IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

DEPRESSION OF PYRITE BY METABISULFITE AND SULFITE IONS IN SEAWATER AND

FRESH WATER

Lina M. Uribe1, *Sergio Castro1, Leopoldo Gutierrez2 and Janusz S. Laskowski3

1Water Research Center for Agriculture and Mining (CRHIAM), University of Concepcin, Chile
(*Corresponding author: scastro@udec.cl)

2Department of Metallurgical Engineering, University of Concepcion, Chile

3N.B. Keevil Institute of Mining Engineering, University of British Columbia, Canada

ABSTRACT

The effect of sulfite and metabisulfite ions on the amyl xanthate flotation of copper-activated
pyrite, in distilled water and seawater, has been studied by micro-flotation tests and redox potential
measurements. The activation of pyrite was carried out varying copper ions concentration. It was found that
in the presence of copper ions in solution, sulfite and metabisulfite are able to depress copper-activated
pyrite at neutral or slightly acid pH. After the addition of sulfite or metabisulfite ions the resulting pH is
more acidic with metabisulfite ions. A significant increase of the redox potential of the solution was
observed as copper ions concentration increased. Then, the initial reducing conditions brought about by
sulfite and metabisulfite ions, change abruptly to oxidizing conditions in the presence of copper ions.
Under these oxidizing conditions, the metabisulfite showed to be an effective depressant for pyrite mainly
in seawater. However, sulfite was a pyrite depressant in both distilled water and seawater. Based on these
results, the pyrite depression by sulfoxy-depressants during the flotation of Cu/Mo ores in distilled water
and seawater is discussed.

KEYWORDS

Pyrite depression, copper-activation, sulfite, metabisulfite, seawater.

Page 1 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

INTRODUCTION

Depression of pyrite by sulfoxy-depressants (sulfite and metabisulfite) in the presence of copper

ions is an important issue. This is particularly true when pyrite depression in the flotation of Cu/Mo sulfide
ores is carried out in seawater. The use of lime in seawater must be avoided because the formation of
magnesium hydroxy-complexes and precipitating magnesium hydroxide strongly depresses molybdenite
flotation (Castro et al., 2014). In order to solve this problem, one large plant in Chile uses sodium
metabisulfite (MBS) instead of lime to depress pyrite in seawater. In plant practice, this also improves
molybdenite flotation since with the use of MBS the pyrite depression is carried out at pH 6-7, instead the
pH 11-12 usually employed with lime.

From a general point of view, pyrite exhibits some natural oatability over acidic pH ranges and
may be partially oated without thiol collectors (a coating of sulfur/polysulfides has been claimed).
Therefore, pyrite flotation with xanthates is usually high in the acidic pH region, but decreases greatly at
alkaline pH (Leppinen, 1990; Fornasiero and Ralston, 1992; Zhang et al., 1997).

It is also known that pyrite can be activated by some transition metal cations, such as Cu2+ and
2+
Pb . Pyrite is activated either by copper ions added to the pulp or by copper ions leached out of copper
sulfide minerals (chalcopyrite, chalcocite) (Voigt et al., 1994). In the last case activation may be an
inadvertent effect, which is not desirable but can takes place during the flotation of Cu/Mo sulfide ores.

To minimize the activation of pyrite by copper ions, inorganic depressants are used to suppress its
improved floatability (Agorhom, et al., 2014). Sulphoxy-type depressants, in the form of sulfite (SO32-),
bisulfite (HSO3-), metabisulfite (S2O52-) or sulfur dioxide (SO2) have been used to depress copper-
activated pyrite (Grano et al., 1997a, 1997b; Khmeleva et al., 2002, 2003; Shen et al., 2001; Chander and
Khan, 2000). These reagents are usually employed in flotation of poly-metallic ores as depressants for
copper activated pyrite.

