Minerals Engineering 6668 (2014) 2532

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Cyanide chemistry and its effect on mineral otation

Bao Guo a,, Yongjun Peng a,, Rodolfo Espinosa-Gomez b
a
b

School of Chemical Engineering, University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia
Minseg Pty. Ltd., Carindale, Brisbane, QLD 4152, Australia

a r t i c l e

i n f o

Article history:
Received 17 December 2013
Revised 13 June 2014
Accepted 25 June 2014
Available online 14 July 2014
Keywords:
Base metal minerals
Precious minerals
Flotation depression
Flotation activation
Cyanide speciation

a b s t r a c t
Cyanide has been widely used as a depressant in sulphide mineral otation. It occasionally activates mineral otation as well. In addition, cyanide species in the water from gold cyanidation process may be
recycled to otation circuits and have an inadvertent effect on mineral otation. Therefore, the investigation on mineral otation in the presence of cyanide with different speciation is of great importance.
Even after decades of research, the mechanisms of cyanide depression and activation processes are not
fully understood and effective ways to solve problems encountered in minerals otation plants using
cyanide-containing recycled water are not currently available. In this paper, a review of previous literature on the effect of free cyanide, weak acid dissociable (WAD) cyanide and strong acid dissociable (SAD)
cyanide on the otation of base metal and precious minerals is presented, with a particular focus on the
underpinning mechanisms and process solutions. Ultimately, an overall picture of current status of
studies in this area is provided and the future research associated with using cyanide in mineral otation
is suggested.
2014 Elsevier Ltd. All rights reserved.

Contents
1.
2.

3.

4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of cyanide on mineral flotation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
The action of xanthate on sulphide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Effect of cyanide on iron sulphide minerals flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
The formation of iron cyanide surface compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Effect of electrochemical potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Effect of cyanide on the flotation of copper sulphide minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Effect of cyanide on sphalerite flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Effect of cyanide on galena flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.
Effect of cyanide on gold flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Ways to mitigate the depression effect of cyanide on minerals flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
The addition of activators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Alternative collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

25
26
26
26
27
28
28
29
29
30
30
30
31
31
31
31

1. Introduction

Corresponding authors. Tel.: +61 7 3365 7156; fax: +61 7 3365 3888.
E-mail addresses: uqbguo1@uq.edu.au (B. Guo), yongjun.peng@uq.edu.au
(Y. Peng).
http://dx.doi.org/10.1016/j.mineng.2014.06.010
0892-6875/ 2014 Elsevier Ltd. All rights reserved.

Cyanide was introduced commercially over a century ago and

since then it has been used in several types of industry and mining
is one industrial activity that uses a signicant amount of cyanide,
about 20% of the total production (Logsdon et al., 1999). The cyanide

26

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

species discussed in this paper can be broadly classied into three

categories: free cyanide including hydrocyanic acid (HCN) and the
cyanide anion (CN); weak acid dissociable (WAD) cyanide (cyanide
complexes with Cd, Cu, Ni, Ag or Zn which dissociates under mildly
acidic conditions to free cyanide); strong acid dissociable (SAD) cyanide (cyanide complexes with Fe, Co or Au which dissociates only
under extreme acidic conditions). The thermodynamic stability constants for some of the metal cyanide complexes or compounds commonly existing in mineral processing plant water are summarized in
Table 1. The stability constants of some metal xanthate complexes
are also listed in Table 1 for further discussions.
Cyanide is among the most commonly used reagents for
enhancing the separation efciency of base metal sulphide
minerals by otation, particularly when the depression of iron
and zinc sulphides is desired. At early stages, Sutherland and Wark
(Sutherland and Wark, 1955; Wark, 1938) comprehensively
reviewed the depression of many sulphide minerals by cyanide
in the presence of several collectors of xanthate type, which has
been regarded as a standard reference for industry application of
cyanide in otation for many decades. Their work was mainly on
the basis of captive bubble contact tests, giving the theoretical possibility of mineral separations in otation. However, many of these
early studies have been of a phenomenological nature and the surface interaction of cyanide species with minerals and the inuence
of electrochemical environments of otation have not been fully
addressed. In fact, mineral separations by the use of cyanide are
practically not easy and have relied entirely on empirical testing.
It has been reported that cyanide activates, rather than depresses,
mineral otation under some conditions (Prestidge et al., 1993a;
Rao et al., 2011; Seke and Pistorius, 2006). This paper reviews
the action of cyanide species in otation based on mineral type
followed by ways to mitigate their depression effects. Thermodynamic and kinetic aspects are considered to develop a rational
scheme for the interpretation of cyanide depression and activation.

2. Effect of cyanide on mineral otation

(1968) reported that non-oxidised pyrite adsorbed xanthate ions

through specic interactions while on oxidised pyrite the adsorption took place through the oxidation of xanthate to dixanthogen.
Miller et al. (2002) found that dixanthogen was the dominant
species on pyrite at low pH while at high pH ferric xanthate complexes were found to be prevalent. It was also presented by
Leppinen (1990) using surface analyses that ferric ethyl xanthate
(Fe(EX)3) was the main species of monolayer coverage on pyrite
when the xanthate concentration was low (less than 3  105 M)
while dixanthogen multilayers covered on this ferric ethyl
xanthate at a higher xanthate concentration. It was conrmed that
both ferric xanthate and dixanthogen were responsible for the
surface hydrophobicity (Leppinen, 1990).
The formation of metal xanthate complexes on sulphide mineral surfaces has been regarded as an electrochemical process
involving the charge transfer (Ralston, 1991). The anodic reactions
occur as Eqs. (1) and (2) while the reduction of oxygen occurs on
the cathode as Eq. (3).

X ! Xads e

MS 2X ! MX2 S 2e

1=2O2 H2 O 2e ! 2OH

where MS, MX2, X , and Xads represent the sulphide mineral, the
metal xanthate, the xanthate ion, and the adsorbed xanthate,
respectively. S represents elemental sulphur or polysulphide.
Dixanthogen forms through the anodic oxidation of xanthate
ions at the pyrite surface via Eq. (4), coupled with the reduction
of ferric hydroxide to ferrous ions via Eq. (5) (Haung and Miller,
1978; Janetski et al., 1977; Valdivieso et al., 2005).

2Xads ! X2 2e

2FeOH3 s 6H 2e ! 2Fe2 6H2 O

2.2. Effect of cyanide on iron sulphide minerals otation

2.1. The action of xanthate on sulphide minerals

Xanthate is commonly used as collector to oat sulphide
minerals, and the depression of cyanide occurs mainly by altering
the action of xanthate on mineral surfaces. The adsorption of
xanthate on pyrite has been studied extensively and various
adsorption mechanisms have been proposed including surface specic interactions with the formation of iron xanthate complexes
(Fuerstenau and Mishra, 1980; Wang and Forssberg, 1990b) and
the oxidation of xanthate to dixanthogen on the pyrite surface
(Allison et al., 1972; Majima and Takeda, 1968). Fuerstenau et al.

