Hydrometallurgy 108 (2011) 165170

Contents lists available at ScienceDirect

Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Removal of arsenic from Waelz zinc oxide using a mixed NaOHNa2S leach
Yuhu Li , Zhihong Liu, Qihou Li, Zhongwei Zhao, Zhiyong Liu, Li Zeng
Metallurgical Science and Engineering School, Central South University, Changsha 410083, China

a r t i c l e

i n f o

Article history:
Received 4 January 2011
Received in revised form 2 April 2011
Accepted 5 April 2011
Available online 13 April 2011
Keywords:
Waelz zinc oxide
Arsenic leaching
Sodium hydroxide
Sodium sulde
Calcium arsenate
Zinc sulde

a b s t r a c t
Arsenic was selectively leached from Waelz zinc oxide with a mixed NaOH + Na2S solution followed by
hydrogen peroxide oxidation and lime precipitation. The effects of temperature, L/S ratio, leaching time and
reagent concentration on the leaching of arsenic were investigated. With the mixed solution of 25 g/L NaOH
and 25 g/L Na2S9H2O and L/S ratio of 4:1, more than 90% As was extracted at 30 C in 3 h, while the
concentrations of lead and zinc in the leach solution were below 0.005 and 0.02 g/L, respectively. After
recycling the leach solution and doubling the concentration of arsenic, the leach solution was treated by
hydrogen peroxide oxidation followed by lime precipitation which removed 99.86% As, leaving 2 mg/L As in
the solution. The ltrate was recycled with additional NaOH and Na2S9H2O and the precipitate of calcium
arsenate was solidied with cement and treated in landll.
2011 Elsevier B.V. All rights reserved.

1. Introduction
In many non-ferrous metallurgical processes, arsenic co-exists with
metal values as complex by-products, which should be properly
disposed and comprehensively utilized to obtain the maximum
economic and environmental benets (Montenegro et al., 2010).
Arsenic-containing materials can be treated by pyrometallurgical or
hydrometallurgical processes. The pyrometallurgical-process commonly involves anoxic roasting at 300600 C, in which arsenic is volatilized
as As2O3 in ue dust and then collected (Shibayama et al., 2010).
However, the dust-collection is often unsatisfactory and the volatilized
arsenic may form a source of secondary pollution. In addition, As2O3 is
not suitable for solidication and disposal (Leist et al., 2000; Drahota and
Filippi, 2009). Due to these disadvantages, arsenic removal is now
mainly focused on hydrometallurgical processes, such as solvent
extraction (Demirkiran and Rice, 2002), selective alkali leaching
(Brostow et al., 2010; Tongamp et al., 2009, 2010), pressure leaching
(Xu et al., 2010), mechanical activation leaching and otation (Balaz
et al., 2000; Welham, 2001).
The most widely used method is acid leaching in which both metal
values and arsenic dissolve into solution and arsenic is then separated
and nally solidied as calcium arsenate or ferric arsenate (Ke et al.,
1984; Nunez et al., 1985; Bolin and Sundkvist, 2008). However, the
stability of calcium arsenate and ferric arsenate is a concern and various
methods of increasing the crystallinity and stability of these arsenates

