Chemosphere 213 (2018) 305e313

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Chemosphere
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Structural substitution for SO4 group in tooeleite crystal by As(V) and

As(III) oxoanions and the environmental implications
Jinqin Yang a, Yuchen Yan a, Keren Hu a, Guanshi Zhang a, Dongyi Jiang a, Qingzhu Li a, b, *,
Bin Ye c, d, Liyuan Chai a, b, **, Qingwei Wang a, b, Hui Liu a, b, Ruiyang Xiao a, b
a
School of Metallurgy and Environment, Central South University, Changsha 410083, China
b
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha 410083, China
c
Guangdong Provincial Key Laboratory of Soil and Groundwater Pollution Control, School of Environmental Science and Engineering, Southern University of
Science and Technology, Shenzhen 518055, China
d
State Environmental Protection Key Laboratory of Integrated Surface Water-Groundwater Pollution Control, School of Environmental Science and
Engineering, Southern University of Science and Technology, Shenzhen 518055, 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

Two different SO4-free tooeleite

were prepared for the first time
through substituting for SO4 group
by As(V) or As(III).

SO4-free tooeleite have similar crys-
talline structure to SO4-tooeleite but
different anions in the interlay space.

The removal of As can reach 94% by
forming SO4-free tooeleite.

As leaching of SO4-free tooeleite can
be lower than that of SO4-tooeleite.

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

Article history: Two different SO4-free tooeleite were prepared for the first time through structural substitution for SO4
Received 10 March 2018 group by As(V) and As(III). As(III)-tooeleite and As(V)-tooeleite have similar crystalline structure to SO4-
Received in revised form tooeleite but incorporate different anions in the interlayer space. The removal of As can reach 94% by
4 September 2018
forming SO4-free tooeleite crystals, and As leaching in TCLP tests can be much lower than that of SO4-
Accepted 6 September 2018
Available online 11 September 2018
tooeleite. Therefore, SO4-free tooeleite crystals are of great potential in As removal and immobilization.
Moreover, our study indicates the different affinities of Fe(III) towards As(III), As(V) and SO4, which can
Handling Editor: X. Cao explain that a) the coordination structure of As(III)-tooeleite is much closer to the ideal crystal structure
but easily affected by As(V) and SO4 group; b) tooeleite mineral found in natural environments is
commonly a SO4-containing mineral and associated with scorodite due to the abundance of As(V) and
SO4 group.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction

* Corresponding author. School of Metallurgy and Environment, Central South
University, Changsha 410083, China.
** Corresponding author. School of Metallurgy and Environment, Central South
University, Changsha 410083, China.
E-mail addresses: qingzhuli@csu.edu.cn (Q. Li), chailiyuan@csu.edu.cn (L. Chai).
Arsenic (As) contamination in groundwater has pose a health
risk of global concern due to the intake of drinking water with
elevated concentrations (Chai et al., 2016a; Fei et al., 2017; Liu et al.,
2017a). As-bearing minerals are of a great relevance for the

https://doi.org/10.1016/j.chemosphere.2018.09.040
0045-6535/© 2018 Elsevier Ltd. All rights reserved.
306 J. Yang et al. / Chemosphere 213 (2018) 305e313
precipitation-dissolution equilibrium and geochemical recycling of
As (Chai et al., 2017a; Yan et al., 2017). Accordingly, the incorpo-
ration of As into mineral crystals offers an alternative remediation
strategy for As-contaminated waters (Yang et al., 2015a; Liu et al.,
2017b). Scorodite (FeAsO4$2H2O) is an important As carrier but it
incorporates As only in arsenate (As(V)) oxidation state (Min et al.,
2015; Yang et al., 2015b; Liang et al., 2016). In recent years, tooeleite
(Fe6(AsO3)4SO4(OH)4$4H2O) has attracted increasing attention to
decontaminate trivalent As (As(III)) (Opio, 2013; Li et al., 2014; Chai
et al., 2016b, 2017b; Malakar et al., 2016). Tooeleite has been widely
accepted as an unique As(III)-containing sulfate mineral (Guillaume
et al., 2003; Morin et al., 2007; Nishimura and Robins, 2008; Egal
et al., 2009; Liu et al., 2013), however, it was originally described
as an iron arsenate mineral when discovered by Cesbron and
Williams (Morin et al., 2007). The illusion of As valence was trig-
gered by that tooeleite is an oxide zone mineral (Cesbron and
Williams, 1992). Since As occurs as arsenate in nearly all oxide
zone minerals, we hope that As(V) can also occur in tooeleite
mineral. Tooeleite is layered structure with positively charged
FeO6eAsO3 layers, and SO4 groups are isolated within the interlayer
space (Nishimura and Robins, 1996). Its crystalline structure is
similar to layered double hydroxides (LDHs), in which the positively
charged double metal hydroxide layers are compensated for by the

