Minerals Engineering 94 (2016) 21–28

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

A review of the effects of grinding media and chemical conditions

on the flotation of pyrite in refractory gold operations
A. Rabieh, B. Albijanic, J.J. Eksteen ⇑
Department of Mining Engineering and Metallurgical Engineering, Western Australia School of Mines, Curtin University, GPO Box U1987, Perth, WA 6845, Australia

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

Article history: Flotation performance of gold-bearing pyrite in refractory gold ores depend upon the interplay among
Received 12 April 2015 process water chemistry, grinding chemistry, and ore mineralogy. The nature of pyrite itself (finely dis-
Revised 7 April 2016 seminated reactive pyrite vs. low reactivity) also plays a role in its surface reactivity. This paper reviews
Accepted 21 April 2016
the experimental studies examining the interactions between grinding media, gold bearing pyrites and
Available online 10 May 2016
process water occurring during grinding of refractory gold ores and the effect of these interactions on
flotation response of pyrite. The literature review reveals that the interactions are highly convoluted. It
Keywords:
appears that the galvanic interactions between forged steel media and sulfide minerals ores are particu-
Grinding
Pulp chemistry
larly significant after grinding of massive sulfide ores. Process water chemistry can also have an ampli-
Flotation fying effect, as the process water becomes more laden with cyanide species and other ionic species.
Refractory gold ore This paper should contribute an improved understanding of electrochemical and chemical processes
occurring during the grinding of refractory gold ores, which is essential to improve flotation performance
of pyrite. Judgement is reserved with regards to the overall economics associated with the use of various
grinding media. Media consumption due to wear will have to be balanced against flotation recovery of
gold bearing sulfides and whole circuit behaviour where gold in tailing may also be further recovered
through leach processes.
Ó 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2. Effect of ore type and galvanic interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1. Effect of galvanic interactions on pulp chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.1. Dissolved oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.1.2. Pulp potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.1.3. Coating of mineral surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.2. Control of galvanic interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3. Influence of addition of reagents during grinding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.1. Collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2. Activators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
4. Influence of chromium media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
5. Influence of gas atmosphere during grinding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
7. Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

⇑ Corresponding author.
E-mail address: jacques.eksteen@curtin.edu.au (J.J. Eksteen).

http://dx.doi.org/10.1016/j.mineng.2016.04.012
0892-6875/Ó 2016 Elsevier Ltd. All rights reserved.
22 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28