Of all the sulphide minerals studied so far, the depression of

pyrite by free cyanide is the best understood. Free cyanide at a concentration as low as 10 mg/L NaCN was found to signicantly
depress pyrite otation using sodium isopropyl xanthate (SIPX)
as collector (Wet et al., 1997). The addition of 200 mg/L NaCN at
pH 11 resulted in a drop in sulphur recovery from 90% to less than
10% in pyrite otation with 50 g/t SIPX (Wet et al., 1997). Using

Table 1
Thermodynamic stability constants of various metal cyanide (Wang and Forssberg,
1990a) and metal xanthate species (Wang et al., 1989a).
Species

log b or pKsp

Species

log b or pKsp

Zn(CN)2(s)
Zn(CN)
3
Zn(CN)2
4
CuCN(s)
Cu(CN)
2
Ag(CN)
2
Cu(CN)2
3
Cu(CN)3
4
2
Ni(CN)4
4
Fe(CN)6
Au(CN)
2
Fe(CN)3
6
Fe4[Fe(CN)6]3(s)

15.5
16.0
19.6
19.4
16.3
20.5
21.6
23.1
30.2
35.4
39.3
43.6
40.5

Fe2[Fe(CN)6](s)
Cu2[Fe(CN)6](s)
Cu3[Fe(CN)6]2(s)
K2Cu3[Fe(CN)6](s)
K2Zn3[Fe(CN)6](s)
KCu10[Fe(CN)6]7(s)
Zn(EX)2(s)
CuEX(s)
Ni(EX)2(s)
Fe(EX)2(s)
Fe(EX)3(s)
PbEX2(s)

14.1
17
24.5
34.3
38.5
74
8.3
14.2
12.5
7.2
24.8
16.7

Fig.
1. EhpH
stability
diagram
for
FeEXCNH2O
system
([Fe] = [EX] = 1.0  103 M, [CN] = 5.0  103 M) (Wang and Forssberg, 1996).

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

Fig. 2. Eh-pH stability diagram for FeSCNH2O system ([Fe] = 5.0  105 M,
[S] = 3.0  104 M, [CN] = 6.0  104 M) (Elgillani and Fuerstenau, 1968).

ultraviolet (UV) visible spectroscopy, Prestidge et al. (1993b)

conrmed that free cyanide reduced the rate and extent of ethyl
xanthate (EX) adsorption on pyrite. The addition of free cyanide
prior to xanthate produced the most marked reduction in ethyl
xanthate adsorption. Prestidge et al. (1993b) also found that the
depression action of cyanide was stronger on pyrrhotite than on
pyrite probably due to the greater solubility of pyrrhotite in cyanide solution, leading to more iron cyanide complexation.
The depression effect of free cyanide on the otation of iron sulphide minerals with xanthate as collector was generally explained
to occur through the following two processes:
(1) Free cyanide preferentially adsorbs on iron sulphide mineral
surfaces as iron cyanide compounds, therefore inhibiting the
chemisorption and oxidation of xanthate (Elgillani and
Fuerstenau, 1968; Wang and Forssberg, 1996).
(2) Free cyanide inhibits the electrochemical activities and
reduces the mixed potential on minerals surface, preventing
the chemisorption and oxidation of xanthate (Wet et al.,
1997).
These two processes will be explained further below.
2.2.1. The formation of iron cyanide surface compounds
The thermodynamic stability diagram of Fe-EX-CN-H2O system
shown in Fig. 1 was established by Wang and Forssberg (1996). It
shows that the insoluble ferric ethyl xanthate (Fe(EX)3) is unstable,
whilst hexacyanoferrous ion (Fe(CN)4
6 ) is stable over a pH range
from 6.5 to 11 that commonly used in otation. The thermodynamic stability diagram is consistent with the stability constants
given in Table 1 where the ferric and ferrous xanthate complexes
are less stable and replaced by Fe(CN)4
and Fe(CN)3
6
6 . It is also
shown from this thermodynamic stability diagram that compared
3
to Fe(CN)4
6 , the formation of Fe(CN)6 dominates at higher potential and Fe2[Fe(CN)6] is the only stable insoluble iron cyanide complex dominant at pH from 4.5 to 6.5. Nonetheless this pH range is
not used for the above observed depression of pyrite otation (Wet
et al., 1997), thus Fe2[Fe(CN)6] might not be responsible for the
depression. The soluble species Fe(CN)4
and Fe(CN)3
are sug6
6
gested to interact with ferric and ferrous ions respectively to form
insoluble and hydrophilic Prussian Blue compound Fe4[Fe(CN)6]3
(Abbaspour and Kamyabi, 2005). Fe4[Fe(CN)6]3 was included in
the thermodynamic stability diagram of FeSCNH2O system
(shown in Fig. 2) established by Elgillani and Fuerstenau (1968).
This compound may precipitate on the pyrite surface, inhibiting
mineral interactions with ethyl xanthate and then rendering the

27

mineral surface hydrophilic. In fact, hexacyanoferrous and especially hexacyanoferric complexes were also found to depress pyrite
(Sutherland and Wark, 1955).
However, the existence of insoluble iron cyanide compounds on
pyrite surfaces has not been well conrmed by experimental
studies. The main stretching frequencies for cyanoferrous and
cyanoferric complexes at 2098 cm1 and 2135 cm1, respectively,
did not occur on the infrared spectra of pyrite samples treated with
free cyanide, whilst the stretching band at 2037 cm1 was
observed on pyrrhotite corresponding to the adsorbed surface
cyano species (Prestidge et al., 1993b). XPS provided some certainty on the adsorbed cyano species on pyrite surfaces due to
the appearance of N 1s signal, but it might originate from cyanide
species such as thiocyanate (SCN) (Prestidge et al., 1993b). Wet
et al. (1997) conducted electrochemical measurements to systematically examine the interaction between pyrite and cyanide in
otation. No signicant change in the capacitance value occurred
indicating that no continuous surface layer formed through the
interaction of pyrite with cyanide because the formation of such
surface layer would reduce the electrode capacitance. The above
results suggest that the existence of insoluble iron cyanide surface
species remains uncertain. Furthermore, it is difcult to correlate
the spectrophotometric studies to otation behaviour since much
higher cyanide concentrations have to be used in the spectrophotometric studies due to their detection limit.
Therefore, the above mechanism explaining the depression
effect of free cyanide on iron sulphide minerals on the basis of
thermodynamic calculations and spectrophotometric studies may
be questionable. On the other hand, Wet et al. (1997) showed that
free cyanide appeared to reduce the surface electrochemical activity, limiting both anodic and cathodic reactions on the pyrite surface since a higher impedance value in the low frequency region
with a lower anodic and cathodic current density was observed.
The impedance spectrum was measured at open circuit potential
of a pyrite electrode in this work. It is promising to investigate
the electrochemical impedance of the pyrite electrode at other
potential values, since the formation of iron cyanide compounds
involve oxidation or reduction processes, consequently relying on
the electrochemical potential of the mineral surface (Abbaspour
and Kamyabi, 2005). An attempt made by Sutherland and Wark
(1955) showed a direct and important correlation between the
prevention of xanthate adsorption by cyanide and the potential
of a copper electrode. It is unfortunate this method has not been
used to study the action of cyanide on sulphide mineral surface
then.
Although thiocyanate was shown to have a minor depression
effect on pyrite otation (Sutherland and Wark, 1955), it is worth
noting that free cyanide may also react with sulphur in reactive
iron sulphide minerals such as pyrrhotite to form thiocyanate