inclusion of anions (SO2 2
4 , CO3 , NO3 etc.) in the interlayer region
(Prasanna and Kamath, 2009; Bujdos et al., 2009). Due to the
exchangeability of interlayer anions, LDHs intercalated with As(V)
and As(III) are regarded as effective candidates for As removal (Goh
et al., 2009). As(V) occurring as AsO4 tetrahedral oxyanions is
similar to SO4 group in size and shape, and thus can occupy the SO4
sites in crystalline structures. The substitution for SO4 by AsO4 in
jarosite (Kþ, Naþ, NHþ 2þ
4 and Pb ) has been established by the
presence of AsO4 in the SO4 site, and without changes in the unit
cell parameters (Dutrizac and Jambor, 2014; Dutrizac et al., 2013).
The AsO4-for-SO4 substitution was also reported in alunite (KAl3(-
SO4)2(OH)6) and hydronium alunite ((H3O)Al3(SO4)2(OH)6), and the
degree of AsO4 substitution depended on the solution composition
(Sunyer et al., 2013). However, Jing Liu et al. (Liuet al., 2015) found
that As(V) was not trapped into tooeleite and detrimental to the
formation of tooeleite, where SO4 anion was provided. While in SO4
and As(V) free system, it was noticed that SO4 was substituted by
As(III) in form of AsO3 3 and the lattice parameters of tooeleite
increased (Liu et al., 2012). Therefore, there is a great possibility
that interlayered SO4 can be substituted by As(III) or As(V), how-
ever, the substitution may be closely dependent on solution
composition. An attempt to trap As(V) or As(III) into the crystalline
structure of tooeleite is great meaningful for As removal and
immobilization.
The objective of this study is to prepare SO4-free tooeleite
crystal through the structural substitution for SO4 group by As(V)
and As(III), and estimate the potential applications of tooeleite in As
removal and immobilization. We also focus on As species, coordi-
nation structures and phase predominance of tooeleite-type crys-
tals, which may afford an opportunity to understand the role of As
species in controlling the geometric topology and environmental
potentials of As-containing crystals.
2. Experimental section
2.1. Batch experiments
Typical tooeleite (Fe6(AsO3)4SO4(OH)4$4H2O) was labelled as
SO4-tooeleite in this study, which was prepared by employing ferric
sulfate (Fe2(SO4)3), sodium arsenite (NaAsO2) and sulfuric acid
(H2SO4) (Chai et al., 2016b). In order to refrain from sulfate (SO4)
anion, ferric nitrate (Fe(NO3)3), sodium arsenite (NaAsO2) and
sodium arsenate (Na3AsO4) was respectively used as the source of
Fe(III), As(III) and As(V), while nitric acid (HNO3) and sodium hy-
droxide (NaOH) were used to adjust the pH of reaction solutions.
The substitution for SO4 by As(V) was conducted in test No.1 and
the substitution by As(III) was conducted in test No.2 and 3. In
particular, 1.30 g NaAsO2, 1.06 g Na3AsO4$12H2O and 6.06 g
Fe(NO3)3$9H2O were dissolved in test No.1 by deionized water to
100 mL and the pH was 1.79. In test No.2 and 3, 1.94 g NaAsO2,
6.06 g Fe(NO3)3$9H2O and 0.20 g NaOH were dissolved by deion-
ized water to 100 mL and the solution pH was 1.76. In test No.1 and
2, precipitation reaction was conducted in a hydrothermal reaction
vessel at 120  C and autogenous pressure for 8 h, while at 25  C and
atmospheric pressure for 4 days in test No.3. The function of pH
value was investigated by adjusting pH to 1.12e2.45 by HNO3 or
NaOH in test No.1e3. The ratio of As(III):As(V) varying from 15:0,
14:1, 13:2, 12:3, 11:4, 10:5 to 0:15 was tested respectively under
hydrothermal or atmospheric conditions. And the molar ratio of
Fe(III):As(III) varying from 0.1 to 3.3 was tested and other more
details were shown in Table S1. The precipitates were filtered by
0.22 mm membrane, dried at 80  C in vacuum oven and then ground
with an agate mortar.
2.2. Analysis and characterization
X-ray diffraction (XRD) patterns were all collected using a
Rigaku D/Max-RB diffractometer. Incident X-ray radiation
(l ¼ 0.15406 nm) was produced at 35 kV and 40 mA with Cu Ka
radiation of 1.540596 Å. X-ray photoelectron spectroscopy (XPS)
were carried out on a Thermo Fisher Scientific K-Alpha 1063 using
Al K X-ray as the excitation source. Fourier transformed infrared
spectra (FTIR, Nicolet IS10) was collected at a resolution of 4 cm1
by using KBr pellets technique. The Raman spectra was excited by
highly polarized light at 532 nm and recorded in the range between
100 and 2000 cm1. Repeated acquisition on the crystals using the
highest magnification (50) was accumulated to improve the
signal to noise ratio. The micrographs of precipitates were observed
by SEM (Quanta FEG 250, FEI) at 5000 and 50000 magnification
operated at an accelerating voltage of 20 kV. Precipitates and re-
action solutions were dissolved and diluted by HNO3 beforehand
and the concentration of Fe and As were measured by an induc-
tively coupled plasma-optical emission spectroscopy (ICP-OES,
ICAP 7000).
X-ray absorption spectroscopy (XAS) experiments for Fe K-edge
and As K-edge were conducted at Beamline 07A1 at Taiwan Light
Source (TLS) at the National Synchrotron Radiation Research Center
(NSRRC). Monochromatic X-rays were produced with a Si(111)
double crystal monochromator. The energy calibration of the
monochromator was checked by K-edge of Fe foil and L3-edge
(11919 eV) of Au foil in transmission mode for Fe K-edge (7112 eV)
and As K-edge (11867 eV) measurements. The absorption spectra
were collected in the energy range of 6910e7910 eV for the Fe K-
edge spectra and in the range of 11660e12680 eV for the As K-edge
spectra in the transmission mode at room temperature. The pre-
processing of spectra was performed by using the Athena and
Artemis programs in the Demeter package (version, 0.9.20).
The short-term stability of precipitates was tested by a modified
US EPA Method 3111 Toxicity Characteristic Leaching Procedure
(TCLP) (U.S. EPA, 1998). A 1000 mL extraction fluid
(pH ¼ 4.93 ± 0.05) was prepared by mixing 5.7 mL acetic acid
(CH3CH2OOH) and 64.3 mL NaOH (1.0 mol/L) in deionized water in
advance. 0.5 g precipitates were mixed with the extraction fluid in a
50 mL volumetric flask, i.e., at a solid-liquid ratio of 5%. Flasks were
continuously shaken on a shaker (30 ± 2 rpm, 30  C) for 18 ± 2 h
(Opio, 2013). The concentration of As and Fe of the filtrate was
determined by ICP-OES.
 J. Yang et al. / Chemosphere 213 (2018) 305e313
3. Results and discussion
3.1. Structural substitution for SO4 group by As(V) and As(III) to
form SO4-free tooeleite
The precipitates obtained from pH ¼ 1.79 and 1.76 solutions in
test No.1e3 were all in lemon yellow. Their XRD patterns were very
close to SO4-tooeleite (Fe6(AsO3)4SO4(OH)4$4H2O), agreeing with
PDF#44e1468 (Fig. 1a). Since SO4 was not provided, it is very likely
that As(III) or As(V) might be entrapped into the structure of SO4-