have been investigated, such as the hydrothermal process (Monhemius

and Swash, 1999) and calcination (Riveros et al., 2001).
Waelz zinc oxide is generated by reductive volatilization in the
metallurgical processing of lead and zinc. It often contains lead and
arsenic (typically Zn + Pb N 50%, As:515%) and it is generally returned
to sintering for the recovery of lead and zinc. However, arsenic may
accumulate in the metallurgical system and pose a pollution and
potential safety hazard. Some research on the removal of arsenic from
Waelz zinc oxide has been reported. Tan (1998) employed a process of
caustic soda roasting followed by water leaching to extract N90% As
which was nally precipitated as crude sodium arsenate, while zinc
remained in the leach residue and was re-leached using acid. Zhang
(1997) used an acid leach-oxidation-hydrolysis process in which As(III)
was oxidized to As(V) and then precipitated as iron and manganese
arsenate. Other methods, such as sulfation-roasting-leach (Chen et al.,
2001) and ammonia leaching (Yi, 2001) have been also reported, but
these methods were complex and had low economic benet. Moreover,
arsenic could not be completely solidied, which caused pollution
problems. To solve these problems, a novel process of selective arsenic
leaching with alkaline sodium sulde followed by oxidative precipitation of calcium arsenate was applied in this study, leaving zinc and lead
sulde in the leach residue which could be returned to the pyrometallurgical process to recover zinc and lead.
2. Experimental
2.1. Materials

Corresponding author. Tel.: +86 0731 88830478; fax: +86 0731 88830478.
E-mail addresses: hu115_2hu@hotmail.com, lyh_csu@163.com (Y. Li).
0304-386X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.04.002

The Waelz zinc oxide sample was obtained from the Shaoguan
Smelter, Guangdong Province, China and was used as received. Particle

166

Y. Li et al. / Hydrometallurgy 108 (2011) 165170

Table 1
Chemical components of Waelz zinc oxide sample.
Element

Zn

Pb

As

Ge

Content (%)

51.2

11.8

7.1

0.03

Table 2
Chemical phase analysis of arsenic in Waelz zinc oxide.
Chemical phase

As2O3

As2O5

Arsenite

Arsenate

Content (%)
Proportion (%)

6.44
87.1

0.52
7.1

0.31
4.2

0.12
1.6

analysis found that N90% particles were less than 44 m with a specic
surface area of 2.39 m2/g. The chemical composition of the sample that
is shown in Tables 1 and 2 shows the chemical phases of arsenic in
Waelz zinc oxide determined by selective dissolution procedure (Luo,
1990; Neaman et al., 2004). The XRD of the Waelz zinc oxide sample,
presented in Fig. 1, shows only two main phases of ZnO and As2O3 with
no evidence of lead phases, due to their amorphous states. The SEM
(Fig. 2) indicated that the sample contained a mixture of micron sized
polyhedral crystals and aggregates of spherical nano-particles. The EDS
analysis (Fig. 3) found that the crystalline phase was ZnO and the
aggregates were mainly a mixture of As2O3 and PbO.
Reagents of NaOH and Na2S9H2O were analytical grade and
deionized water was used in all experiments.
2.2. Experimental procedures
In batch tests, 100 g Waelz zinc oxide was mixed with leach reagent
and stirred at 500 rpm at a certain temperature. After leaching and
ltration, the residue was washed by hot water three times and then
dried and recycled to the factory's sintering process to recover zinc and

Fig. 3. EDS analysis results of Waelz zinc oxide sample. A coarse polyhedral particles.
B spherical nano-particles.

lead. The leach solution was mixed with the wash water and oxidized by
hydrogen peroxide and then calcium arsenate was precipitated by the
addition of lime.

2.3. Characterization and analyses

Fig. 1. XRD of Waelz zinc oxide sample.

The phases of Waelz zinc oxide and the leach residue were analyzed
by X-ray diffraction (Siemens D5000, CuKa, = 1.542 10 10 m), and
the content of arsenic in the leach residue was determined by the sodium
hypophosphite reduction-iodometric method. The content of As(III) and
As(V) in the leach solution was determined by the iodometric method
and the content of zinc and lead was determined by EDTA complex
titration or by ICP-MS (IRIS Interpid II XSP, Thermo Electron Corporation)
when present in trace amount. The morphologies of Waelz zinc oxide
were observed using a JSM-6360LV SEM-EDS instrument.

3. Results and discussion

3.1. Thermodynamic calculation of ZnOZnSAs2O3H2O system
Waelz zinc oxide was mainly composed of ZnO and As2O3 (Fig. 1),
however, ZnS may be formed in the alkaline sulde leach system.
The main reactions with the alkaline sulde system are as follows:

Fig. 2. SEM of Waelz zinc oxide sample.