Fig. 3. Speciation of cyanide as a function of cyanide to copper ratio in solutions

containing 1 mM copper at pH 10 (Dai et al., 2012).

28

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

Fig. 4. Flotation recovery as a function of potential for chalcocite, chalcopyrite, and

pyrite at pH = 9.2; [EX] = 1.44  105 M for chalcocite and 2  105 M for other
sulphides (Ralston, 1991).

thereby removing any surface hydrophobic entity. Wark (1938)

observed that the contact of sulphide minerals with air bubbles
was still possible at mildly alkaline pH at a CuSO4/NaCN ratio of
approximately 3/1, under which the formation of cuprous dicyanide complex Cu(CN)
2 is favoured in addition to cyanate (OCN),
an oxidation product of cyanide by Cu2+. Therefore, Cu(CN)
2 was
believed not as a depressant for the otation of sulphide minerals
including pyrite. Cyanide speciation studies (Dai et al., 2012; Lu
et al., 2002) shows that cuprous tricyanide complex Cu(CN)2
3
and cuprous tetracyanide complex Cu(CN)3
4 form at CN/Cu(I) > 2
as shown in Fig. 3. The third or fourth of the cyanide ligand complexes with copper is relatively unstable (Lu et al., 2002) and
may react with iron sulphide minerals considering that iron has
much stronger afnity with cyanide than copper. However, the
WAD cyanide speciation largely depends on the cyanide concentration, pH and salinity of the solution (Lukey et al., 1999). The
interaction of various WAD cyanide species with iron sulphide
minerals needs to be further examined.
2.2.2. Effect of electrochemical potential
It is clear that xanthate adsorption and oxidation are electrochemical activities depending on the potential across the minerals-solution interface. Dixanthogen forms if the mineral surface
attains a mixed potential value higher than the xanthate/dixanthogen equilibrium potential. The xanthate/dixanthogen equilibrium
potential depends on the type of xanthate such as the functional
group and the number of carbon atoms in a hydrocarbon chain
(Chander, 2003). Chander (2003) reported that the higher the
number of carbon atoms in the hydrocarbon chain, the lower the
equilibrium potential of the xanthate/dixanthogen couple. Miller

Fig. 5. Contact curves for several sulphide minerals with 25 mg/L potassium ethyl
xanthate (KEX), bubble attachment occurs at the left side of the curve for each
mineral (Wark, 1938).

et al. (2006) reported that in 1  103 M amyl xanthate solution,

a hydrophobic pyrite surface was observed at potential more than
190 mV (SHE) corresponding to that of the oxidation of xanthate to
dixanthogen for the amyl xanthate/diamyl dixanthogen couple. A
strong correlation between potential of sulphide mineral electrode
and otation recovery with ethyl xanthate as collector is shown in
Fig. 4 where the otation recovery is only signicant above certain
potential values for a specic sulphide mineral (Ralston, 1991).
Additionally, the collectorless otation of sulphide minerals is also
dependent on the potential across the minerals-solution interface
due to the formation of the elemental sulphur or metal decient
and sulphur rich surface relevant to the oxidation of mineral surfaces (Ralston, 1991).
In the presence of free cyanide, the surface potential of pyrite
may be lower than the xanthate/dixanthogen equilibrium potential, thus inhibiting the electrochemical oxidation of xanthate
according to Eqs. (4) and (5). Furthermore, the xanthate adsorption
and iron xanthate formation will also be inhibited by the decrease
in potential according to Eqs. (1)(3). The potential of pyrite electrode decreased from 195 mV to 125 mV (SHE) with the addition of
200 mg/L NaCN at pH 11 (Wet et al., 1997), at which the otation
of pyrite was almost completely depressed. A comparison shows
that the otation of pyrite becomes more tolerant to the addition
of cyanide after oxidation of the mineral surface (Grano et al.,
1990). It is similarly reported that pyrite is still able to contact with
air bubbles in the presence of 20 mg/L NaCN at pH 8 after oxidation
(Sutherland and Wark, 1955). However, increasing pyrite potential
back to 195 mV (SHE) by adding oxidant H2O2 did not reverse the
depression effect of cyanide in the study by Wet et al. (1997). It is
also observed that the depression of pyrite otation may also occur
at a potential higher than the xanthate/dixanthogen equilibrium
potential as a result of low cyanide concentration addition such
as 10 mg/L NaCN (Hodgkinson et al., 1994; Wet et al., 1997).
Therefore, it is valuable to investigate the oxidation of xanthate
to dixanthogen in the presence of cyanide and its dependence on
the potential.
2.3. Effect of cyanide on the otation of copper sulphide minerals
The addition of free cyanide depresses the otation of chalcopyrite with high natural oatability after coating with graphitic
carbon on the surface (Grano, 1990). A slightly higher concentration of NaCN is required to reduce chalcopyrite hydrophobicity in
the presence of xanthate compared to pyrite. Much higher NaCN
concentrations are required to completely depress the hydrophobicity of chalcocite as can be seen from Fig. 5 (Wark, 1938).
Chalcocite is known to oat at potential values more negative than
pyrite due to the formation of cuprous xanthate species which are
thermodynamically more stable than the oxidised form of collector
such as dixanthogen, while both cuprous xanthate and dixanthogen attribute to the hydrophobicity on chalcopyrite surfaces. The
depression effectiveness of NaCN on different sulphide minerals
may be related to the specic potential range required for the
otation of each mineral as shown in Fig. 4.
Castro and Larrondo (1981) found that the depression effect of
free cyanide on chalcocite otation was dependent on the conditioning time. At the initial period with the addition of 150 mg/L
NaCN, the completely depressive action of free cyanide on
chalcocite otation was similar to that in pyrite otation with
the potential of chalcocite electrode dropped almost instantly from
150 mV to 300 mV (SHE) at which the xanthate oxidation was
inhibited according to spectrophotometric evidence. The leaching
of chalcocite by free cyanide in otation and the occurrence of
reactions between cyanide and copper imply that free cyanide
can be extensively consumed, which also explains the possible
attenuation of the depressant action of cyanide on chalcocite.