tooeleite and substituted for SO4 group to form SO4-free tooeleite.
Therefore, SO4-free tooeleite might hold same FeO6eAsO3 layer
framework to SO4-tooeleite but different anions in the interlayer
space. According to the FTIR spectroscopy in Fig. 1b, SO4-tooeleite
exhibited strong SO4 vibrations at 512 (v2), 1098 (v3), 620 (v4) cm1
but these vibrations were not found in precipitates of tests No.1e3.
This confirms that the precipitates were all SO4-free tooeleite. The
bands at 1380, 1350 and 830 cm1 might correspond to the vibra-
tions of NO3-absorbed on surface, which was further discussed in
supporting material (Fig. S3). As shown by Raman spectroscopy in
Fig. 1c, SO4-tooeleite gave As(III)eO vibrations at 500e700 cm1,
which were also found in test No.2 and 3. The As(V)eO vibrations in
scorodite were located at 800e890 cm1, which strongly appeared
in test No.1 but were scarcely found in test No.2 and 3. This indi-
cated that SO4-free tooeleite obtained in test No.1 definitely con-
tained As(V), and is thus defined as As(V)-tooeleite. In test No.2e3,
As(III) was provided in the initial solutions, and no As(V) but only
As(III) would be incorporated in SO4-free tooeleite if As(III) oxida-
tion can be completely avoidable. This means that As(III) reacts
with Fe(III) to form FeO6eAsO3 layers and simultaneously might
Fig. 1. (a) XRD, (b) FTIR, (c) Raman and (d) XPS of SO4-free tooeleite prepared at pH ¼ ~1.8 in test No.1e3. SO4-tooeleite and scorodite were references.
307
enter in interlayered space, thus SO4-free tooeleite obtained in test
No.2e3 can be defined as As(III)-tooeleite.
XPS was employed to evaluate the content of As(III) and As(V) in
SO4-free tooeleite. It was confirmed that As in SO4-tooeleite is only
As(III) with an As3d binding energy at 44.0 eV (Nishimura and
Robins, 2008), and in scorodite is only As(V) with an As3d bind-
ing energy at 45.7 eV (Nishimura and Robins, 1996). As displayed in
Fig. 1d, As(III) in SO4-tooeleite was fitted by two peaks at 44.0 and
~44.52 eV. The peak at 44.52 eV might be attributed to the higher
binding energy for As(III)eO coordination to an iron atom, i.e.,
As(III)eOeFe(III) (Pozdnyakov et al., 2016). These two peaks at 44.0
and 44.52 eV were found in all precipitates of tests No.1e3 and they
contributed to As(III) content, which was 61.4%, 88.1% and 91.5% in
test No.1e3, respectively. Another peak at ~45.7 eV was assigned to
As(V)eOeFe(III) (Pozdnyakov et al., 2016). It is obvious that As(V)
content was much higher in test No.1 (38.6%) than in test No.2
(11.9%) and No.3 (8.5%). The ratio of As(V):As(III) was correspond-
ingly estimated as 0.63, 0.14, 0.09 in test No.1e3. Therefore, As(V)-
tooeleite has much higher As(V):As(III) ratio than As(III)-tooeleite,
and they all exhibited some fluffy cloud-like or cotton-like mor-
phologies, very similar to SO4-tooeleite (Fig. S1).
3.2. Formation pH condition of SO4-free tooeleite
The function of pH on SO4-free tooeleite formation was further
tested in pH range of 1.12e2.45 and many precipitates gave the
characteric XRD peaks of SO4-tooeleite. Since SO4 was not provided
and thus these precipitates contain SO4-free tooeleite. In test No.1,
SO4-free tooeleite is As(V)-tooeleite, which and scorodite was
respectively detected by XRD in pH range of 1.68e2.06 and
308 J. Yang et al. / Chemosphere 213 (2018) 305e313
1.12e1.87 (Fig. S2a). In the intersectant pH range 1.68e1.87, As(V)-
tooeleite and scorodite were found simultaneously, which means
As(V)-tooeleite can coexist with scorodite. As shown in Fig. 2, bulky
scorodite particles and fluffy As(V)-tooeleite were simultaneously
found in pH range 1.25e1.68 in test No.1. However, As(V)-tooeleite
was not detected by XRD in pH 1.25e1.57, probably because the
content was lower than the detection limit of XRD (5 wt%).
Remarkably, with pH increasing, As(V)-tooeleite content increased
and scorodite changed from globular to layered globular
morphology (inset of Fig. 2). Accordingly, As(V)-tooeleite may
coexist with scorodite in pH range 1.25e1.87 but have great effect
on the morphology of scorodite when pH higher than 1.47.
In test No.2 and 3, SO4-free tooeleite is As(III)-tooeleite, which
was obtained in pH range 1.41e2.45 (Fig. S2b and c). Besides,
scorodite and amorphous phase detected at pH ¼ 1.27 confirmed
the occurrence of As(V), which was only owing to the oxidation of
As(III), because As(V) was not provided in the reaction solutions.
Therefore, in order to avoid scorodite and amorphous phase in test
No.2 and 3, favorable pH range for As(III)-tooeleite formation is
1.40e2.08. As depicted in Fig. 2, As(III)-tooeleite prepared in test
No.2 and 3 exhibited similar fluffy cloud-like or cotton-like
morphologies.
Raman results of the precipitates obtained under different pH
conditions in test No.1e3 were depicted in Fig. 3. It reveals that
precipitates in As(V)-free systems (i.e., test No.2e3) had intense
bands at 508, 615 and 670 cm1, which may be As(III)-related
bands. However, the precipitate at pH ¼ 1.27 in test No.2 exhibi-
ted two strong bands at 800 and 890 cm1 and shoulder bands at
Fig. 2. SEM images of precipitates prepared under different pH conditions in test No.13.
Fig. 3. Raman spectra of precipitates prepared under different pH conditions in test No.1e3.
810, 830 and 870 cm1. Since scorodite was detected by XRD in this
precipitate (Fig. S2b), these bands probably correspond to vibra-
tions of As(V) group. As evidenced in Fig. 3a, these As(V) group
bands were vindicated in precipitates of test No.1. Accordingly, the
intense bands of As(V) and As(III) may be respectively located in the
range of 800e890 cm1 and 500700 cm1. In addition, according
to Frost R and Silmarilly Bahfenne's report (Frost and Silmarilly,
2011), the band observed at 831 cm1 on the Raman spectra of
metal arsenite (M3AsO3) was the evidence of AsO3 3 oxidation to
1
AsO44, and the intense band of AsO3 3 was observed at 670 cm .
Therefore, the band at 830 cm in test No.1 and band at 670 cm1
1
in test No.2e3 confirmed the presence of AsO3 4 and AsO3 3 ,
respectively. Furthermore, it was reported that the Raman band at
885 and 813 cm1 is respectively assigned to the symmetric and
antisymmetric stretching mode of AsO3OH2 (Frost et al., 2010).
The shoulder bands found at 890 and 810 cm1 in Fig. 3a are very
close to these two bands (885 and 813 cm1), which indicated that
the precipitates of test No.1 contained HAsO2 4 . Therefore, HAsO4
2
2
may substitute for SO4 to form As(V)-tooeleite. Some bands at
lower wavenumbers such as 180 cm1 in test No.1 as well as 172
and 275 cm1 in test No.2e3 are thought to be associated with
lattice vibrations and hydrogen bonding of the water molecules in


