Materials Transactions, Vol. 50, No. 2 (2009) pp.

321 to 331
#2009 The Mining and Materials Processing Institute of Japan

Immobilization of Arsenic from Novel Synthesized ScoroditeAnalysis

on Solubility and Stability
Tetsuo Fujita1; * , Ryoichi Taguchi1 , Hisashi Kubo1 , Etsuro Shibata2 and Takashi Nakamura2
1
2

Dowa Metals & Mining Co. Ltd., Akita 011-8555, Japan

Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan

The solubility of scorodite synthesized in a novel atmospheric process was investigated. Stable scorodite (FeAsO4
2H2 O) particles were
produced by introducing oxidizing gas into a reaction mixture containing ferrous sulfate and high-concentration arsenic (V) to convert ferrous
ion to ferric ion. The obtained scorodite crystals released a very low, almost negligible concentration of arsenic in the pH range of 3 to 6,
suggesting its long-term stability. The thermodynamic parameters for the dissolution reaction of scorodite, Ksp and
Gf , were similar to those
reported previously. The results show scorodite released a considerably high concentration of arsenic under specic leaching conditions. In
particular, the combination of CaO and NaCl present in the alkaline leaching solution had a signicant eect on the mobilization of arsenic.
Although this study did not cover all possible natural environments in which scorodite would be stored, it seems practically impossible to
develop conditions that would completely prevent the dissolution of arsenic from scorodite. It is crucial to develop scorodite storage methods
that will minimize the risk of environmental arsenic contamination based on accurate evaluation of the conditions for the leaching of arsenic.
[doi:10.2320/matertrans.M-MRA2008844]
(Received June 19, 2008; Accepted November 4, 2008; Published January 8, 2009)
Keywords: scorodite, solubility, NaOH, NaCl and CaO, reduction, risk management

1.

Introduction

Arsenic contamination is one of the worlds major

environmental issues. In Bangladesh, for example, a serious
health problem has occurred with people drinking arsenic
polluted groundwater. Research is being vigorously carried
out to address this problem.15) Many methods have been
reported for the removal of arsenic from the water environment.619) Most of them involve adsorption of arsenic to iron
compounds, and this phenomenon has long been a subject of
interest.2022) In particular, arsenic sorption onto schwertmannite developed by Fukushi et al.14) is believed to be a
useful method for the elimination of arsenic. This process,
however, has disadvantages partly because of the lack of an
eective strategy for treating the resulting arsenic-rich
schwertmannite solids (residues). Sarkar et al.19) recently
proposed a method for recycling the adsorbent, but their work
did not discuss methods for treating the resulting condensed
arsenic compound. The schwertmannite adsorption method
reported by Fukushi et al. eliminated at best 6 to 8% of
arsenic, and the produced arsenic-bearing iron oxide compounds had insuciently low arsenic content and were thus
not suitable for dumping. Moreover, as suggested by Dixit
and Hering,11) the adsorbed arsenic may leach under certain
pH and other chemical or physical conditions.
Treatment of arsenic has also been a signicant issue in
nonferrous metallurgy. Arsenic is included in the ores as
impurities and is generated as by-products in metallurgical processes. Arsenic compounds were formerly used in
pesticides, herbicides, fungicides, and wood preservers.
However, owing to the environmental impact of the toxicity
of As2 O3 , many countries have banned the use of arseniccontaining agricultural products, and arsenic consumption
has greatly reduced. Thus, the production volume of arsenic
far exceeds industrial expenditure, and the development of
eective technologies for arsenic elimination, xation, and
*Corresponding

author, E-mail: fujitat2@dowa.co.jp

storage has been highly demanded.

A novel atmospheric process for the synthesis of scorodite
has been developed and reported.2326) The essential feature
of this process involved precipitation of scorodite by
oxidizing ferrous ions contained in a high-concentration
arsenic (V) solution. The practical application of this process
along with the toxic metal attenuation process proposed by
Wang and Mulligan27) will contribute to the promotion of a
sustainable society where production and consumption are
proportionate.
Scorodite crystals release only a very low and negligible
level of arsenic when tested according to the procedure of the
Japanese Ministry of the Environment Notication No. 13
method. This test result, however, should not be construed as
the sole basis for judgment of scorodite stability. A wide
range of experimental conditions must be used for comprehensive analysis of the scorodite leaching behavior.
Investigations on the leaching of arsenic are widely
reported in literature. Nishimura and Tozawa28,29) calculated
the solubility products for FeAsO4 and found heat treatment enhanced its immobilization. Robins3034) conducted a
series of studies on the solubility and stability of scorodite
comparing thermodynamic properties of FeAsO4 and scorodite (FeAsO4
2H2 O). Dove and Rimstidt35) calculated the
Gibbs free energy of formation (
Gf ) from the solubility
constant (Ksp) for scorodite. Krause and Ettel3638) examined
solubilities of ferric arsenate at various Fe/As molar
ratios. Harris and Monette39,40) reported solubilities of
smelter/renery-associated arsenic compounds including
ferric arsenate. Emett and Khoe41,42) explored the eect of
co-present impurities such as cadmium and lead on the
solubility of arsenic. The recent work by Langmuir et al.43,44)
provided new insight in thermodynamic discussions on
scorodite. Bluteau and Demopoulos45,46) presented extensive
discussion on the mechanism of leaching of arsenic from
scorodite.
Despite the large number of studies reported to date, they
seem to fall short of establishing the safest and most

322

T. Fujita, R. Taguchi, H. Kubo, E. Shibata and T. Nakamura

convincing methods for scorodite storage. This is primarily

because of the lack of evidence for long-term scorodite
stability, which is duly aected by time-dependent changes
in the environment surrounding stored scorodite. Therefore,
research geared toward reducing the risk of arsenic dissolution to zero will be unlikely to yield decisive conclusions
regarding storage or disposal.
Many of the basic scientic studies conducted for
minimizing the arsenic leaching risk to zero lack substantial
suggestions for industrial application. It is thought that the
practical need for analysis and assessment of arsenic leaching
outweighs the value of developing scientic methods for
eradicating the risk, particularly in the industrial sector. It is
an urgent task to investigate scorodite solubility in various
external environments, rather than the long-term stability
itself.
The objectives of the present study are to (1) measure and
compare the levels of arsenic leached from synthesized
scorodite and (2) examine the concentrations of arsenic
leached from scorodite to various aqueous solutions with
dierent pH values.
2.