As2 O3 2NaOH 2NaAsO2 H2 O

As2 O3 NaOH NaHAsO2 2

ZnO 2NaOH Na2 ZnO2 H2 O

Y. Li et al. / Hydrometallurgy 108 (2011) 165170

99

As2O3

-4

The leaching of arsenic (%)

ZnO

L1
L2

log C

-8

L3

-12

L4
-16

-20
0

10

12

Leaching with NaOH

Leaching with NaOH and Na 2S

96
93
90
87
84
81

14

pH

10

Fig. 4. Log CpH relationship in ZnOZnSAs2O3H2O system. L1:CAs(CS = 0 mol/L).

L2:CZn(CS = 0 mol/L). L3:CZn(CS = 10 6 mol/L). L4:CZn(CS = 10 1 mol/L).

20

30

40

50

60

70

80

Alkali concentration (g/L)

Fig. 5. Effect of leaching system on the leaching of arsenic. Mixed alkaline leach was
conducted with a mass ratio of Na2S9H2O/NaOH of 3:1 and L/S of 4 at 30 C for 3 h. The
single alkali leach was carried out with only NaOH under the same conditions.

Therefore, the equilibrium concentration diagram of ZnOZnS

As2O3H2O system was determined as shown in Fig. 4 based upon
thermodynamic relationships described in Table 3 which shows all the
possible species (Dean, 2003; Kuchar et al., 2006). The total zinc(II)
and arsenic(III) concentrations at two different concentrations of
sulde ion (Cs) between pH 0 and 14 are described by the curves.
Regions enclosed by curve L1 and L2 are stable regions for As2O3 and ZnO,
respectively in the absence of sulde ion. As seen from Fig. 4, the
following conclusions were made:
(1) It is better to employ an alkaline system in the range pH 811
for the selective leaching of arsenic and the recovery of zinc
oxide than an acid system.
(2) The addition of sulde ion effectively decreases the concentration
of zinc (as well as lead) in the leach solution ensuring a high
recovery of metal values which can be returned to pyrometallurgical operations.
3.2. Effect of leaching system on the leaching of arsenic and the loss of
lead and zinc
Both single and mixed alkaline leaching systems were studied. The
effects of the leaching system on the extraction of arsenic, zinc and
lead are shown in Figs. 5 and 6.
As seen from Fig. 5, the total alkali concentration was the most
important factor. The leaching of arsenic in NaOH alone was a little
higher than that in the mixed NaOHNa2S system when the total
alkali concentration was below 39 g/L, otherwise the leaching of

Table 3
Balance relationships of ions in ZnOZnSAs2O3H2O system.
Balance relationship

log K

Zn2 + + OH = Zn(OH)+
Zn2 + + 2OH = Zn(OH)2(aq)
Zn2 + + 3OH = Zn(OH)
3
Zn2 + + 4OH = Zn(OH)24
AsO+ + OH = HAsO2(aq)
AsO+ + 2OH = H2AsO
3
AsO+ + 3OH = H3AsO24
+

