Journal of Cleaner Production 221 (2019) 635e643

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Journal of Cleaner Production

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Selective recovery of ferrous oxalate and removal of arsenic and other

metals from soil-washing wastewater using a reduction reaction
Eun Jung Kim a, *, Kitae Baek b, **
a
Department of Environmental Engineering, Mokpo National University, 1666 Yongsan-ro, Cheongye-myeon, Muan-gun, Jeollanam-do, 58554, Republic of
Korea
b
Department of Environmental Engineering and Soil Environment Research Center, Chonbuk National University, 567 Baekje-daero, Deokjin-gu, Jeonju,
Jeollabuk-do, 54896, Republic of Korea

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

Article history: Oxalic acid can effectively extract arsenic bound to amorphous iron oxides via dissolution of iron oxides
Received 12 September 2018 containing arsenic. Therefore, soil washing with oxalic acid is a promising method to remediate arsenic-
Received in revised form contaminated soil, since arsenic is often associated with amorphous iron oxides in soil. However, high
17 January 2019
cost of oxalic acid compared to the other inorganic acids commonly used for remediation of metal-
Accepted 2 March 2019
Available online 2 March 2019
contaminated soils is the main disadvantage of using oxalic acid for soil washing. In this study, in or-
der to increase the economic feasibility of soil washing using oxalic acid, selective recovery of iron and
oxalate as resources was suggested via two step reduction reaction using dithionite as a reductant during
Keywords:
Iron oxalate
soil-washing wastewater treatment. In the first step, high levels of oxalate and iron present in waste-
Arsenic water was recovered as a ferrous oxalate phase. Under mild reducing conditions, ferric iron in the
Dithionite wastewater was reduced to ferrous iron, which could form a complex with oxalate and precipitate as the
Wastewater treatment ferrous oxalate phase with low solubility. The ferrous oxalate phase did not affect dissolved arsenic
retention in this step. The recovered ferrous oxalate phase can be applied in the industry as useful re-
sources, which can contribute to the sustainable development and cleaner production. In the second
step, arsenic in wastewater was removed by forming a realgar-like phase from the reaction with
dithionite. Sulfide produced by the decomposition of dithionite reacted with arsenic and other metals in
wastewater, and formed sulfide phases such as realgar (As4S4)/orpiment (As2S3) and lead sulfide (PbS).
© 2019 Published by Elsevier Ltd.

1. Introduction various solid-phase species in arsenic-contaminated soil, depend-

ing on interactions with soil minerals. Among these species, arsenic
Arsenic contamination in soils has been a serious problem in is often found to be strongly bound to iron oxide minerals (Smedley
many parts of the world due to its toxic effects. Arsenic- and Kinniburgh, 2002). Our previous study showed that oxalic acid
contaminated soils can contaminate surface/groundwater and can effectively extract arsenic bound to amorphous iron oxides via
plants/crops, and eventually can affect human health. Therefore, dissolution of iron oxides containing arsenic (Lee et al., 2016, 2017).
effective remediation of arsenic-contaminated soils is required. Oxalate can form a strong complex with iron on the surface of iron
Recently, soil washing based on chemical extraction with various oxides and the iron-oxalate complex can be detached, which results
chemical reagents has been widely applied to remediate arsenic- in the dissolution of the iron oxides and subsequent release of
contaminated soils because it can permanently separate arsenic associated arsenic (Cornell and Schwertmann, 2003; Kim et al.,
from soil in a short period of time (Dermont et al., 2008). In the soil- 2015). Therefore, soil washing with oxalic acid is a promising
washing process, efficiency is greatly affected by the chemistries of method to remediate arsenic-contaminated soil, since arsenic is
both the washing reagent and the arsenic solid-phase species often associated with amorphous iron oxides in soil. However, the
present in the soil (Kim et al., 2014). Arsenic can be present as main problem with using oxalic acid for soil washing is the high
cost compared to the other inorganic acids commonly used for
remediation of metal-contaminated soils, such as hydrochloric or
* Corresponding author.
nitric acids. Therefore, in order to increase the feasibility of
** Corresponding author.
E-mail addresses: ejkim@mokpo.ac.kr (E.J. Kim), kbaek@jbnu.ac.kr (K. Baek).
applying oxalic acid as a soil-washing reagent, it is necessary to