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

The main anodic and cathodic reactions are described in Eqs. (6)
and (7) (Castro and Larrondo, 1981).

29

make Cu2+ available, which is described in Eq. (8) (Casella and

Gatta, 2000).

Cu2 S 3CN ! CuS CuCN2 1=2CN2 2e

2CuCNn1n 3H2 O ! CuOH2 CuO 6H 2nCN 4e

1=2O2 H2 O 2e ! 2OH

The copper activation of sphalerite otation has recently been

reviewed by Chandra and Gerson (2009). It has been well established (Gerson et al., 1999; Popov and Vucinic, 1990; Prestidge
et al., 1997; Ralston and Healy, 1980a) that under mildly acidic
conditions, Cu2+ activating sphalerite follows an ion exchange
mechanism where the uptake of Cu2+ results in exchange and
release of Zn2+ into the solution. Under alkaline conditions the generally accepted copper activation mechanism involves Cu(OH)2
surface precipitation, followed by copperzinc exchange and zinc
hydroxide dissolution or dispersion (Ralston and Healy, 1980b;
Wang et al., 1989b). The copper species on sphalerite surfaces react
with xanthate leading to the adsorption of hydrophobic cuprous
xanthate complexes.
The potential required for the thermodynamic decomposition of
cuprocyanide in Eq. (8) is 500 mV (SCE) which is not likely to be
achieved in normal otation. For example, in the study of Seke
and Pistorius (2006) the pulp potential measured in otation ranged from 100 to 130 mV (SHE). However, it is observed by Casella
and Gatta (2000) that the deposition of cupric complexes started at
potential values at which cuprocyanide was still thermodynamically stable. Nevertheless, from Eq. (8) free cyanide has been
released simultaneously with the oxidation of copper. While the
competition between the depression effect of free cyanide and
the activation effect of cupric species is unclear, the mechanism
by which cuprocyanide species themselves activate sphalerite cannot be ignored.
Therefore, the depression effect of cyanide on the otation of
sphalerite depends greatly on copper environments in the ore
and otation pulp because sphalerite otation is always associated
with the use of copper activation. It is also found that the leaching
of copper ions from chalcopyrite by cyanide resulted in the activation of sphalerite (Rao et al., 2011). The activation of sphalerite in
the presence of cuprocyanide species is detrimental to the otation
of galena against sphalerite. The activation of sphalerite can be
completely deactivated by the addition of excess free cyanide,
leaching out copper that was previously adsorbed onto the sphalerite surface, subsequently removing the adsorbed xanthate
(Buckley et al., 1989; Prestidge et al., 1997; Seke and Pistorius,
2006).

Cu(CN)
2

Of the reaction products,

was suggested not to be a
depressant for the otation of copper minerals (Wark, 1938).
Castro and Larrondo (1981) observed that once the concentration
of free cyanide had rapidly decreased to a certain value, the chalcocite started recovering its oatability due to xanthate ions being
reabsorbed. There was also a steady increase in potential with time
as the cyanide was consumed and the reactivation of chalcocite
occurred when the potential value became more than 40 mV
(SHE).
The depression effect of hexacyanoferrous and hexacyanoferric
complexes on chalcocite otation is pronounced with its recovery
being completely decreased at 30 g/t K3Fe(CN)6 and 90 g/t
K4Fe(CN)43H2O (Sutherland and Wark, 1955). The depressant
effect of hexacyanoferrous complex has also been reported on
chalcocite otation by Castro and Larrondo (1981).
2.4. Effect of cyanide on sphalerite otation
Free cyanide is used as depressant as well to suppress the otation of sphalerite in leadzinc ores in the lead otation circuit to
improve the otation selectivity with xanthate as collector. However, the depression action of free cyanide on sphalerite is not
effective compared with pyrite. A case study on Rosh Pinah Zinc
Lead Mine (Seke, 2005) shows that the maximal depression of
sphalerite recovery from 37% to 28% was achieved by the addition
of up to 100 g/t NaCN with 50 g/t SNPX collector at pH 8.5. The
mechanism by which cyanide depresses sphalerite otation is
not well understood yet. Some researchers thought that the sphalerite surface became coated with insoluble hydrophilic Zn(CN)2
compound (Sutherland and Wark, 1955). Although this hypothesis
has not been proved, there is an obvious amount of Zn(CN)2 precipitating at CN/Zn ratio smaller than 4 according to cyanide speciation study (Osathaphan et al., 2008; Penneman and Jones, 1961).
Controversial viewpoints were raised when XPS was used to determine the modication of cyanide on the sphalerite surface. XPS
analysis indicated that the formation of zinc cyanide remained in
the solution rather than at the sphalerite surface due to weak afnities between metal cyanide complexes and the parent mineral
(Prestidge et al., 1997). Zinc xanthate complexes are suggested to
be responsible for the hydrophobicity of sphalerite in the otation
with xanthate, favoured by the oxidation of sphalerite at positive
pulp potential values (Seke and Pistorius, 2006). Therefore, the
electrochemically reducing ability of free cyanide might explain
its depression on sphalerite otation.
Similar with pyrite, the ratio of cyanide to copper plays an
important role in the depression of sphalerite otation due to its
determining effect on cyanide speciation. Sphalerite still exhibits
hydrophobicity in the presence of cuprous dicyanide Cu(CN)
2 by
mixing NaCN and CuSO4 at a mole ratio of 3/1, while sphalerite
loses its hydrophobicity with higher coordinated complexes being
predominant such as Cu(CN)2
and Cu(CN)3
together with CN
3
4
(Wark, 1938). However, opposite observations were made by
Seke and Pistorius (2006) that Cu(CN)2
3 (prepared by mixing CuCN
and NaCN at a CN/Cu mole ratio of 3/1) activated sphalerite otation, increasing the zinc recovery from 55% to 70%. Their results
showed that sphalerite was also activated by CuCN, but deactivated at CN/Cu mole ratio of 4/1. It is suggested that the activation
of sphalerite by cuprocyanide species can occur if they undergo
decomposition and oxidation at elevated positive potential to

