Int. J. Miner. Process.

93 (2009) 8994

Contents lists available at ScienceDirect

Int. J. Miner. Process.

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 / i j m i n p r o

Rejection of arsenic minerals in sulde otation A literature review

X. Ma , W.J. Bruckard
CSIRO Minerals, Box 312, Clayton, Victoria, Australia

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

Article history: Arsenic is one of the most dangerous inorganic pollutants and thus a penalty element in many base metal
Received 19 February 2009 concentrates. Arsenic removal in sulphide otation has been studied extensively with various approaches,
Received in revised form 30 June 2009 including pre-oxidation of otation pulp, Eh control during otation and the use of selective depressants/
Accepted 11 July 2009
collectors. Pre-oxidation of otation pulp using oxidizing agents or aeration conditioning represents a simple
Available online 18 July 2009
approach in arsenic removal and was found effective in many cases. Selective otation of arsenic minerals
Keywords:
through Eh control has made signicant advances in recent years with promising results achieved. In
Arsenic removal addition, various depressants and collectors have also been studied in arsenic removal. In this
Pre-oxidation communication, the various approaches used in selective otation of arsenic minerals are reviewed with
Eh control emphasis on the development in recent years.
Flotation Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2. Flotation behavior of arsenic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.1. Oxidization of arsenic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
2.2. Collector-less otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
2.3. Xanthate induced otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3. Selective otation of arsenic minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.1. Pre-oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2. Eh control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3. Selective otation reagents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

1. Introduction this paper presents a review of the developments in rejection of

Arsenic is one of the most dangerous inorganic pollutants, causing
environmental and health emergencies in several areas of the world
(Lattanzi et al., 2008). It is a penalty element in many base metal
concentrates that are destined for smelting to produce the relevant
metallic products. It is of economic and environmental interest to
remove arsenic minerals at an early stage of processing such as
otation. Unfortunately, arsenic minerals generally have similar
otation behavior to the valuable minerals with which they are
associated. Extensive research has been performed in this area and
Corresponding author. Tel.: +61 3 95458731; fax: +61 3 95628919.
E-mail address: mark.ma@csiro.au (X. Ma).
arsenic minerals in sulde otation.
2. Flotation behavior of arsenic minerals
2.1. Oxidization of arsenic minerals
Oxidization of arsenic minerals is of critical importance in
understanding their otation behavior. In aqueous solutions, enargite
(Cu3AsS4) is easily oxidized at low pH, during which elemental
sulphur is commonly formed. Similar to enargite, sulfur was also
found on arsenopyrite (FeAsS) surfaces after oxidation in acidic
solutions (Buckley and Walker, 1988; Filippi, 2004). At pH 11, XPS
spectra of enargite surfaces indicates the presence of cupric oxide and
arsenic oxide (Lattanzi et al., 2008). Studies using SEM and EDX also