1. Introduction Table 2
Rest potentials (vs. SHE) of mild steel (M.S.), austenitic stainless steel (A.S.S), and
martensitic stainless steels (M.S.S.) (Adam et al., 1984).
Selection of grinding media is very important since the con-
sumption of grinding media is one of the major operating costs Electrolyte pH EA.S.S. (V) EM.S.S. (V) EM.S. (V)
in mineral processing industry, which can be up to 50% of the over- 0.5 M NaCl (air exposed) 6.7 0.088
0.056
0.396
all grinding expenditure (Aldrich, 2013). The consumption of Distilled water (N2 bubbling) 6.8 0.118
0.298
0.516
Distilled water (air exposed) 4.0 0.150
0.106
0.374
grinding media can be caused by abrasion, impact, and corrosion
6.8 0.206 0.098
0.336
wear mechanisms. While, abrasion and impact occur due to the 10.0 0.010
0.088
0.242
mechanical forces, corrosion takes place in wet grinding environ- Distilled water (O2 exposed) 6.6 0.027 0.066
0.176
ments, and depends on many factors such as oxygen content, hard-
ness, chloride and cupric ions, galvanic interactions, and sulfur and
sulfate content (Fontana, 1987). It should also be noted that the gold ores on pulp chemistry and froth stability. This is followed
daughter products generated by these wear mechanisms can con- by a review of the effect of flotation reagents and nitrogen gas
tribute to corrosive wear significantly due to their greater surface added during the grinding. Last, the influence of high chrome white
area. iron grinding media and their effect on flotation performance are
Apart from the influence on the grinding cost, the choice of also briefly reviewed.
grinding media is essential to optimize the flotation response of
valuable sulfide minerals. For example, the comprehensive review
of the influence of different types of grinding media on flotation of 2. Effect of ore type and galvanic interactions
copper sulfide minerals was published by Bruckard et al. (2011).
However, in the case of refractory gold ores (i.e. ores in which Galvanic interactions, occurring between different materials,
the gold is hosted mainly in pyrite and/or arsenopyrite), the strongly depend on electrochemical activity of the materials
detailed analysis based on the literature data has not yet been per- (Rao, 2004). The measure of electrochemical activity of the mate-
formed. In this context, the main focus of this paper is to review rial is the rest potential which represents the difference between
past research concerning with the influence of grinding media on the potential of the selected material and the potential of the ref-
flotation response of pyrite from refractory gold ores. erence electrode when the oxidation and reduction current are
Although the selection of grinding media is very influential to equal (Rao, 2004). Tables 1 and 2 present the rest potential of var-
maximize flotation performance, other factors such as flotation ious sulfide minerals at pH 4 and a range of steels in a number of
reagents and dosages, aeration, gas dispersion, machine properties, aqueous environments, respectively.
and the use of nitrogen gas during grinding (e.g. as used in the When the difference between the rest potential of the sulfide
N2Tech technology (Dunne et al., 2009; Simmons et al., 1999)) mineral and that of the grinding media is high, the galvanic inter-
affect the achieved redox state and the flotation recovery of valu- actions are more pronounced during the grinding stage due to the
able minerals. The grinding media, ore mineralogy, and process large galvanic current. In other words, electrons are transferred
water chemistry is therefore expected to play an important part from the anode (i.e. grinding media, less cathodic mineral) to the
in flotation recovery. It should be noted that the flotation recovery cathode (i.e. cathodic mineral), causing the change of the potential
of valuable minerals can still be manipulated by a range of other of both materials from their rest potential to the mixed potential
factors as well, as discussed below. due to the tendency to achieve the equilibrium potential (Adam
As already mentioned above, the scope of this paper covers et al., 1984; Martin et al., 1991). As a result, the corrosion of the
refractory gold ores which are located in Western Australia (e.g. less cathodic material (low rest potential) increases and the corro-
Wiluna and Granny Smith gold mine), Nevada (e.g. Twin Creeks sion of the more cathodic material (high rest potential) decreases
mine), and South Africa (e.g. Fairview mine). Refractory gold ores (Fontana, 1987). Given that pyrite has the highest rest potential,
are classified as if a cyanidation process cannot recover more than and thus it is the least electrochemically active sulfide mineral,
80% of gold even though fine grinding is used (Guay, 1981). The grinding with forged steel grinding media causes the significant
reason for the refractoriness of gold ores is either because gold is galvanic interactions due to the large difference between the rest
hosted in solid solution, or as colloidal particles, in pyrite and/or potential of pyrite and that of the forged steel grinding media
arsenopyrite. Therefore, the treatment of refractory gold ores is (see Tables 1 and 2).
very complex, and involves numerous unit operations (e.g. gravity Fig. 1 shows the schematic representation of the galvanic inter-
and flotation separation, roasting, oxidative leaching, bacterial action model for the following systems:
leaching, neutralization) to render the gold amenable to cyanida-
tion (Iglesias and Carranza, 1994). (a) forged steel media-cathodic mineral,
The following section reviews the influence of galvanic interac- (b) forged steel media-anodic mineral-cathodic mineral,
tions, which occur during the grinding of particularly refractory (c) forged steel media-cathodic mineral-cathodic mineral.

