Journal of Hazardous Materials 441 (2023) 129884

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Journal of Hazardous Materials

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

In-situ production of iron flocculation and reactive oxygen species by

electrochemically decomposing siderite: An innovative Fe-EC route to
remove trivalent arsenic
Mengfei Chen b, Huimin Hu b, Min Chen b, Chao Wang b, Qian Wang b, Chaocheng Zeng b,
Qing Shi b, Weijie Song a, Xuewei Li a, *, 1, Qiwu Zhang b, **, 2
a
Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, PR China
b
School of Resources and Environmental Engineering, Wuhan University of Technology, Luoshi Road 122, Wuhan 430070, PR China

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

• Iron ions can be produced continuously

by electrochemical action.
• As (III) can be oxidized via the gener­
ated active oxide species.
• Arsenic in solution was reduced from
1000 μg/L to below 10 μg/L.
• The process can work well for a long-
term operation.

A R T I C L E I N F O A B S T R A C T

Editor: Haizhou Liu The removal of trivalent arsenic (As (III)) from water has received extensive attention from researchers. Iron
electrocoagulation (Fe-EC) is an efficient technology for arsenic removal. However, electrode passivation hinders
Keywords: the development and application of Fe-EC. In this work, an innovative Fe-EC route was developed to remove As
Novel Fe-EC (III) through an electrochemical-siderite packed column (ESC). Ferrous ions were produced from siderite near the
As (III) removal
anode, and hydroxide was generated near the cathode during the electrochemical decomposition of siderite. As a
Siderite
result, an effect of Fe-EC-like was obtained. The results showed that an excellent removal performance of As (III)
Electrochemistry
(>99%) was obtained by adjusting the parameters (As (III) concentration at 10 mg/L, pH at 7, Na2SO4 at 10 mM
and the hydraulic retention time at 30 min) and the oxidation rate of As (III) reached 84.12%. The mechanism
analysis indicated that As (III) was oxidized to As (Ⅴ) by the produced active oxide species and electrode, and

* Correspondence to: Institute of Resources and Ecological Environment, Ganjiang Innovation Academy, PR China.
** Correspondence to: School of Resources & Environmental Engineering, Wuhan University of Technology, PR China.
E-mail addresses: lixuewei126@126.com (X. Li), zhangqw@whut.edu.cn (Q. Zhang).
1
Address: 1 Kexueyuan Road, Ganxian District, Ganzhou, Jiangxi, China.
2
Address:122 Luoshi Road, Hongshan District, Wuhan, Hubei, China.

https://doi.org/10.1016/j.jhazmat.2022.129884
Received 19 December 2021; Received in revised form 28 July 2022; Accepted 28 August 2022
Available online 31 August 2022
0304-3894/© 2022 Elsevier B.V. All rights reserved.
M. Chen et al. Journal of Hazardous Materials 441 (2023) 129884

then was removed by capturing on the iron oxide precipitates. As (III) was likely to be oxidized in two ways, one
by the reactive oxygen species (possibly •OH, Fe(IV) and •O-2 species), and another directly by the anode. The
long-term effectiveness of arsenic removal demonstrated that ESC process based on the electrochemical-siderite
packed column was an appropriate candidate for treating As (III) pollution.