https://doi.org/10.1016/j.jclepro.2019.03.014
0959-6526/© 2019 Published by Elsevier Ltd.
636 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643

reduce the overall cost of the process. 2. Materials and methods

One strategy to increase the feasibility of using oxalic acid as a
washing reagent would be recycling or reuse of oxalate after soil 2.1. Wastewater produced from soil washing with oxalic acid
washing. Recycling of soil washing reagents such as EDTA have
been investigated via precipitation or electrochemical treatment in Wastewater was produced from soil washing of arsenic-
order to improve the cost-effectiveness of the soil washing process contaminated soils with oxalic acid. Two different soil samples
(Pociecha and Lestan, 2012; Zeng et al., 2005). In addition, effective were applied collected at a former smelter site and an abandoned
and efficient wastewater treatment could reduce the overall cost of gold mine site in Korea. The arsenic concentrations in the smelter
the soil-washing process. Washing of arsenic-contaminated soils and mine soils were 35 mg/kg and 6800 mg/kg, respectively. Soil
using oxalic acid produces acidic wastewater containing arsenic washing was conducted with 0.2 M oxalic acid in a 1: 3 soil: liquid
and other heavy metals such as lead and copper extracted from suspension for 3 h at 20
C and 150 rpm. After soil washing, the
soils. In addition, high concentration of iron is present in waste- samples were filtered with 0.45-mm pore sized membrane filter and
water, which was extracted from soil due to the strong iron-oxalate the filtrate were used for wastewater treatment experiment. The
complexes (Table 1). There are many available techniques to treat pH of the filtrate was measured by a pH-ISE meter (Thermo-Orion
arsenic-contaminated water and wastewater, which includes 710, USA). Total major and trace elements of the wastewater were
adsorption, ion exchange, membrane, oxidation, and coagulation analyzed via inductively coupled plasma optical emission spec-
((co)precipitation) (Lee et al., 2003; Mohana and Pittman, 2007; troscopy (ICP-OES, SPECTRO Arcos, SPECTRO Analytical In-
Ungureanu et al., 2015; Wang et al., 2011; Wu et al., 2011). struments, Germany). The pH and major elemental concentrations
Among them, coagulation by iron or aluminum and adsorption has of the wastewater are summarized in Table 1.
been most frequently applied to remove arsenic from drinking
water (Ungureanu et al., 2015). In those processes, iron phases such 2.2. Treatment of soil-washing wastewater by a reduction reaction
as ferric (Fe(III)) or ferrate (Fe(VI)) salts, iron oxides, and iron-
manganese binary oxides are often applied as coagulants of ad- Treatment of soil-washing wastewater by a reduction reaction
sorbents due to the high affinity of arsenic for multiple iron phases was investigated with sodium dithionite (Na2S2O4) as a reductant.
(Lee et al., 2003; Ungureanu et al., 2015; Wu et al., 2011). The high Various amounts of sodium dithionite were added to the 30 mL of
concentration of iron in the wastewater can be applied to remove wastewater to final concentration of 0e100 mM for smelter soil
arsenic via coagulation or adsorption by increasing pH. However, wastewater and 0e300 mM for mine soil wastewater. Reduction
this method requires input of large amounts of alkali to increase the reaction with sodium dithionite was conducted in a completely
pH of the wastewater and produces large amounts of solid products mixed batch reactor system for 3 h at 20
C and 150 rpm. After re-
such as iron hydroxides contaminated with arsenic, which should action, the wastewater was centrifuged at 8000 rpm for 10 min and
be treated as waste. filtered with 0.45-mm pore sized membrane filter. The filtrates were
On the other hand, the high levels of iron and oxalate in analyzed by ICP-OES (SPECTRO Arcos, SPECTRO Analytical In-
wastewater can be useful resources if they are recovered. Recently, struments, Germany) and the solid precipitates recovered by filtra-
recovery of resources from waste or wastewater have been tion were stored in a desiccator after air-dry for characterization.
receiving attention due to the concern for the environment and
resource depletion (Hero Paul R. Guevara et al., 2017; Li et al., 2018; 2.3. Solid characterization
Hoang et al., 2019). Therefore, the objective of this study is to
recover iron and oxalate from wastewater as resources during soil- The morphology and chemical elemental composition of the
washing wastewater treatment in order to increase the economic solid precipitates recovered from wastewater were characterized
feasibility of soil washing using oxalic acid, which could contribute by a scanning microscope with energy dispersive spectroscopy
to the sustainable development and cleaner production. In order to (JEOL JSM-5900 SEM/EDS). The mineral phases in solid precipitates
do this, a reduction reaction was investigated to recover iron and were qualitatively identified via X-ray diffraction analysis (Empy-
oxalate from wastewater during treatment. Ferric iron and oxalate rean, Malvern Panalytical, Cu Ka radiation at 40 kV and 30 mA). The
complex in wastewater can be recovered as a ferrous iron-oxalate surface composition and speciation of the precipitates were studied
solid phase, which has low solubility in water, by a reduction re- using Kratos Axis Ultra Imaging X-ray photoelectron spectroscopy
action. Ferrous oxalate dihydrate (humboldtine) can be used as a with monochromatic Al Ka X-rays. A broadscan and narrow high
solid electrolyte in various fields due to its high proton conduc- resolution scans of As 3d, Fe 2p, and S 2p were obtained using pass
tivity, and environmentally it can be applied as an adsorbent or energy of 80 eV and 40 eV, respectively. The charge effect was
Fenton reagent to remediate contaminants (Liu et al., 2016; Yamada corrected using C1s from contamination at 284.5 (±0.1 eV). The
et al., 2009). In this study, reduction reaction was applied to obtained narrow scan spectra were fitted using a curve-fitting
selectively recover the iron-oxalate phase and to remove arsenic program (XPSPEAK41). The spectra were fitted using a least-
and heavy metals in wastewater produced from soil washing of squares procedure with peaks of 80% of Lorentzian-Gaussian peak
arsenic-contaminated soils from smelter and mine sites. The shape after subtraction of a Shirley baseline and the component
recovered iron-oxalate phase was characterized by X-ray diffraction peaks were identified by comparison of their binding energies with
(XRD), scanning electron microscopy with energy dispersive values in the literature (Kim and Batchelor, 2009; Nesbit et al.,
spectroscopy (SEM/EDS), X-ray photoelectron spectroscopy (XPS), 1998). The elemental compositions of precipitates were deter-
and X-ray fluorescence (XRF). mined by X-ray fluorescence (XRF) spectrometer (Axios Minerals,
Malvern Panalytical).
Table 1
Characteristics of soil-washing wastewater. 3. Results and discussion
Sample pH Concentration (mg/L)
3.1. Soil-washing wastewater treatment by a reduction reaction
As Pb Cu Fe