Fig. 1 Experimental apparatus for the scorodite formation.

Experimental

2.1 Materials
An arsenic (V) acid solution (labeled H3 AsO4 content: 58
62%; mean: 60%; no indication of grade). The specic
gravity of the solution was 1.585 g/mL. Inductively coupled
plasma (ICP) measurements provided an arsenic concentration of 500 g/L and the solution was treated as 500 g/L
arsenic acid solution. Analytical-reagent grade iron (II)
sulfate 7-hydrate was used as the iron source. All chemicals
used in the tests were purchased from Wako Pure Chemical
Industries, Ltd. (Osaka, Japan). Compressed oxygen gas
(purity: 99.9%, Akisan Kogyo K.K., Akita, Japan) was used
as an oxidizing agent.
2.2 Experimental apparatus
The apparatus used in experiment is schematically
illustrated in Fig. 1. The reaction mixture in the vessel was
indirectly heated by an electric device.
The temperature was measured with a glass-insulated Ktype thermocouple. Reaction temperature was controlled by
an ON/OFF controller with a predetermined allowable range
of plus or minus 3 C. A 5-L Pyrex
beaker was used as the
reaction vessel. A stirrer comprising a titanium shaft and two
90-mm titanium turbine blades was used for agitation. The
vessel was equipped with four baes, which were attached to
the upper vessel cover. A variable-speed motor (01500 rpm)
attached to the stirrer shaft was used for mixing.
The gas inlet nozzle, xed to the upper vessel cover, was a
glass tube 5 mm in internal diameter. The upper cover was
coated with isobutyleneisoprene rubber. A several millimeter gap was set between the stirrer shaft and the edge of the
cover opening, exposing the reaction chamber to the atmosphere.
2.3 Preparation of scorodite
The experimental procedure for the production of scorodite is schematically summarized in Fig. 2.

Fig. 2

Procedure for scorodite formation experiments.

4 L of arsenic-containing test solution was measured and

poured into the beaker, and an adequate amount of iron (II)
sulfate 7-hydrate reagent was weighed and added to the
solution. Distilled water was added to a total volume of 4 L.
The beaker was set with a heater and the titanium stirrer, and
the reaction mixture was agitated at 200 rpm until it reached
the pre-determined temperature. When the temperature was
attained, oxygen gas was introduced into the mixture via the
glass tube to begin reaction with 800 rpm stirring. After the
reaction progressed for a pre-dened period of time, part of
the slurry was collected, cooled to 60 C, and its pH and
oxidation reduction potentials (ORP) were measured. The pH
value was determined from manual temperature compensation (MTC), which was set at 30 C. The ORP measurements
used a Ag/AgCl reference electrode. The lling solution was
a 3.3 mol/L KCl solution. The remaining reaction slurry was
pressure-ltered through a 1-mm pore-size polytetrauoroethylene (PTFE) membrane lter at 0.4 MPa to separate solid
from liquid. The ltrate was subjected to ICP measurements.

Immobilization of Arsenic from Novel Synthesized ScoroditeAnalysis on Solubility and Stability

Table 1

323

Conditions of solvent in the 6-hour leach test.

Condition

pH

Distilled water

5.74

TCLP2.88 (0.1 mol/L CH3 COOH solution)

3.00

TCLP4.93 (0.1 mol/L CH3 COOH and NaOH solution)

4.88

Alkaline water conditioned by CaO

Alkaline water conditioned by Mg(OH)2

12.52, 12.30, 10.75, 10.14, 9.00

10.48, 10.41, 10.64, 9.00

Alkaline water conditioned by NaOH

12.50, 11.06, 9.70

Acid water conditioned by H2 SO4

3.96, 2.97, 1.97, 1.22, 0.35

Acid water conditioned by HCl

3.99, 2.99, 1.98, 1.11, 0.13

Acid water conditioned by HNO3

3.98, 2.99, 1.99, 1.12, 0.12

8.2 g/L NaCl solution conditioned by CaO

12.50, 12.00, 11.06

8.2 g/L NaCl solution conditioned by H2 SO4

5.80, 2.99

16.5 g/L NaCl solution conditioned by CaO

16.5 g/L NaCl solution conditioned by H2 SO4

12.51, 12.00, 11.01

5.55, 2.99

33 g/L NaCl solution conditioned by CaO

12.51, 12.00, 11.05

33 g/L NaCl solution conditioned by H2 SO4

5.47, 2.96

The solid lter cake was repulped and washed with

distilled water three to ve times. The number of washings
varied because the washing process was repeated until the pH
of the washing water exceeded 3.9. The weight ratio of solid
to distilled water was 1 to 10. After each washing, the solid
was separated from liquid through pressure ltration. The
solid was dried at 60 C for 18 hours and carefully pulverized
in a mortar. The obtained solids were subjected to chemical
composition and powder characteristics analyses.
2.4 Analytical method
ICP analysis was performed on the solid and post-reaction
ltrate using inductively coupled plasma atomic emission
spectroscopy (ICPAES) (ICAP577, Nippon Jarrell-Ash Co.
Ltd., Kyoto, Japan) to determine their chemical compositions. Scanning electron microscopy (SEM) was conducted
on solids using a Hitachi FE-SEM S-4500 (Hitachi Ltd.,
Tokyo, Japan).
2.5 Leach test
2.5.1 Long-term leach test
A long-term leach test was performed according to the
United States Environmental Protection Agencys Toxicity
Characteristic Leaching Procedure (TCLP) test (method
1311), with minor modications. According to TCLP, the
leach test is usually carried out as shown below. A 100 g of
sample and 2 L of acetic acid buer solution (pH 2:88
or 4.95) are mixed in a polyethylene bottle. The extraction
is done by rotary shaking for 18 hours. The solid-liquid
separation is made by a 0.60.8 mm pore-size glass ber
lter (GFF). In this study, a 5-g (dry weight) sample was
added to 100 g of extraction uid in a high-density polyethylene sample bottle, and the mixture was horizontally
shaken for a period of 6 hours to 35 days. The maximum
duration of 35 days was set based on data given by Bluteau
and Demopoulos45,46) showing the attainment of equilibrium
in 5 weeks. After a pre-determined time, the sample bottle
was removed from the shaker, the mixture was ltered
through a 0.2 mm PTFE membrane lter, and the ltrate was
analyzed by inductively coupled plasma mass spectrometry

(ICPMS) (SPQ9000, Seiko Instruments Inc., Chiba, Japan).