AsO + 4OH = H4AsO35

H2S(aq) = HS + H+
HS = H+ + S2
H2O = H+ + OH
ZnS = Zn2 + + S2

4.40
11.30
14.14
17.66
14.33
18.73
20.60
21.20
6.97
12.90
13.995
23.80

arsenic was a little higher in the alkaline sulde system. However,

with the NaOH system, a large amount of lead and zinc were also
extracted, as shown in Fig. 6, resulting in the precipitation of insoluble
lead arsenite and zinc arsenite. Therefore, complete arsenic extraction
into solution was inhibited at high NaOH concentration (Fig. 5),
whereas in the mixed alkaline sulde system, the dissolved Pb2+ and
Zn2+ preferred to precipitate with S2 rather than AsO
2 which not
only reduced the loss of metal values, but also promoted the leaching
of arsenic, as shown in Fig. 6. Therefore, the mixed alkaline sulde
leaching system is clearly better for the selective removal of arsenic
from Waelz zinc oxide.
3.3. Effect of temperature on the leaching of arsenic
The effect of temperature on the extraction of arsenic, shown in
Fig. 7, indicates that the leaching of arsenic increased only slightly
with the increase of temperature. About 92% As was leached out at
30 C in comparison to 96% As at 90 C. However, the loss of metal
values increased rapidly with the elevation of temperature. At 30 C,
the concentration of lead and zinc in the leach liquor was 0.02 g/L and
0.04 g/L respectively, in comparison to 0.11 g/L and 0.18 g/L at 90 C,
respectively. Therefore, given the considerations on the cost and
energy consumption, 30 C was determined to be the optimum
reaction temperature.

The concentration of Pb and Zn (g/L)

Na2 ZnO2 Na2 S 2H2 O ZnS 4NaOH

1
2
3
4
5
6
7
8
9
10
11
12

167

3.5
[Pb], leaching with NaOH and Na2S
[Zn], leaching with NaOH and Na 2S

3.0

[Pb], leaching with NaOH

[Zn], leaching with NaOH

2.5
2.0
1.5
1.0
0.5
0.0
10

20

30

40

50

60

70

80

Alkali concentration (g/L)

Fig. 6. Lead and zinc concentrations in different leaching systems. (Conditions as Fig.5).

The extration of arsenic

Zn concentration
Pb concentration

96

0.28

0.24

0.20

92
0.16

88

0.12

0.08

84
0.04

80

0.00

30

40

50

60

70

100

96

0.16

94
92

0.12

90
88

0.08

86
0.04

84
82

0.00

80

90

80

0.20
The extraction of arsenic
Zn concentration
Pb concentration

98

The extraction of arsenic (%)

The extraction of arsenic (%)

100

Temperature (C)

Pb and Zn concentration in leach liquor (g/L)

Y. Li et al. / Hydrometallurgy 108 (2011) 165170

Pb and Zn concentration in leach liquor (g/L)

168

L/S ratio

Fig. 7. Effect of temperature on the leaching of arsenic with mixed alkaline solution.
(75 g/L Na2S9H2O and 25 g/L NaOH and L/S of 4 for 3 h).

Fig. 9. Effect of L/S ratio on the leaching of arsenic with mixed alkaline solution. (75 g/L
Na2S9H2O and 25 g/L NaOH at 30 C for 3 h).

3.6. Effect of Na2S9H2O on the leaching of arsenic

3.4. Effects of leaching time on the extraction of arsenic
The effect of time on the leaching of arsenic was carried out with
the same alkaline sulde solution at 30 C and the results in Fig. 8
show 90% As was easily leached out after 1 h and only increased to
94% after 4 h. It can be inferred that arsenic mainly existed as single
phase in the Waelz zinc oxide rather than as an inclusion or
encapsulated. In addition, the concentration of lead and zinc in the
leach liquor decreased slightly before 3 h, which attributed to the
consumption of alkali by the dissolution of arsenic. Therefore, the
optimum leach time was determined to be 3 h.

The effect of varying the amount of Na2S9H2O on the leaching of

arsenic was shown in Fig. 10. With 10 g/L Na2S9H2O, about 96% As
was extracted and little change in arsenic extraction was observed
when the amount of Na2S9H2O was increased from 10 g/L to 55 g/L.
In the leach system, it appears that the minimum concentration of
Na2S9H2O required to precipitate Pb2+ and Zn2+ was about 10 g/L.
Since excess Na2S addition would cause negative effects, such as the
formation of As2S3 (Delni et al., 2003), the optimum concentration of
Na2S was chosen as 25 g/L.
3.7. Optimum operating conditions

The extraction of arsenic (%)

The extraction of arsenic

Zn concentration
Pb concentration

96

0.16

92

0.12

88

0.08

84

0.04

0.00

80
1

Time (h)
Fig. 8. Effect of leaching time on the leaching of arsenic with mixed alkaline solution.
(75 g/L Na2S9H2O and 25 g/L NaOH and L/S of 4 at 30 C).