Smelter 1.4 14.3 34.8 31.7 3790 A soil-washing process using oxalic acid produced highly acidic
Mine 1.2 1590 40.1 1.62 2890
wastewater containing high concentrations of iron, arsenic, lead,
 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643 637

and copper extracted from soils (Table 1). Treatment of smelter soil- in the formation of rather irregular-shaped particles with various
washing wastewater by a reduction reaction was investigated with sizes, which were mostly composed of carbon (87.3 atomic %), ox-
dithionite varying its concentration from 0 to 100 mM. When ygen (5.4%), and iron (5.2%). Reaction with 20 mM dithionite
wastewater was reacted with dithionite, precipitation of a solid formed cuboid-like morphologies with an average length of
phase occurred and the levels of metals in wastewater decreased in approximately 20 mm. The EDS analysis indicated that the cuboid-
the order of copper, lead, iron, and arsenic as dithionite concen- like particles were composed of iron, carbon, and oxygen,
trations increased (Fig. 1a). The levels of copper and lead in the contributing 15.6, 28.9, and 55.5 atomic %, respectively, which was
wastewater were significantly decreased by reaction with approximately consistent with the stoichiometric ratio of the
10e20 mM dithionite (Fig. 1a). An initial high concentration of iron ferrous oxalate phase (Fe(C2O4)$2H2O, humboldtine), i.e. an iron to
(1850 mg/L) decreased to less than 100 mg/L as the dithionite carbon to oxygen molar concentration ratio of 1:2:4 (Andre
concentration increased to 30 mM. On the other hand, arsenic Angermann, 2008). Reaction with higher concentrations of
concentration only decreased when dithionite concentration was dithionite (50 and 100 mM) formed cuboid-like particles and some
higher than 20 mM. particles with irregular shapes covering the cuboid-like particles,
The precipitates formed in smelter wastewater by the reaction which contained sulfur, lead, and arsenic in addition to carbon and
with various concentrations of dithionite were characterized with iron (Table 2). The presence of sulfur in the precipitates might be
SEM/EDS and XRD. SEM images and EDS parameters are summa- due to elemental sulfur or oxidized sulfur compounds such as SO23
rized in Fig. 2 and Table 2. Reaction with 10 mM dithionite resulted and SO24 formed by the oxidation of dithionite.