1. Introduction adsorption (Guo et al., 2013), solid catalyst (Fang et al., 2018; Zhang
et al., 2019), and so on. With the advantages of easy availability and low
Arsenic (As) has a high abundance in the crust, and ranks 20th in cost, the siderite can be used as an iron source.
element content of the crust (Sun et al., 2014). It was often used as The purpose of this work is to investigate the feasibility of forming
additives inside herbicides, preservatives and semiconductors since its iron-based flocculant by electrochemical decomposition of siderite, and
isolation in 1250 A.D. (Sharma and Sohn, 2009; Servanton and Pantel, to determine whether the new Fe-EC treatment system consisting of
2010). However, as elementary As and P are in the same main group, electrochemical siderite packed column (ESC) and power devices can
elementary As can easily replace P and thus be absorbed by organisms remove As (III) effectively. The effect of arsenic removal and the cor­
because of their similar chemical properties, which will pose abnormal responding change in valence of As (III/V) species were examined by
metabolism of organisms and resulting toxication (Rehman et al., 2021). controlling the main influencing factors to study the involved mecha­
The mining and smelting of arsenic-containing minerals and the use of nism. It was confirmed that the new Fe-EC process is likely to change the
arsenic-containing pesticides are the main reasons for the excessive oxidation pathway of arsenic compared with the ordinary Fe-EC process.
arsenic content in water bodies (Yan et al., 2015). The World Health
Organization (WHO) has regarded the removal of arsenic a priority 2. Materials and methods
because of its toxicity to humans (Zhang et al., 2018).
The current methods for removing arsenic mainly include precipi­ 2.1. Materials
tation (Luong et al., 2018), adsorption (Cañas Kurz et al., 2020), mem­
brane separation (Cañas Kurz et al., 2021), biological (Upadhyaya et al., The chemical agents used in this work (NaAsO2, Na2SO4, H2SO4 and
2010) and electrochemical methods (Wan et al., 2011). Coprecipitation NaOH) and the quartz sand with a diameter of 0.5 − 1 mm were
is currently the best practiced available technology for removal of analytical grades (purity >99%). All agents were purchased from
arsenic from industrial effluents (Li et al., 2020). The main forms of Sinopharm chemical reagent Co., Ltd. (Shanghai China). The siderite ore
arsenic in water are inorganic anions such as arsenite (As (III)) and was bought from Anhui Province, China. It was crushed and screened
arsenate (As (V)), with latter the toxicity and migration activity are less. out with a particle size of 0.85–1.4 mm. The ultrapure water was used to
Compared with As (V), As (III) is harder to fixed due to its weaker ability prepare solution in this work.
of being adsorbed, coagulation or precipitation (Kim and Kim, 2014;
Chen et al., 2021a, 2021b). Coprecipitation will generate large amounts
2.2. Electrochemical reactor set-up
of hazardous solid wastes containing leachable arsenate, which in turn
causes secondary pollution (Sun et al., 2022). At present, As (III) is
The reactor diagram of ESC is shown in Fig. 1. The column was made
generally oxidized to As (V) before being removed (Hu et al., 2022). The
from plexiglass resin, and its size was vertical rectangular (L × W × H:
potassium permanganate (Matthess (1981)), nitrate (Sun et al., 2009) or
20 mm × 20 mm × 100 mm). To prevent the packing from clogging the
oxygen (Brunsting, McBean, 2014) was injected to arsenic-containing
ESC, a square cone with a side length of 5 mm and a height of 5 mm was
wastewater to induce biotic or abiotic oxidative precipitation of Fe (II)
connected to the bottom of the column and filled with absorbent cotton.
for As (III) oxidation and immobilization. O2 has attracted more and
To improve operation sensitivity and prevent compaction, a mixture of
more attention because of its environmental friendliness and easy
siderite and quartz sand was packed in the column. The packing of the
availability (Tong et al., 2014, 2016). An Fe anode was used to produce
column was 9 g siderite and 36 g quartz sand, and a new packing would
Fe (II) when Fe (II) was insufficient in the aquifer. In the process of
be replaced after each experiment. The effective volume of the retained
electrically-driven dissolution of iron plates, arsenic was removed by
solution was 18.2 mL. A titanium ruthenium mesh (Ti/RuO2) was used
fixing on insoluble Fe (III) oxide precipitates. It has been further
as an anode, with length of 75 mm and width of 13 mm, as well as a
oxidized by oxygen to form Fe (III) (oxyhydr) oxide (Lakshmanan et al.,
loading capacity of RuO2 as 10 g/m2. Correspondingly, the cathode made
2010). In addition, reactive Fenton-type intermediates were generated
from pure titanium mesh of the same size was used. Both electrodes were
in the process of Fe (II) oxidation with the participation of O2. As a
purchased from Beijing Heng Li Ti Co., Ltd., China. The distance be­
result, As (III) was selectively oxidized to As (V) by the reactive in­
tween the two electrodes was 1.6 cm. Dahua Instrument Corporation of
termediates and then adsorbed rapidly onto Fe (III) (oxyhydr) oxide
Beijing, China provided the power supply required for the experimental
precipitates (Hug and Leupin, 2003; Delaire et al., 2017; Glade et al.,
2021). However, there exists a severe phenomenon: namely electrode
passivation, in electrocoagulation (EC). It will cause operational prob­
lems such as reduction in electrical conductivity, decrease in coagulant
output, and decrease in pollutant removal efficiency (Bandaru et al.,
2020; Chow and Pham, 2021). Herein, we propose a new route of EC.
That is, the acid produced by inert anode is used to decompose iron
minerals to provide active iron species, instead of directly sacrificing
anode to produce flocculant, so as to avoid anode passivation. In order to
verify the feasibility of the proposed new EC route, a study of trivalent
arsenic removal by electrochemical decomposition of iron mineral was
performed here.
Siderite is a widely distributed mineral that is usually used as a raw
material for refining iron. Its chemical composition is ferrous carbonate
(FeCO3). Some scholars have developed the environmental applications
of siderite, such as lead adsorption (Erdem and Özverdi, 2005), arsenic
Fig. 1. Reactor diagram of ESC to remove trivalent arsenic.