0301-7516/$ see front matter. Crown Copyright 2009 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2009.07.003
90 X. Ma, W.J. Bruckard / Int. J. Miner. Process. 93 (2009) 8994
conrmed the formation of a layer of oxidized material on enargite
surfaces in alkaline solutions (Velsquez et al., 2000). The oxidation
behavior of tennantite (Cu12As4S13) was reported to be similar to that
of enargite (Asbjornsson et al., 2004; Lin, 2006; Fullston et al., 1999b).
The oxidation rate of arsenic minerals and non-arsenic minerals
has been compared in a series of papers to explain the selective
otation of arsenic minerals from other sulde minerals. According to
Iwasaki et al. (1988), nickel arsenide (Ni11As8) is much more easily
oxidized than pyrrhotite, pentlandite, chalcopyrite and cubanite.
Using the electrochemical corrosion current method, Feng et al.
(1993) measured the natural oxidation rate of arsenopyrite and pyrite
and found that the natural oxidation rate of arsenopyrite is faster than
that of pyrite in sodium carbonate solutions, which was conrmed by
Monte et al. (2002). However, disagreements on the oxidation rate
of some minerals also exist in literature. For example, Fullston et al.
(1999a,b,c) and Fornasiero et al. (2001) reported that the oxidation rate
of minerals at pH 11.0 follows the order: chalcocite N tennantite N
enargite N covellite N chalcopyrite. In contrast, Guo and Yen (2005)
compared the oxidation of chalcopyrite and enargite at pH 10 and found
that chalcopyrite is more readily oxidized than enargite.
2.2. Collector-less otation
According to Kantar (2002), enargite displays natural oatability
under oxidizing conditions, and nonoatability under reducing
conditions. In acidic solutions of pH b 5.5, the hydrophobicity of
enargite increased with increasing solution potential due to the
formation of elemental sulfur on the mineral surface. However, in
alkaline solutions, the hydrophobicity decreased with increasing
solution potential due to the formation of CuO. Such observations
are in line with the ndings of Arribas (1995) and Lattanzi et al.
(2008). However, it is noteworthy to point out that Castro and
Honores (2000) reported poor otability of enargite in a wide pH
range and thus concluded the nonexistence of natural oatability of
enargite.
2.3. Xanthate induced otation
Arsenic minerals are readily oatable using xanthates as collectors.
Different adsorption mechanisms of xanthates on arsenic minerals
have been proposed. For realgar (AsS), orpiment (As2S3), and
arsenopyrite, it is generally agreed that, using ethyl xanthate as a
collector, diethyl dixanthogen and arsenic(III) ethyl xanthate are
formed as major products on these mineral surfaces, since arsenic in
realgar and arsenopyrite is probably oxidized to the +3 state (Persson,
1994; Valli et al., 1994; Kydros and Matis, 1995; Lpez Valdivieso et al.,
2003; Lpez Valdivieso et al., 2006). Yekeler and Yekeler (2005)
computed that the interaction energy for the formation of (C2H5SCS2)2
to be higher than that of (C2H5OCS2)2 and hence (C2H5SCS2)2 is favored
in these formations.
For enargite, however, a totally different adsorption mechanism for
xanthates was proposed. Kantar (2002) summarized the studies by
Pauporte and Schuhmann (1996), Allison et al. (1972) and Leja et al.
(1963) and suggested that, since the adsorption of xanthate (X) on
copper oxide surfaces results in the formation of the chemisorbed
cuprous xanthate (CuX), for enargite, the reaction mechanism
responsible for the formation of CuX can be represented as follows:
2 2
Cu3 AsS4 3X 20H2 O 3CuX HAsO4 4SO4 39H 32e
E 0:375V:
The formation of a monovalent copper xanthate and dixanthogen
on the mineral surface was conrmed by Pauporte and Schuhmann
(1996) using voltammetric investigation of the enargiteethylxanthate
system.
In addition to the adsorption of collectors, other factors such as
grinding medium and metal cations in otation pulp also signicantly
affect the otation behavior of arsenic minerals. Huang et al. (2006)
studied the effect of grinding conditions on arsenopyrite surface
properties using X-ray Photoelectron Spectroscopy (XPS) and found
that the more electrochemically active the grinding media, the higher
amounts of hydrophilic oxidized iron and oxygen species at the
surface, which impaired the oatability of arsenopyrite particles.
Copper activation was found effective on cobalt arsenide, arseno-
pyrite (Formanek and Lauvernier, 1963; Abeidu and Almahdy, 1980; Li
and Zhang, 1989; Monte et al., 2002) and nickel arsenide (Nakazawa
and Iwasaki, 1986; Iwasaki et al., 1988). Nakazawa and Iwasaki (1986)
and Iwasaki et al. (1988) reported that nickel arsenide is extremely
susceptible to oxidation leading to markedly decreased oatability.
Using inert atmosphere during grinding and otation and copper