the crystalline structure (Cejka et al., 2010; Frost et al., 2012). In test
No.1, bands at 420 and 335 cm1 are attributed to AsO2 and As2O2
4
bending mode (Frost and Bahfenne, 2010), and the latter consist of
arrays of OeAseOeAseO structures (Ghose et al., 1987). However,
AsO3 groups are not polymerized together and share an edge with
 J. Yang et al. / Chemosphere 213 (2018) 305e313
an FeO6 octahedron in tooeleite structure (Morin et al., 2007).
Therefore, a degree of polymerization of AsO3 groups occurred in
precipitates of test No.1, but was avoided in As(III)-tooeleite
because these bands of As2O2 4 polymeric chains were not found
in test No.2e3. This means that the presence of As(V) will lead to
the polymerization of AsO3 groups in the resultant crystals. The
protonation of AsO3 2
3 to HAsO3 will result in the reduction of C3v
symmetry to Cs with only a mirror plane and the E mode will split in
A0 and A00 . The band at 615 cm1 (Fig. 3b and c) is very close to the
reported band at 606 cm1 and thus was assigned to A00 AseO
stretching vibration (Müller et al., 2010). Additionally, the AseOH
vibrations occur at lower wavenumbers than the uncomplexed
AseO vibrations (Müller et al., 2010), and thus the band at 508 cm1
in test No.2e3 are thought to be A0 stretching vibration of AseOH.
For example, an intense band of dixenite at 526 cm1 is assigned to
1
n2(E) AsO33 bending mode and has a component band at 505 cm
0
(Bahfenne and Frost, 2010), which also is the A stretching vibration
of AseOH. Accordingly, As(III)-tooeleite prepared in test No.2e3
contained both AsO3 2
3 and HAsO3 . The structure of SO4-tooeleite is
layered with positively charged Fe(III)eAs(III) oxyhydroxide layers
and SO24 within the interlayer space (Morin et al., 2007). It is very
likely that HAsO2 2
3 substituted for SO4 in interlayer space and
AsO3
3 occurs as Fe(III)eAs(III) oxyhydroxide layers. Consequently,
SO4-tooeleite, As(V)-tooeleite and As(III)-tooeleite probably have
similar layered framework but respectively incorporating SO2 4 ,
Fig. 4. XRD of precipitates prepared under different conditions. (a) Molar ratio of As(III):As(V) at 25  C, (b) molar ratio of As(III):As(V), (c) molar ratio of Fe(III):As(III) and (d) sulfate
(SO2 
4 ) concentration at 120 C.
309
HAsO2 2
4 and HAsO3 in their interlayer space.
The removal of Fe and total As during the process of SO4-free
tooeleite formation in test No.1e3 were shown in Fig. S4a. It is
obvious that As removal was higher than Fe removal under strong
acidic conditions (pH < 1.5), and it's quite the reverse under higher
pH conditions (pH > 1.9). In test No.2e3, total As removal was
almost equal to Fe removal in pH range of 1.5e1.9, which was
consistant with the formation pH range 1.40e2.08 of As(III)-
tooeleite. Accordingly, through forming As(III)-tooeleite, As
removal increased from 82% to 94% in test No.2 and from 40 to 76%
in test No.3 with pH increasing in the range of pH 1.40e2.08. In test
No.1, the equal removal of As and Fe was only found at pH ¼ ~1.7,
which was located in the formation pH range 1.68e2.06 of As(V)-
tooeleite. Therefore, As removal by forming As(V)-tooeleite
reached ca. 94%. These indicated that SO4-free tooeleite, both
As(III)-tooeleite and As(V)-tooeleite, are potential in As removal.
The environmental stability is of importance for the safe storage
of SO4-free tooeleite and the results of TCLP tests were displayed in
Fig. S4b. Except for test No.2, the leaching concentration of As
decreased with increasing pH values and the lowest leaching was
14.1 mg/L at pH 1.94 in test No.1, and 35.9 mg/L at pH 1.89 in test
No.3. In test No.2, As leaching concentration was around 33 mg/L in
pH range of 1.40e1.56, and increased from 51.5 to 86.4 mg/L as pH
increased from 1.62 to 2.08. The lowest leaching concentration of As
in test No.1e3 all exceeded the national criteria (5 mg/L), but was
310 J. Yang et al. / Chemosphere 213 (2018) 305e313