(a) 16 2000
As
Concentrations of As, Pb, Cu, Zn (mg/L)

14 Cu
Pb
Fe

Concentration of Fe(mg/L)
12 1500

10

8 1000

4 500

0 0

0 20 40 60 80 100
Concentration of dithionite (mM)

3000
(b) As
Cu 40
Pb
Concentrations of Cu, Pb (mg/L)
Concentrations of As, Fe (mg/L)

2500
Fe

30
2000

1500
20

1000

10
500

0 0

0 50 100 150 200 250 300

Concentration of dithionite (mM)

Fig. 1. Effect of dithionite concentrations on levels of metals in (a) smelter and (b) mine wastewater.
638 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643

(a) (b)

(c) (d)

Fig. 2. SEM images of solid phases formed in smelter wastewater by the reaction with various concentrations of dithionite. (a) 10 mM, (b) 20 mM, (c) 50 mM, and (d) 100 mM of
dithionite (Yellow asterisks indicate the point where EDS analysis was conducted.).

Fig. 3 shows XRD peaks of precipitates formed in smelter and elemental sulfur. Dithionite is a labile compound, which is
wastewater by reaction with various concentrations of dithionite. rapidly decomposed in aqueous solution by the following reactions
The XRD study confirmed the formation of b-iron (II) oxalate (Carvalho and Schwedt, 2001).
dihydrate (Fe(C2O4)$2H2O) by the reaction with dithionite, which

was consistent with the EDS study (Andre Angermann, 2008). Our 2 S2O2 2
4 þ H2O / S2O3 þ 2 HSO3 (1)
previous study showed that the majority of iron extracted from soil
þ 
by oxalate was in the ferric form (Lee et al., 2017). The addition of S2O2 2
4 þ S2O3 þ 2H2O þ H / H2S þ 3 HSO3 (2)
dithionite reduces ferric iron to ferrous (Fe(II)) iron, which could
form a complex with oxalate and precipitate as the ferrous oxalate 2 H2S þ HSO 0
3 þ Hþ / 3S þ 3H2O (3)
phase with low solubility (log Kso ¼ 6.68) (Bolz and Tuve, 1973).
The ferrous oxalate phase can be present as a- or b-type depending Elemental sulfur could be formed at a high concentration of
on the formation reaction temperature: a-type oxalate phase can dithionite by the self-decomposition of dithionite. In addition,
be obtained after precipitation and ageing at 90
C, while b-type sulfide produced by the decomposition of dithionite could react
can be formed at room temperature (Andre Angermann, 2008). In with metals in wastewater such as zinc, lead, and copper, and form
this study, the b-iron (II) oxalate phase was formed from the metal sulfides, which are highly insoluble in water. The solubility
wastewater since the reaction with dithionite was conducted at constants (log Kso) for CuS, PbS, and ZnS are 35.96, 28.05,
room temperature. In the XRD pattern of particles formed with and 21.97, respectively (Benjamin, 2002). In addition, removal of
100 mM dithionite, other small peaks were observed in addition to arsenic by the reaction with higher dithionite concentrations
the ferrous oxalate peaks, which were identified as calcium oxalate (above 20 mM) could be attributed to the precipitation of arsenic

Table 2
EDS parameters of particles formed from wastewater reacted with various concentrations of dithionite (Yellow asterisks marked in SEM images in Fig. 2 indicate the point
where EDS analysis was conducted.).