2
M. Chen et al.
process (DH1765–2). The entire system was powered by peristaltic
pump (LONGER, L100 − 1S − 1, China).
2.3. Experimental process
Firstly, the raw siderite ore was characterized to determine its phase
and chemical composition. Then, to investigate the effect of current
intensities (0, 5, 10, 20, 30, 50 mA) on Fe (II) release from siderite, a
solution containing only 10 mM Na2SO4 was fed into the ESC with hy­
draulic retention time (HRT) at 30 min and initial pH at 7. After each
experiment, a 30 mL sample was taken from the effluent water and
dissolved with 0.4 mL concentrated HCl to test its Fe (T) concentration.
Comparative experiments for removing As (III) with and without
current applied to ESC were carried out. An instantaneous sampling
method was used, with 8 mL sample taken from the effluent every 2 h,
for total reaction time of 24 h.
After that, the influences of initial concentration (5, 10, 15, 20,
30 mg/L), current intensity (0, 5, 10, 20, 30, 50 mA), initial pH (3, 5, 7,
9, 11) and hydraulic retention time (60, 30, 20, 15, 10 min) on the
oxidation and removal of As (III) were investigated. For each experi­
ment, effluent was collected for analysis after 24 h of continuous oper­
ation to ensure the stability of the ESC. The suspension after reaction
was entirely collected, half of which was filtered by 0.22-um membrane,
followed by determination of As (V), As (total) in the supernatant to
calculate the total removal rate. The rest of the suspension was added
with 0.4 mL concentrated HCl to dissolve the precipitate for testing the
As (V) and As (T) in the effluent. The siderite was replaced with pure
quartz sand as a packed column to quantify the direct oxidation of
electrolysis. 14 mM methanol and 14 mM dimethyl sulfoxide were
added to the ESC as a quencher for •OH (Narayanan et al., 2021) and Fe
(IV) (Pestovsky and Bakac, 2006; Chen et al., 2021a, 2021b), respec­
tively, to quantify the effects of these two oxidants in the system.
Finally, the packing was removed to investigate the direct oxidation
of arsenic by the anode and to determine the oxidizing substances.
Among the simulated conditions, the pH of the solution was set at 2,
which was similar to the pH environment near the anode in the packed
column. 14 mM p-benzoquinone was added as a quencher for •O-2 to test
the effect of •O-2 on trivalent arsenic oxidation. Finally, the •OH in the
simulation system was tested. To verify the long-term stability and the
cost of the ESC, the system had been running for 15 d continuously
under optimal conditions. All experiments were carried out at room
temperature (23 ± 2 ℃), and each experiment was performed in
triplicate.
2.4. Analyses and calculations
Concentration of arsenic was measured by molybdenum blue color­
imetry at a wavelength of 880 nm (Donaldson, 1977; Dhar et al., 2004).
The Fe2+ concentration was determined by a 1, 10-phenanthroline
colorimetric method using the same UV–visible spectrophotometer
(Spectrophotometer UV mini-1240, Japan) at 510 nm (Weerasundara
et al., 2021). The total iron content was measured by flame atomic ab­
sorption spectrometry (CONTRAA-700, Germany). The H2O2 concen­
tration in the simulated system was determined by the titanium salt
photometric method at a wavelength of 400 nm (De Laat and Gallard,
1999; Gallard and De Laat, 2000). The phases of the precipitations were
analyzed by X-ray diffraction (XRD, Rigaku D/Max-RB, Japan) at 2
Theta between 10◦ and 70◦ . Electron spin resonance (ESR, Bruker A300,
Germany) was used to determine •OH in simulated system. The chem­
ical compositions of siderite were analyzed by X-ray fluorescence
spectrometer (Zetium, Panalytical Axios Max WD-XRF, Netherlands).
X-ray photoelectron spectrometer measurements were carried out to
identify the valence states of As and Fe in the precipitation (XPS, k-Alpha