far below the result of SO4-tooeleite in Raghav's report (>100 mg/L)

(Raghav et al., 2013). Therefore, SO4-free tooeleite was more
attractive than SO4-tooeleite for As immobilization.

3.3. Key components for SO4-free tooeleite formation

The effect of As(III):As(V) ratio on SO4-tooeleite formation has

been investigated at 95  C by Jing Liu et al. (Liuet al., 2015) They
found that SO4-tooeleite vanished and the precipitates became
some poorly crystalline Fe(III)eAs(III/V) compounds when the
initial ratio of As(III):As(V) was lower than 7:3. Similar finding was
obtained at room temperature (25  C) in the present study that
SO4-free tooeleite changed to poorly crystalline phases when the
As(III):As(V) ratio was lower than 14:1 (Fig. 4a). However, SO4-free
tooeleite changed to scorodite at 120  C under As(III):As(V) lower
than 11:4 conditions (Fig. 4b), i.e., As(III) lower than ~73% of total As.
This is because that the reaction between Fe(III) and As(V) would
produce amorphous iron arsenate at lower temperature but scor-
odite at higher temperature. It's obvious in Fig. S5 that scorodite
particles were formed in the presence of As(V). Therefore, the phase
competition between SO4-free tooeleite and scorodite occurred
under different As(III):As(V) conditions at higher temperature (e.g.,
120  C).
Fig. 5. Structure model of SO4-tooleite (Fe12As8S2.6O50.4). a ¼ 8.9575, b ¼ 6.4238,
Except As(III):As(V) ratio, the phase composition of precipitates
c ¼ 9.7912, a ¼ g ¼ 90, b ¼ 96.032. Cell size: 1ⅹ1ⅹ2, slate blue polyhedron is FeO6 unit,
also depend on Fe(III):As(III) ratio. As shown in Fig. 4c, amorphous violet polyhedron is AsO3 unit, balls in red, yellow and violet respectively represents O,
phase was formed under lower Fe(III):As(III), and the formation of S and As atom. (For interpretation of the references to colour in this figure legend, the
As(III)-tooeleite was more favorable under higher Fe(III):As(III) reader is referred to the Web version of this article.)
molar ratio. According to the structure of SO4-tooeleite (Morin
et al., 2007) shown in Fig. 5, if As(III) occupy all SO4 sites, the
As(III):As(V) ratio was 13:2, 12:3 and 11:4 (Fig. S7a). And As
Fe:As atom ratio of As(III)-tooeleite will equal to the Fe:(As þ S)
leaching was only 2.44 mg/L when As(III):As(V) ratio 14:1. Under
atom ratio in SO4-tooeleite, i.e., 1.13. And the Fe:As atom ratio on
these conditions, fluffy SO4-free tooeleite covered evenly over the
main layers in As(III)-tooeleite will equal to the Fe:As atom ratio of
scorodite particles (Fig. S5). In addition, when Fe(III):As(III) molar
SO4-tooeleite, i.e., 1.5. Therefore, As(III)-tooeleite formed at
ratio was near to 1.5, there was no scorodite but only As(III)-
Fe(III):As(III) molar ratio higher than 1.0 were all cloud-like or
tooeleite. It was noticed from Fig. S7b that As leaching was only
cotton-like but became less fluffy under Fe(III):As(III) molar ratio
2.19 and 7.28 mg/L and As and Fe removal were both close to 80%.
much higher than 1.7 (Fig. S6). This probably because that the
Therefore, As(III)-tooeleite has a good potential in As removal and
Fe(III):As(III) ratio was too higher and there was no enough As(III)
immobilization.
to fill in the interlayer space, and thus As(III) will only be bonded to
Fe(III) to form main layer structure.
In order to verify the morphology related to the amount of anion 3.4. Discussion on crystalline structures
in the interlayer space, sulfate (SO4) anion in different concentra-
tions was added into reaction solutions. Fig. 4d indicated that all As investigated above, As(V)-tooeleite and As(III)-tooeleite
resultant precipitates formed in 0e0.45 M SO4 solution consist of crystals can be formed in absence of SO4 anion and they exhibi-
tooeleite-type crystals. Based on SO4-tooeletie molecule (Fe6(A- ted the same XRD pattern and similar morphology to SO4-tooeleite.
sO3)4SO4(OH)4$4H2O), 0.05 M SO4 is enough for 0.15 M As(III) so- SO4-tooeleite, As(V)-tooeleite and As(III)-tooeleite have same
lution to form SO4-tooeletie. Therefore, it's concluded that SO4- layered framework but respectively intercalate SO4, As(V) and
tooeletie was formed in the presence of 0.05e0.45 M SO4 and As(III) group into their interlayer space. Since As(V) is strongly
As(III)-tooeleite was formed in the absence of SO4 (0 M). As competitive against As(III) to react with Fe(III) and form scorodite
exhibited in Fig. 6, As(III)-tooeleite and SO4-tooeletie formed under or amorphous iron arsenate solids, the formation of pure As(V)-
low SO4 concentration (0.05e0.10 M) are similar in morphology tooeleite is challenging and the coexistence of different phases
structure, but SO4-tooeletie formed under high SO4 concentration makes it difficult to investigate the coordination structure of As(V)-
(0.20e0.45 M) showed different plate-like structure, which may be tooeleite. In this section, the crystalline structure of As(III)-tooeleite
because the interlayer space was filled with more SO4 anions. It's was compared to SO4-tooeleite and scorodite, and X-ray absorption
also found that much more SO4 (0.20e0.45 M) even caused a new fine structure (XAFS) spectroscopy was used for the structural
natrojarosite (NaxFey(SO4)m(OH)n) phase (Fig. 4d). Consequently, characterization. The normalized As and Fe K-edge XANES spectra
the relative amount of As(III), As(V), Fe(III) and SO4 are the key of scorodite, SO4-tooeleite and As(III)-tooeleite are compared in
determinant of the morphology structure and the formation of Fig. 7a and b, which indicates that the valence of As is pentavalent
different tooeleite-type crystals and other phases like scorodite and in scorodite and mainly trivalent in both SO4-tooeleite and As(III)-
natrojarosite. tooeleite, and the valence of Fe is same trivalent. In addition, Fe K-
The removal of As and Fe during the formation of different edge and As K-edge EXAFS spectra of As(III)-tooeleite, SO4-tooeleite
phases and As leaching of different phases were respectively and scorodite are shown in Fig. 7c and d, and the corresponding
compared in Fig. S7, and it's very likely that there were some proper fitting results are listed in Table 1.
conditions for SO4-free tooeleite formation with high Fe and As Firstly, every Fe atom coordinated with approximately 6.0 O
removal and low As leaching. Specially, Fe and As removal were atoms at 1.99 Å in tooeleite and 1.98 Å in scorodite. The FeeAs shell
both close to 93% and As leaching was 20e30 mg/L when is very different, which gives much shorter interatomic distance
 J. Yang et al. / Chemosphere 213 (2018) 305e313 311