A quantitative determination of As(III)/(V) in the leachate
was not made, because the arsenic concentration in the
leachate was too low to analyze the valence of arsenic. In
addition, the analysis technique condensing a dilute leachate
has not been established yet. We assumed that most of
arsenic in the leachate was pentavalent, because the scorodite
was synthesized in an arsenic (V) solution in this study.
In these tests, buers were used for the extraction uid:
0.1 mol/L aqueous acetic acid solution (pH of 2.88), a
mixture of 0.1 mol/L acetic acid solution and 0.1 mol/L
sodium hydroxide solution (pH of 4.93), a mixture of 0.025
mol/L potassium dihydrogen phosphate and 0.025 mol/L
sodium dihydrogen phosphate (pH of 6.86), and 0.01 mol/L
sodium tetraborate (pH of 9.18).
The samples were sealed in the bottle both under nitrogen
and under a normal air atmosphere to compare the eect of
CO2 and O2 present in the contained air and extraction uid.
All leaching operations relating to the nitrogen-lled sample bottle were conducted in a nitrogen-purged glove box
(O2 < 100 ppm).
2.5.2 Solvent-specic leach test
Leach tests using dierent extraction uids were carried
out according to the method stipulated by the Japanese
Ministry of the Environment, with several changes. After a
10-g sample and 100 g of extraction uid were weighed and
mixed in a high-density polyethylene bottle, the bottle was
sealed and horizontally shaken for 6 hours. Upon completion,
the mixture was ltered through a 0.20 mm PTFE membrane
lter, and the ltrate was analyzed by ICP-MS. These
experiments employed the extraction uids listed in Table 1.
2.5.3 Leach test using detergents
Detergents used in the human environment can reach
rivers and other bodies of water. Therefore, a series of leach
tests were performed using extraction uids containing a
given amount of detergents: 2, 4, and 8 g of a 27% solution of
sodium alkylether sulfate which is made from straight-chain
alkylbenzene sulfonate were added per liter of water. Chemical oxygen demand (COD) values were determined for the
detergent-containing solvent to indicate its organic content.

324

T. Fujita, R. Taguchi, H. Kubo, E. Shibata and T. Nakamura

Table 2 Analytical contents of arsenopyrite.

Fe
(%)

As
(%)

S
(%)

Zn
(%)

Pb
(%)

Na
(%)

K
(%)

Mg
(%)

Ca
(%)

Al
(%)

Si
(%)

Au
(ppm)

Ag
(ppm)

31.59

17.33

25.81

1.25

0.60

0.42

0.39

0.41

1.04

1.18

7.31

149

178

Table 3

Conditions of scorodite formation.

Solution composition
Initial

Final

ORP

pH

pH

mV

1.11

0:22

474

Table 4 Characterization of precipitated scorodite.

Precipitation
Free

As

Fe

mol/L

g/L

g/L

g/L

As

Fe

1.44

1.44

22.55

34.57

97.1%

59.7%

acid

(%)

Solid composition

Precipitation
wet base
(g/L)

Moisture
(%)

168.2

11.2

Fe

Na

(%)

(%)

(ppm)

(ppm)

Fe/As
molar
ratio

31.36

24.20

24

4208

1.036

As

Particle size
(D50)
(mm)

BET
ssa (m2 /g)

Density
(kg/m3 )

Compression
density
(kg/m3 )

17.10

0.30

3.29

2.13

30 m

6 m

Fig. 3 SEM pictures of precipitated samples.

The leach tests were carried out based on the minor changed
Japanese method as mentioned above (section 2.5.2).
2.5.4 Leach test involving arsenopyrite
Arsenopyrite (FeAsS) is a poorly soluble arsenic sulde
mineral. Varying mixtures of scorodite and arsenopyrite were
subjected to leach testing. The leach tests were carried out
based on the Japanese Ministry of the Environment method.
Table 2 summarizes the measured contents of arsenopyrite
provided by Bralorne Gold Mines Ltd.
3.

Results

3.1

Scorodite synthesis and characteristics of the scorodite precipitate

Data relating to the 7-hour scorodite synthesis reaction and
the characteristics of the produced scorodite grains are
summarized in Tables 3 and 4, respectively. Figure 3
presents SEM pictures of the scorodite precipitate. These
results indicate large scorodite crystals with low moisture
content were formed, yielding a high arsenic precipitation
percentage.
3.2

Scorodite long-term leach tests performed under an

atmospheric condition
Tables 5 and 6 summarize the results of scorodite leach
tests with dierent buers as the solvent. The pH values
depicted in the tables were taken immediately after shaking

was complete (before solid/liquid ltration and separation).

These results show that scorodite crystal was quite stable
with arsenic leaching less than 0.5 mg/L in the pH range of 3
to 5, though arsenic leached at a concentration of 3 mg/L
when pH was 6.9 and at a concentration of 300 mg/L when
pH was 9. The value of 300 mg/L indicates that about 2% of
arsenic was released from scorodite.
3.3

Scorodite long-term leach tests performed under a

nitrogen atmosphere
Tables 7 and 8 summarize the results of scorodite leach
tests conducted under nitrogen gas using the same buer
conditions as those in tests performed under a normal air
atmosphere. Considering the possible eect of having an
oxidative atmosphere with gases such as O2 and CO2 , the
ORP was measured in addition to pH after shaking of the
slurry mixture was complete. Leach testing using the pH 9.18
buer was not carried out because the leaching arsenic
concentration was apparently high. under atmospheric conditions as shown in Table 6.
The produced scorodite crystal was quite stable in the pH
range of 3 to 5, with arsenic leaching at a concentration of
0.5 mg/L or less, and at pH 6.9, leaching of arsenic was
slightly higher (though lower than the value derived under a
normal air atmosphere). These data suggest the eect of the
ambient gas was negligible compared with that of pH.
However, since the change in pH of the buer solution led to

Immobilization of Arsenic from Novel Synthesized ScoroditeAnalysis on Solubility and Stability

Table 5 Long-term scorodite leach tests under normal air atmosphere
using pH 2.88 and 4.93 buer solutions.

pH
0.25
1

2.88
2.90

As

Fe

pH

(mg/L) (mg/L) (mg/L)

0.19
0.24

Table 6 Long-term scorodite leach tests under normal air atmosphere

using pH 6.86 and 9.18 buer solutions.