The electrochemical reactions which might occur during the

Table 1
galvanic interactions are explained in Section 2.1. It should be
Rest potential (vs. SHE) of sulfide minerals at pH 4 (Rao, 2004).
noted that a sulfide mineral with a moderate rest potential can
Minerals E (V) act as a cathode or an anode depending on the thermodynamic
Molybdenite, MoS2 0.11 and kinetic properties of two sulfide minerals and forged steel
Stibnite, Sb2S3 0.12 media, (Pozzo et al., 1988).
Argentite, Ag2S 0.28
However, the understanding of galvanic interactions only tells
Galena, PbS 0.40
Bornite, Cu5FeS4 0.42
the small part of the story. When these minerals are considered,
Covelite, CuS 0.45 it is also important to note that, particularly for gold ores, the min-
Sphalerite, ZnS 0.46 eralogical association, particle grain morphology and the texture of
Chalcopyrite, CuFeS2 0.56 (anomalous) gold ores influence the gold recovery. In most cases gold is associ-
Marcasite, (Zn,Fe)S 0.63
ated with or hosted in pyrite. When the aim is gold recovery, either
Pyrite, FeS2 0.66
via direct exposure for leaching, liberation for gravity recovery, or
 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28
Fig. 1. Galvanic interaction between (a) forged steel media and cathodic mineral, (b) forged steel media-anodic mineral-cathodic mineral and (c) forged steel media-cathodic
mineral-cathodic mineral (Adam et al., 1984; Iwasaki et al., 1988).
recovery through flotation of liberated sulfide minerals, it is impor-
tant to understand the deportment mechanisms that would influ-
ence overall recovery. While free gold occurs in too low amounts to
influence milling chemistry, the chemistry in the mill (through the
impact of barren sulfides (i.e. pyrite and arsenopyrite are free of
gold and process water) can be expected to influence free gold
behaviour due to potential surface coatings and potential passiva-
tion effects. On the other hand, when the gold is size-refractory (i.e.
can still be liberated through ultra-fine grinding), colloidal – sub-
microscopic, or in solid solution in the crystal lattice, recovery is
dependent on sulfide (i.e. pyrite and arsenopyrite) recovery. The
relative exposed surface of sulfide in ore to grinding media can
strongly influence the redox conditions in the mill and subsequent
flotation behaviour. In the refractory gold ores, solid solution Au
can take on oxidation states of 0, +1 (Simmons et al., 1999) or even
+3 (Arehart et al. (1993). Similarly, arsenopyrite grains can also
host Au0 and Au1+ according to Cabri et al. (2000, 1989, 1998),
and Cathelineau et al. (1989) who mention that gold in sulfide
and sulfarsenide phases (the concentration of gold can be from
tens of ppb to more than 1% w), and occurring as invisible or visible
phases that were deposited or remobilized by multistage
hydrothermal or metamorphic events. Pyrite in refractory gold
ores can either exist as the predominant mineral (e.g. most placer
and orogenic deposits) or locked in carbonaceous-pyrite double
23
refractory ores (e.g. Carlin trend). Smaller proportions are associ-
ated with skarn and black shale deposits. In orogenic systems as
found in Western Australia, gold commonly has a bimodal distri-
bution in which gold within pyrite and arsenopyrite is overprinted
by later visible gold (Morey et al., 2008). The metallurgical implica-
tion of this is that gold has to be recovered through gravity for gold,
flotation for gold-bearing sulfides, and leaching for the flotation
tailings. The sulfide flotation concentrate can, in turn, be ultra-
fine ground (for size-refractory gold), roasted, biologically leached
or pressure leached, in all cases with the aim of exposing or liber-
ating the locked gold, followed by cyanide leaching.
Robert et al. (1997) discussed 16 general gold deposit styles and
their geological classification. From a metallurgical perspective,
these classes can be simplified to evaluate the metallurgical inter-
actions. Kesler and Wilkinson (2010) indicated that most of the
remaining global gold is associated in hydrothermal ores of which
total gold is mostly distributed with epithermal (18.2%), orogenic
(34.1%) and copper porphyry (29.8%) ores. Hydrothermal ores
now make up more than 80% of the world’s gold resources whereas
placer and paleo-placer deposits are contributing less and less of
the remaining gold resources. The hydrothermal ores are much
more complex with multiple minerals contributing to the
overall chemistry state when in contact with process water and
grinding media. Of these, the orogenic ores such as found in the