Fig. 6. SEM images of precipitates prepared under different sulfate (SO4) anion concentrations.

Fig. 7. (a) Fe K-edge XANES, (b) As K-edge XANES, (c) K3-weighted Fe K-edge EXAFS and (d) K3-weighted As K-edge EXAFS of As(III)-tooeleite, SO4-tooeleite and scorodite. Solid lines
and circle symbols respectively refer to raw and fitted data without phase shift correction.

(2.85e2.86 Å) in tooeleite than in scorodite (3.35 Å). Besides, the
coordinated number of FeeAs shell was 2.0, 1.0 and 4.0 in As(III)-
tooeleite, SO4-tooeleite and scorodite, respectively. On the Fe K-
edge EXAFS spectra of As(III)-tooeleite and SO4-tooeleite, a FeeFe
shell was located at 3.55 Å and the coordinated number is 6.0 and
3.9 in As(III)-tooeleite and SO4-tooeleite, respectively. The different
coordinated number of FeeAs and FeeFe shell indicates that the
coordination structure of Fe in As(III)-tooeleite and SO4-tooeleite is
discrepant. The As K-edge EXAFS spectra of As(III)-tooeleite, SO4-
tooeleite and scorodite were shown in Fig. 7d. In scorodite, As
atoms coordinate with 4.0 O atoms and 4.0 Fe atoms at 1.69 and
3.38 Å, respectively. In As(III)-tooeleite and SO4-tooeleite, the
interatomic distance of As and O is longer (1.74e1.75 Å) than in
scorodite and the coordinated number is 3.0, which confirmed that
As is trivalent. In addition, the AseFe shell have two peaks on As K-
edge EXAFS spectra of As(III)-tooeleite and SO4-tooeleite, which
312 J. Yang et al. / Chemosphere 213 (2018) 305e313

Table 1
Fe K-edge and As K-edge EXAFS fitting results of As(III)-tooeleite, SO4-tooeleite and scorodite. Coordination number (CN), interatomic distance (R), Debye-Waller factor (d2),
and residual factor (Rf).

Label c2n Rf(%) S20 Shell CN R(Å) d2 c2n Rf(%) S20 Shell CN R(Å) d2
Fe K-edge As K-edge
a
As(III)-tooeleite 94 0.15 0.82 FeeO 6 1.993 ± 0.060 0.0058 2114 0.94 0.94 AseO1 3a 1.743 ± 0.058 0.0027
FeeAs 2a 2.860 ± 0.029 0.0134 AseFe1 1a 2.869 ± 0.021 0.0028
FeeFe 6a 3.554 ± 0.025 0.0069 AseO2 6.7 3.309 ± 0.019 0.0589
AseFe2 4a 3.437 ± 0.037 0.0128
SO4-tooeleite 70 0.12 0.82 FeeO 5.8 1.990 ± 0.063 0.0065 2464 0.53 0.94 AseO1 3a 1.749 ± 0.052 0.0037
FeeAs 0.9 2.851 ± 0.039 0.0080 AseFe1 1a 2.890 ± 0.001 0.0042
FeeFe 3.9 3.554 ± 0.055 0.0075 AseO2 9.8 3.565 ± 0.237 0.0597
AseFe2 4a 3.468 ± 0.006 0.0131
Scorodite 21 0.18 0.82 FeeO 6a 1.983 ± 0.078 0.0060 3389 0.72 0.94 AseO 4a 1.686 ± 0.009 0.0008
FeeAs 4a 3.353 ± 0.009 0.0052 AseOeO 10.9 3.140 ± 0.086 0.0008
FeeAseO 8a 3.888 ± 0.398 0.0030 AseFe 4a 3.379 ± 0.033 0.0060
a
Values were fixed during the fitting procedure. Rf residual factor indicates the quality of fitting results.

