation of dissolved
iron ions (1 mg L−1) for surface Fenton reaction [46]. Such low
leaching Fe contents suggested that surface Fe played a dominate role in
the solar/hematite/oxalate system. Therefore, we explored the role of
surface iron ions in the ROX degradation with using high-resolution
XPS technique to characterize the hematite samples separated from
different systems after the ROX degradation. As shown in Fig. 2c, the
binding energies of Fe 2p3/2 and Fe 2p1/2 XPS peaks of raw hematite
sample were located at 710.4 eV and 724.4 eV, respectively, which
were consistent with the previous reports [47,48]. For the hematite
sample separated from the solar/hematite system, the binding energies
of Fe 2p3/2 and Fe 2p1/2 XPS peaks did not change. However, the Fe
2p1/2 peak of the hematite sample separated from the solar/hematite/
oxalate reaction system shifted from 724.4 eV to 723.9 eV (Fig. 2c). The
deconvolution of the Fe XPS spectrum was performed on the XPSPEAK
software with using true Shirley background and an 80% Gaussian,
20% Lorentzian peak model [49,50]. For the hematite sample separated
from the solar/hematite/oxalate system, we observed a new peak at the
lower binding energies of 722.4 eV and 709.1 eV for Fe 2p1/2 and Fe
2p3/2 peaks, respectively, which was assigned to Fe(II) (Fig. 2c) [48].
This result indicated that the surface Fe(III) of hematite could be
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reduced to Fe(II) during the ROX degradation in the solar/hematite/
oxalate system. To further check the depth of reduction process oc-
curred, XPS depth profiling technique was adopt. Fe(II) was only ob-
served on the hematite surface or under hematite surface of
depth ≤ 1.25 nm. When the depth was higher than 2.5 nm, the XPS
spectrum could not be deconvoluted into Fe(II) (Fig. 2d and Table S2) .
This result suggested that the reduction of Fe(III) to Fe(II) nearly oc-
curred on the surface of hematite.
It was reported that oxalate could chelate with Fe(III) to form Fe
(III)-oxalate complex, which was highly photoactive and could be re-
duced to Fe(II)-oxalate complex with the generation of carbon dioxide
free radical (%CO2–) under light irradiation [36]. %CO2–, with strong
reducing potential (E0 = −1.8 V (NEH)), then activated molecular
oxygen to generate ROS via electrons transfer [29]. We therefore em-
ployed ESR technique with DMPO as the spin-trapping agent to check
these radicals generation in this solar/hematite/oxalate system. As ex-
pected, a sextet signal, the characteristic spectrum of DMPO-%CO2–
adduct, was observed within 60 min (Fig. 3a) [29]. Meanwhile, hy-
droxyl radicals were also captured to form DMPO-%OH adduct having
four-line spectrum with relative intensities of 1:2:2:1, which was
overlapped with DMPO-%CO2– (Fig. 3a) [51,52]. Based on these results,
the possible ROS generation process in the solar/hematite/oxalate
system were proposed as follows (Fig. 3b). Oxalate was first chelated
with surface Fe(III) of hematite to form surface Fe(III)-oxalate com-
plexes. Subsequently, the formed surface Fe(III)-complexes were ex-
cited to produce various carbon-centered radicals (e.g., %C2O4− and
%CO2–) under the simulated solar light irradiation, and simultaneously
reduced to surface Fe(II)-oxalate complexes. The generated %CO2– ac-
tivated molecular oxygen via electrons transfer to generate %O2–. %O2–
further reacted with H+ to form H2O2. Then, the surface Fe(II)-oxalate
complexes catalyzed the decomposition of H2O2 to produce •OH, along
with their oxidation to Fe(III)-oxalate complexes, and thus realized the
whole surface Fe(III)/Fe(II) cycle mediated molecular activation pro-
cess.