The use of sulfite, bisulfite, metabisulfite and sulfur dioxide, to control the unwanted flotation of
pyrite in mildly alkaline environments is generally considered to be caused by sulfite ions, (Chander,
1988). As the oxidation of xanthate ions into dixanthogen is an electrochemical reaction, any reagent
system which is more reducing than the xanthate-dixanthogen couple will inhibit the formation of
dixanthogen. Sulfite as a reducing reagent is readily oxidized to form sulfate (Yamamoto, 1980; Fuerstenau
et al., 1985). Different mechanisms have been proposed to explain the effect of sulfite ions on the copper-
activated pyrite. The following classification was proposed by Khmeleva, et al. (2002):

Interaction of Sulfite Ions with the Mineral Surface

The precipitation of a metal sulfite (e.g. copper sulfite) may form a hydrophilic surface layer
rendering the mineral surface hydrophilic (Misra et al. (1985). Miller (1970) used zeta potential
measurements and found the evidence of specific adsorption of sulfite ions onto pyrite. Khmeleva, et al.,
(2002) suggested that iron hydroxy species were formed on the pyrite surface, rendering it hydrophilic.

Sodium sulfite promotes the oxidation of copper on pyrite as copper hydroxide and these
oxidation products on the pyrite surface decreases xanthate adsorption (Shen, et al. 2001). Sulfite ions are
also known to react with polysulfide or elemental sulfur, forming thiosulfate ions which decrease its
surface hydrophobicity. Results have been reported by Khmeleva et al. (2005) suggesting that the decrease
in the oatability of the activated sphalerite is due to the decomposition of elemental sulfur by bisulte
ions, resulting in the formation of thiosulfate ions, which is subsequently oxidized to sulfate ions in the
presence of copper species.

At a low pH value, copper activation of pyrite occurs through adsorption of Cu(II) ions onto
reactive sulfur surface sites with the reduction of Cu(II) to Cu(I). This reduction of Cu(II) to Cu(I) and the
oxidation of sulfur with the surface layer were also observed in the XPS studies of Szargan et al (1992) and
Voigt et al. (1994). Therefore, sulfite promotes the oxidation of copper on pyrite as copper hydroxide and

Page 2 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

these oxidation products on the pyrite surface decreases xanthate adsorption (Shen, D. Fornasiero, and J.
Ralston, 2001).

Interaction of Sulfite Ions with Collector either in Solution or in its Adsorbed State

Yamamoto (1980) proposed that sulfite ions depress pyrite by desorbing xanthate species from the
pyrite surface. Sulfite ions are able to decompose xanthate ions in solution forming perxanthate ions.
Miller (1970) reported desorption of pre-adsorbed collector species, such as dixanthogen, by sulfite ions.
Illyuvieva et al. (1984) proposed the mechanism involving the consumption of dissolved oxygen by sulfite.
The Eh of the solution might be reduced because of sulfite oxidation to sulfate. Due to the lack of oxygen
in solution, the formation of dixanthogen and collector adsorption may also be minimized (Illyuvieva et al.
1984).

Miller (1970) considered that sulfite acts as a depressant for pyrite due to its reducing properties.
As xanthate adsorption onto pyrite takes place via xanthate dimerisation to dixanthogen, the introduction of
a more reducing couple can minimize adsorption via this mechanism.

Khmeleva, et al., (2002), demonstrated that the depression effect was greater when air was used.
These authors suggested that both the decomposition of the xanthate in solution via perxanthate formation
and dixanthogen desorption from the pyrite surface were responsible for pyrite depression by sulfite.

According to Chen et al., (2013), Cu2+ ions first adsorb on pyrite surfaces and then are reduced to
+
Cu ions coupled with the oxidation of sulfite or metabisulfite ions. Weisener and Gerson (2000) claim no
increase in iron oxide/hydroxide formation upon copper activation, indicating that the exchange of copper
for iron does not occur, contrary to the case of copper activation of sphalerite where zinc is exchanged with
copper ions.

The activation process is dependent on pH. The pH range of 6 to 10 favors the adsorption of
xanthate on copper-activated minerals (Leppinen, 1990; Zhang et al., 1997; Dichmann and Finch, 2001),
whereas the acidic pH (4 to 5) favors the adsorption of xanthate on non-activated pyrite.