24 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28
Western-Australian and West-African greenstone belts have the
simplest sulfide chemistry, where total sulfide mineral content is
typically less than 5%, and the composition is dominated by pyrite,
with smaller amounts of arsenian pyrite, arsenopyrite, and some
pyrrhotite present.
It is also important to indicate that all pyrites are not equal with
respect to gold processing, even when they occur in the absence of
other sulfide minerals. For example, Orlich et al. (2009) indicated 4
morphological types that can be found in their Carlin operations in
Nevada, namely coarse, fine-grained, micro-crystalline, and dis-
seminated. Orlich et al. (2009) note that it is the finely dissemi-
nated pyrite that contains most of the gold that needs to be
recovered to ensure good gold recoveries. Often, the denser barren
pyrites are changed by late-stage hydrothermal alteration with
gold-bearing and arsenic-bearing fluids, causing alteration of the
rim of pyrites and leading to the generation of finer and more reac-
tive pyrites. Conversely, the coarse cubic pyrites are often barren
(of gold) and fairly unreactive. Due to the finely-locked nature of
the sulfides, it is a difficult flotation separation to achieve (flotation
will therefore recover more of the low grade/barren pyrites than
the locked disseminated pyrites). It is also noted that even though
finer grinding may improve pyrite liberation, it will lead to surface
oxidation of more reactive arsenian pyrites and arsenopyrite,
which leads to reduce the floatability. This is over and above the
economically challenging aspect of fine grinding bulk ore, com-
pared to fine grinding (regrinding) of flotation concentrates. Thus,
from a reduction-oxidation perspective, pyrite in contact with the
grinding media can be expected to behave differently based on
degree of dissemination and crystallinity. This makes the deconvo-
lution of the pyrite-process water-media system very challenging,
and emphasises the need for continued research in this area, there-
fore mechanistic models can be developed to predict the down-
stream effects on flotation and leaching when gold ore type
(where the relative amount and types of sulfides are important),
pyrite dissemination/alteration and textures, process water (corro-
sive ions and surface active ions), and grinding media composition
and media physical metallurgy can vary.
2.1. Effect of galvanic interactions on pulp chemistry
Different electrochemical reactions occur during the galvanic
interactions between sulfide minerals and forged steel media, giv-
ing rise to variations in the pulp chemistry variables (i.e. Eh, pH,
dissolved oxygen, oxygen demand, and surface chemistry). The
main consequence of galvanic interactions is the oxidation of iron
from grinding media (Rao, 2004). As seen in Fig. 2, which shows an
Eh/pH diagram for the iron–water system. Given that the ball mill
Fig. 2. Eh-pH diagram for the iron–water system ([Fe]tot = 0.01 M) (Grano, 2010).
discharge has low Eh and neutral to slightly alkaline pH typically
between 7 and 9 after the grinding of refractory gold ores
(O’Connor and Mills, 1990). The corrosion of forged steel media
might be explained with the following electrochemical reactions:
Fe0 þ 2OH
¼ FeðOHÞ2 þ 2e
ð1Þ
FeðOHÞ2 þ OH
¼ FeðOHÞ3 þ e
ð2Þ
Fe2þ þ 3OH
¼ FeðOHÞ3 þ e
ð3Þ
The released electrons in the electrochemical reactions (see Eqs.
(1)–(3)) are being transferred to the cathodic sulfide mineral,
resulting in the cathodic reduction of oxygen:
0:5O2 þ H2 O þ 2e
¼ 2OH
ð4Þ
If the ore contains two sulfide minerals, the one with the lower
rest potential is the anodic mineral, and it is anticipated that ele-
mental sulfur forms on its surface thereby improving the floatabil-
ity of that mineral:
MS þ 2OH
¼ MðOHÞ2 þ S þ 2e
ð5Þ
Eq. (5) shows forming of both a metal hydroxide and elemental
sulfur during the reaction. The sulfur may undergo a further, but
slower, oxidation to a range of anionic sulfur-oxygen compounds
(thiosulfates, sulfites and sulfates).
The reactions, shown in Eqs. (1)–(5), can be used to explain the
main effects of the galvanic interactions on pulp chemistry vari-
ables i.e. dissolved oxygen content, pulp potential, and coating of
mineral surface. The influence of galvanic interactions on these
variables is described below.
2.1.1. Dissolved oxygen
Concentration of dissolved oxygen concentration of pulp
strongly depends on numerous factors such as grinding media,
ore type, and pulp temperature (Bruckard et al., 2011). The corro-
sion of forged steel grinding media can reduce the dissolved oxy-