sulfate activation, the otation of nickel arsenide was improved
signicantly.
Surprisingly, copper depression was also reported for the otation
of arsenic minerals. Shackleton et al. (2007) observed a slight decrease
in otation recovery of sperrylite (PtAs2) and palladoarsenide (Pd2As)
in the presence of copper sulfate. The decreased otation recovery was
attributed to the preferential occupation of specic sites by Cu(OH)2
species which inhibits the adsorption of xanthates.
3. Selective otation of arsenic minerals
3.1. Pre-oxidation
The oxidation of minerals plays an important role in sulde
otation and the hydrophilic behavior of most sulde minerals is
attributed to the presence of an oxide or hydroxide layer, which
prevents the adsorption of xanthates on sulde surfaces. Pre-
oxidation of otation pulp has been used in a number of studies to
achieve selective otation of arsenic minerals.
In the literature, enargite and tennantite are often oated while
non-arsenic minerals are selectively oxidized. According to Menacho
et al. (1993), after a pre-oxidation procedure using sodium hypo-
chlorite at pH 11.5, only slight depression of enargite was observed.
The resistance to oxidation demonstrated by enargite has been used to
separate it from other minerals in otation. Huch (1994) developed a
process to separate enargite from chalcocite using hydrogen peroxide
as an oxidizing agent. In this process, chalcocite was oxidized and
depressed, while enargite was recovered as the froth product. Along
the same line, Fornasiero et al. (2001) successfully separated copper
sulde minerals of chalcocite, covellite and chalcopyrite from enargite
and tennantite through selective pre-oxidation of the mineral surfaces
with hydrogen peroxide in slightly acidic pH conditions (pH 5.0), or
after oxidation and selective dissolution of the surface oxidation
products with a complexant (EDTA) in basic pH conditions. The
otation tests were conducted on articial mineral mixtures in a
modied Partridge and Smith column (Partridge and Smith, 1971)
using diethyl dithiophosphate (DEDTP) as a collector.
As mentioned above, in the case of enargite and tennantite
removal, pre-oxidation was used to selectively oxidize non-arsenic
minerals, while enargite and tennantite were oated due to their
strong resistance to oxidation. In the case of gersdorfte (NiAsS),
however, pre-oxidation with hydrogen peroxide was reported to
enhance the depression of gersdorfte in the otation of Garson NiCu
ore using magnesia mixture or TSS (the combination of triethylenete-
tramine and sodium sulte) as depressants (Dai et al., 2005). It is
noteworthy to point out that the effect of pre-oxidation on gersdorfte
depression was not dramatic. By visual observation of the reported
gures, pre-oxidation with 800 g/t hydrogen peroxide only decreased
the recovery of gersdorfte by 5 8%.
In addition to the use of chemicals, aeration conditioning was also
found effective in pre-oxidation. Using relatively pure arsenopyrite,
 X. Ma, W.J. Bruckard / Int. J. Miner. Process. 93 (2009) 8994
Poling and Beattie (1984) and Beattie and Poling (1988) demonstrated
the necessity of pre-aeration in the depression of arsenopyrite at high
pH. Wang and Heiskanen (1990) studied a high As-containing nickel
concentrate from Partek, Finland, and found that aeration condition-
ing before batch otation greatly improved the oatability of
pentlandite and pyrrhotite while the increase in the oatability of
nickel arsenide was much lower and thus a high selectivity between
pentlandite and nickel arsenides was obtained. It was proposed that
aeration conditioning supplied sufcient oxygen for the otation of
pentlandite and pyrrhotite, but oxidized the surfaces of nickel
arsenides and hence improved the selectivity of the separation.
3.2. Eh control
The otation of enargite is strongly Eh dependent (Jaime and
Cifuentes, 1995; Kantar, 2002). According to Kantar (2002), in the
presence of ethyl xanthate at pH 10.5, enargite recovery reaches a
maximum value of nearly 100% at potentials between 0.15 and 0.27 V
SHE, and decreases sharply towards lower or higher potentials. Such
results are similar to the phenomena observed by Heyes and Trahar
(1979) for the otation of chalcocite with ethyl xanthate at pH 11.
Kantar (2002) offered a detailed explanation for the upper otation
edge. Firstly, for a xanthate concentration of 5 10 3 M at pH 10.5, the
potential where the oxidation of CuX to CuO occurs is 0.400 V SHE,
which is in good agreement with the upper otation edge. Secondly,
according to Woods and Richardson (1986), the formation of
signicant quantities of CuO on the mineral surface could inhibit the
otation process at high potentials. Thirdly, as pointed out by Toperi
and Tolun (1969), considerable amounts of oxidation products (e.g.
CuO) accumulated at the surface could not be continuously depleted