On the other hand, the reducing environment during grinding promotes the activation of pyrite,
while the oxidizing environment inhibits the activation (Peng and Grano, 2010). The effect of different
grinding media and the electro-chemical potential on pyrite activation by Cu2+ ions has been also studied
(Chen and Bradshaw, 2013). It was shown that the activation of pyrite by copper ions occurs via a galvanic
interaction where Cu(II) added as copper sulfate or dissolved from chalcopyrite adsorbs on the pyrite
surface and is reduced to Cu(I) (Voigt et al,1994; Ekmekci and Demirel, 1997; Finkelstein, 1997). When
chalcopyrite is in contact with a more cathodic sulfide mineral such as pyrite, galvanic interactions
between the two sulphide minerals can occur and this increases the rate of chalcopyrite oxidation and
hence increase Cu (II) dissolution.

The Effect of Metabisulfite

Metabisulphite is more effective at pH 6.5 or 6.9 than pH 10 or 12. Dvila-Pulido, et al. (2011)
found that sodium metabisulte (MBS, Na2S2O5) is slightly more effective than sodium sulte (Na2SO3) to
depress Cu(II) activated sphalerite in the presence of sodium IsopX. Results corroborate the benecial
effect of using an aeration stage before collector addition in order to maximize the depressant action over
the hydrophobizing species present on the sphalerite surface and to avoid xanthate oxidation. The
simultaneous presence of dissolved oxygen and metabisulfite presumably promotes their synergetic action
on sphalerite depression. Therefore, sodium metabisulte (MBS) is slightly more effective than sodium
sultein depression of the Cu (II) activated sphalerite. Depression is mainly due to oxidation of the
elemental sulfur (or polysulde) of the mineral surface. When Cu (II) activated sphalerite is depressed with
sulte or metabisulte, the presence of dissolved oxygen contributes to the elimination of hydrophobic
species from the mineral surface, due to the joint action of sulte/metabisulte and dissolved oxygen.

Page 3 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

EXPERIMENTAL

Micro-Flotation Tests

Crystals of natural pyrite (1g by test) were floated in a Partridge-Smith flotation cell. First, pyrite
was conditioned for 5 min with a solution of copper ions, with concentrations ranging from 0-50 ppm (as
CuSO4). Then, amyl xanthate (25 ppm) and MIBC (7 ppm) were added and conditioned for other 3 min;
and finally pyrite was floated for 2 min. When sulfite and metabisulfite were used (1x10-3M in both cases),
these reagents were added after the 3 min conditioning time with the flotation reagents, and a new
conditioning time of 5 min was applied. Then, the final pH and Eh were measured. When seawater (from
the coast of Concepcion) was used, the pH was the natural pH (pH 8). However, when distilled water was
employed, the pH was previously adjusted, before copper ions addition, to pH 8.

Redox Potential Measurements

A Pt electrode was employed for redox potential measurements using a Ag/AgCl reference. Redox
potentials are referred to the Ag/AgCl reference electrode. Every day the electrodes were tested by a
standard solution at +200mV.

RESULTS

In the Absence of Sulfite and Metabisulfite

As it was expected, at low concentration of Cu2+ ions (< 5ppm) the floatability of pyrite was high.
However, at high Cu2+ions concentration the floatability of pyrite was strongly depressed. Figure 1 shows
that in distilled water (during pyrite conditioning with Cu2+ ions), the redox potential varied from +110mV
to +200mV when the concentration of Cu2+ ions increased from 0 to 50 ppm; and pH varied from 8.7 to 7.6
However, after the addition of the flotation reagents (AmX + MIBC) the redox potential changed abruptly
from -140mV to +200mV; and pH from 7.7 to 7.8 (when the concentration of Cu2+ ions increases from 0 to
50 ppm).

Similar results were obtained in seawater, but in this case the activation of pyrite was not clearly
observed, and the depression of pyrite by an excess of Cu2+ ions was strong (see Figure 2).

100 0.3

80 0.2
Pyrite Recovery, (%)

Redox Potential, V

60 0.1
Pyrite Recovery, %
Redox Potential, V
40 0.0

20 -0.1

0 -0.2
0 10 20 30 40 50 60

Cu 2+ Ions Concentration, [ppm]

Figure 1 - Pyrite recovery and redox potential as a function of the Cu2+ ions concentration in distilled water
in the absence of sulfite and metabisulfite

Page 4 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

100 0.3

80 0.2

Pyrite Recovery, (%)

Redox Potential, V
60 0.1
Pyrite Recovery, %
Redox Potential,V
40 0.0

20 -0.1

0 -0.2
0 10 20 30 40 50 60
Cu 2+ Ions Concentration, [ppm]