1063, America). The Fourier transform infrared spectroscopy (FT-IR:
Nicolet IS10, America) was employed to distinguish the chemical
structure of the substance. The morphology and mapping of the
3
Journal of Hazardous Materials 441 (2023) 129884
precipitation were analyzed by field emission scanning electron
microscope-electron spectroscopy (SEM: JEM-7500 F; EDS: X-max 50X,
Germany). Low concentration of arsenic was analyzed with Inductively
Coupled Plasma Mass Spectrometry (ICP-MS, 7800, Agilent).
The removal rate of As (T) was calculated using (Eq. (1)):
(M − M1 )
R= × 100% (1)
M
Among them, R represents the total removal rate of As, M represents
the concentration of As (T) in influent water. M1 represents the con­
centration of residual As (T) in the supernatant. The units of M and M1
are mg/L.
3. Results and discussion
3.1. Fe migration from siderite into the aqueous solution
The chemical and mineral components are shown in Fig. S1. As
shown in Fig. S1a, the contents of Fe2O3, SiO2, MnO, Al2O3, CaO, MgO
and others are 58.85%, 3.47%, 3.22%, 1.56%, 0.93%, 0.63% and
31.34%, respectively. In Fig. S1b, the main crystal phase of the ore is
siderite (FeCO3) (PDF#83–1764). This indicates that the mineral can
provide sufficient Fe source for the removal of As (III) and eliminate the
interference of other ions in this work. The solubility product constant of
FeCO3 is 3.13 × 10− 11 (Haynes et al., 2014), and the theoretical solu­
bility of Fe2+ in siderite is 5.59 × 10− 6 mol/L. The concentration is too
low to remove As (III) from wastewater spontaneously. Thus, a contin­
uous decomposition of siderite must depend on the effect of the applied
electrochemical process. In typical electrolysis, H+ and OH- are pro­
duced by the dissociation of H2O (Eqs. (2) and (5)). However, in the
siderite packed column, the siderite near the anode would release Fe2+
by the produced H+ (Eq. (3)). At the same time, O2 produced by the
anode would also accelerated the dissolution of siderite (Eq. (4)) (Xing
et al., 2020).
Anode: 2 H2O - 4e- → 4 H+ + O2↑ (2)
+
FeCO3 + H → Fe 2+
+ HCO-3 (3)
4FeCO3 + O2 + 6 H2O → 4Fe(OH)3 + 4CO2 (4)
Cathode: 2 H2O + 2e- → 2OH- + H2↑ (5)
Thus, in order to verify the validity of the Eq. (3), the electrolyte
containing only 10 mM Na2SO4 was fed into the siderite packed column,
and the concentration of Fe in effluent at different current intensities
was determined. The results are shown in Fig. 2a. Almost no Fe ions was
dissolved from siderite into the electrolyte without current input
(0 mA), indicating the very low dissolution capacity of siderite. The
concentration of Fe ions increased with the increase of current. From
5–50 mA, the concentration of Fe reached 1.3, 49.1, 60.0,
92.8105.2 mg/L, respectively. It is clear that the dissolution of iron ions
from siderite depends on the current intensity, represented by Eq. (3).
After that, comparative experiments were carried out to determine
the feasibility of arsenic removal. As shown in Fig. 2b, the removal rate
of As (III) markedly deceased with the running time without current, and
the removal rate of As (III) dropped to 53.10% after running for 24 h.
After the application of 30 mA current, the removal rate remained high
and stabilized above 99% during the 24 h treatment. It can be concluded
that the current played important role in the ESC for the As (III) removal.
3.2. Performance of arsenic removal by the ESC
The influences of main operating variables on arsenic removal per­
formance were investigated and the results are shown in Fig. 3. The
concentration of As (III) in the feed solution was adjusted to 5, 10, 15, 20
and 30 mg/L, respectively. As shown in Fig. 3a, the removal rate of
arsenic exceeded 99% when the concentration of As (III) was in the
M. Chen et al. Journal of Hazardous Materials 441 (2023) 129884