Regarding that the oxalate played an significant role in promoting
surface Fe(III)/Fe(II) cycle of hematite, and thus enhanced its photo-
catalytic oxygen molecular activation performance to degrade ROX, we
therefore systematically investigated the effect of initial oxalate con-
centrations on the ROX degradation in the solar/hematite/oxalate
system. Along with enhancing the initial concentration of oxalate from
0.5 to 4.0 mmol L−1, the ROX degradation efficiency and rate first re-
spectively increased from 34.1 ( ± 4.8)% and 0.125 ( ± 0.019) h−1 to
85.1 ( ± 2.0)% and 0.361 ( ± 0.027) h−1, and then respectively de-
creased to 64.8 ( ± 5.9)% and 0.199 ( ± 0.015) h−1 when further in-
creased the initial concentration of oxalate to 4.0 mmol L−1 (Fig. 3c and
d). As ROX degradation efficiency and rate were highly depended on
the amount of %OH, we then determined the generated accumulative %
OH concentration in the solar/hematite/oxalate system at different
initial oxalate concentrations. Differently, the accumulative %OH con-
centration gradually increased from 154.2 ( ± 8.4) to 348.4 ( ± 14.0)
μmol L−1 along with promoting the initial concentration of oxalate
from 0.5 to 4.0 mmol L−1 (Fig. 3d). Therefore, the decrease of ROX
degradation efficiency at higher oxalate concentration was possibly
arisen from the competitive consumption of ROS by excess oxalate.
Therefore, we monitored the variations of oxalate concentration, and
found that oxalate could be simultaneously removed along with ROX in
the solar/hematite/oxalate system (Fig. S8), preventing its chelation
with various metal ions from inducing pernicious environmental risk.
As the removal of oxalate may influence the pH value of the reaction
system, we then checked the temporal pH value variations during the
ROX degradation in the solar/hematite/oxalate system at different in-
itial oxalate concentrations, and found that all of the pH values in-
creased and reached neutral after the 6 h of ROX degradation (Fig. S9),
implying the proton consumption and/or the hydrous ions generation
during the ROX degradation.
N. Chen, et al. Chemical Engineering Journal xxx (xxxx) xxxx

Fig. 2. (a) Time profiles of ROX degradation in solar/hematite/oxalate system with or without 1,10-phenanthroline. (b) Changes of Fe leaching contents during ROX
degradation in different systems. (c) Fe 2p XPS high resolution spectra of hematite samples separated from different reaction systems. (d) Fe 2p XPS depth profiling
spectra of hematite sample separated from solar/hematite/oxalate system. The initial concentrations of ROX, hematite, and oxalate were 20 mg L−1, 0.5 g L−1, and
2 mmol L−1, respectively. The initial pH values were 4.5.

Fig. 3. (a) ESR signals of the generated radicals in solar/hematite/oxalate system. (b) Proposed ROS generation process in solar/hematite/oxalate system. (c) Time
profiles of ROX degradation in solar/hematite/oxalate system at different initial oxalate concentrations. (d) ROX degradation rate constants and accumulative •OH
generation in solar/hematite/oxalate system at different initial oxalate concentrations. The initial concentrations of ROX and hematite were 20 mg L−1 and 0.5 g L−1,
respectively. The initial pH values were 4.5.

5
N. Chen, et al.
3.3. pH effect on roxarsone degradation in solar/hematite/oxalate system
The influence of pH values on the ROX degradation in the solar/
hematite/oxalate system was thus investigated. It was found that low
acidic conditions (pH = 2.5 and 3.6) were more beneficial for the ROX
degradation than the case of 4.5. When the pH value increased from 4.5
to 7.2, the ROX degradation percentage and rate sharply decreased
from 85.1 ( ± 2.0)% and 0.361 ( ± 0.027) h−1 to 3.0 ( ± 0.6)% and
0.0024 ( ± 0.001) h−1, respectively (Fig. S10). We also determined the
concentrations of accumulative %OH generated in the solar/hematite/
oxalate system at different initial pH values, and noticed that %OH
generation trend was consistent with that of ROX degradation (Fig.