Element 10 mM 20 mM 100 mM

Elemental % Atomic % Elemental % Atomic % Elemental % Atomic %

C 67.95 87.34 16.45 28.85 62 82.96

O 5.61 5.42 42.18 55.54 5.09 5.11
Fe 18.74 5.18 41.37 15.6 4.29 1.23
Pb 4.87 0.36 e e 9.09 0.71
As e e e e 0.67 0.14
S e e e e 7.41 3.72
Na 1.11 0.74 e e 5.13 3.58
Al 0.38 0.22 e e e e
Si 1.33 0.73 e e e e
Ca e e e e 6.33 2.54

Total 99.99 99.99 100 99.99 100.01 99.99

 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643 639

*
* -ferrous oxalate
calcium oxalate
elemental sulfur

* *
* * * * 100 mM
* * *

50 mM

20 mM

10 mM

5 mM

10 20 30 40 50 60 70

2 theta
Fig. 3. X-ray diffraction peaks of particles formed from wastewater reacted with various concentrations of dithionite.

sulfides such as realgar (As4S4) and orpiment (As2S3). Sulfide concentrations of 100, 150, and 300 mM, at which about half of
formed by decomposition of dithionite seemed to be consumed by arsenic was removed (100 mM), maximum arsenic removal was
cationic metals first; further addition formed the arsenic sulfide achieved (150 mM), and arsenic removal was slightly decreased
phase. Thus, when wastewater produced by soil washing with (300 mM). XPS surface atomic concentrations of the solid phase
oxalic acid is reacted with dithionite, high concentrations of iron were calculated using the carbon 1s, oxygen 1s, sulfur 2p, iron 2p,
and oxalate could be precipitated as the iron (II) oxalate phase, and and arsenic 3d peak areas from the survey scan spectra, which are
arsenic and other metals could form sulfide phases such as PbS and summarized in Table 3. The narrow scan XPS spectra of As 3d, Fe
As4S4/As2S3. 2p3/2, and S 2p are reported in Fig. 4. The As 3d and S 2p spectra
were modeled as doublets of 3d3/2 and 3d5/2 and 2p1/2 and 2p3/2,
respectively. The surface compositions are shown in Table 4.
3.2. Arsenic removal by a reduction reaction: X-ray photoelectron
The surface of the solid phase was mainly composed of carbon
spectroscopy investigation
and oxygen; iron, arsenic, and sulfur were also present (Table 3).
The surface concentration of sulfur increased as dithionite con-
Wastewater treatment by a reduction reaction was further
centration increased, indicating that the sulfur on the particle
investigated with mine soil-washing wastewater with a high
surface was mainly contributed by the dithionite. The major peaks
arsenic concentration (1590 mg/L, Table 1). When dithionite con-
of the S 2p spectra of the surface of the solid phase were hydrogen
centrations were varied from 0 to 300 mM, the metal concentra-
sulfite (SO2 2
3 ) and thiosulfate (S2O3 ) ions, which are the main
tions in mine wastewater decreased in the order of copper, lead,
decomposition products of dithionite as described in reaction (1).
iron, and arsenic, similar to the reaction of smelter wastewater
In addition, the presence of sulfides (S2 2
2 and Sn ) could indicate the
(Fig. 1b). A higher dithionite concentration was required to decrease
precipitation of metal sulfides by the reaction between metals in
arsenic in mine wastewater than in smelter wastewater. Arsenic
wastewater and sulfide resulting from the self-decomposition of
concentrations remained almost constant when dithionite con-
dithionite. The surface concentration of arsenic was highest (5.93%)
centration was less than 60 mM, and decreased as dithionite con-
with 150 mM dithionite, which was consistent with the solution
centration increased to 200 mM. The initial arsenic concentration
was decreased by approximately 93% at a dithionite concentration
of 200 mM. But when dithionite concentration further increased
above 200 mM, arsenic and lead concentrations slightly increased. Table 3
Atomic concentration of particles formed in mine wastewater reacted with various
The increased solution concentrations could be due to the
concentrations of dithionite (100, 150, and 300 mM).
increased solubility of metal sulfides at the high sulfide concen-
tration resulting from the self-decomposition of dithionite. This Dithionite Concentration (mM)

will be further discussed later in this section. 100 150 300

In order to understand the arsenic removal mechanism of the C 1s 36.36 42.55 42.13
reduction reaction, the surface of the precipitates formed by reac- O 1s 52.57 44.02 43.3
tion with various concentrations of dithionite was investigated by S 2p 2.63 3.66 5.07
XPS. Based on the arsenic removal (Fig. 1b), XPS analysis was con- Fe 2p 5.17 3.84 4.99
As 3d 3.27 5.93 4.52
ducted for three solid phases formed by reaction with dithionite
640 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643

Fig. 4. XPS spectra of (a) As 3d, (b) Fe 2p3/2, and (c) S 2p of particles formed in mine wastewater reacted with various concentrations of dithionite (100, 150, and 300 mM).