Fig. 2. The concentration of Fe in effluent at different current intensity (a) and the removal rate of As (T) with and without current (b). Conditions: HRT 30 min,
initial pH 7, As (III) 10 mg/L and Na2SO4 10 mM.

Fig. 3. As (T), As (V) contents and total removal rate in the effluent from the ESC by adjusting the initial concentration of arsenic (a), current intensity (b), initial
influent pH (c) and HRT (d). Conditions: aqueous solution contained 10 mg/L As (III) and 10 mM Na2SO4, current 30 mA, initial pH 7.0, HRT 30 min.

range of 5–20 mg/L. Among them, the concentration of As (T) in the
supernatant water after treatment was below 0.1 mg/L. As the concen­
tration increased to 30 mg/L, the removal rate dropped to 92.17%. The
residual concentration of As (T) in the supernatant was 2.35 mg/L. The
reason may be that the amount of iron ion dissolved at 30 mA was not
enough to precipitate 30 mg/L As (T).
The current intensity was changed at 0, 5, 10, 20, 30 and 50 mA (0,
5.1, 10.2, 20.4, 30.6 and 51.3 A/m2) to study its effect on the As (III)
removal. The results as shown in Fig. 3b indicate that the removal rate of
As (T) was 57.8% in the absence of current applied on the ESC. Natural
siderite has a specific adsorption capacity to arsenic, and it can reach
1.04 mg/g in the particle size of 0.8–2 mm (Guo et al., 2013). The
removal rate of As (T) increased from 89.8% to 99.4% as the current
increased from 5 m to 50 mA. Considering both removal and economic
performances, the current intensity of the subsequent experiment was
selected as 30 mA.
The effect of influent pH on the removal rate of As (T) was further
investigated by presetting initial pH at 3, 5, 7, 9 and 11, respectively.
The results as shown in Fig. 3c demonstrate that the removal rate can be
maintained at about 99% as the initial pH increased from 5 to 11. It is
worth noting that there was still 0.76 mg/L As (T) in the supernatant at a
weak acidic value of 3. The pH value of the influent and effluent was