2.5. Effect of cyanide on galena otation

Galena otation in the presence of free cyanide behaves differently from iron, copper and zinc sulphide minerals. Similar to copper minerals, the adsorption of xanthate on the galena surface is
through the complexation of lead xanthate, which is positively
enhanced by the oxidation of galena with more Pb2+ ions available
to react with xanthate. However, there is no competitive adsorption between free cyanide and xanthate on the galena surface
under otation conditions and the hydrophobicity of galena is
not inuenced by free cyanide (Sutherland and Wark, 1955).
Furthermore, free cyanide increases the xanthate adsorption onto
the galena surface at Eh values less than +200 mV (SHE). The
activation of free cyanide on galena otation is sensitive to Eh
and cyanide has little effect on ethyl xanthate adsorption at Eh
values higher than 200 mV (SHE) (Prestidge et al., 1993a). There
exists evidence supporting the activation of galena otation by
cyanide and the selectivity of galena from pyrite and sphalerite
achieved using free cyanide. Grano et al. (1990) found that the otation recovery of galena of Mount Isa Mines leadzinc ore was

30

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

increased by more than 20% with the addition of 200 g/t cyanide at
Eh of 200 mV (SHE).
Direct surface chemical interactions between cyanide and
galena have been observed (Prestidge et al., 1993a). Unlike iron
cyanide complexes, lead cyanide complexes are relatively weak
and therefore cyanide interacts with the sulphur moiety of galena,
leaving a lead-rich galena surface more susceptible to ethyl xanthate interaction. In selective otation, the depression of iron, copper and zinc sulphide minerals by cyanide promotes xanthate and
oxygen to interact with galena, which may lead to indirect activation of galena otation.
However, when free cyanide is used in combination with ferrous ions, the kinetics of galena otation is greatly dependent on
pH and depressed under some conditions. It is reported by Popov
et al. (1988) that FeSO4 and NaCN at a molar ratio of 1 or higher
have a depressive effect on galena otation in the presence of xanthate with recovery dropping from nearly 100% to 40% at pH 6,
while the depression effect on galena otation became less pronounced when pH increased up to 8. It is suggested by Popov
et al. (1988) that besides hexacyanoferrous ions, Fe2+ ions are also
present at pH lower than 8, the adsorption of which on galena surfaces provides active sites to react with hexacyanoferrous ions to
form hydrophilic ferrous hexacyanoferrous compounds. Although
the existence of ferrous hexacyanoferrous compounds has to be
questioned, the presence of insoluble species on galena surfaces
were conrmed based on infrared data with a stretching band at
2045 cm1, a characteristic of the cyanoferrous group (Popov
et al., 1988). As a result, the presence of ferrous ions can be
detrimental to the selective otation of leadzinc ores using free
cyanide as depressant for sphalerite.

2.6. Effect of cyanide on gold otation

The largest cyanide consumption in the mining industry lies in
the cyanidation process which has been the dominant means of
dissolving precious metal such as gold from ores for the last
100 years due to its high afnity with these precious metals
(Fleming, 1992; Hilson and Monhemius, 2006; Marsden and
House, 2006). The water discharged from cyanidation process
contains a signicant amount of free cyanide as well as metal
cyanide complexes due to the cyanide consumers co-existing in
the ore with precious metals such as Cu, Zn, Ni, Fe, Ag and Co.
Thiocyanate (SCN) may also form by the reaction of cyanide with
sulphur in the ore in the cyanidation process. The oxidation of
cyanide to cyanate (OCN) can be realised due to the majority
of cyanide destruction processes are based on the oxidation
of cyanide using different oxidants in alkaline chlorination
process, copper-catalysed sulphur dioxide and air process, coppercatalysed hydrogen peroxide process, and Caros acid process
(Logsdon et al., 1999; Marsden and House, 2006; Teixeira et al.,
2013). Most gold processing plants around the world are required
by law to destroy or recover cyanide and metal cyanide complexes
in their cyanidation tailings prior to discharge from the metallurgical site into the natural environment, so as to minimise the
exposure of wildlife to these toxic solutions. It is worth noting on
the other hand that the process water after detoxication is recycled to upstream minerals processing circuits due to the negative
water balance in many plants. Furthermore, the water discharged
from cyanidation tailings may be recycled to the upstream directly
without cyanide destruction since this process requires large
capital and operating costs. This issue has drawn the attention of
Adams (Adams, 2013) recently, reviewing the impact of recycle
cyanide and its associated reaction products in cyanide bearing
streams or cyanide recovery streams on upstream unit operations
including milling, otation, and bioleaching. The attempt to oat

sulphide minerals from gold leaching residues also encounters a

similar problem.
The presence of small quantity of cyanide species in the pulp
may signicantly affect the otation of precious minerals. There
have been a great number of studies on the otation of gold based
on both single minerals and real ore systems. Liberated gold are
hydrophobic during conditioning in otation where they readily
adsorb collectors such as xanthate (Allan and Woodcock, 2001;
Tennyson, 1980). It is generally believed that cyanide depresses
the otation of liberated gold through the formation of stable gold
cyanide complexes Au(CN)
2 , dissolving gold into solutions and
therefore reducing Au and Ag recoveries (Rees and van Deventer,
1999; Sparrow and Woodcock, 1995; Yin et al., 2011).
In addition to liberated gold, gold is often associated with sulphide minerals such as pyrite, chalcopyrite, sphalerite and galena.
In some cases as much as 20% gold is associated with pyrite
(Botelho De Sousa et al., 1986). Gold associated with pyrite in
Witwatersrand gold ores occurs mainly as minute inclusions and
veinlets (a few microns in size) locked in the pyrite matrix
(Anhaeusser et al., 1987). In general the otation of gold associated
with sulphides follows the same trend as the otation of these
sulphide minerals which are greatly affected by cyanide, mainly
through depression. Therefore, possible ways have been proposed
and attempted to recovery sulphide minerals in the presence of
cyanide in order to recover the valuable precious metals associated
with these sulphides.
3. Ways to mitigate the depression effect of cyanide on minerals
otation
Many researchers have been investigating the possibility of low
cost otation process suitable for auriferous pyrite and other sulphides in gold plants. One possible way to mitigate the depression
effect of cyanide in the past has been to wash the pulp with
freshwater to dilute cyanide. However, this pre-treatment method
cannot be applied considering the current water balance in many
gold plants; therefore economical and feasible ways have to be
implemented.
3.1. The addition of activators
Both of the addition of activators and alternative collectors to
replace xanthate has been considered by researchers to mitigate
the depression effect of cyanide on minerals otation. These
available mitigation methods were developed on the basis of the
depression mechanisms of cyanide on mineral otation which
has been described previously in this paper. Cyanide may prevent
the chemisorption of xanthate on minerals surface due to its higher
afnity with metals in the sulphide minerals. Agent that can
decompose the strong complexion of metal cyanide, detaching
cyanide from minerals surface thus providing available sites for
xanthate adsorption may be considered to mitigate the depression
of cyanide. It is reported by Reddy et al. (1991) that nickel sulphate
is used as an activator for sphalerite otation in the presence of
cyanide since Ni(CN)2
forms with higher stability than zinc
4
cyanide, staying in the solution preventing the adsorption of cyanide onto sphalerite surfaces. Besides, the use of formaldehyde
(HCHO) improves the cyanide depressed sphalerite otation due
to the decomposition of zinc cyanide complexes by formaldehyde
(Reddy et al., 1991). Because formaldehyde is much cheaper than
copper sulphate, it is suggested to be an alternative activator to
replace a large amount of copper sulphate, and then a small
amount of copper sulphate is used to nalize the activation
process. However, the depression effect of cyanide on pyrite otation is unlikely to be affected by either nickel ions or formaldehyde
because cyanide has a stronger afnity with iron than nickel as can