0.1 mol/L
CH3 COOH and NaOH

0.1 mol/L
CH3 COOH

Stirring
days

0.70
0.90

<10
<10

As

Fe

0.16
0.16

0.06
0.06

pH
0.25
1

<10
<10

0.01 mol/L
Na2 B4 O7

0.025 mol/L
KH2 PO4 and NaH2 PO4

Stirring
days

(mg/L) (mg/L) (mg/L)

4.95
4.95

325

6.92
6.92

As

Fe

(mg/L) (mg/L) (mg/L)

1.05
1.50

<0:04
0.06

<10
<10

pH
9.26
9.20

As

Fe

(mg/L) (mg/L) (mg/L)

4.18
32.3

0.60
9.11

<10
<10

2.90

0.28

0.93

<10

4.96

0.25

0.07

<10

6.91

1.53

0.06

<10

9.19

40.3

13.3

<10

2.90

0.38

1.09

<10

4.95

0.26

0.06

<10

6.91

1.88

0.07

<10

9.15

71.3

28.1

<10

2.91

0.32

1.04

<10

4.95

0.20

0.07

<10

6.91

2.13

0.12

<10

9.04

137.0

54.9

<10

2.88

0.31

1.03

<10

4.94

0.23

0.07

<10

6.89

2.07

0.09

<10

9.08

117.0

42.5

<10

14

2.90

0.34

1.14

<10

4.96

0.19

0.09

<10

14

6.91

2.49

0.13

<10

8.84

253.0

15.6

10

21

2.91

0.50

1.33

<10

4.96

0.18

0.07

<10

21

6.91

3.00

0.11

<10

8.75

321.7

24.4

<10

28
35

2.90
2.89

0.43
0.40

1.39
1.23

<10
<10

4.95
4.95

0.20
0.18

0.12
0.09

<10
<10

28
35

6.90
6.89

2.77
3.14

0.17
0.15

<10
<10

8.69
8.66

312.0
351.7

26.6
26.3

10
<10

Table 7
Stirring
days

Long-term scorodite leach tests under nitrogen atmosphere using pH 2.88 and 4.93 buer solutions.
0.1 mol/L CH3 COOH

pH

0.1 mol/L CH3 COOH and NaOH

ORP

As

Fe

(mV)

(mg/L)

(mg/L)

(mg/L)

pH

ORP

As

Fe

(mV)

(mg/L)

(mg/L)

(mg/L)

0.25

2.88

384

0.19

0.84

<10

4.97

222

0.15

0.15

<10

2.86

380

0.27

1.00

<10

4.92

227

0.17

0.16

<10

2.96

379

0.31

1.08

<10

5.03

228

0.16

0.17

<10

2.92

373

0.32

1.12

<10

4.98

223

0.17

0.19

<10

2.88

370

0.49

1.33

<10

4.97

226

0.22

0.24

<10

7
14

2.95
2.89

373
378

0.47
0.50

1.32
1.36

<10
<10

5.02
4.99

226
246

0.23
0.19

0.23
0.20

<10
<10

21

2.87

363

0.51

1.38

<10

4.94

229

0.17

0.17

<10

28

2.84

365

0.49

1.44

<10

4.93

247

0.14

0.17

<10

35

2.86

372

0.53

1.44

<10

4.91

258

0.16

0.18

<10

Table 8 Long-term scorodite leach tests under nitrogen atmosphere using a

pH 6.86 buer solution.
Stirring
days

0.025 mol/L KH2 PO4 and NaH2 PO4

pH

ORP

As

Fe

(mV)

(mg/L)

(mg/L)

(mg/L)

0.25
1

6.90
6.87

91
87

0.85
1.10

0.03
0.02

<10
<10

6.97

91

1.19

0.04

<10

6.93

96

1.35

0.03

<10

6.92

86

1.68

0.04

<10

6.95

91

1.76

0.05

<10

14

6.98

133

1.80

0.02

<10

21

6.86

137

1.86

0.01

<10

28
35

6.92
6.88

127
112

1.91
1.96

0.01
0.01

<10
<10

a change in the ORP, these results were not sucient for

concluding the scorodite crystal was stable under a reductive
condition.
3.4 Leach tests using various solvents
Tables 9 and 10 show the results of 6-hour scorodite leach
tests conducted using various solvents. The leach tests using

pH 2.88 and 4.93 buer solutions were performed again in

this series of experiments, and the results are thereby
dierent from the corresponding data reported above.
Table 10 gives the results of leach tests that involved the
presence of a given amount of sodium chloride. In this
experiment, CaO or H2 SO4 was used for adjustment of pH.
When Mg(OH)2 or CaO was used, the leaching arsenic
concentration was as low as approximately 3 mg/L under
strongly basic conditions of pH 10 or higher, whereas arsenic
leached at a higher concentration of 10 mg/L in the pH range
of 8 to 10. The arsenic leaching concentration under alkaline
conditions using NaOH was as high as 99.2 mg/L. Liquidsolid ratio was 10 : 1 in this leach test, and it was calculated
that about 0.3% of arsenic was released from scorodite.
When HCl, H2 SO4 , or HNO3 was employed, the arsenic
leaching concentration was less than 1 mg/L at pH 3 and
2 mg/L at pH 2. However, when pH was decreased from 1 to
zero, the concentration of leaching arsenic increased considerably. The sequence of acids arranged in decreasing order of
arsenic leaching was HNO3 , H2 SO4 , and HCl.
For leach tests conducted with the presence of NaCl,
the arsenic leaching concentration was 0.3 mg/L or less
under acidic to neutral pH conditions, though it exceeded
1000 mg/L (dissolved As ratio: approx. 3%) under basic
conditions.