4
M. Chen et al.
measured at the same time, and the results are shown in Fig. S2. The pH
of the effluent from the ESC was 3.7 when the inlet water pH was
adjusted to 3, which could not go back to the neutral pH. The reason may
be that the amount of siderite in the ESC was small, and there was not
enough CO2- 3 in the system to form a buffer to neutralize the H (Chen
+
et al., 2021a, 2021b). At the same time, it became more difficult to form
Fe (OH)3 floc due to the acid environment in the effluent, therefore the
removal of As (T) was difficult.
The hydraulic retention time of the influent will affect the treatment
efficiency. The influence of different HRT (The HRT was set to be 60, 30,
20, 15, 10 min, and the corresponding flow rate was 0.4, 0.7, 1, 1.3 and
1.9 mL/min, respectively) on the removal of As (T) is shown in Fig. 3d. It
can be seen from the figure that the removal of As (T) decreased slightly
with the decrease of the HRT. The concentration of As (T) in the su­
pernatant was 0.8 mg/L when the HRT was 10 min, indicating that the
ESC could not dissolve enough iron ions to precipitate arsenic when the
flow rate was too fast.
3.3. Oxidation of As (III)
The proportion of As (III) and As (V) in the effluent represents the
oxidation capacity of the ESC process to a certain extent. The ratio of As
(III) to As (V) under different conditions is shown in Fig. 4. The pro­
portion of As (V) decreased from 84.44% at 5 mg/L to 47.1% at 30 mg/L
in Fig. 4a. However, the concentration of As (V) in the effluent increased
from 1.90 mg/L to 9.17 mg/L, which indicated that the system could
convert a large amount of As (III) into As (V). The oxidation effect of
current intensity on As (III) is shown in Fig. 4b. The proportion of As (V)
in the effluent increased with the increase of current intensity. The
conversion efficiency was up to 88.98% at 50 mA, which indicated that
Fig. 4. The proportion of As (III) and As (V) in the effluent treated under the following conditions: initial concentration of arsenic (a), current intensity (b), initial
influent pH (c) and HRT (d).
5
Journal of Hazardous Materials 441 (2023) 129884
current intensity had a significant influence on the oxidation of As (III).
Fig. 4c shows that the proportion of As (V) in the effluent dropped
slightly as the pH of the influent increased from 3 to 11, maintaining a
high value above 70%. It was concluded that the oxidation capacity of
the ESC was not affected largely by change in pH in the range of 3–11.
Fig. 4d shows the influence of HRT on the oxidizing ability of the system.
The oxidation rates of As (III) reached 90.32%, 80.79%, 54.34%,
43.22% and 37.12%, respectively, when the HRT was 60, 30, 20, 15 and
10 min. Therefore, the HRT is a key parameter to determine the con­
version efficiency of As (III) to As (V). At the same time, it is worth
noting that only 40% of As (T) flew into the collection tank after each
experiment, and 60% of As (T) was still trapped in the reaction column.
In order to further confirm the total oxidation rate of the system,
experiments were carried out under the optimal conditions (10 mg/L As
(III), 10 mM Na2SO4, current 30 mA, initial pH 7.0, HRT 30 min).
Arsenic in the packed column was desorbed with 100 mL of 0.5 mol/L
NaOH to test the oxidation effect of As (III) in the packed column. The
results showed that the proportions of As (III) and As (V) were 7.9% and
92.1%, respectively. As (T) trapped in the packed column accounted for
40% of the influent water. The proportion of As (III) and As (V) in the
effluent was 78.8% and 21.2% respectively, so the total oxidation rate of
As (III) by ESC process could reach 84.12%.
3.4. Sediment characteristics
In order to reveal the existence states of arsenic in the sediment, a
series of characterization tests were carried out to examine morphology
phase, chemical structure and valence in the sediment. The arsenic-
containing precipitate was obtained by filtering the effluent under
optimal conditions previously selected: current 30 mA, 10 mg/L As (III),
M. Chen et al.
initial pH 7 and HRT at 30 min. At the same time, the ESC process ran
without arsenic under the same conditions to give arsenic-free precipi­
tation as a comparison. As shown in Fig. 5a and b, both sediments are
irregular massive particles with diameter of about 1.5 µm, and the sur­
face is loose and porous. It can be seen from Fig. 5c and d that the
content of O, Fe and As were 63%, 24% and 7%, respectively. The dis­
tribution of As was positively correlated with the distribution of Fe, and
the quantitative analysis of sediment shows that the mole ratio of Fe/As
was 20. It was suggested that the removal mechanism of arsenic may be
mainly based on the adsorption of As by Fe (II)/Fe (III) precipitates.
XRD patterns of the sediment for phase analysis are shown in Fig. 6a.
It was found that there was no well-crystallized phase in the sediment,
and the Fe2O3 phase was the main composition after calcination at
1000 ℃ for 2 h. Then, FT-IR spectroscopy was conducted to determine