gen concentration to well below 1 ppm (Kelebek and Yoruk,
2002) due to the corrosion of the grinding media, or by the reaction
of the dissolved oxygen with reactive sulfides, or by the reactions
with ions in solutions such as chlorides and cupric ions. It should
be noted that the reduction of the dissolved oxygen content is par-
ticularly significant after the grinding of volcanogenic massive sul-
fide ores, which contain a large amount of pyrite (Greet and Van
den Bosch, 2014). The decrease of the dissolved oxygen content
also hinders the successful adsorption of xanthate on the surface
of sulfide minerals (Fuerstenau et al., 2007), and thus retards the
floatability of these minerals (see Section 3.1).
An increase in the pulp temperature reduces the dissolved oxy-
gen content (Huang and Schmitt, 2014) due to a decrease of the
solubility of oxygen in the aqueous phase. The reduced dissolved
oxygen content prevents the oxidation of pyrite surfaces, which
is essential to improve the floatability of pyrite. It should also be
noted that elevated temperature causes the decomposition of xan-
thate collector (Mustafa et al., 2004).
Apart from the measurements of dissolved oxygen content, it is
also very useful to determine the oxygen demand rate constant
which represents the oxygen consumption of system from the pulp
phase (Grano, 2010). The oxygen demand rate constant depends
particularly on ore mineralogy and specific surface area (Owusu
et al., 2013). For example, Owusu et al. (2013) found that non-
arsenian pyrite had 7.5 times higher the oxygen demand rate con-
stant than arsenian pyrite (i.e. pyrite in which As is incorporated
into pyrite crystals). The reason for the less activity of arsenian pyr-
ite is probably that as an electron acceptor makes this mineral less
conductive (Owusu et al., 2013). Additionally, the decrease in the
 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28
particle size of arsenian pyrite considerably increased the oxygen
demand rate constant due to the presence of more reactive sites
at pyrite surfaces (Owusu et al., 2013).
2.1.2. Pulp potential
Pulp potential is particularly affected by the dissolved oxygen
content. As explained in Section 2.1.1, the dissolved oxygen con-
tent is low when grinding of sulfide ore is performed with forged
steel grinding media. If there is not enough dissolved oxygen to
consume the excess amount of electrons, being produced due to
the corrosion processes (Eqs. (1)–(4)), the pulp potential decreases.
The lowering of pulp potential can prevent the adsorption of col-
lector at the cathodic mineral surface, reducing the floatability of
the sulfide mineral which is more floatable in an oxidizing environ-
ment (Woods, 1976; He et al., 2005). It should be noted that pyrite
is also floatable when the pulp potential is reducing and the dis-
solved oxygen content is low probably because the reduced dis-
solved oxygen content prevents the oxidation of pyrite, making
pyrite more floatable. There is therefore a trade-off between the
natural hydrophobicity of pyrite under reducing conditions and
the need for slightly oxidizing conditions for improved collector
adsorption. There is therefore a significant redox sensitivity that
must be kept in mind and no one-directional argument can be
made with regards to redox potential.
2.1.3. Coating of mineral surface
Galvanic interactions occurring during wet grinding of sulfide
ores with forged steel grinding media cause the dissolution of iron
from the grinding media which leads to the formation of iron
hydroxide species such as Fe(OH)3 and Fe(OH)2 as seen in Eqs.
(1)–(3) (Bruckard et al., 2011). The amount of iron hydroxide spe-
cies at mineral surfaces is typically determined by EDTA (ethylene
diamine tetraacetic acid) extraction method (Greet et al., 2004).
The origin of EDTA extracted iron at pyrite surfaces, after the
grinding of refractory gold ores, can be due to the oxidation of pyr-
ite and corrosion of the forged steel grinding media. However, when
pyrite and forged media are in direct contact, the oxidation rate of
pyrite (electrochemically less active material) decreases, while the
opposite is true for the oxidation rate of forged steel grinding media
(electrochemically more active material) (Fontana, 1987). Given
that pyrite is electrochemically less active, the oxidation of pyrite
is insignificant, and thus the amount of EDTA extracted iron is a
measure for the corrosion rate of the grinding media. For example,
Greet et al. (2004) found that the amount of EDTA extracted iron
was 1.75 times higher when grinding of the refractory gold ore