100

0.5

96

0.4

The extraction of arsenic

Zn concentration
Pb concentration

92

0.3

88

0.2

84

0.1

80

0.0
0

10

20

30

40

50

60

Pb and Zn concentration in leach liquor (g/L)

0.20

100

Pb and Zn concentration in leach liquor (g/L)

The effect of L/S ratio on the leaching of arsenic is presented in

Fig. 9 and shows that arsenic extraction increased from 84% to 95%
with the increase of L/S ratio from 2 to 8. Clearly, when the L/S ratio
was below 4, the leaching of arsenic was not complete with the low
amount of total alkali. Although the lead and zinc concentration was
almost constant, the increase volume of leach liquor meant the
increase loss of metal values. Therefore the optimum L/S ratio of 4 was
determined.

Based on the above results, the optimal leaching conditions were

determined to be a mixed alkaline sulde solution of 25 g/L NaOH and
25 g/L Na2S9H2O with L/S ratio of 4 at 30 C for 3 h. Under these
conditions 9296% As was selectively extracted to give a leach
solution containing 5.45 g/L As, b0.005 g/L Zn and 0.02 g/L Pb. The
XRD of the leach residue showed only the diffraction lines of ZnO with
no lines associated with As2O3, ZnS or PbS. The chemical analysis
found that the leach residue contained 0.47% As, 54.7% Zn and 12.6%
Pb as mainly oxide phases with only 0.65% ZnS and 1.92% PbS as
amorphous phases.

The extraction of arsenic (%)

3.5. Effect of L/S ratio on the leaching of arsenic

Na2S concentration (g/L)

Fig. 10. Effect of Na2S9H2O amount on the leaching of arsenic with 25 g/L NaOH
solution. (L/S of 4 at 30 C for 3 h).

Y. Li et al. / Hydrometallurgy 108 (2011) 165170

Table 4
Effect of lime/As mole ratio and temperature on the removal of arsenic from solution as
calcium arsenate.
Factors

Removal of arsenic (%)

Lime/As mole ratio (at 80 C for 2 h)

Temperature (lime/As mole ratio of 3 for 2 h)

1.7
2.4
3
4
20 C
40 C
70 C
90 C

72.3
88.4
99.5
99.6
56.1
65.6
85.3
99.8

When the same leach solution was recycled to treat a second batch
of Waelz zinc oxide, very similar extraction results were obtained and
the concentration of arsenic in solution increased from 5.45 g/L to
10.37 g/L As while the concentration of zinc and lead remained low
(0.005 and 0.03 g/L, respectively). Therefore, recycling of the leach
liquor was feasible, with reagent make-up as required and a bleed
circuit to precipitate arsenic from the more concentrated arsenic
solution.
4. Arsenic precipitation
Hydrogen peroxide oxidationlime precipitation is a classic
technique for the removal of arsenic and has been widely used in
practical applications (Moon et al., 2004; Camacho et al., 2009). The
toxicity and mobility of As(III) is much higher than that of As(V) and
the solubility of As(III) salts is also higher than that of the
corresponding As(V) insoluble salts (Driehaus, 1995; Suzuki et al.,
1997; Deschamps, 2003), Therefore, it is essential to convert As(III) to
As(V). Many oxidants for As(III) have been investigated, including