Figure 2 - Pyrite recovery and redox potential as a function of the Cu2+ ions concentration in seawater in
the absence of sulfite and metabisulfite

In the Presence of Sulfite Ions

The redox potentials of the solutions prepared with 1x10-3M of sodium sulfite, in the presence of
amyl xanthate and MIBC (but in absence of Cu2+ions), was initially negative (-130mV), in a good
agreement with the reducing properties of sulfite ions. However, after the addition of Cu2+ ions the redox
potential change abruptly from negative to positive values, from -130mV to +130mV at 50 ppm of Cu2+
ions, i.e., it changes from reducing to oxidizing conditions.

Figure 3 shows the redox potential and pyrite depression after the addition of Cu2+ and sulfite
ions, in distilled water. The final pH of the solution varied from pH 8.3 to 9.4 (see Figure 5). A similar
change of the redox potential was observed with sulfite ions in seawater, where the change in redox
potential was from -110MV to +310mV (from 0 to 50 ppm Cu2+ ions). However, the pH was reduced from
pH 8 to 6.2, as the redox potential increased with the Cu2+ ions concentration (see Figure 4 and 6).

100 0.4
Pyrite Recovery, %
Redox Potential, V
0.3
80
Pyrite Recovery, (%)

Redox Potential, V

0.2
60

0.1

40
0.0

20
-0.1

0 -0.2
0 10 20 30 40 50 60
Cu 2+ Ions Concentration, [ppm]

Figure 3 - Pyrite recovery and redox potential as a function of the Cu2+ ions concentration in 1x10-3 M
solution of Na2SO3 in distilled water

Page 5 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

100 0.4

0.3
80

Pyrite Recovery, (%)

Redox Potential, V
0.2
60

0.1

40
Pyrite Recovery,% 0.0
Redox Potential, V
20
-0.1

0 -0.2
0 10 20 30 40 50 60
Cu2+ Ions Concentration, [ppm]

Figure 4 - Pyrite recovery and redox potential as a function of Cu2+ ions concentration in 1x10-3 M solution
of Na2SO3 in seawater

10 100

9
90

Pyrite Recovery, %
pH Sulfite
8 pH MBS
80
Py Recovery MBS
7 Py Recovery Sulfite
pH

70
6

60
5

50
4

3 40
0 10 20 30 40 50 60

2+
Cu Ions Concentration, [ppm]

Figure 5 - Pyrite recovery and final pH as a function of the Cu2+ ions concentration in the presence of
either sulfite or MBS (1x10-3M) in distilled water

Page 6 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

8.5 90

8.0 pH Sulfite 80
pH MBS

Pyrite Recovery, %
7.5 Py Recovery MBS 70
Py Recovery Sulfite
7.0 60
pH

6.5 50

6.0 40

5.5 30

5.0 20

4.5 10
0 10 20 30 40 50 60 70

2+
Cu Ions Concentration, [ppm]

Figure 6 - Pyrite recovery and final pH as a function of the Cu2+ ions concentration in the presence of
either sulfite and or MBS (1x10-3M) in seawater.

In the Presence of Metabisulfite Ions

As Figure 7 shows, the redox potential changed from -100mV to +240 mV with the concentration
of Cu2+ ions (0-50 ppm) for MBS in distilled water. After the addition of MBS the pH was low (pH 4) but
as Cu2+ ions concentration increases from 0 to 50 ppm, the pH increases up to pH 6.2 (see Figure 5). Pyrite
depression was less intensive than in distilled water with sulfite ions.

A similar behavior was observed in seawater, where the redox potential changed from -40mV to +300MV
(from 0-50 ppm of Cu2+ ions) (see Figure 8). At the same time pH decreased from 6.4 to 5.0 (see Figure 6).

100 0.4

80 0.3
Pyrite Recovery, (%)

Redox Potential, V

60 0.2

40 0.1

20 0.0
Pyrite Recovery, %
Redox Potential, V
0 -0.1
0 10 20 30 40 50 60
Cu 2+ Ions Concentration, [ppm]

Figure 7 - Pyrite recovery and redox potential as a function of the Cu2+ ions concentration in 1x10-3 M
solution of MBS in distilled water.