the chemical bonding on the surface of precipitate particles. The
methods for obtaining two kinds of precipitates were the same as above,
and the results are shown in Fig. 6b. The band at 796 cm− 1 is consistent
with the characteristic peak of As-O (Goldberg and Johnston, 2001),
which indicates that arsenic was immobilized in the Fe-precipitate. The
band at 1484 cm− 1 are contributed to the characteristic peak of CO2- 3.
The valence states of As and Fe in the precipitate were examined by XPS
analysis (Fig. 6c). The B.E. at 45.5 eV and 43.9 eV were ascribed to As
(V) and As (III) in As-3d spectrum, respectively, and the content of As (V)
accounted for 71.58%. This is consistent with the same conditions in
Fig. 4, which indicates that most of As (III) was indeed oxidized through
the ESC process. Fig. 6d shows the XPS spectrum of Fe2p orbital in the
arsenic-containing precipitation. It is found that the ratios of Fe (II) and
Fe (III) are 27.35% and 72.65%, respectively, which is basically
consistent with the 26.34% and 73.66% of Fe (II) and Fe (III) in the
Fig. 5. SEM (a, b) and EDS (c, d) images of the precipitate. Conditions: HRT 30 min, initial pH 7, As (III) 10 mg/L, current 30 mA.
6
Journal of Hazardous Materials 441 (2023) 129884
precipitate tested by the o-phenanthroline. This indicates that Fe (II)
produced by the ESC had not be oxidized completely into Fe (III) as it
flew out into the beaker.
3.5. Mechanism analysis
It can be found that ESC had clearly demonstrated oxidizing ability
on As (III) in the influent from Fig. 4. Therefore, the influences of various
kinds of free radicals possibly involved on the arsenic oxidation in the
ESC were investigated. First of all, the packed column containing only
SiO2 was run. As shown in Fig. 7, the As (V) accounted for 38.87% of the
As (T) in the effluent after being treated with SiO2 packed column. It
indicates that direct oxidation on the electrode had an essential contri­
bution to the oxidation of As (III). After adding one-fifth of siderite, the
proportion of As (V) in the effluent increased to 76.77%, indicating
clearly the involvement of siderite with As (III) oxidation. Then, 14 mM
methanol as the quencher of •OH and 14 mM dimethyl sulfone (DMSO)
as the quencher of Fe (IV) were added separately to the influent. It can be
seen that the oxidation efficiency of As (III) was reduced by 13.03% and
15.87% for methanol and dimethyl sulfone, respectively. The negative
effects of methanol and DMSO indicated that the reactive oxygen species
of •OH and Fe (IV) had contributed to the As (III) oxidation.
According to the above experimental phenomena, it can be known
that the electro-Fenton reaction may take place in ESC. To further un­
derstand the role of •O-2 played in the ESC, a 250 mL solution containing
60 mg/L As (III) and 2 mM Fe (II) (the amount of ESC system dissolved
at 30 mA) was electrolyzed as a simulation system for ESC. Fig. 4c
suggests that the pH of the solution has little influence on the oxidation
of As (III) in the ESC. AsO-2 would be attracted by the anode and migrate
M. Chen et al.
Fig. 6. XRD (a), FT-IR (b), XPS spectra of As3d (c) and Fe2p (d) of the precipitation. Conditions: HRT 30 min, initial pH 7, As (III) 10 mg/L, current 30 mA.
Fig. 7. The ratio of As (V) to As (III) in the effluent after adding different
quencher. Conditions: current 30 mA, HRT 30 min, initial pH 7, As (III)
10 mg/L.
to the anode, the cathode had no oxidation capacity in the meantime.
The oxidation of As (III) was speculated to occur near the anode in the
ESC. According to the literatures of (Lei et al., 2017) and (Honda et al.,
1998), a highly alkaline and highly acidic environments will be formed
within 0.5 mm from the cathode and anode, respectively, when a certain
current is applied. The pH of the whole solution was adjusted to 2 to
ensure that Fe (II) can exist stably in the simulation system. Firstly, the
7
Journal of Hazardous Materials 441 (2023) 129884
H2O2 produced by different concentrations of Fe (II) was determined.
The experimental conditions were set as follows: current intensity at
30 mA, the solution capacity was 250 mL, stirring speed at 120 rpm,
reaction pH at 2 and the concentration of As (III) was 60 mg/L. The
result is shown in Fig. S3a. It can be seen that the produced amount of
H2O2 increases with the increase of Fe (II) dosage. The concentration of
H2O2 could be increased from 120 μmol/L at 0 mM to 270 μmol/L at
8 mM. The reason may be that the amount of •O-2 increases with the
increase of Fe (II) (Eq. (6)) (Fang et al., 2013; Liang et al., 2019), and the
amount of •O-2 converted to H2O2 also increases, so the addition of Fe (II)
promoted the generation of H2O2 (Eq. (7)) (Hug and Leupin, 2003).
Fig. S3b shows that the impact of the addition of PBQ on the oxidation of
As (III), where the oxidation of As (III) was lower than that by the
electrode directly after PBQ was added. It suggests that •O-2 played a