S10b). The pH-dependent ROX degradation and %OH generation were
mainly ascribed to the pH-dependent interactions between oxalate and
surface Fe(III). At lower pH values, oxalate could strongly interact with
surface Fe(III) to form inner-sphere complex, which was beneficial for
the fast ligand–metal charge transfer under visible light irradiation,
leading to the higher photoactivity. With increasing the pH value, this
strong interaction gradually decreased and tended to the formation of
outer-sphere complex, thus decreasing the ligand–metal charge transfer
rate and photoactivity [53]. Although our solar/hematite/oxalate
system could not work well under neutral pH conditions which typi-
cally encountered in wastewater treatment, after 6 h of photodegrada-
tion reaction, all the pH values increased to pH 5.2–7.2, which were
closed to the pH value of natural water environment (Fig. S11), thus
avoiding the further pH value adjustment after the treatment. Ob-
viously, this charactersitic of the solar/hematite/oxalate system makes
it very promising for practical application.
3.4. Roxarsone degradation pathway in solar/hematite/oxalate system
It was reported that the electron-rich C-As bond in benzene arsenic
acid compounds could be easily attacked and cleaved by •OH to gen-
erate organic OH-adduct products and inorganic As(IV) [54]. As(IV)
with poor stability could be subsequently converted into As(III) and As
(V) with the ratio of 1:1 via a dismutation process [55]. Therefore, we
monitored the concentration of the generated inorganic arsenic during
the ROX degradation in the solar/hematite/oxalate system, and found
that the As(III) concentration increased to 0.24 ( ± 0.12) mg L−1 in the
first 2 h and then decreased to 0.05 ( ± 0.03) mg L−1, while the As(V)
concentration constantly increased to 4.58 ( ± 0.21) mg L−1 within 6 h
(Fig. 4a). The final concentration ratio of As(III) and As(V) was ap-
proximately 1:90, indicating that As(III) was oxidized to As(V) by some
strong oxidants, such as %OH [56]. Meanwhile, the organic OH-adduct
product, 2-nitrohydroquinone, was also identified and determined by
HPLC. As shown in Fig. 4b, the concentration of 2-nitrohydroquinone
first increased to 0.22 ( ± 0.02) mg L−1 and then decreased to 0.02
( ± 0.008) mg L−1 within 6 h in the solar/hematite/oxalate system.
This result indicated that the generated 2-nitrohydroquinone could be
further degraded by •OH, as validated by the formation of NO3– during
the ROX degradation (Fig. 4b). On the basis of these results, we pro-
posed the possible ROX degradation pathway in the solar/hematite/
oxalate system as follows (Fig. 4c). First, the C-As bond of ROX was
cleaved by %OH to form inorganic As(IV) and 2-nitrohydroquinone.
Then, the As(IV) was dismutated to produce As(III) and As(V), while the
2-nitrohydroquinone was further oxidized by %OH to generate in-
organic species. During this process, about 25.3% of TOC was miner-
alized in the solar/hematite/oxalate system within 6 h (Fig. 4d).
3.5. Inorganic arsenic immobilization in solar/hematite/oxalate system
Subsequently, we evaluated the ability of this solar/hematite/ox-
alate system to immobilize the resulted inorganic arsenic. We first
employed XPS technique to characterize the variation of elements
composition on the hematite surface before and after the ROX de-
gradation in the solar/hematite/oxalate system. As shown in Fig. 5a, a
6
Chemical Engineering Journal xxx (xxxx) xxxx
weak peak at the binding energy of 45 eV, which was attributed to As
3d [57], appeared in the XPS survey spectra of hematite after the ROX
degradation, suggesting the generated inorganic arsenic in the solar/
hematite/oxalate system could be further adsorbed on the hematite
surface. High resolution As 3d XPS spectra revealed that the im-
mobilized inorganic arsenic species was mainly As(V) (Fig. 5b) [11,58].
We then prolonged the reaction time from 6 h to 24 h in dark for sa-
turated As(V) adsorption under different pH conditions. It was found
that the inorganic arsenic concentration in the solution first increased
and then decreased at initial pH values of 2.5 and 3.6, while first in-
creased and then keep constant at initial pH ≥ 4.5, indicating that the
lower pH value favored inorganic arsenic immobilization (Fig. 5c).