was performed with the forged steel grinding media than that with
the high chrome white iron grinding media. These authors also con-
firmed that the increase of EDTA extracted iron resulted in the
reduction of flotation recovery of pyrite since adsorbed iron species
at pyrite surfaces prevented collector adsorption.
The removal of the iron hydroxide species from the sulfide min-
eral surfaces can improve the floatability of these minerals
(Bruckard et al., 2011). For example, high-intensity agitation of the
pulp (Li and Iwasaki, 1992) and high alkaline conditioning (Senior
and Trahar, 1991) can be applied to minimize their generation of
the iron hydroxide species from the sulfide minerals. However, fur-
ther work is needed to investigate the suitability of these techniques
to enhance the floatability of pyrite from refractory gold ores.
2.2. Control of galvanic interactions
The reduction of galvanic interactions during grinding of sulfide
ores is of critical importance in mineral processing industry since a
significant amount of media wear can be caused due to the corro-
sion process. Different techniques might be applied to reduce the
detrimental effect of galvanic interactions.
25
One approach to reduce the galvanic interactions is to increase
the pulp pH due to the decrease of potential difference between
pyrite and forged steel grinding media (Rao, 2004). The increase
of pH above 10.5 also depresses pyrite due to the formation of Fe
(OH)3 on the pyrite surface which reduces the adsorption of collec-
tor (Bulatovic, 2007). Additionally, the dissolved oxygen is needed
for the xanthate adsorption as explained in Section 3.1, and thus
the level of dissolved oxygen should not be below the certain
concentration.
Galvanic interactions can be also dramatically reduced by add-
ing corrosion inhibitors such as sodium nitrate, sodium chromate,
and sodium metasilicate (Hoey et al., 1975, 1977). The critical con-
centration of these inhibitors is below 0.5% (i.e. above this concen-
tration, these inhibitors cannot reduce the corrosion process).
3. Influence of addition of reagents during grinding
There is limited available information about the influence of
added reagents during the grinding on flotation response of pyrite.
The reagents added during the grinding can be collectors and
activators.
3.1. Collectors
Collectors are used to change the wettability of selected mineral
particles from a hydrophilic to a more hydrophobic surface state by
adsorbing on mineral surfaces. The most important collector used
to recover sulfide minerals is xanthate. Although different theories
have been used to describe the adsorption of xanthate on the sul-
fide minerals, the electrochemical theory is becoming increasingly
popular (Martin et al., 1991). In the electrochemical theory of flota-
tion, both the cathodic oxidation of oxygen and anodic reduction of
X
take place at the surface of sulfide minerals. The cathodic reduc-
tion of oxygen is already shown in Eq. (4). The anodic oxidation of
X
might occur on the mineral surface, resulting in the formation
of dixantogen (X2) or metal xanthate (MX2):
2X
¼ X2 þ 2e
or ð6Þ
MS þ 2X
¼ MX2 þ S þ 2e
ð7Þ
According to the Le Chatelier’s principle, the cathodic reduction
of oxygen (see Eq. (4)) is depressed at low dissolved oxygen con-
tent, preventing the adsorption of xanthate. In other words, when
the cathodic reduction is inhibited, the excess amount of electrons
(i.e. reducing conditions which means negative pulp potential)
block the anodic oxidation of X
(see Eqs. (6) and (7)), and hence
prevent the adsorption of xanthate. In the case of copper-
activated pure pyrite, the xanthate adsorption at pyrite surfaces
is significantly reduced when the pulp Eh is lower than 50 mV
(SHE) (He et al., 2005).
In order to increase the pulp Eh, the high-chrome white iron
grinding media should be used, and thus, the addition of xanthate
before the grinding of sulfide ores might be beneficial to make
unoxidised ground sulfide minerals hydrophobic. On the other
hand, the opposite might be true when the forged media is
employed since the grinding with this media dramatically reduces
the pulp Eh. In the case of grinding of refractory gold ores, there is
no information about the influence of added xanthate before grind-
ing on flotation response of pyrite, and a significant amount of fur-
ther work is required.
3.2. Activators
Cu2+ ions are typically added prior to flotation of pyrite as an
activator since pyrite has poor flotation performance with xanthate
26 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28