Waelz zinc oxide

51.2% Zn
11.8% Pb
7.1% As

NaOH
25 g/L

169

chlorine (Sorlini and Gialdini, 2010), ozone (Kim and Nriagu, 2000),
manganese oxides (Tournassat et al., 2002), TiO2/UV (Lee and Choi,
2002) and hydrogen peroxide (Pettine et al., 1999). These oxidants are
powerful for the transformation of As(III) to As(V), but the treatment
costs were high. Undoubtedly, catalytic air oxidation is the most
promising cost effective method (Zhang et al., 2000), but it is not
suitable for concentrated arsenic solutions.
In this study, hydrogen peroxide was chosen to oxidize As(III) to
As(V) in view of its advantages of a clean and simple reagent with no
impurity introduced. At room temperature, As(III) can be completely
oxidized to As(V) using 1.2 times the stoichiometric amount of
hydrogen peroxide in 0.5 h.

4.1. The effect of lime/As mole ratio and temperature on arsenic

precipitation
The effect of lime/As mole ratio on the removal of arsenic was
carried out at 80 C for 2 h. The results in Table 4 show that although
the theoretical lime/As mole ratio for the precipitation of Ca5
(AsO4)3OH is 1.67, it is necessary to use an excess amount of lime
up to a mole ratio of 3 to remove 99.5% As.
Elevating the temperature from 40 to 90 C not only increased the
removal of As (Table 4), but also improved the crystallinity of the
calcium arsenate precipitate. The removal of arsenic was 65.6% at 40 C,
with no XRD diffraction lines for arsenic species, and increased to 99.9%
at 90 C with XRD diffraction lines of crystallite Ca5(AsO4)3OH clearly
evident (Fig. 11). The nal solution contained only 2 mg/L As together
with 18 g/L NaOH which can be recycled and returned to the leaching
process with extra addition of NaOH and Na2S.
Based on the investigation above, the conceptual ow sheet of
removing arsenic from arsenical Waelz zinc oxide is proposed in
Fig. 11.

Na 2S9H2O
25 g/L

Selective leaching
30C
3h

First leaching
As3+:5.45
Zn2+:0.02g/L
Pb2+: 0.005g/L

First leaching:94.1% As
H2O2

Second leaching:91.3% As

Second leaching
As3+:10.37
Zn2+:0.03 g/L
Pb2+: 0.005g/L

Ca(OH)2

lime/As=3:1
90 C
2h

Return to pyrometallurgical processing

Removal of As: 99.5%

Tailings
Fig. 11. The proposed process scheme.