phase results showing the highest arsenic removal at 150 mM

dithionite. The major peak of the As 3d5/2 spectrum of the solid
Table 4 phase reacted with 100 and 150 mM dithionite was attributed to
XPS peak parameters of particles formed in mine wastewater reacted with various species similar to realgar located at 42.4 eV, which indicates that
concentrations of dithionite (100, 150, and 300 mM). precipitation of arsenic occurred in wastewater as a realgar-like
Binding Energy (eV) Species Dithionite phase from the reaction with dithionite. In reduced sulfidic water,
Concentration (mM) arsenic can be present as thioarsenic species such as As(SH)3 and
100 150 300 arsenic sulfide solid phase species such as orpiment and realgar,
depending on pH and sulfide concentration (Gomez-Caminero
As 3d 38.6 As(-III), As(0) 40.0 29.0 27.1
42.2 As4S4 60.0 71.0 16.4 et al., 2001; Wilkin et al., 2003). The initial pH of the wastewater
44.2 AsSn (n > 2) 0.0 0.0 56.5 was highly acidic (pH 1.2) and change of the solution pH was
minimal (less than 0.5) during the reduction reaction. Under highly
Fe 2p3/2 706.4 Fe(II)-S 15.1 18.7 22.5 acidic conditions, formation of realgar is thermodynamically
708.7 Fe(III)-S 22.4 16.3 8.9 preferred to the orpiment phase, which is consistent with the XPS
710.8 Fe(II)-O 42.3 45.5 49.1
713 Fe(III)-O 20.2 19.5 19.5
results (Gomez-Caminero et al., 2001). On the other hand, the
major peak of the As 3d5/2 spectrum of the solid phase after
S 2p3/2 162.2 S*-SO2- 2-
3 , S2 16.1 10.2 21.0 reacting with 300 mM dithionite was located at 44.2 eV, which is
163.8 S2
n , S0 28.3 24.6 12.1 considered to be a thioarsenic phase with a sulfur to arsenic molar
166.4 SO2-
3 32.0 38.6 20.1 ratio higher than 2 (S/As > 2). Under a sulfate-reducing environ-
168 SS*-O2-
3 , SO4
2-
23.6 26.6 46.8
ment, high sulfide concentration increases the solubility of arsenic
 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643 641

16 1800 500

Concentrations of As, Pb, and Cu (mg/L)

(a) 14
As
Cu 1600
(b) Initial Eh
Pb 450

Concentration of Fe (mg/L)
12 Fe 1400

10 1200 400

Eh (mV)
8 1000
350
6 800

4 600 300

2 400
250
0 200

0 200
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Reaction Time (min) Reaction Time (min)

350 400
(c) 7 As (d) initial Eh
Concentrations of As and Cu (mg/L)

Cu 300
Fe

Concentration of Fe (mg/L)
6 300
250
5
200

Eh (mV)
200
4

3 150
100

2 100
0
1 50

0
0 -100
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200

Reaction Time (min) Reaction Time (min)

Fig. 5. Changes in concentrations of arsenic, lead, and iron, and in redox potential in the two-step reduction reaction. (a) and (b) for ferrous oxalate recovery step; (c) and (d) for
arsenic removal step.