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

be seen from the thermodynamic stability constants in Table 1 and

formaldehyde has no decomposition action over iron cyanide
complexes.
The cupric ion Cu2+, generally in the form of sulphate or
nitrate salts, is the most widely used activator for the otation
of sulphide minerals such as pyrite (Chandra and Gerson, 2009;
Finkelstein, 1997; Weisener and Gerson, 2000). The activation of
pyrite by Cu2+ ions is considered to be an electrochemical process
involving Cu2+ adsorption onto the surface of pyrite, the cupric
ion reduced to cuprous ion with subsequent oxidation of sulphide
surface during adsorption. The pyrite surface is covered with Cu2S
more than CuS to activate the surface for hydrophobic collector
attachment, and cuprous xanthate is the dominant activation
product, as was suggested by Leppinen (1990). He et al. (2005)
demonstrated that the electrochemical potential was an important factor in the otation of the copper activated pyrite with
the maximum pyrite recovery being obtained at 35 mV (SHE) at
pH 9.
Cyanide may reduce the otation pulp potential and inhibit the
electrochemical activity on pyrite surface which is however essential for the action of copper activation. Therefore, the use of cupric
ion as an activator for pyrite otation in the presence of cyanide
only resulted in a slight improvement in a series of contact angle
measurements (Miller et al., 2006). Moreoever, the formation of
cuprous xanthate is inhibited by the formation of cuprocyanide
species with higher thermodynamic stability (Wang and
Forssberg, 1996). Millers work showed that the activation of pyrite
otation in cyanide solution could be achieved more effectively
with Pb2+ than with Cu2+. For potassium amyl xanthate (PAX)
and lead nitrate concentration at 1  103 M, the hydrophobic pyrite surface state could be sustained at 70 mg/L NaCN. The activation of Pb2+ occurs via the adsorption of Pb2+ onto pyrite surfaces
as lead complexes such as hydroxides or carbonates, independent
on the electrochemical potential. Furthermore, lead xanthate was
conrmed as a more stable species than lead cyanide, thus unlike
copper, cyanide ions will not be competing with xanthate for active
lead sites, facilitating xanthate adsorption at the lead-treated pyrite surface, resulting in hydrophobic pyrite surfaces (Pecina et al.,
2006). However, lead salts are relatively more expensive than
copper salts and lead is a more toxic heavy metal, which must be
considered in industry operations. Similar with Pb2+, Ca2+ ions
can also provide high density of surface active sites on pyrite which
electrostatically attract negatively charged xanthate (Zhang et al.,
1997). Therefore, opportunities for other low cost activators that
have a stronger afnity with xanthate than cyanide and interact
with xanthate electrostatically remain to be explored.
It is worth noting that lead ions as activator could not result in
fully mitigation of the depression effect of galena otation caused
by hydrophilic ferrous hexacyanoferrous coatings (Popov et al.,
1988). The desorption of hydrophilic iron cyanide compounds from
mineral surface does not take place in the presence of lead nitride,
which reduces the free surface sites available for Pb2 ions
adsorption.
3.2. Alternative collectors
It is examined by Sutherland and Wark (1955) that the
adsorption of dithiophosphates was most inuenced by cyanide
depression, while the adsorption of dithiocarbamates was least
inuenced and the xanthates were intermediate. While these
are still not effective collectors, amine has been identied as a
possible alternative collector for auriferous pyrite otation in
the presence of cyanide (Hodgkinson et al., 1994; Wet et al.,
1995). It was tested at both GENMIN Process Research and onsite
at Buffelsfontein that sulphur recovery of 83% was achieved at
alkaline pH using Trocol S50, a proprietary amine based collector

31

(Hodgkinson et al., 1994). At pH 9 with 4  105 M dodecylamine

(DDA) acetate, the presence of 200 mg/L NaCN decreased the total
sulphur recovery by 20%, compared to a decrease by 80% with
xanthate as collector (Wet et al., 1995). The higher pH values
favoured amine adsorption on the pyrite surface. The depression
effect by cyanide was completely overcome by amine at a pH
value of 11 (Wet et al., 1995). The effect of amine thioacetate
(cocoakyl amine thioacetate, commercially known as Armac)
was also identied in the presence of cyanide with sulphide
recovery being increased up to 95% with a concentration of
100 g/t Armac (Benzaazoua et al., 2000).
Amine oats pyrite in the presence of cyanide is possibly due to
its reaction with pyrite surfaces is through electrostatic, rather
than electrochemical interactions. Cyanide affects pyrite otation
through depressing electrochemical activities on the pyrite surface,
as stated previously. The collecting power of amine does not
depend on an electrochemical reaction, and there is no signicant
oxidised amine species detected on the surface of pyrite (Kongolo
et al., 2004). Furthermore, the decrease of potential in the presence
of cyanide enhances the absorption of amine as a cationic reagent
(Elgillani and Fuerstenau, 1968).
4. Conclusions
Cyanide has been used to improve the selectivity in the otation of base metal sulphide minerals. Iron, copper and zinc
sulphides can be depressed by free cyanide when xanthate is
used as collector. The mechanisms underlying the depression
effect on pyrite otation may be attributed to the formation
of insoluble hydrophilic iron cyanide compounds on mineral
surfaces, preventing the chemisorption of xanthate. Free cyanide
signicantly inhibits the electrochemical activities and decreases
the mixed potential on pyrite surface which is of vital
importance for the chemisorption and oxidation of xanthate.
However, the depression effects of free cyanide on copper and
zinc sulphide otation are much more complicated depending
on ore properties and pulp environments, and free cyanide acts
as activator for galena otation. The effects of metal cyanide
species including WAD cyanide on sulphide mineral otation
are unclear due to their complicated speciation subject to otation environments. Precious minerals such as gold may also be
depressed in otation using recycled water containing cyanide
species.
Acknowledgement
The authors gratefully acknowledge the nancial support of this
work from Morobe Mining Joint Venture.
References
Abbaspour, A., Kamyabi, M.A., 2005. Electrochemical formation of Prussian blue
lms with a single ferricyanide solution on gold electrode. J. Electroanal. Chem.
587, 117123.
Adams, M.D., 2013. Impact of recycling cyanide and its reaction products on
upstream unit operations. Miner. Eng. 53, 241255.
Allan, G.C., Woodcock, J.T., 2001. A review of the otation of native gold and
electrum. Miner. Eng. 14 (9), 931962.
Allison, S.A., Gold, L.A., Nicol, N.G., Granville, A., 1972. A determination of the
product of reaction between various sulde minerals and aqueous xanthate
solutions, and a correlation of the products with electrode rest potentials.
Metall. Trans. B, Process Metall. 3 (10), 26132618.
Anhaeusser, C.R., Feather, C.E., Liebenberg, W.R., Smits, G., Snegg, J.A., 1987. The
geology and mineralogy of the principal goldelds in South Africa. In: Stanley,
G.G. (Ed.), The Extractive Metallurgy of Gold in South Africa, South African
InstItute of Mining and Metallurgy, Johannesburg, pp. 167.
Benzaazoua, M., Bussiere, B., Kongolo, M., McLaughlin, J., Marion, P., 2000.
Environmental desulphurization of four Canadian tailings. Int. J. Miner.
Process. 60, 5774.