rapidly by the action of xanthate ions and thus the dixanthogen
produced at high potentials could not adhere to the oxidation products.
Interestingly, the strong depression of enargite at Eh higher than
+0.27 V SHE at pH 10.5 was not observed by Guo and Yen (2005) at
pH 10, either in collectorless otation or otation induced by
potassium amyl xanthate. Senior et al. (2006) also reported strong
otation of enargite in the pulp of high potentials at pH 11 using 20 g/t
potassium ethyl xanthate (KEX) as a collector. Senior et al. (2006) also
reported otation recovery of enargite at pH 8 at various pulp
potentials, which was found to be very close to the results obtained at
pH 11. It is noteworthy to point out that the otation tests conducted
by Kantar (2002) and Guo and Yen (2005) were microotation tests in
a modied PatridgeSmith type otation cell and a modied
Hallimond tube, respectively, using 1 g sample, while Senior et al.
(2006) performed the otation tests in a 3 L modied stainless steel
Denver cell with automatic control of pulp level and the impeller was
driven from below, allowing the whole surface of the froth to be
scraped at a constant depth (Guy, 1992).
The strong Eh dependence of arsenic mineral otation has been
widely utilized to selectively remove arsenic minerals in sulde
otation. Enargitechalcopyrite separation through Eh control has
been intensively studied since enargite associated with chalcopyrite
reports to copper concentrate in conventional otation due to their
similar otation properties. Unfortunately, there is still signicant
disagreement on the effect of Eh on the otation of chalcopyrite.
According to Heyes and Trahar (1977), chalcopyrite oats well from a
pulp potential of +0.111 V SCE to +0.293 V SCE. Gardner and Woods
(1979) found that the oatability of chalcopyrite increased gradually
from 0.214 V SCE with a recovery of about 10% to +0.56 V SCE with
a recovery of about 70%. Recently, Senior et al. (2006) reported strong
otation of chalcopyrite at Eh range from 0.045 to + 0.105 V SCE at
pH 8. Guo and Yen (2003) reported that, at pH 10, chalcopyrite oated
in the potential range of 0.2 to + 0.205 V SCE in 7 10 4 M
potassium amyl xanthate solution.
Despite the disagreements on the effect of Eh on the otation
behavior of enargite and chalcopyrite in the literature, successful
91
enargitechalcopyrite separation has been achieved through Eh
control. Guo and Yen (2005) compared the oatability of chalcopyrite
and enargite at various Eh and successfully conducted selective
otation tests on articial mineral mixtures at Eh higher than
+0.2 V SCE and lower than + 0.55 V SCE, where enargite could be
oated well while chalcopyrite was completely depressed.
In a single mineral study, Senior et al. (2006) studied the otation
behavior of a variety of minerals at various Eh, pH and concluded that
chalcocite and cuprite could be oated from enargite at pH 11,
125 mV SHE; enargite could be oated from chalcopyrite at pH 8 or
pH 11, 0 mV SHE; enargite could be oated from chalcocite and cuprite
at pH 11, +290 mV SHE. The possible interactions between the
minerals which could affect the otation results of mixed minerals
were not considered in this single mineral study.
In addition to enargite, the removal of other arsenic minerals has
also been studied. Tuteja et al. (1992) investigated the role of Eh in
arsenopyritepyrite separation using a otation concentrate from
Western Australia and found that, adjusting Eh with NaOCl, the
recovery of arsenopyrite did not change signicantly with Eh, but the
recovery of pyrite decreased with increasing Eh. The best performance
of arsenopyritepyrite separation was achieved at pH 10.7 and low Eh
(b150 mV SCE) adjusted with NaOCl. Byrne et al. (1995) studied the
effect of Eh controlled by the addition of hydrogen peroxide on the
separation of tetrahedrite from chalcopyrite using a sample collected
from the Iberian Pyrite Belt, Portugal. They found that hydrogen
peroxide depressed tetrahedrite while chalcopyrite maintained its
oatability. However, this reagent had the effect of enhancing pyrite
oatability. The increased pyrite otation at high Eh was attributed to
the increased stability of the dimer of xanthate and dithiophosphate at
high Eh. Smith and Bruckard (2007) successfully removed tennantite
from chalcopyrite and bornite using controlled-potential otation.
The separation was made on a bulk copperarsenic concentrate after
reducing the pulp potential to about 150 mV SHE at pH 12 and
oating the tennantite from the other copper minerals. The otation
behavior of arsenic metal was studied by Bruckard et al. (2007). It was
found that metallic arsenic has no natural oatability but it oats
readily (up to 95% recovery in 8 min) over a wide range of pH and Eh
using KEX (Fig. 1).