Final solution
As5+:2.09 mg/L
NaOH:18 g/L

170

Y. Li et al. / Hydrometallurgy 108 (2011) 165170

5. Conclusions
A novel process of treating Waelz zinc oxide containing a
high content of arsenic(III) oxide is proposed, involving a selective
arsenic(III) leach with mixed alkaline sulde, hydrogen peroxide
oxidation of As(III) to As(V) and lime precipitation of calcium
arsenate. Sulde ion passivates the zinc oxide surface and precipitates
any soluble Zn(II) and Pb(II) as ZnS and PbS.
(1) N90% As was selectively leached from Waelz zinc oxide with
25 g/L NaOH and 25 g/L Na2S9H2O at 30 C for 3 h using a liquid/
solid ratio of 4, to give a solution containing 5.45 g/L As(III)
together with b0.005 g/L Pb and 0.02 g/L Zn. The leach residue
was mainly zinc and lead oxide together with 0.6% ZnS and 1.9%
PbS.
(2) The recycled leach solution gave similar leach results and
doubled the concentration of arsenic.
(3) The second round leach solution was oxidized by 1.2 times
stoichiometric hydrogen peroxide at room temperature.
(4) 3 moles lime/mole As were required to precipitate 99.9% As at
90 C as Ca5(AsO4)3OH leaving only 2 mg/L As in the nal
solution. The nal solution can be returned to the leaching step
with extra addition of alkali and sulde, and the calcium arsenate
can be treated in landll after solidication with cement.
This preliminary investigation offers a low cost process with low
loss of metal values and no secondary contamination. Therefore it
warrants further larger scale work to make it practical and viable for
the industry.
Acknowledgments
This work was nancially supported by the National Science
Foundation of China, namedThe Applied Basic Research on
The Treatment of High Arsenic Bearing Materials in Nonferrous
Metallurgy(50874121).
References
Balaz, P., Achimovicova, M., Bastl, Z., Ohtani, T., Sanchez, M., 2000. Inuence of
mechanical activation on the alkaline leaching of enargite concentrate. Hydrometallurgy 54, 205216.
Bolin, N.J., Sundkvist, J.E., 2008. Two-stage precipitation process of iron and arsenic
from acid leaching solutions. Transactions of Nonferrous Metals Society of China 18,
15131517.
Brostow, W., Gahutishvili, M., Gigauri, R., Lobland, H.E.H., Japaridze, S., Lekishvili, N.,
2010. Separation of natural trivalent oxides of arsenic and antimony. Chemical
Engineering Journal 159, 2426.
Camacho, J., Wee, H.Y., Kramer, T.A., Autenrieth, R., 2009. Arsenic stabilization on water
treatment residuals by calcium addition. Journal of Hazardous Materials 165, 599603.
Chen, S.M., Cheng, D.K., Li, Y.H., 2001. Study of comprehensive recovery of high-contents As
Waelz zinc oxide. Non-Ferrous Mining and Metallurgy 5, 2932 (in Chinese).
Dean, J.A., 2003. Lange's Handbook of Chemistry. Science Press, Beijing.
Delni, M., Ferrini, M., Manni, A., Massacci, P., Piga, L., 2003. Arsenic leaching by Na2S to
decontaminate tailings coming from colemanite processing. Minerals Engineering
16, 4550.
Demirkiran, A., Rice, N.M., 2002. The extraction of arsenic(V) from copper renery
electrolytes with tri-n-butyl phosphate (TBP):II owsheet development. In: Sole,
K.C., Cole, P.M., Preston, J.S., Robinson, D.J. (Eds.), Proc. Intl. Solvent Extraction Conf.,
ISEC2002, Cape Town. C. van Rensburg Publications, Johannesburg, South Africa,
pp. 890895.