Fig. 3. Influence of grinding media in the presence of copper ions on floatability of

Fig. 4. Influence of grinding media in the presence of lead ions on floatability of
pyrite at pH 9 (Peng and Grano, 2010).
pyrite at pH 9 (Peng and Grano, 2010).

Table 3
Zeta potential values (n) of iron hydroxide and pyrite in the presence of Cu2+ with
oxygen purging as a function of pH.

pH n (mV) of iron hydroxide n (mV) of pyrite with Cu2+

5 20 22
6 0 23
7
19.5 22
8
29.5 18
9
40 8
10
42
17
11
45
29

collector, especially at alkaline conditions in the absence of any

activators (Trahar et al., 1994). The mechanism of activation of pyr-
ite is due to the reduction of Cu2+ to Cu+ followed by the sulfide ion
oxidation on the pyrite surface (Weisener and Gerson, 2000). The
presence of Cu+ on the pyrite surface has been confirmed using
XPS technique (Laajalehto et al., 1999; Leppinen, 1990; Peng
et al., 2003). It should be also noted that the activation of pyrite
might be due to the formation of chalcopyrite-like phase (CuFeS2) Fig. 5. Influence of collector dosage on flotation of a single pure pyrite in the
on the pyrite surface (Laajalehto et al., 1999). absence of Cu2+ during regrinding (Chen et al., 2013).