Eh control in combination with pre-oxidation was also reported for
the removal of arsenic minerals. Feng et al. (1993) found that pre-
oxidation at 300 mV SHE in 2.26 10 2 mol/L sodium carbonate
solution for 6 minutes strongly depressed the otation of arsenopyrite
but only slightly reduced the recovery of pyrite, which was successfully
Fig. 1. Cumulative arsenic metal recovery after 1 min and 8 min otation with 40 g/t KEX
as a function of pulp potential at pH 6 (Bruckard et al., 2007).
92 X. Ma, W.J. Bruckard / Int. J. Miner. Process. 93 (2009) 8994
applied in pilot scale tests to remove arsenopyrite from pyrite. In a
single mineral study, Castro et al. (2003b) found that, after pre-
oxidation with hydrogen peroxide at pH 9.8, the otation of chalcocite
and pyrite was strongly depressed in the Eh range 340420 mV SHE.
Chalcopyrite also demonstrated medium depression while enargite
was only slightly depressed. When Eh was reduced to 280 mV SHE,
however, the depression of all the minerals disappeared. This is in good
agreement with the observation of Castro and Honores (2000) and
Castro and Baltierra (2001) who reported that the oatability of
enargite was only slightly altered after pretreated with hydrogen
peroxide in acidic and alkaline slurries.
3.3. Selective otation reagents
Herkenhoff (1944) patented a method to oat pyrite from
arsenopyrite using 0.125 kg/t alkali permanganate as a depressant
for arsenopyrite, demonstrating the possibility of selective otation of
arsenic minerals using a selective reagent. Draskic et al. (1982), Azim-
zade and Chernykh (1997) and Tapley and Yan (2003) also success-
fully used permanganate as a selective depressant in pyrite
arsenopyrite separation using real-life ore samples.
Abeidu and Almahdy (1980) found that magnesia mixture forms a
strongly hydrophilic layer of AsO4NH4Mg 6H2O on arsenopyrite
surfaces which inhibits the adsorption of xanthates on arsenopyrite.
Abeidu and Almahdy (1980) used this property of magnesia mixture
to selectively depress arsenopyrite while oating pyrite in the pH
range 89 using articial mineral mixtures. Matis et al. (1992) used
magnesia mixture as a selective depressant to separate arsenopyrite
from a bulk auriferous pyrite concentrate from the Olympias plant in
Chalkidiki (Greece). Yen and Tajadod (2000) used magnesia mixture
as a depressant in the selective otation of chalcopyrite (CuFeS2) from
enargite (Cu3AsS4). It was reported that the adsorption density of
potassium amyl xanthate on both synthetic and natural enargite
decreases with increasing magnesia mixture concentration while the
collector adsorption density on chalcopyrite was not affected,
allowing a selective separation of the two minerals from articial
mineral mixtures. Castro et al. (2003a) studied the depression effect of
magnesia mixture on a pure enargite sample and reported some
results opposite to the ndings of Yen and Tajadod (2000). No
depression was observed in the pH range 79 using 011 kg/t
magnesia mixture. At pH 10, weak depression of enargite was
observed using 24 kg/t magnesia mixture. However, when the
dosage increased to 7 kg/t, the depression disappeared completely.
According to Dai et al. (2005), magnesia mixture does not depress
gersdorfte (NiAsS) in the Garson NiCu ore without pre-aeration.
Yen and Tajadod (2000) pre-aerated the otation pulp which was not
practiced by Castro et al. (2003a).
Some conventional depressants in sulde otation have also been
reported as effective depressants in arsenic rejection. For example,
Beattie and Duteroue (1992) patented a otation method to separate
arsenopyrite from pyrite using HSO 3 as a selective depressant of
arsenopyrite at elevated temperature and pH below about 8. Along the
same line, Kydros et al. (1993b) removed arsenopyrite from an
industrial pyrite concentrate using sodium dithionite and sodium
sulphite as depressants of arsenopyrite in acidic media. The use of
sodium dithionite led to slight activation of pyrite, possibly due to the
coverage of its surfaces with a sulphur-containing hydrophobic layer.
Using an arsenic containing ore from Broken Hill, Australia, David and
Quast (1991) reported that 90 g/t potassium cyanide resulted in 75%
reduction in the recovery of leollingite (FeAs2) and arsenopyrite, with
galena recovery unaffected. Lime was found to be a moderate
depressant for leollingite and arsenopyrite at pH 10. At pH 11, both
arsenic and lead minerals are depressed by lime. TSS, the combination
of triethylenetetramine and sodium sulte which is known as an
effective depressant of pyrrhotite in the otation of coppernickel
ores (Xu et al., 2000; Xu et al., 2001), was also reported as an effective
depressant for arsenic minerals. According to Dai et al. (2005), TSS
selectively depressed gersdorfte in the otation of Garson NiCu ore