sulfides such as orpiment, which is governed by thioarsenic species solubility of the arsenic sulfide phase and increase soluble thio-
in solution (Wilkin et al., 2003). When wastewater was reacted arsenic species, which could contribute to the increased arsenic
with a high dithionite concentration, high sulfide concentrations concentration in solution after the reaction with 300 mM dithionite
resulting from the self-decomposition of dithionite could increase (Wilkin et al., 2003). In addition, a portion of the thioarsenic species
could adsorb to or precipitate on the surface of the solid phase, as
observed in the XPS spectra.
Table 5
XRF analysis of precipitates formed during a two-step reduction reactions. 3.3. Two-step reactions: ferrous oxalate recovery and arsenic
Element Concentration (%) removal
First-step reaction Second-step reaction
The wastewater treatment with various dithionite concentra-
Fe 66.5 29.1
tions suggested a two-step reaction depending on the dithionite
O 29.7 42.7
S e 17.5 concentration, i.e. redox condition. In the first step, high levels of
As e 0.67 oxalate and iron present in wastewater can be recovered as the
Pb 0.95 e ferrous oxalate phase under mild reducing conditions. The
Cu 0.41 0.97
solution-phase arsenic concentration is not affected by the pre-
Zn 0.35 0.01
Mn 0.8 0.14 cipitation of the ferrous oxalate phase in this stage (Fig. 1), indi-
Ca 0.47 8.15 cating the ferrous oxalate phase did not affect dissolved arsenic
Al 0.16 e retention. After recovery of the ferrous oxalate phase in the first
Co 0.14 0.08 step reaction, arsenic in wastewater could be removed by further
Ni 0.05 e
addition of dithionite in the second step reaction.
Mg 0.26 e
Na 0.21 0.41 In order to test this method of iron oxalate recovery and arsenic
K 0.02 e removal from smelter wastewater, we conducted two-step reaction
Ce 0.04 0.15 experiments, i.e. reaction with 20 mM dithionite followed by re-
Bi 0.05
e
action with additional 30 mM dithionite after filtration. Fig. 5
Y e 0.04
Sr e 0.01
summarizes the changes in concentrations of arsenic, copper,
lead, and iron, and in redox potential (EH), in wastewater after
100.01 99.99
addition of dithionite. Immediately after adding dithionite to the
642 E.J. Kim, K. Baek / Journal of Cleaner Production 221 (2019) 635e643

wastewater, the redox potential of the wastewater decreased sud- reduction reaction was suggested using dithionite as a reductant.
denly from 477 mV to 241 mV. Dithionite is a widely used reducing In the first step, high levels of oxalate and iron present in waste-

agent and the redox potential for the couple of S2O2
4 /HSO3 at pH 7 water was recovered as the ferrous oxalate phase with low solu-
was reported to be 386 mV (Mayhew, 1978). Then, the redox bility under mild reducing conditions. The solution-phase arsenic
potential increased rapidly for the first hour to 340 mV and then concentration was not affected by the precipitation of the ferrous
gradually increased as the reaction continued; this indicates that oxalate phase in this stage, indicating the ferrous oxalate phase did
the redox reaction occurred rapidly for the first hour, similar to the not affect dissolved arsenic retention. XRF study showed that
metal concentrations changes. Addition of dithionite decreased the relatively pure b-iron (II) oxalate phase containing about 3.8% of
lead concentration rapidly; the lead concentration decreased by other metals was recovered from the wastewater in this step. In the
approximately 98% within 15 min. Iron concentration also rapidly second step, arsenic in wastewater was removed by forming a
decreased within 15 min; no further decrease was observed after realgar-like phase by the reaction with sulfide produced by the
30 min. Copper gradually decreased for the first hour, after which decomposition of dithionite. Therefore, the two-step reduction
the concentration was approximately 50% of the initial value. On reaction using dithionite could recover iron and oxalate as re-
the other hand, arsenic concentration remained almost constant sources and treat wastewater produced from soil washing of
during the reactions. When dithionite was introduced, ferric iron in arsenic-contaminated soils. The recovered ferrous oxalate phase
the wastewater was reduced to ferrous iron, which was followed by can be used in the industry as a solid electrolyte and environ-
the precipitation of the ferrous oxalate phase by reaction with ox- mentally applied to remediate contaminants as an adsorbent or
alate. Other heavy metals in the wastewater such and lead and Fenton reagent, which could increase the economic feasibility of
copper seemed to be removed by precipitation as metal sulfide soil washing using oxalic acid and also contribute to the sustainable
phases, such as PbS and CuS, by reaction with sulfide formed by development and cleaner production.
self-decomposition of dithionite. After a 3-h reaction with 20 mM
dithionite, the yellow-colored precipitates were separated from Acknowledgement
solution by filtration and identified as b-iron (II) oxalate by XRD
analysis (data not shown). XRF analysis of precipitates showed that This study was supported by the Korea Environment Industry and
iron and oxygen composed 96.2% and other metals (such as lead, Technology Institute (KEITI) through the Geo-Advanced Innovation
manganese, calcium, and copper) composed the remaining 3.8% of Action Program (2016000550001) and the Basic Science Research
the solid phase, which indicates that the relatively pure b-iron (II) Program through the National Research Foundation of Korea (NRF)
oxalate phase can be recovered from wastewater by a reduction funded by the Ministry of Education (2016R1D1A3B03934814).
reaction (Table 5).
After recovery of ferrous oxalate, a second-step reaction was
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