Page 7 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

100 0.4

80 0.3

Pyrite Recovery, (%)

Redox Potential, V
60 0.2
Pyrite Recovery,%
Redox Potential, V
40 0.1

20 0.0

0 -0.1
0 10 20 30 40 50 60
Cu2+ Ions Concentration, [ppm]

Figure 8 - Pyrite recovery and redox potential as a function of the Cu2+ ions concentration, in 1x10-3M
solution of MBS in seawater.

DISCUSSION

It is still not clear whether the Cu activation of pyrite and xanthate adsorption mechanisms are
electrochemical, chemical, or a combination of both types of reactions (Chandra, et al., 2012; Chandra and
Gerson, 2009; Hicyilmaz et al., 2004; Pecina et al., 2006; Zhang et al., 1997). However, it is clear that
electrochemical reactions play an important role. Therefore, it seems that the redox potential of the solution
is very important.

The activation of pyrite by copper ions usually occurs via a galvanic interaction where Cu (II)
added as copper sulfate or leached out from chalcopyrite adsorbs on the pyrite surface and is reduced to Cu
(I) (Voigt et al, 1994; Ekmekci and Demirel, 1997; Finkelstein, 1997). When chalcopyrite is in contact
with a more cathodic sulfide mineral such as pyrite, galvanic interactions between the two sulfide minerals
can occur which will increase the rate of chalcopyrite oxidation and hence increase Cu (II) dissolution.

Therefore, the activation of pyrite first needs a step of interactions of the pyrite surface with the
dissolved copper ions. These copper ions may be partially adsorbed on the pyrite surface and partially in
excess at the bulk solution. Hence the mechanisms involved in the pyrite activation may be different
depending on the extent of these two concentrations and the redox potential of the solution. For large
excess of copper ions, the precipitation of copper-xanthate may takes place. For high concentration of
sulfite or metabisulfite ions their reducing properties may affect the oxidation state of copper ions.

One of the common properties of sulfoxy-depressants is their reducing character. Thus, at the
surface of pyrite different electrochemical phenomena combined with chemical reactions may occur at the
same time. Copper ions can result from dissolution of copper sulfides, but can also be aided by galvanic
(electrochemical) effects between different metal sulfides. At the mineral interface with bulk solution, Cu
(II) ions can be reduced in the presence of sulfite and metabisulfite, coupled to the oxidation of these
sulfoxy-ions. Similarly, the precipitation of metal sulfite and copper hydroxide may occur.

However, our work showed that the redox potential of sulfite and metabisulfite solutions, in the
presence of Cu2+ ions, changed abruptly from reducing to oxidizing conditions, both in distilled and
seawater. These results suggest that this is the way by which a reducing agent like sulfite or metabisulfite
can participate in oxidizing reactions, when dissolved or adsorbed copper ions are involved.

Page 8 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

Based in the sulfite species distribution (for a total sulfite concentration of 0.02 M) reported by
Muller et al. (2013), below pH 1 sulfur dioxide (SO2) dominates; between pH 1.5 and 5.6 the bisulfite ions
(HSO3-) dominate. However, the amount of S2O52- ions is very small between pH 1.5 and 5.6. Finally, in
the alkaline pH range (pH>7) the ions SO32- ions dominate. Theoretically, both in sulfite and metabisulfite
aqueous solutions the dominant ion around pH 7-8 is the sulfite ion. However, the effect of MBS and
sulfite ions as pyrite depressant is very different in distilled water and seawater. MBS is an effective pyrite
depressant in seawater but not in fresh water.

The pH of the solutions of sulfite and metabisulfite is also very important. As this work indicates
both sulfite and metabisulfite depress pyrite at low pH, compared with lime, which is of great interest for
the flotation of Cu/Mo sulfide ores in seawater. This low pH prevents losses of Mo by depression with
magnesium hydroxide, and additionally, it is well known that molybdenite exhibits an improved natural
floatability as pH decreases.