32

B. Guo et al. / Minerals Engineering 6668 (2014) 2532

Botelho De Sousa, A.M.R., OConnor, C.T., Dunne, R.C., 1986. The inuence of various,
chemical, physical and mineralogical factors on the otation of gold-bearing
pyrites. GOLD 100. In: Proc. Conference on Gold Extractive Metallurgy of Gold.
South African InstItute of Mining and Metallurgy, Johannesburg, pp. 493503.
Buckley, A.N., Wood, R., Wouterlood, H.J., 1989. An XPS invistigation of the surface
of natural sphalerite under otation related conditions. Int. J. Miner. Process. 26
(12), 2949.
Casella, I.G., Gatta, M., 2000. Anodic electrodeposition of copper oxide/hydroxide
lms by alkaline solutions containing cuprous cyanide ions. J. Electroanal.
Chem. 494 (1), 1220.
Castro, S., Larrondo, J., 1981. An electrochemical study of depression of otation of
chalcocite by cyanide and iron-cyanide comple. J. Electroanal. Chem. 118,
317326.
Chander, S., 2003. A brief review of pulp potentials in sulde otation. Int. J. Miner.
Process. 72 (14), 141150.
Chandra, A.P., Gerson, A.R., 2009. A review of the fundamental studies of the copper
activation mechanisms for selective otation of the sulde minerals, sphalerite
and pyrite. Adv. Colloid Interface Sci. 145 (14), 97110.
Dai, X., Simons, A., Breuer, P., 2012. A review of copper cyanide recovery
technologies for the cyanidation of copper containing gold ores. Miner. Eng.
25 (1), 113.
Elgillani, D.A., Fuerstenau, M.C., 1968. Mechanisms involved in cyanide depression
of pyrite. Trans. AIME (Soc. Min. Eng.) 241, 437445.
Finkelstein, N.P., 1997. The activation of sulphide minerals for otation: a review.
Int. J. Miner. Process. 52 (23), 81120.
Fleming, C.A., 1992. Hydrometallurgy of precious metals recovery. Hydrometallurgy
30 (13), 127162.
Fuerstenau, D.W., Mishra, R.K., 1980. On the mechanism of pyrite otation with
xanthate collectors. In: Jones, J.J. (Ed.), Complex Sulde Ores, The Institution of
Mining and Metallurgy, London, pp. 271278.
Fuerstenau, M.C., Kuhn, M.C., Elgillani, D.A., 1968. The role of dixanthogen
in xanthate otation of pyrite. Trans. Am. Inst. Min., Metall. Petrol. Eng. 241,
148156.
Gerson, A.R., Lange, A.G., Prince, K.E., Smart, R.S.C., 1999. The mechanism of copper
activation of sphalerite. Appl. Surf. Sci. 127 (14), 207223.
Grano, S., Ralston, J., Smart, R.S.C., 1990. Inuence of electrochemical enviroment on
the otation behaviour of Mt. Isa copper and leadzinc ore. Int. J. Miner. Process.
30, 6997.
Haung, H.H., Miller, J.D., 1978. Kinetics and thermochemistry of amyl xanthate
adsorption by pyrite and marcasite. Int. J. Miner. Process. 5 (3), 241266.
He, X., Fornasiero, D., Skinner, W., 2005. Correlation between copper-activated
pyrite otation and surface species: effect of pulp oxidation potential. Miner.
Eng. 18 (12), 12081213.
Hilson, G., Monhemius, A.J., 2006. Alternatives to cyanide in the gold mining
industry: what prospects for the future? J. Clean. Prod. 14 (1213), 11581167.
Hodgkinson, G., Sandenberghs, R.F., Hunter, C.J., 1994. Pyrite otation from gold
leach residues. Miner. Eng. 7 (56), 691698.
Janetski, N.D., Woodburn, S.I., Woods, R., 1977. An electrochemical investigation of
pyrite otation and depression. Int. J. Miner. Process. 4, 227239.
Kongolo, M., Benzaazoua, M., de Donato, P., Drouet, B., Barres, O., 2004. The
comparison between amine thioacetate and amyl xanthate collector
performances for pyrite otation and its application to tailings
desulphurization. Miner. Eng. 17, 501515.
Leppinen, J.O., 1990. FTIR and otation investigation of the adsorption of ethyl
xanthate on activated and non-activated sulde minerals. Int. J. Miner. Process.
30 (34), 245263.
Logsdon, M.J., Hagelstein, K., Mudder, T.I., 1999. The management of cyanide in
gold extraction. International Council on Metals and The Enviroment, Ottawa,
pp. 121.
Lu, J.M., Dreisinger, D.B., Cooper, W.C., 2002. Thermodynamics of the aqueous
coppercyanide system. Hydrometallurgy 66 (13), 2336.
Lukey, G.C., Van Deventer, J.S.J., Huntington, S.T., Chowdhury, R.L., Shallcross, D.C.,
1999. Raman study on the speciation of copper cyanide complexes in highly
saline solutions. Hydrometallurgy 53 (3), 233244.
Majima, H., Takeda, M., 1968. Electrochemical studies of the xanthatedixanthogen
system on pyrite. Trans. Am. Inst. Min. Metall. Petrol. Eng. 241, 431436.
Marsden, J.O., House, C.L., 2006. The chemistry of gold extraction, second ed.,
Society for Mining, Metallurgy, and Exploration, Inc., Littleton, pp. 233270 and
486497.
Miller, J.D., Plessis, R.D., Kotlyar, D.G., Zhu, X., Simmons, G.L., 2002. The low
potential hydrophobic state of pyrite in amyl xanthate otation with nitrogen.
Int. J. Miner. Process. 67 (14), 115.
Miller, J.D., Kappes, R., Simmons, G.L., LeVier, K.M., 2006. Pyrite activation in amyl
xanthate otation with nitrogen. Miner. Eng. 19 (68), 659665.
Osathaphan, K., Boonpitak, T., Laopirojana, T., Sharma, V.K., 2008. Removal of
cyanide and zinc-cyanide complex by an ion-exchange process. Water Air Soil
Pollut. 194 (14), 179183.
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. Miner. Eng. 19,
172179.