vital role in the entire system. The mechanism of the electric-Fenton
reaction is still complex and controversial (Hug and Leupin, 2003;
Pang et al., 2011; Tong et al., 2014). Herein, •OH was detected by the
electron spin resonance (ESR) spectroscopy during the current applica­
tion process. The result is shown in Fig. S4, and there were four char­
acteristic peaks of DMPO-•OH observed in the solution (Goldberg and
Johnston, 2001). Generation reaction of •OH happened in the system
from Fe (II) reacting with H2O2 (Eq. (8)) (Ren et al., 2018). Fe (IV) would
also be produced as a side reaction at the same time (Eq. (9)) (Hug and
Leupin, 2003; Li et al., 2012; Zhang et al., 2021). In summary, the
oxidation of As (III) in the ESC may be caused by the joint oxidation of
anode (Eq. (10)), •O-2 (Eq. (11)) (Kim et al., 2015), •OH (Eq. (12)) and Fe
(IV) (Eq. (13)).
Fe (II) + O2 → •O-2 + Fe (III) (6)
Fe (II) + •O-2 + 2 H+ → Fe (III) + H2O2 (7)
Fe (II) + H2O2 → Fe (III) + •OH + OH -
(8)
Fe (II) + H2O2 → Fe (IV) + 2OH -
(9)
M. Chen et al.
As (III) - 2e- → As (V) (10)
As (III) + 2•O-2 + 2 H+ → As (V) + 2HO-2 (11)
As (III) + 2•OH → As (V) + 2OH -
(12)
2Fe (IV) + As (III) → 2Fe (III) + As (V) (13)
3.6. Capability and economic evaluation
The ESC was operated continuously for 21 d to assess the stability
under optimized conditions. The results shown in Fig. S5 indicate that
the removal rate of As (T) (10 mg/L) could maintain above 90%, and the
effluent pH could always be maintained at 7.0 ± 1. Then, the ratio of ore
and SiO2 was adjusted to 1:1, and the concentration of As (III) was set as
1 mg/L to explore the treatment effect of the ESC on low-concentration
arsenic wastewater. Fig. 8 shows that the residual concentration of As
(T) in the effluent could still reach below 10 μg/L after 15 d of contin­
uous operation of the system, which could meet the drinking water
standards of the World Health Organization (10 μg/L). Compared with
the traditional ferric salt flocculation method to remove As (III), the ESC
cost of wastewater treatment can be significant reduced, and the con­
centration of effluent As (T) can be reduced to less than 10 μg/L. The
profitability analysis calculation details are shown in Tables S1-S4.
Therefore, the ESC has the advantages of stable operation at low cost.
4. Conclusions
The siderite column can provide a continuous source of Fe under the
stimulation of electrochemical. The feasibility of using the new route to
remove As (III) was discussed in detail. Results showed that the removal
rate of As (T) could be over 99%, and the effluent pH could be stable at
neutral under optimized operating conditions: 10 mg/L As (III), 10 mM
Na2SO4, current 30 mA, initial pH 7.0, HRT 30 min 40% arsenic was
trapped in the packed column; the remaining arsenic flowed out and
settled in the.
effluent collection tank. The proportion of As (V) and As (III) in the
packed column was 92.1% and 7.9%, respectively. While, the propor­
tion of As (Ⅴ) in the precipitate in the collection tank was 78.8% and that
of As (III) was 21.2%. Therefore, 84.12% As (III) in the ESC will be
oxidized to As (V) by the ESC. The residual content of 1 mg/L As (III)
could be reduced to less than 10 μg/L after being treated by the ESC for
15 d. Due to the advantages of stability, high efficiency and low cost, the
ESC can not only provide a new application method for Fe ore resources,
but also provide a new idea for As (III) removal.
CRediT authorship contribution statement
Mengfei Chen: Writing − original draft, Investigation, Huimin Hu:
Methodology. Min Chen: Visualization, Investigation. Chao Wang:
Visualization, Formal analysis. Qian Wang: Formal analysis. Chao­
cheng Zeng: Data collection. Qing Shi:Supervision. Weinjie Song:
Methodology. Xuewei Li: Writing − review & editing, Methodology.
Qiwu Zhang: Methodology, Conceptualization, Supervision, Resources.
Novelty statement
A new Fe- electrocoagulation (EC) treatment system consisting of
electrochemical siderite packed column and power devices was pro­
posed to remove As (III). The inert anode was used to decompose iron
(aluminum) minerals to produce flocculation and precipitation, avoid­
ing the iron passivation that may occur in the traditional sacrificial
anode method. The removal rate of As (III) in the effluent could reach
100% and the oxidation rate could also reach 78.8% after the arsenic-
8
Journal of Hazardous Materials 441 (2023) 129884
Fig. 8. The removal efficiency of As (T) by the ESC in a long-term operation.
Conditions: one-half siderite, As (III) 1 mg/L, current 30 mA, initial pH 7,
HRT 30 min.
containing wastewater passed through the system. This study was
proven to be an new concept for treating As (III) pollution.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This study was financially supported by the National Key Research
and Development Program of China (Project No. 2019YFC1805600 and
2019YFC1805601).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jhazmat.2022.129884.
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