CONCLUSIONS

1. It was confirmed that the floatability of pyrite with amyl xanthate, after the addition of low amount of
Cu2+ ions (<5 ppm), was improved in distilled water (activation of pyrite), but in seawater the
activation of pyrite was not so clear.
2. Sulfite and metabisulfite were able to depress copper-activated pyrite at a significantly lower pH than
the conventional pH employed with lime. This may be beneficial for the recovery of the by-product
molybdenum in the flotation of Cu/Mo sulfide ores.
3. In distilled water, the pH of the solution with sulfite and metabisulfite were very different; these values
were much more acidic in the case of metabisulfite for the same concentration (1x10-3M).
4. At concentrations of copper ions higher that 5 ppm, a strong depression of pyrite was observed with
sulfite and metabisulfite ions, but this might be due to the precipitation of copper xanthate in the bulk
solution.
5. A significant increase of the redox potential of the solution (aprox. from -130mV to + 230mV) was
observed as the concentration of copper ions was increased. The reducing conditions initially imposed
by the sulfite and metabisulfite ions, in an excess of copper ions changed abruptly to oxidizing
conditions. These oxidizing conditions may explain a series of oxidation reactions reported in the
literature, as the decomposition of xanthate via perxanthate, the oxidation of thiosulfate to sulfate, and
the importance of the application of aeration step.
6. Metabisulfite is a very effective depressant for pyrite in seawater, but not in distilled water. Contrarily,
sulfite is a good pyrite depressant in both distilled water and seawater. Further studied are needed with
real copper-molybdenum ores.

AKNOWLEDGEMENTS

The authors wish to thank CRHIAM-University of Concepcion (Water Research Center for
Agriculture and Mining), for financing this work through the CONICYT/FONDAP-15130015 research
project.

REFERENCES

Agorhom, E.A., Skinner, W., Zanin, M. (2014). Diethylenetriamine (DETA) depression of Cu-activated
pyrite hydrophobised by xanthate. Minerals Engineering, 57, 3642.
Castro S., Uribe, L. Laskowski. J.S. (2014). Depression of inherently hydrophobic minerals by
hydrolyzable metal cations: molybdenite depression in seawater. Proc. 27th Int. Mineral
Processing Congress, Santiago.
Chander, S. (1988). On the design of a feedback reagent control system for sulfide mineral flotation. In:
Forssberg, K.S.E. (Ed.), Proc. 16th International Mineral Processing Congress. Stockholm, pp.
16801699. Part B.