was different from that of scorodite. The coordinated number is 1.0
for the first peak at 2.87e2.89 Å and 4.0 for the second peak at
3.44e3.47 Å. According to the reported structure of SO4-tooeleite
(Morin et al., 2007), the interatomic distance between Fe/As on
layers and As/S in interlayer space is longer than 4.7 Å, and thus it's
hard to distinguish the interlayered atoms by XAFS techniques.
By contrast of the fitting results, we found the coordination
structure of Fe in As(III)-tooeleite is much closer to the reported
theoretical structure of SO4-tooeleite (Morin et al., 2007), and the
disproportionate coordination of Fe occurs in SO4-tooeleite sample.
This means that SO4 group can cause the degradation of tooeleite
crystal structure. In fact, it's impossible to form As(III)-tooeleite in
SO4-containing systems. Besides, scorodite is a strong competitive
phase, which makes it difficult to form As(III)-tooeleite in As(V)-
containing systems. Therefore, As(III)-tooeleite has the ideal crys-
tal structure but can be easily affected by the presence of As(V) and
SO4 group. For example, the mineral tooeleite found in waste
dumps (Nishimura and Robins, 2008), arsenic-bearing acid mine
drainage (Guillaume et al., 2003; Morin et al., 2007) and the acid
hydrometallurgy wastes (Ma rquez et al., 2016) commonly contains
SO4 group and is associated with scorodite. The basic reason for all
these could be that the affinity of Fe(III) to As(V) and SO4 is much
stronger than As(III).
4. Conclusion
Tooeleite (Fe6(AsO3)4SO4(OH)4$4H2O) is a potential phase for
As(III) removal and storage. In this study, SO4-free tooeleite were
prepared through substituting for SO4 group by As(V) or As(III). The
substitution occurred in absence of SO4 anion under hydrothermal
or atmospheric conditions. As(III)-tooeleite and As(V)-tooeleite
crystals have very similar XRD pattern and surface morphology to
SO4-tooeleite. However, EXAFS results indicated that the coordi-
nation structure of As(III)-tooeleite is much closer to the ideal
crystal model, and SO4 group can cause the degradation of coor-
dination structure in SO4-tooeleite sample. Batch experiments
showed that the favorable pH range for As(V)-tooeleite and As(III)-
tooeleite formation is 1.40e2.08 and 1.68e2.06, respectively.
Additionally, by forming SO4-tooeleite, the removal of As can reach
94%, and As leaching in TCLP tests can be lower than that of SO4-
tooeleite. Therefore, SO4-free tooeleite are of great potential in As
removal and immobilization. Moreover, the relative amount of
As(III), As(V), Fe(III) and SO4 group are the key determinants of the
morphology structure and the formation of different tooeleite-type
crystals and other phases like scorodite and natrojarosite.
Acknowledgments
This work was supported by National Key R&D Program of China
(2017YFC0210401) and the Key Project of National Natural Science
Foundation of China (51634010). The authors appreciate experi-
mental help from Beamline 07A1 at Taiwan Light Source (TLS) at
the National Synchrotron Radiation Research Center (NSRRC,
Hsinchu). This work was also sponsored by Guangdong Provincial
Key Laboratory of Soil and Groundwater Pollution Control (No.
2017B030301012), and State Environmental Protection Key Labo-
ratory of Integrated Surface Water-Groundwater Pollution Control.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.chemosphere.2018.09.040.
References
Bahfenne, S., Frost, R.L., 2010. Raman spectroscopic study of the multi-anion min-
eral dixenite CuMn2þ14Fe3þ(AsO3)5(SiO4)2(AsO4)(OH)6. J. Raman Spectrosc. 41,
465e468.
Bujdos, T., et al., 2009. Adsorption of arsenic components on layered double hy-
droxides and mixed oxides for water purification. J. Eng. Fasc. 3, 171e178.