326

T. Fujita, R. Taguchi, H. Kubo, E. Shibata and T. Nakamura

Table 9 6-hour leach tests of the scorodite with various solvents.

Solvent

Initial
pH

Leachate

Final
pH

As

Fe

(mg/L)

(mg/L)

(mg/L)

Solvent

Initial
pH

Final
pH

Leachate
As

Fe

(mg/L)

(mg/L)

(mg/L)

Water

5.74

4.61

0.01

0.56

<10

H2 SO4

3.96

3.99

0.05

0.91

TCLP2.88

3.00

3.02

0.11

1.48

<10

H2 SO4

2.97

3.03

0.21

1.37

<10
20

TCLP4.93

4.88

4.89

0.16

0.21

<10

H2 SO4

1.97

1.99

1.83

2.87

210

CaO

12.52

12.17

2.55

0.09

<10

H2 SO4

1.22

1.28

11.00

9.84

1630

CaO
CaO

12.30
10.75

12.10
8.36

2.20
3.91

0.11
0.54

<10
<10

H2 SO4
HCl

0.35
3.99

0.42
3.98

94.74
0.04

78.04
0.97

15130
<10

CaO

10.14

6.83

0.51

0.27

<10

HCl

2.99

3.04

0.13

1.68

<10

CaO

9.00

5.14

<0:01

0.24

<10

HCl

1.98

2.03

1.06

2.94

<10

Mg(OH)2

10.48

10.03

1.66

0.05

<10

HCl

1.11

1.12

6.70

7.73

<10

Mg(OH)2

10.41

9.88

8.59

<0:05

<10

HCl

0.13

0.15

202

166

<10

Mg(OH)2

10.64

9.26

6.66

0.12

<10

HNO3

3.98

3.99

0.05

0.98

<10

Mg(OH)2

9.00

7.58

1.27

0.60

<10

HNO3

2.99

3.01

0.08

1.72

<10

NaOH
NaOH

12.50
11.06

9.46
8.28

99.20
21.20

60.50
5.43

30
<10

HNO3
HNO3

1.99
1.12

2.04
1.12

0.78
3.89

2.90
5.93

<10
<10

NaOH

9.70

5.83

0.09

0.05

<10

HNO3

0.12

0.16

29.34

26.11

<10

Table 10 6-hour leach tests of the scorodite with various solvents and the
co-existence of sodium chloride.
Initial
pH

Solvent

Final
pH

Leachate

Table 11 6-hour leach tests of the scorodite with detergent.

Detergent
(g/L)

As
(mg/L)

pH

Fe
(mg/L)

S
(mg/L)
<10

COD
(mg/L)

As

Fe

4.92

0.01

0.25

(mg/L)

(mg/L)

(mg/L)

2
4

5.97
6.21

0.75
1.02

0.55
0.61

26
52

6.56

1.23

1.06

105

NaCl 8:2 g/L

12.51

10.47

927

29.9

NaCl 8:2 g/L

12.00

9.55

258

26

<10

30

NaCl 8:2 g/L

NaCl 8:2 g/L




11.06
5.80

8.46
4.61

25.80
0.04

0.07
0.58

<10
<10

NaCl 8:2 g/L



2.99

3.05

0.18

1.54

20

NaCl 16:5 g/L

NaCl 16:5 g/L




12.51
12.00

10.52
9.71

1041
278

26.7
2.76

40
10

NaCl 16:5 g/L

11.01

8.32

22.05

<0:05

<10

Scorodite
(%)

Detergent: 27% solution of sodium alkylrther sulfate (straight-chain

alkylbenzene sulfonate)
Table 12 6-hour leach tests of scorodite and arsenopyrite.
Arsenopyrite
(%)

pH

ORP
(mV)

As
(mg/L)

Fe
(mg/L)

S
(mg/L)

NaCl 16:5 g/L



5.55

4.49

<0:01

0.66

<10

100

4.92

256

0.01

0.25

<10

NaCl 16:5 g/L



2.99

3.05

0.10

1.55

20

NaCl 33 g/L

12.51

10.54

1164

21.9

50

75
50

25
50

6.70
6.60

218
201

1.54
1.80

0.03
tr

20
40

NaCl 33 g/L

12.00

9.85

309

2.54

10

25

75

6.58

180

1.95

tr

60

NaCl 33 g/L

11.05

8.36

26.63

<0:05

<10

100

6.51

178

2.17

tr

70

NaCl 33 g/L



5.47

4.42

<0:01

0.68

<10

NaCl 33 g/L



2.96

3.03

0.30

1.61

20

pH

ORP
(mV)

As
(mg/L)

Fe
(mg/L)

S
(mg/L)

Scorodite
(%)

: CaO was used for adjustment of pH.

: H2 SO4 was used for adjustment of pH.

3.5 Leach tests using detergents

The results of 6-hour leach tests carried out using the
scorodite and detergent are presented in Table 11. The
detergent is a 27% solution of sodium alkylether sulfate
which is made from straight-chain alkylbenzene sulfonate.
The COD values of the solutions are shown as a surrogate
measure of the organic contents.
3.6 Leach tests involving arsenopyrite
The results of 6-hour leach tests carried out using the
mixture of scorodite and arsenopyrite are presented in
Table 12. The table also lists the results of leach tests
conducted on arsenopyrite alone.

4.
4.1

Arsenopyrite
(%)

5.60

320

tr

tr

tr

25

6.51

257

1.40

tr

20

50

6.41

252

2.00

tr

40

75

6.37

243

2.20

tr

60

100

6.51

178

2.17

tr

70

Discussion

Thermodynamic consideration of long-term scorodite leaching behavior

The above results indicate that scorodite in this study
hardly releases arsenic in the pH range of 3 to 5. Considering
the arsenic concentration reached equilibrium in 35 days
except for pH 9, as indicated by Bluteau and Demopoulos,45,46) the solubility product, Ksp, for scorodite was
determined from the 35-day data. Solubility products were
calculated based on equation (1).