Deschamps, E., 2003. Arsenic sorption onto soils enriched in Mn and Fe minerals. Clays
and Clay Minerals 51, 197204.
Drahota, P., Filippi, M., 2009. Secondary arsenic minerals in the environment: a review.
Environment International 35, 12431255.
Driehaus, W., 1995. Oxidation of arsenate(III) with manganese oxides in water
treatment. Water Research 29, 297305.
Ke, J.J., Qiu, R.Y., Chen, C.Y., 1984. Recovery of metal values from copper smelter ue
dust. Hydrometallurgy 12, 217224.
Kim, M.J., Nriagu, J., 2000. Oxidation of arsenite in groundwater using ozone and
oxygen. The Science of the Total Environment 247 (1), 7179.
Kuchar, D., Fukuta, T., Onyango, M.S., Matsuda, H., 2006. Suldation of zinc plating
sludge with Na2S for zinc resource recovery. Journal of Hazardous Materials 137,
185191.
Lee, H., Choi, W., 2002. Photocatalytic oxidation of arsenite in TiO2 suspension: kinetics
and mechanisms. Environmental Science & Technology 36 (17), 38723878.
Leist, M., Casey, R.J., Caridi, D., 2000. The management of arsenic wastes: problems and
prospects. Journal of Hazardous Materials 76, 125138.
Luo, S.H., 1990. Phase analysis of arsenic in smelting dust. Jiangxi Metallurgy 10 (2),
5758 (in Chinese).
Monhemius, A.J., Swash, P.M., 1999. Removing and stabilizing As from copper rening
circuits by hydrothermal processing. Journal of the Minerals Metals & Materials
Society 51 (9), 3033.
Montenegro, V., Sano, H., Fujisawa, T., 2010. Recirculation of high arsenic content
copper smelting dust to smelting and converting processes. Minerals Engineering.
doi:10.1016/j.mineng.2010.03.020.
Moon, D.H., Dermatas, D., Menounou, N., 2004. Arsenic immobilization by calcium
arsenic precipitates in lime treated soils. The Science of the Total Environment 330,
171185.
Neaman, A., Moul, F., Trolard, F., Bourri, G., 2004. Improved methods for selective
dissolution of Mn oxides: applications for studying trace element associations.
Applied Geochemistry 19, 973979.
Nunez, C., Espiell, F., Roca, A., 1985. Recovery of copper, silver and zinc from Huelva
(Spain) copper smelter ue dust by a chloride leach process. Hydrometallurgy 14,
93103.
Pettine, M., Campanella, L., Millero, F., 1999. Arsenite oxidation by H2O2 in aqueous
solutions. Geochimica et Cosmochimica Acta 63 (18), 27272735.
Riveros, P.A., Dutrizac, J.E., Spencer, P., 2001. Arsenic disposal practices in the
metallurgical industry. Canadian Metallurgical Quarterly 40 (4), 395420.
Shibayama, A., Takasaki, Y., William, T., Yamatodani, A., Higuchi, Y., Sunagawa, S., Ono,
E., 2010. Treatment of smelting residue for arsenic removal and recovery of copper
using pyro-hydrometallurgical process. Journal of Hazardous Materials.
doi:10.1016/j.jhazmat.2010.05116.
Sorlini, S., Gialdini, F., 2010. Conventional oxidation treatments for the removal of
arsenic with chlorine dioxide, hypochlorite, potassium permanganate and monochloramine. Water Research 44 (19), 56535659.
Suzuki, T.M., Bomani, J.O., Matsunaga, H., 1997. Removal of As(III) and As(V) by a
porous spherical resin loaded with monoclinic hydrous zirconium oxide. Chemistry
Letters 11, 11191120.
Tan, X.T., 1998. Recycling and reclamation research of acid leaching residue from Waelz
zinc oxide. Nonferrous Metals (Extractive Metallurgy) 5, 1821 (in Chinese).
Tongamp, W., Takasaki, Y., Shibayama, A., 2009. Arsenic removal from copper ores
and concentrates through alkaline leaching in NaHS media. Hydrometallurgy 98,
213218.
Tongamp, W., Takasaki, Y., Shibayama, A., 2010. Selective leaching of arsenic from
enargite in NaHSNaOH media. Hydrometallurgy 101, 6468.
Tournassat, C., Charlet, L., Bosbach, D., Manceau, A., 2002. Arsenic(III) oxidation by
birnessite and precipitation of manganese(II) arsenate. Environmental Science &
Technology 36 (3), 493500.
Welham, N.J., 2001. Mechanochemical processing of enargite (Cu3AsS4). Hydrometallurgy 62, 165173.
Xu, Z.F., Li, Q., Nie, H.P., 2010. Pressure leaching technique of smelter dust with highcopper and high-arsenic. Transactions of Nonferrous Metals Society of China 20,
176181.
Yi, Q.S., 2001. Preparation of activated zinc oxide from arsenic-containing crude zinc
oxide. Environmental Protection of Chemical Industry 21, 217220 (in Chinese).
Zhang, C.M., 1997. Research and application of the process for removing As from Waelz
zinc oxide by oxidationhydrolysis. Nonferrous Metals (Extractive Metallurgy) 2,
911 (in Chinese).
Zhang, W., Singh, P., Muir, D.M., 2000. Kinetics of oxidation of As(III) with SO2/O2 and
UV light. In: Young, C.Y. (Ed.), Minor Metals 2000, Processing and Environmental
Aspects of As, Sb, Se, Te, Bi. SME, Warrendale, pp. 333344.