Page 9 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

Chander, S., Khan, A. (2000). Effect of sulfur dioxide on flotation of chalcopyrite. Int. J. Miner. Process.
58, 4555.
Chandra, A.P., Gerson, A.R. (2009). A review of the fundamental studies of the copper activation
mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite. Adv. Colloid
Interface Sci. 145, 97110.
Chandra, A. P., Puskar, L., Simpson, D. J., Gerson, A. R. (2012). Copper and xanthate adsorption onto
pyrite surfaces: Implications for mineral separation through flotation. Int. J. Mineral Processing
114117, 1626.
Chen, X., Peng, Y., Bradshaw, D. (2013). Effect of regrinding conditions on pyrite flotation in the presence
of copper ions. Int. J. Mineral Processing. 125, 129136.
Dvila-Pulido, G.I., Uribe-Salas A. and, Espinosa-Gmez, R. (2011). Comparison of the depressant action
of sulfite and metabisulfite for Cu-activated sphalerite. Int. J. Mineral Processing 101, 7174.
Dichmann, T.K., and Finch, J.A. (2001). The role of copper ions in sphalerite-pyrite flotation selectivity.
Minerals Engineering, 14, 217-225.
Ekmekci, Z., Demirel, H. (1997). Effects of galvanic interactions on collectorless flotation behavior of
chalcopyrite and pyrite. Int. J. Mineral Processing. 52, 3148.
Finkelstein, N.P. (1997). The activation of sulphide minerals for flotation: a review. Int. J. Mineral
Processing, 52, 81120.
Fornasiero, D., Ralston, J. (1992). Iron hydroxide complexes and their influence on the interaction between
ethyl xanthate and pyrite. J. Colloid Interface Sci. 151, 225235.
Fuerstenau, M.C., Miller, J.D., Kuhn, M.C. (1985). Chemistry of Flotation. AIME, New York, pp. 177.
Grano, S.R., Prestidge, C.A., Ralston, J. (1997). Sulphite modification of galena surfaces and its effect on
flotation and xanthate adsorption. Int. J. Mineral Processing, 52, 129.
Hicyilmaz, C., Altun, N.E., Ekmekci, Z., Gokagac, G. (2004). Quantifying hydrophobicity of pyrite after
copper activation and DTPI addition under electrochemically controlled conditions. Minerals
Engineering 17, 879890
Illyuvieva, G.V., Gorshtein, A.E., Toropova, M.N. (1984). Role of sulphite and thiosulphate ions in the
coppernickel sulphide ore flotation process. Chemical Abstracts 101, 175164n.
Khmeleva, T.N., Skinner, W., Beattie, D.A., Georgiev, T.V. (2002). The effect of sulphite on the xanthate-
induced flotation of copper activated pyrite. Physicochemical Problems of Mineral Processing 36,
185195.
Khmeleva, T.N., Beattie, D.A., Georgiev, T.V., Skinner, W.M. (2003). Surface study of the effect of sulfite
ions on copper-activated pyrite pre-treated with xanthate. Minerals Engineeing, 16, 601608.
Khmeleva, T.N., Skinner, W.M., Beattie, D.A. (2005). Depressing mechanisms of sodium bisulfate in the
collectorless flotation of copper-activated sphalerite. Int. J. Mineral Processing, 76, 4353.
Miller, J.D. (1970). Pyrite depression by reduction of solution oxidation potential. Report to EPA Water
Quality Office, Grant No. 12010 DIM.
Misra, M., Miller, J.D., Song, Q.Y. (1985). The effect of SO2 in the flotation of sphalerite and chalcopyrite.
Flotation of sulphide minerals. In: Forssberg, K.S.E. (Ed.), Developments in Mineral Processing.
Elsevier, Amsterdam, Vol. 6, pp. 175196.
Muller, I. A., Brunner, B. Breuer, C. Coleman, M. Bach, W. (2013). The oxygen isotope equilibrium
fractionation between sulfite species and water. Geochimica et Cosmochimica Acta 120, 562581.
Leppinen, J.O. (1990). FTIR and flotation investigation of the adsorption of ethyl xanthate on activated and
non-activated sulfide minerals. Int. J. Mineral Processing 30, 245-263.
Peng, Y., Grano, S. (2010). Effect of grinding media on the activation of pyrite flotation. Minerals Eng. 23,
600605.
Pecina, E.T., Uribe, A., Nava, F., Finch, J.A. (2006). The role of copper and lead in the activation of pyrite
in xanthate and non-xanthate systems. Minerals Engineering 19, 172179.
Peng, Y., Wang, B., Gerson, A. (2012).The effect of electrochemical potential on the activation of pyrite
by copper and lead ions during grinding. Int. J. Mineral Processing 102103, 141149.
Shen, W.Z., Fornasiero, D., Ralston, J. (2001). Flotation of sphalerite and pyrite in the presence of sodium
sulfite. Int.J. Mineral Processing, 63, 1728.
Szargan, R., Karthe, S. (1992). XPS studies of xanthate adsorption on pyrite. Applied Surface Science, 55,
227232.

Page 10 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum
IMPC 2016: XXVIII International Mineral Processing Congress Proceedings - ISBN: 978-1-926872-29-2

Yamamoto, T. (1980). Mechanism of depression of pyrite and sphalerite by sulphide. In: Jones, M.J. (Ed.),
Complex Sulphide Ores, Institute of Mining and Metallurgy, London, pp. 71-78.
Voigt, S., Szargan, R., and Suoninen, E. (1994). Interaction of Copper (II) Ions with Pyrite and its
Influence on Ethyl Xanthate Adsorption, Surface and Interface Analysis, 21, 526-536.
Weisener C. and Gerson, A. (2000). An investigation of the Cu (II) adsorption mechanism on pyrite by
ARXPS and SIMS. Minerals Engineering, 13, 1329-1340.
Zhang, Q., Xu, Z., Bozkurt, V., and Finch, J.A. (1997). Pyrite flotation in the presence of metal ions and
sphalerite, Int. J. Mineral Processing, 52, 187-201.

Page 11 of 11
Published by the Canadian Institute of Mining, Metallurgy and Petroleum