Immobilization of Arsenic from Novel Synthesized ScoroditeAnalysis on Solubility and Stability

327

Table 13 Chemical formula and the thermodynamic data used for calculation of scorodite solubility product.
Formula

Species

Gf
(kJ/mol)

lnK

pK

KFE1
KFE2

Fe3 H2 O Fe(OH)2 H
Fe3 2H2 O Fe(OH)2 2H

Fe(OH)2
Fe(OH)2

12.38
40.91

4:99
16:51

6:78  103
6:79  108

2.17
7.17

KFE3

Fe3 3H2 O Fe(OH)3 3H

Fe(OH)3

56.77

22:90

1:13  1010

9.95

111.57

45:01

2:83  1020

19.55

AsO4 3

117.63

47:45

2:46  1021

20.61

3

104.82

42:29

4:32  1019

18.36

AsO4 3

66.22

26:72

2:50  1012

11.60

No.
Ferric

Fe

KFE4

4H2 O Fe(OH)4 4H

Fe(OH)4

Arsenate
H3 AsO4 AsO4 3 3H

KAS1

3

KAS2

H2 AsO4 AsO4

2H

KAS3

HAsO4 2 AsO4 3 H

AsO4

Table 14 Time-course change in the reaction mixture pH, Fe3 and AsO4 3 activities, solubility product, and free-energy dierence for
scorodite synthesis with the duration of agitation.
stirring
days

pH

(aFe3 )

(aAsO4 3 )

Ksp
(scorodite)

pKsp

G
(kJ/mol)

Gf
(scorodite)
(kJ/mol)

2.88

2:96  106

8:36  1019

2:47  1024

23.61

134.7

1262:8

14

2.90

6

3:15  10

18

1:01  10

3:19  1024

23.50

134.1

1262:1

21

2.91

3:60  106

1:57  1018

5:64  1024

23.25

132.7

1260:7

28

2.90

3:84  106

1:28  1018

4:92  1024

23.31

133.0

1261:1

35

2.89

3:46  106

1:13  1018

3:93  1024

23.41

133.6

1261:6

4.94

1:65  1011

9:90  1015

1:63  1025

24.79

141.5

1269:5

14

4.96

1:85  1011

8:96  1015

1:66  1025

24.78

141.4

1269:5

21

4.96

1:44  1011

8:49  1015

1:22  1025

24.91

142.2

1270:2

28

4.95

2:64  1011

9:01  1015

2:38  1025

24.62

140.5

1268:6

35

4.95

1:98  1011

8:11  1015

1:61  1025

24.79

141.5

1269:5

17

10

27

6.89

3:03  10

3:07  10

9:32  10

26.03

148.6

1276:6

14

6.91

3:82  1017

3:94  1010

1:51  1026

25.82

147.4

1275:4

21

6.91

3:23  1017

4:75  1010

1:53  1026

25.81

147.3

1275:4

28
35

6.90
6.89

5:35  1017
5:06  1017

4:25  1010
4:66  1010

2:27  1026
2:36  1026

25.64
25.63

146.4
146.3

1274:4
1274:3

FeAsO4
2H2 O Fe3 AsO4 3 2H2 O

Ksp (aFe3 )  (aAsO4 3 )

1
2

where (aFe3 ) is the 3 valent iron ion activity, which is

assumed to be the concentration of Fe3 in the testing
solution, and (aAsO4 3 ) is the AsO4 3 activity. Both activity
coecients were set at unity because of the extremely low
ionic strength of the solution.
Total Fe and As content could be only measured in the
solution after leaching tests, then, (aFe3 ) and (aAsO4 3 )
were estimated from following equations considering the
equilibrium in Table 13.

KFE1
KFE2
3
[aFe ] [Fetotal ]  1

aH aH 2

KFE3
KFE4

3
aH 3 aH 4
(aFe3 ) 1  [aFe3 ];

1 ; 1
3

4
2

aH
aH

KAS1
KAS2


aH

1
KAS3

[aAsO4 3 ] [Astotal ] 

(aAsO4 3 ) 2  [aAsO4 3 ];

2 ; 1

For calculation of the thermodynamic parameters, the data

provided by US Department of Commerce National Bureau
of Standards (Wagman et al.47,48)) and the values given in
Standard Potentials in Aqueous Solution edited by Bard,
Parsons, and Jordan49) were used.
Gibbs free energy (
G) was also determined by using the
calculated scorodite solubility products.
G by the duration
of shaking in days as well as solubility product Ksp, pH, Fe3
and AsO4 3 activities are shown in Table 14. In addition,
Gibbs free energy of formation (
Gf ) was calculated by
applying
Gf of Fe3 , AsO4 3 and H2 O from the NBS data
to the
G.
The calculated Ksp values were similar to those derived
previously but smaller than those reported by Dove and
Rimstidt.35) The
Gf values were also smaller than those
estimated by them but larger than those by Bluteau and
Demopoulos.46) These discrepancies presumably resulted
from dierences in the processes for scorodite production.
The scorodite particles produced in this study had a higherthan-unity Fe/As molar ratio of 1.04, which suggests the
precipitate had higher iron content in the later stage of
precipitation reaction compared with the former stage. This is

328

T. Fujita, R. Taguchi, H. Kubo, E. Shibata and T. Nakamura

likely to have contributed to a decrease in the scorodite

solubility, thereby diminishing the solubility product. In
deriving the scorodite solubility product, Langmuir et al.44)
took into account ferric hydroxide, ferric sulfate, and ferric
arsenate complexes. The reaction scheme they proposed
probably played a part in reducing the arsenic solubility.
The results of leach tests in Table 5 to 10 indicate that
the solubility of scorodite depends on pH remarkably. In
addition, some arsenic concentration can be calculated by
utilizing the thermodynamic property in Table 14. In the case
of scorodite, the following four equations can be set and the
K-value is calculated through the
Gf of these chemical
species. The concentration of each arsenic species is
evaluated by ferric concentration, pH and the K-value. The
estimated arsenic concentration is almost consistent with the
result of experiment in acidic condition where the lower the
pH becomes, the higher the concentration of arsenic as well
as iron increases. However, it conicts with the result in
alkaline condition. The calculation suggests that the higher
the pH increases, the lower the concentration of arsenic
decreases. On the other hand, the results of experiments
indicate that the higher pH value makes the concentration of
arsenic increase. It is suspected that another chemical species
of arsenic exists in a NaOH alkaline solution, because
incongruent dissolution occurred in the alkaline solution.
FeAsO4
2H2 O 3H ! Fe3 H3 AsO4
7
8
FeAsO4
2H2 O 2H ! Fe3 H2 AsO4 