Penneman, R.A., Jones, L.H., 1961. Infra-red absorption studies of the aqueous
cyanide complexes of mercury, cadmium, and zinc. J. Inorgan. Nucl. Chem. 20,
1931.
Popov, S.R., Vucinic, D.R., 1990. The ethylxanthate adsorption on copper-activated
sphalerite under otation-related conditions in alkaline media. Int. J. Miner.
Process. 30 (34), 229.
Popov, S.R., Vucinic, D.R., Calic, N.M., 1988. Effect of the depressing agents FeSO4
and NaCN on the surface properties of galena in the otation system. Int. J.
Miner. Process. 24, 111123.
Prestidge, C.A., Ralston, J., Smart, R.S.C., 1993a. The role of cyanide in the interaction
of ethyl xanthate with galena. Colloids Surfaces A: Physicochem. Eng. Asp. 81,
103119.
Prestidge, C.A., Ralston, J., Smart, R.S.C., 1993b. The competitive adsorption of
cyanide and ethyl xanthate on pyrite and pyrrhotite surfaces. Int. J. Miner.
Process. 38 (34), 205233.
Prestidge, C.A., Skinner, W.M., Ralston, J., Smart, R.S.C., 1997. Copper(II) activation
and cyanide deactivation of zinc sulphide under mildly alkaline conditions.
Appl. Surf. Sci. 108, 333344.
Ralston, J., 1991. Eh and its consequences in sulphide minerals otation. Miner. Eng.
4 (711), 859878.
Ralston, J., Healy, T.W., 1980a. Activation of zinc sulphide with CuII, CdII and PbII: I.
Activation in weakly acidic media. Int. J. Miner. Process. 7 (3), 175201.
Ralston, J., Healy, T.W., 1980b. Activation of zinc sulphide with CuII, CdII and PbII: II.
Activation in neutral and weakly alkaline media. Int. J. Miner. Process. 7 (3),
203217.
Rao, S.R., Nesset, J.E., Finch, J.A., 2011. Activation of sphalerite by Cu ions produced
by cyanide action on chalcopyrite. Miner. Eng. 24 (9), 10251027.
Reddy, G.S., Reddy, C.K., Sekhar, D.M.R., Ravindranath, K., Chulet, M.R., 1991. Effect
of formaldehyde and nickel sulphate solutions on the activation of cyanidedepressed sphalerite. Miner. Eng. 4 (2), 151160.
Rees, K.L., van Deventer, J.S.J., 1999. The role of metal-cyanide species in leaching
gold from a copper concentrate. Miner. Eng. 12 (8), 877892.
Seke, M.D., Selective otation of galena and sphalerite at Rosh Pinah Mine. PhD
dissertation, University of Pretoria, Pretoria, 2005.
Seke, M.D., Pistorius, P.C., 2006. Effect of cuprous cyanide, dry and wet milling on
the selective otation of galena and sphalerite. Miner. Eng. 19 (1), 111.
Sparrow, G.J., Woodcock, J.T., 1995. Cyanide and other lixiviant leaching systems for
gold with some practical applications. Miner. Process. Extr. Metall. Rev. 14 (3
4), 193247.
Sutherland, K.L., Wark, I.W., 1955. Principles of otation. Australian InstItute of
Mining and Metallurgy (Inc.), Melbourne, pp. 113149.
Teixeira, L.A.C., Andiaa, J.P.M., Yokoyamac, L., Arajoc, F.V.F., Sarmientod, C.M.,
2013. Oxidation of cyanide in efuents by Caros Acid. Miner. Eng. 45, 8187.
Tennyson, S., 1980. The hydrophilic nature of a clean gold surface. J. Colloid
Interface Sci. 75 (1), 5155.
Valdivieso, A.L., Sanchez, A.A.L., Song, S., 2005. On the cathodic reaction coupled
with the oxidation of xanthates at the pyrite/aqueous solution interface. Int. J.
Miner. Process. 77, 154164.
Wang, X.H., Forssberg, E.K.S., 1990a. The chemistry of cyanidemetal complexes in
relation to hydrometellurgical processes of precious metals. Miner. Process.
Extr. Metall. Rev. 6, 81125.
Wang, X.H., Forssberg, E.K.S., 1990b. Mechanisms of pyrite otation with
xanthathes, in: Forssberg, E.K.S. (Ed.), Flotation of Sulphide Minerals. Elsevier,
Amsterdam, pp. 275290.
Wang, X.H., Forssberg, K.S.E., 1996. The solution electrochemistry of
suldexanthatecyanide systems in sulde mineral otation. Miner. Eng. 9
(5), 527546.
Wang, X.H., Forssberg, E.K.S., Bolin, N.J., 1989a. Thermodynamic calculations on
iron-containing sulphide mineral otation systems, I. The stability of ironxanthates. Int. J. Miner. Process. 27, 119.
Wang, X.H., Forssberg, E.K.S., Bolin, N.J., 1989b. The aqueous and surface chemistry
of activation in the otation of sulphide minerals-a review. Part II: A surface
precipitation model. Miner. Process. Extr. Metall. Rev. 4 (3-4), 167199.
Wark, I.W., 1938. Principles of otation. Australian Institute of Mining and
Metallurgy (Inc.), Melbourne, pp. 182233.
Weisener, C., Gerson, A., 2000. An investigation of the Cu (II) adsorption mechanism
on pyrite by ARXPS and SIMS. Miner. Eng. 13 (13), 13291340.
Wet, J.R.D., Hodgkinson, G., Pistorius, P.C., Prinsloo, L.C., Sandenbergh, R.F., 1995.
The inuence of cyanide on the otation of pyrite from Witwatersrand gold
leach residues. Miner. Eng. 8 (11), 13331345.
Wet, J.R.D., Pistorius, P.C., Sandenbergh, R.F., 1997. The inuence of cyanide on
pyrite otation from gold leach residues with sodium isobutyl xanthate. Int. J.
Miner. Process. 49 (34), 149169.
Yin, X., Opara, A., Du, H., Miller, J.D., 2011. Molecular dynamics simulations of
metalcyanide
complexes:
fundamental
considerations
in
gold
hydrometallurgy. Hydrometallurgy 106 (12), 6470.
Zhang, Q., Xu, Z., Bozkurt, V., Finch, J.A., 1997. Pyrite otation in the presence of
metal ions and sphalerite. Int. J. Miner. Process. 52, 187201.