After the reaction, the inorganic arsenic species distribution in the so-
lution or on hematite surface was determined. The surface immobilized
inorganic arsenic species were desorbed by the l.0 mmol L−1 of phos-
phate solution [59]. We found that over 60% of inorganic arsenic was
adsorbed on the hematite surface at the initial pH value of 2.5 (Fig. 5d),
but most of inorganic arsenic existed in the aqueous solution at higher
initial pH values. This pH-dependent adsorption performance of he-
matite for inorganic arsenic was mainly arisen from the pH-dependent
arsenate species distribution and hematite surface charge. For the initial
pH value at 2.5, the actual pH value for adsorption process was 5.2 due
to the increase of the pH value after 6 h of degradation process (Fig.
S11). At this pH value, the dominate arsenate species was negatively
charged H2AsO4− (Fig. S12) and the hematite surface was positively
charged (+12.1 mV) (Fig. S2), which was beneficial for arsenate elec-
trostatically adsorption on the hematite surface. When the initial pH
values of 3.6, 4.5, 6.1 and 7.2, the actual pH value for adsorption
process was 6.7, 6.9, 7.2 and 7.3 (Fig. S11), respectively. At these pH
values, the dominate arsenate species were negatively charged
H2AsO4− and HAsO42− (Fig. S12), while the hematite surface was
nearly uncharged (Fig. S2), thus resulting in the lower adsorption ca-
pacity.
It was recently reported that hematite could catalyze scorodite
formation in a pyrite-rich natural geologic material [60]. To check the
crystal structure of the adsorbed As(V) on hematite, we centrifuged and
collected the hematite samples after adsorption process for XRD char-
acterization. The XRD diffraction peaks of hematite did not significantly
changed before and after adsorption arsenate, and the characteristic
diffraction peak of ferric arsenate and/or scorodite was not found (Fig.
S13). This result suggested that the adsorbed arsenate might be of
amorphous particles. As the effect of the co-existed dissolved organic
carbon (DOC) on an adsorption or chemical oxidation process in natural
water environment was unavoidable [61], the actual influence of DOC
on the ROX degradation and inorganic arsenic immobilization in the
solar/hematite/oxalate system was therefore checked under the initial
pH value of 2.5. Humic acid was employed as the representative of DOC
(Text S4). As shown in Fig. S14a, 99.6 ( ± 0.6)%, 90.2 ( ± 0.7)%, 81.5
( ± 0.2)% and 62.0 ( ± 0.6)% of roxarsone were degraded in the pre-
sence of 0, 10, 20 and 50 mg L−1 of DOC, respectively. Inorganic ar-
senic distribution analysis suggested that in the presence of 10 mg L−1
DOC, most of the inorganic arsenic was adsorbed on hematite surface.
When the DOC concentration increased to 20 and 50 mg L−1, the
generated inorganic arsenic mainly existed in the solution (Fig. S14b).
These results confirmed the suppressive effect of DOC of higher con-
centration on roxarsone degradation or inorganic arsenic immobiliza-
tion in the solar/hematite/oxalate system, but DOC of lower con-
centration (within 10 mg L−1) did not significantly influence the
roxarsone degradation or inorganic arsenic immobilization perfor-
mance of the solar/hematite/oxalate system. Similar suppressive phe-
nomenon was also observed by Cheng’s group in treating p-arsanilic
acid with using Fenton reagent, indicating the ubiquity of this sup-
pression [17].
N. Chen, et al. Chemical Engineering Journal xxx (xxxx) xxxx

Fig. 4. (a) Concentrations variations of inorganic arsenic species during ROX degradation in solar/hematite/oxalate system. (b) Concentrations variations of 2-
nitorhydroquinone and NO3– during ROX degradation in solar/hematite/oxalate system. (c) Proposed ROX degradation pathway in solar/hematite/oxalate system.
(d) TOC removal efficiency in solar/hematite/oxalate system. The initial concentrations of ROX, hematite, and oxalate were 20 mg L−1, 0.5 g L−1, and 2 mmol L−1,
respectively. The initial pH values were 4.5.

Fig. 5. XPS spectra of the hematite samples before and after the ROX degradation in the solar/hematite/oxalate system: (a) XPS survey and (b) high resolution As 3d
XPS spectra. (c) Variations of inorganic arsenic contents in solar/hematite/oxalate system within 6 h of simulated solar light irradiation and 18 h of dark adsorption
under different initial pH values. (d) Inorganic arsenic distribution after the reaction under different initial pH values. The initial concentrations of ROX, hematite,
and oxalate were 20 mg L−1, 0.5 g L−1, and 2 mmol L−1, respectively.