3
2
9
FeAsO4
2H2 O H ! Fe HAsO4
10
FeAsO4
2H2 O ! Fe3 AsO4 3
4.2 Solubility of scorodite in various solvents
The above results (Tables 9 and 10) indicate that scorodite
leached at a very low concentration in the pH range of 3 to 6.
The data also show that scorodite leached at an elevated
concentration at a pH below 3, and it leached at a high
concentration when the solvent was made alkaline by adding
NaOH. Considering that under neutral to acidic pH conditions a low concentration of arsenic leached to solvent with
a high NaCl concentration, it may be concluded that alkaline
pH conditions, not Na ions, contributed to the enhanced
arsenic leaching. These results taken from 6-hour leach tests
prove to be a reliable indicator of solubility, though they fall
short of presenting precise scorodite solubility, which would
be derived from long-term tests. The results of this study
seem to emphasize the importance of investigating shortterm scorodite solubility to dierent solvents along with
examining the long-term stability of scorodite.
Low concentrations of scorodite leached to solvents
containing calcium and magnesium ions. This nding is
consistent with the solubility products reported by Nishimura
and Tozawa28) for calcium arsenate and magnesium arsenate.
According to Emett and Khoe and Khoe et al.,41,42) leaching
of arsenic is suppressed in the presence of cadmium and lead
under basic pH conditions. These studies demonstrated low
solubility of arsenic cations under alkaline conditions of
pH 7 to 10. One point worth noting is that the above study by
Nishimura and Tozawa found that no calcium arsenate
leached at pH 8 to 10, resulting in an apparent discrepancy
with the results reported here. The discrepancy is due to the

leach test in this study measuring the leaching of scorodite to

a calcium-containing aqueous solution. It is presumed that
in the test of leaching to the calcium-containing alkaline
solution reported in this article, scorodite leached a low level
of arsenate, which reacted with calcium ions present in
abundance to form calcium arsenate, resulting in a very low
arsenic concentration. Similar reaction schemes probably
dominated in the case with magnesium.
Taking advantage of the low solubility of calcium
arsenate, Jia and Demopoulos50) developed a method for
the enhancing arsenic retention of arsenical ferrihydrite
under neutral to alkaline conditions by the addition of a
small amount of calcium to the starting solution. This method
involves reactions of both ferric arsenate and calcium
arsenate. The method seems to be a promising process for
arsenic retention, since the degree of calcium oversaturation
can be controlled by the seeding of gypsum.51)
It was observed that addition of NaCl to the Ca-containing
alkaline solution promoted leaching of arsenic from scorodite
to a level similar to or higher than that to the NaOHcontaining solution. This observation indicates the eect of
lime on the suppression of arsenic leaching is cancelled by
the presence of NaCl. Calcium chloride, which has a higher
solubility to water than do CaO and NaCl according to the
solubility data compiled by Linke and Seidell,52) is likely to
form a stable complex in water (CaCl2 is retained in the
liquid phase, while CaO and NaCl precipitate when their
solubilities reach saturation points). When NaCl and CaO
are added to solution, NaCl is dissolved to release ions,
and Cl ions present in the solution react with CaO to
form a calcium chloride complex, the dissolution of which
leads to generation of NaOH. The formed NaOH most
likely reacts with scorodite to leach arsenic. The calculated

G for the production of NaOH as shown in the following reaction formula is 264:27 kJ/mol ( 816:05  2 
419:17  2  393:04 604:04), favoring the progress of
the reaction:
2NaCl(aq) CaO(s) ! CaCl2 (aq) 2NaOH(aq)

11

This presumption is consistent with the results of leach

tests in Table 10. It is supposed that the more NaCl was
added in the alkaline slurry prepared with CaO, the more
NaOH was generated in proportion as to the amount of
adjunction. Therefore, the amount of leached arsenic increased by the generated NaOH.
The combination of NaCl and CaO may constitute the
composition of y ash from blast furnaces recently developed
at industrial waste treatment sites. The results of leach testing
in this research demonstrate the absolute necessity for
separating the storage locations for y ashes of blast furnaces
and scorodite precipitates, because these materials provide a
high risk of leaching arsenic when dumped together.
4.3

Possibility of arsenic dissolution from scorodite

through another inuence
In this study, the level of arsenic leaching from scorodite
increased in proportion to the amount of added detergent. The
level was slightly larger than expected from the change in
pH level (an As concentration of 1.23 mg/L at pH 6.56 as
compared with 1.05 mg/L for pH 6.92 buer solution and

Immobilization of Arsenic from Novel Synthesized ScoroditeAnalysis on Solubility and Stability