after pre-aeration. TSS was also found to depress pyrrhotite while
allowing pentlandite to be selectively oated, which made it more
desirable than magnesia mixture for the otation of Garson NiCu ore.
Co-addition of TSS and magnesia mixture did not further reduce the
recovery of gersdorfte. Chen et al. (2001) found that thioglycolic acid
(TGA), an organic depressant that is known to depress pyrite and
chalcopyrite in sulphide otation, does not affect the otation of
arsenopyrite (96.8% pure). Chanturiya et al. (2000) reported that
dimethyldithiocarbamate, a coagulant in the otation of nonferrous
metal ores, signicantly depresses arsenopyrite at pH 10.3 (adjusted
with lime) while pyrite is only affected very weakly (a single mineral
study).
Unsatised with existing reagents, Chanturiya et al. (2001)
synthesized a new reagent, PROKS, which contains cyclic propylene
trithiocarbonate (PTTC) and oxypropylene suldes, as a selective
depressant for arsenopyrite. Interestingly, the reagent was found to
depress arsenopyrite while increasing the otation of pyrite simulta-
neously, when tested on the ores from a number of Russian deposits.
In addition to depressants, selective collectors were also used to
remove arsenic minerals in sulde otation. Both cationic and anionic
collectors have been studied in arsenopyritepyrite separation. Kydros
et al. (1993a) selectively oated arsenopyrite from an industrial
concentrate containing pyrite using cetyltrimethylammonium bro-
mide as a collector. Mavros et al. (1993) found that 2-coco 2-methyl
ammonium chloride selectively oated arsenopyrite from an indus-
trial pyrite concentrate in a laboratory-scale otation column. Using
high purity minerals, Diaz and Gochin (1995) demonstrated that thio-
amine and alkyl propionamide, the so called F series, are both
selective collectors for arsenopyrite and pyrite separation at alkaline
pH adjusted with lime. Sirkeci (2000) reported similar phenomenon
using hexyl thioethylamine as a collector in a single mineral study and
attributed the differential otation to the higher adsorption rate of
hexyl thioethylamine onto pyrite in comparison to arsenopyrite. An
anionic collector (sodium dodecylsulphonate) was used by Kydros
et al. (1993b) to selectively oat arsenopyrite from pyrite with at
pH 4 in a Hallimond cell from an industrial auriferous bulk pyrite
arsenopyrite concentrate. The addition of permanganate, a common
oxidizing agent, enhanced the selectivity of the process. Singer and
Jordaan (1990) patented a method to oat arsenopyrite from pyrite
with a dialkyl-dithiophosphate and monoalkyl-dithiocarbamate
which are used in combination as the collector at a pH in the range
7 to 12. Using dithiophosphate and dithiocarbamate as collectors,
O'Connor et al. (1990) oated an arsenopyrite and gold rich
concentrate from an ore containing arsenopyrite and pyrite.
For cobalt-bearing arsenic minerals, such as erythrite, smolyani-
novite and cobaltite, nitroso-naphthol based collectors were found to
be selective collectors because of the formation of the extremely
stable cobaltic complex (Teoh et al., 1983). Abeidu (1976)'s single
mineral studies indicated that sodium diethyl dithiophosphate
(SDDP) in the presence of sodium sulde could be an effective
collector in the separation of cobaltite from chalcopyrite and pyrite.
Byrne et al. (1995) found that stage addition of dithiophosphate
collector in the otation of a sample from the Iberian Pyrite Belt,
Portugal, produced a relatively selective otation of chalcopyrite from
tetrahedrite. But the chalcopyrite concentrate still contained some
tetrahedrite and must be treated with hydrogen peroxide to depress
tetrahedrite in a cleaning stage to produce a satisfactory concentrate.
4. Summary
Selective otation of arsenic minerals can be achieved through
pre-oxidation of otation pulp, Eh control during otation and the use
of selective depressants/collectors. To selectively oxidize arsenic or
non-arsenic minerals prior to otation, oxidizing agents, such as
 X. Ma, W.J. Bruckard / Int. J. Miner. Process. 93 (2009) 8994
hydrogen peroxide, and aeration conditioning have both been applied
effectively. Selective otation of arsenic minerals through Eh control
has made signicant advances in recent years, with enargite being the
most studied arsenic mineral in this area. Its use in combination with
pre-oxidation was also reported. Various depressants and collectors,
including new reagents and some conventional reagents in sulde
otation, have been found effective in the selective otation of arsenic
minerals such as arsenopyritepyrite separation. The use of selective
reagents represents a traditional approach in arsenic removal and
makes it possible to remove arsenic minerals without additional
operations such as pre-oxidation or Eh control.
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