7
N. Chen, et al.
Fig. 6. (a) Fe leaching contents in each cycle reuse of solar/hematite/oxalate system. Reusability of hematite for ROX degradation (b) and inorganic arsenic
immobilization (c) in solar/hematite/oxalate system. (d) SEM images and XRD patterns of hematite before and after use in solar/hematite/oxalate system. The initial
concentrations of ROX, hematite, and oxalate were 20 mg L−1, 0.5 g L−1, and 2 mmol L−1, respectively. The initial pH values were 2.5.
3.6. Reusability of the solar/hematite/oxalate system
Although low pH value of 2.5 was beneficial for both ROX de-
gradation and inorganic arsenic immobilization, it may induce more
iron ions leaching from hematite and thus weaken its performance after
several times of reuse. Therefore, we checked the reusability of hema-
tite in this solar/hematite/oxalate system at pH value of 2.5 for five
times of reuse by washing the used hematite with deionized water. Each
repeated experiments possessed 6 h of ROX degradation under the si-
mulated solar light irradiation and 18 h of inorganic arsenic adsorption
in dark. It was found that 1.95 mg L−1 of iron ions leached from he-
matite at the first time use, higher than those (in the range of
0.89–1.25 mg L−1) of later four reuse times (Fig. 6a). Although the ROX
degradation efficiency and rate respectively decreased from 99.6% and
1.316 h−1 to 80.0% and 0.400 h−1 after the first time use of hematite,
they could keep steady in later four reuse times (Fig. 6b). Similar trend
was also observed for the inorganic arsenic immobilization (Fig. 6c). In
comparison with the fresh hematite, the crystal structure and mor-
phology of reused hematite did not significantly change (Fig. 6d and
Fig. S15). These results suggested that hematite was reusable for the
simulated solar light driven ROX degradation and As(V) immobilization
in the presence of oxalate.
We also compared the efficiency and feasibility of the solar/hema-
tite/oxalate system with those of other systems on treating roxarsone
[16,40,62,63], which were summarized in Table S3 in the supplemen-
tary material. Compared with those reported ferrate or Fenton oxida-
tion treatment methods, the solar/hematite/oxalate system in this study
possessed relatively lower inorganic arsenic immobilization ability,
which might be arisen from the competitive adsorption of excess ox-
alate. However, hematite, oxalate and solar light in this study are
abundant or widely existed in nature. Therefore, using this solar/he-
matite/oxalate system to treat roxarsone is environmental friendly and
8
Chemical Engineering Journal xxx (xxxx) xxxx
cost effective, and also helpful to understanding the migration and
transformation of arsenic in real natural environment.
4. Conclusion
As iron oxides, oxalate and solar light are abundant or widely ex-
isted in nature, reactions happened in this solar/hematite/oxalate
system might also occur in natural environment, affecting the organic
pollutants transformation as well as heavy metal immobilization. So the
first environmental implication of this study is to shed light on the
environmental effects of iron oxides and oxalate. In this study, we de-
monstrated that roxarsone could be efficiently degraded into inorganic
arsenic in the solar/hematite/oxalate system, and the resulted in-
organic arsenic species could also be simultaneously immobilized on
the hematite surface with prolonging reaction time in dark. More im-
portantly, hematite possessed the superior stability and reusability for
both roxarsone degradation and inorganic arsenic immobilization in the
solar/hematite/oxalate system, and thus is highly attractive for prac-
tical application. Therefore, this study offers a green and effective
strategy for organoarsenicals remediation with using abundant iron
oxides, oxalate and solar light, which is the second environmental im-
plication of this study.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by National Key Research and
N. Chen, et al.
Development Program of China [2018YFC1800701], Natural Science
Funds for Distinguished Young Scholars [Grant 21425728], the 111
Project [Grant B17019], and the CAS Interdisciplinary Innovation Team
of the Chinese Academy of Sciences.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.123254.
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