0.51 mg/L for pH 6.83 calcium-containing solution). Although this discrepancy could not be claried understandably, it is conjectured that the organic content of the detergent
exerted a reductive action on scorodite and thus arsenic it was
leached. The observed phenomenon seems similar to the
reduction of ferric oxyhydroxide aecting the release of the
absorbed load of arsenic in the Bengal Basin, Bangladesh.24)
Release of arsenic from arsenic-bearing iron oxides was
observed under experimentally induced reducing conditions.53) Mobilization of arsenic was also enhanced by an
iron-reducing bacterium.54) Some other microbes are known
to reduce As (V) to As (III),55) and in some cases reduction of
arsenic (V) to arsenic (III) enhanced arsenical mobilization.56) At all events, it is adequate to avoid the suspected
conditions, whatever the mechanisms of arsenic release are.
In developing methods for scorodite synthesis and storage,
the risk of arsenic release should be recognized with
unnecessary care. Scorodite ought to be stored spatially
separated from reductive organic substances. Not only
household cleaner or soap but also coagulants should be
avoided for scorodite synthesis. The scorodite synthesis
process in this study enables the production of large grains of
scorodite with excellent solid-liquid ltration and separation.
The high ltration property is favorable for decreasing the
use of coagulants besides achieving ecient productivity.
The results of the leach tests involving both scorodite and
arsenopyrite failed to demonstrate elevated leaching of
arsenic resulting from the interaction of the two arsenic
minerals, contrary to the prior anticipation. Arsenopyrite is
decomposed by a hydrothermal oxidation reaction to release
iron, sulfate, and arsenate ions.57,58) Walker et al.59) demonstrated the arsenopyrite oxidation reaction is independent of
dissolved oxygen and proposed a new, complex mechanism
in which the rate-limiting step of arsenopyrite oxidation was
reduction of water. It may be speculated that in this study
arsenopyrite decomposed in oxidative aqueous solution to
release arsenic, while scorodite disintegrated owing to the
reductive action of the resulting arsenopyrite derivative,
thereby emitting arsenic.
These experiments found a very low concentration of
leached arsenic, which presumably resulted from arsenopyrite, not scorodite. This study indicates that arsenopyrite is
not involved in the reduction of iron oxides in 6 hours.
The results of the long-term solubility study that examined
the leaching behavior of scorodite under a nitrogen atmosphere in this study indicate that, contrary to the results of
Walker et al., pH, rather than the atmosphere, plays a
dominating role, and reduction of water is not involved in the
leaching of arsenic from scorodite.
When scorodite-containing waste is buried in deep
excavations at a landll site, the level of dissolved oxygen
decrease in the soil environment of the deposited waste. The
reduction of dissolved oxygen is unlikely to enhance leaching
of arsenic from the scorodite landll. Leaching of arsenic
from scorodite may progress by lower redox potentials owing
to an increase in pH and the presence of reductive materials
including organic carbon compounds.
It could not be found that the possibility of dissolution of
arsenic in a reductive condition in this study, but all the
possibilities that scorodite releases arsenic in some reductive

329

conditions are not denied. The leach tests performed in this

study provide only a partial representation of the wideranging natural conditions. For example, domestic household
use of Na2 SO3 as a bleaching agent is very common, and this
compound has a high likelihood of leaching arsenic from
scorodite. Moreover, acid precipitation has recently been
reported in Japan and China,6063) and the acidity is very
likely caused by not only carbon dioxide but also sulfur
dioxide. Emission of sulfur dioxide from industrial plants
must be controlled by reduction programs. It is a pending task
to assess such risks and decide whether scorodite-containing
materials may be stored in open air.
4.4 Risk management for scorodite
Methods for the recovery of heavy metals from soils and
groundwater and the safe storage of scorodite have been
proposed by Wang and Mulligan.27) Storage of arsenic
condensed during metallurgical processes, such as the
synthesis of scorodite, is an eective method. However, to
reduce the risk of environmental pollution, the condensed
arsenic and manufactured scorodite should undergo adequate
treatment that prevents the diusion of arsenic. The scorodite
solids produced in this research have advantages in that the
level of leaching arsenic is low and that they have a high
arsenic content per volume. However, the solids are not
totally free from dissolution of arsenic during storage.
Various scenarios for the risk management of stored
scorodite are illustrated in Fig. 4.
The proposed scenarios are not exhaustive and several
other possible routes of arsenic leaching that include dierent
combinations of elements or compounds may have been
omitted. Given the produced scorodite crystals are not totally
free from leaching of arsenic, appropriate measures should be
taken to minimize the remaining risks. For this purpose, the
series of leach tests reported in this article provide valuable
information. As shown by the results of the leach tests in this
study, arsenic may be leached from scorodite by home-use
detergents, and this underscores the eort of conducting
proper management of scorodite and the necessity of storing
it away from residential areas.
The importance of proper solid waste disposal cannot be
over emphasized. In particular, it should be reinforced that
the need for taking appropriate actions is based on an
assessment of the risk associated with the leaching of arsenic.
Establishment of such measures ought to be based on costeectiveness analysis; otherwise unbalanced concern may
result in increasing the environmental load. The results of this
study pave the way for an assessment of the risk associated
with the leaching of arsenic.
5.

Conclusions

Stable scorodite (FeAsO4
2H2 O) particles were produced

by introducing oxidizing gas into a reaction mixture
containing ferrous sulfate and high-concentration arsenic
(V) to convert ferrous ion to ferric ion. The solubility of
scorodite synthesized in the novel atmospheric process was
investigated. The long term solubility of novel synthesized
scorodite was the same as results of past. In addition, it was
showed that the scorodite solubility was turned greatly by

330

T. Fujita, R. Taguchi, H. Kubo, E. Shibata and T. Nakamura

Fig. 4 Risk management for scorodite dissolution.

outside environmental factors such as pH rather than longterm stability.

The results are summarized as follows:
(1) When Mg(OH)2 or CaO was used, the leaching arsenic
concentration was as low as approximately 3 mg/L
under strongly basic conditions of pH 10 or higher,
whereas arsenic leached at a higher concentration of
10 mg/L in the pH range of 8 to 10.
(2) The arsenic leaching concentration under alkaline
conditions using NaOH was as high as 99.2 mg/L.
(3) When HCl, H2 SO4 , or HNO3 was employed, the arsenic
leaching concentration was less than 1 mg/L at pH 3
and 2 mg/L at pH 2. However, when pH was decreased
from 1 to zero, the concentration of leaching arsenic
increased considerably. The sequence of acids arranged
in decreasing order of leaching arsenic was HNO3 ,
H2 SO4 , and HCl.
(4) For leach tests conducted with the presence of NaCl,
the arsenic leaching concentration was 0.3 mg/L or
less under acidic to neutral pH conditions, though it
exceeded 1000 mg/L under basic conditions.
The results show scorodite released a considerably high
concentration of arsenic under specic leaching conditions.
In particular, the combination of CaO and NaCl present in the
alkaline leaching solution had a signicant eect on the
mobilization of arsenic. Granting that this study fell short of
covering all possible natural environments in which scorodite
would be placed for storage, it seems to be practically
impossible to develop conditions that would completely
prevent the dissolution of arsenic from scorodite.
Acknowledgements
Authors wish to thank Dr. Kazuteru Tozawa, Mr. Taro
Aichi and Mr. Tetsuya Yumoto for helpful discussions and
their advices.
In addition, we greatly acknowledge the Bralorne Gold
Mines Company for providing arsenopyrite sample.

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