Cejka, J., et al., 2010. Raman spectroscopic study of the arsenite mineral vajdakite
[(Mo6þO2)2(H2O)2As3þ2O5]$H2O. J. Raman Spectrosc. 41, 74e77.
Cesbron, F.P., Williams, S.A., 1992. Tooeleite, a new mineral from the US mine,
Tooele County, Utah. Mineral. Mag. 56, 71e73.
Chai, L., et al., 2016. Heavy metals and metalloids in the surface sediments of the
Xiangjiang River, Hunan, China: distribution, contamination, and ecological risk
assessment. Environ. Sci. Pollut. R. 24, 1e12.
Chai, L., et al., 2016. Formation of tooeleite and the role of direct removal of As(III)
from high-arsenic acid wastewater. J. Hazard Mater. 320, 620e627.
Chai, L., et al., 2017. Structure and spectroscopic study of aqueous Fe(III)-As(V)
complexes using UV-Vis, XAS and DFT-TDDFT. Chemosphere 182, 595e604.
Chai, L., et al., 2017. Enhanced stability of tooeleite by hydrothermal method for the
fixation of arsenite. Hydrometallurgy 175, 93e101.
Dutrizac, J.E., Jambor, J.L., 2014. The behaviour of arsenic during Jarosite precipita-
tion: arsenic precipitation at 97  C from sulphate or chloride media. Can. Metall.
Q. 26, 91e101.
Dutrizac, J.E., Jambor, J.L., Chen, T.T., 2013. The behaviour of arsenic during jarosite
precipitation: reactions at 150  C and the mechanism of arsenic precipitation.
Can. Metall. Q. 26, 103e115.
Egal, M., et al., 2009. Kinetic control on the formation of tooeleite, schwertmannite
and jarosite by Acidithiobacillus ferrooxidans strains in an As(III)-rich acid mine
water. Chem. Geol. 265, 432e441.
Fei, J.C., et al., 2017. Health and ecological risk assessment of heavy metals pollution
in an antimony mining region: a case study from South China. Environ. Sci.
Pollut. Res. 24, 27573e27586.
Frost, R.L., Bahfenne, S., 2010. Raman spectroscopic study of the arsenite minerals
leiteite ZnAs2O4, reinerite Zn3(AsO3)2 and cafarsite Ca5(Ti,-
Fe,Mn)7(AsO3)12$4H2O. J. Raman Spectrosc. 41, 325e328.
2þ
Frost, R., Silmarilly, B., 2011. The mineral nealite Pb4Fe (AsO3)2Cl4$2H2O - a Raman
spectroscopic study. Spectrosc. Lett. 44, 22e26.
Frost, R.L., et al., 2010. Raman spectroscopic study of the hydroxy-arsenate mineral
geminite Cu(AsO3OH)$H2O. J. Raman Spectrosc. 41, 1038e1043.
 J. Yang et al. / Chemosphere 213 (2018) 305e313
Frost, R.L., Xi, Y., Pogson, R.E., 2012. Raman spectroscopic study of the mineral
arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6. Spectrochim. Acta A 91,
301e306.
Ghose, S., Sen Gupta, P., Schlemper, E., 1987. Leiteite, ZnAs2O4; a novel type of
tetrahedral layer structure with arsenite chains. Am. Mineral. 72, 629e632.
Goh, K.H., Lim, T.T., Dong, Z., 2009. Enhanced arsenic removal by hydrothermally
treated nanocrystalline Mg/Al layered double hydroxide with nitrate interca-
lation. Environ. Sci. Technol. 43, 2537e2543.
Guillaume, M., et al., 2003. Bacterial formation of tooeleite and mixed arsenic(III) or
arsenic(V)iron(III) gels in the Carnoule s acid mine drainage, France. A XANES,
XRD, and SEM Study. Environ. Sci. Technol. 37, 1705e1712.
Li, X., Zhao, F., Deng, S., 2014. Deng, the removal of arsenic(III) from Acid Mine
Drainage by mineral trap of tooeleite (Fe6(AsO3)4SO4(OH)4$4H2O), the 12th
congress of international mine water association. An Interdisciplinary Response
to Mine Water Challenges 671e674.
Liang, Y., et al., 2016. Stabilization of arsenic sludge with mechanochemically
modified zero valent iron. Chemosphere 168, 1142e1151.
Liu, J., Huang, X., Chen, S., Liu, J., Wu, C., 2012. Mineralogical research on synthesized
tooeleite. Acta Petrol. Mineral. 31, 901e906.
Liu, J., et al., 2013. The mineral tooeleite Fe6(AsO3)4SO4(OH)4$4H2O - an infrared and
Raman spectroscopic study-environmental implications for arsenic remedia-
tion. Spectrochim. Acta A 103, 272e275.
Liu, H., et al., 2017. A comparative evaluation of different sediment quality guide-
lines for metal and metalloid pollution in the Xiangjiang River, Hunan, China.
Arch. Arch. Environ. Con. Tox. 73, 593e606.
Liu, D., et al., 2017. Co-treatment of flotation waste, neutralization sludge, and
arsenic-containing gypsum sludge from copper smelting: solidification/stabi-
lization of arsenic and heavy metals with minimal cement clinker. Environ. Sci.
Pollut. Res. 1e8.
Liu, J., et al., 2015. Spectroscopic characterization and solubility investigation on the
effects of As(V) on mineral structure tooeleite (Fe6(AsO3)4 SO4(OH)4$H2O).
Spectrochim. Acta A 134, 428e433.
Malakar, A., et al., 2016. Efficient artificial mineralization route to decontaminate
arsenic(III) polluted water - the tooeleite way. Sci. Rep-UK 6, 26031.
Ma rquez, M., et al., 2016. Process mineralogy of bacterial oxidized gold ore in Sa ~o
313
Bento Mine (Brasil). Hydrometallurgy 83, 114e123.
Min, X., et al., 2015. Removal and stabilization of arsenic from anode slime by
forming crystal scorodite. T. Nonferr. Metal. Soc. 25, 1298e1306.
Morin, G., Rousse, G., Elkaim, E., 2007. Crystal structure of tooeleite, Fe6(AsO3)4-
SO4(OH)4$4H2O, a new iron arsenite oxyhydroxysulfate mineral relevant to acid
mine drainage. Am. Mineral. 92, 193e197.
Müller, K., et al., 2010. A comparative study of As(III) and As(V) in aqueous solutions
and adsorbed on iron oxy-hydroxides by Raman spectroscopy. Water Res. 44,
5660e5672.
Nishimura, T., Robins, R., 1996. Crystalline phases in the system Fe(III)eAs (V)eH2O
at 25  C. Iron Contr. Dispos. 521e533.
Nishimura, T., Robins, R.G., 2008. Confirmation that tooeleite is a ferric arsenite
sulfate hydrate, and is relevant to arsenic stabilisation. Miner. Eng. 21, 246e251.
Opio, F.K., 2013. Investigation of Fe (III)-As (III) Bearing Phases and Their Potential
for Arsenic Disposal. Queen's University, Canada.
Pozdnyakov, I.P., et al., 2016. Photochemical transformation of an iron(III)-arsenite
complex in acidic aqueous solution. Photochem. Photobiol. Sci. 15, 431e439.
Prasanna, S.V., Kamath, P.V., 2009. Synthesis and characterization of arsenate-
intercalated layered double hydroxides (LDHs): prospects for arsenic mineral-
ization. J. Colloid Interface Sci. 331, 439e445.
Raghav, M., et al., 2013. Scoping candidate minerals for stabilization of arsenic-
bearing solid residuals. J. Hazard Mater. 263, 525e532.
Sunyer, A., Currubí, M., Vin ~ als, J., 2013. Arsenic immobilization as alunite-type
phases: the arsenate substitution in alunite and hydronium alunite. J. Hazard
Mater. 261C, 559e569.
U.S. EPA, 1998. In: Method 1311: Toxicity Characteristic Leaching Procedure, SW-
846: Test Methods for Evaluating Solid Waste. Physical/Chemical Methods.
Available: http://www.epa.gov/epaoswer/hazwaste/test/pdfs/1311.pdf.
Yan, X., et al., 2017. Abiological granular sludge formation benefit for heavy metal
wastewater treatment using sulfide precipitation. Clean. - Soil, Air, Water 45.
Yang, Z., et al., 2015. Arsenic immobilization in the contaminated soil using poorly
crystalline Fe-oxyhydroxy sulfate. Environ. Sci. Pollut. Res. 22, 12624e12632.
Yang, J., et al., 2015. Complexation of arsenate with ferric ion in aqueous solutions.
RSC Adv. 5, 103936e103942.