The small amount of Cu2+ can be added during grinding to

reduce the conditioning time of the pyrite surface which is the
common practice during the processing of some refractory gold
ores (e.g. Kanowna Belle refractory gold ore in Western Australia).
The influence of the addition of Cu2+ during grinding with the
forged steel and high chrome white iron grinding media on the
floatability of a single pure pyrite is shown in Fig. 3. As seen in
Fig. 3, the floatability of a single pure pyrite when grinding was
performed with the forged steel media was almost three times
higher than that with the high chrome white iron grinding media
(Peng and Grano, 2010). The reason for this behaviour can be
ascribed to less oxidizing environment (200 mV (SHE)) produced
during grinding with the forged steel media, which promotes the
reduction of Cu2+ to Cu+ which, in turn, is required to activate
the pyrite surface. Furthermore, the electrostatic repulsion
between copper-activated pyrite and iron hydroxide species in
the case of the grinding with forged steel media prevented the pre-
cipitation of iron hydroxide species on pyrite surface as confirmed
with the zeta potential measurements (see Table 3). In contrast to
this, the oxidizing environment (330 mV (SHE)), produced during
the grinding with the high chrome white iron grinding media,
reduces the adsorption of copper ions on pyrite surface
(Richardson et al., 1996). Additionally, given that the pH of solution
is 9, the formation of Cu(OH)2 might precipitate at pyrite surfaces,
rendering this mineral less floatable. It should be noted that the lit-
erature does not provide any information regarding the influence
of grinding media on floatability of pyrite from its ores when the
grinding was performed in the presence of Cu2+ as an activator.
Apart from Cu2+, the addition of Pb2+ also activates the pyrite
surface (Rao, 2004) due to the formation of surface lead com-
pounds like hydroxides and carbonates, which was confirmed with
cyclic voltametric (Sui et al., 1997) and XPS technique (Laajalehto
et al., 1999).
The addition of Pb2+ during the grinding of pyrite was studied
by Peng and Grano (2010) who found that the floatability of pyrite
with the high chrome white iron grinding media was seven times
higher than that with the forged steel grinding media as seen in
Fig. 4. The reason for the detrimental effect of the forged steel
grinding media was proposed to be the electrostatic attraction
between iron hydroxide species from this media and lead-
activated pyrite, enhancing the precipitation of iron hydroxide spe-
cies on the pyrite surface, and hence making pyrite less floatable
(Peng and Grano, 2010). It should be noted that grinding of pure
pyrite with the high chrome white iron grinding media in the pres-
ence of Pb2+ activator resulted in two times higher recovery than
that in the presence of Cu2+ activator. The reason for that might
be due to the formation of different types of hydroxide at pH 9
 A. Rabieh et al. / Minerals Engineering 94 (2016) 21–28
Table 4
Galvanic current as a function of purging gases (Adam et al., 1986).
Type of purging Galvanic current (lA)
gas
Austenitic stainless Martensitic stainless
steel steel
N2 0.003 2.70
Air 0.023 4.10
O2 0.013 4.00
i.e. Pb(OH)2 was formed in the presence of Pb2+ activator, and Cu
(OH)2 was obtained when Cu2+ activator was added. Given that
the solubility of Cu(OH)2 is 100 times lower than the solubility of
Pb(OH)2, the formation of Cu(OH)2 precipitates on pyrite surfaces,
making this mineral less floatable.
4. Influence of chromium media
There are two types of grinding media: high-carbon low alloy
steel and high chrome white iron. The high-carbon low alloy steel
media has between 0.6% and 1.2% of carbon with trade levels of
chromium, nickel, and molybdenum (Greet and Van den Bosch,
2014). This type of media has a lower price due to the low alloy
content, and thus they are mainly selected as a grinding media
(Chenje et al., 2003). The high chrome white iron media contains
a significant amount of chromium (between 12% and 35% of chro-
mium), and thus these types of media are also commonly called
high chrome grinding media (Greet and Van den Bosch, 2014).
High chrome media has a higher hardness and higher corrosion
resistance than low alloy steel media. High hardness of high
chrome alloys is caused due to the formation of chromium car-
bides, while corrosion resistance of this media depends on the per-
centage of chromium in the matrix which consists of martensite
and austenite (Greet and Van den Bosch, 2014). The heat treatment
determines the amount of chromium carbide and chromium in the
matrix. In other words, even though the alloy has the same compo-
sition, it is possible to produce the grinding media with different
degrees of hardness and corrosion resistance.
Grinding with high chrome grinding media significantly dimin-
ishes the consumption of this media and reduce the contamination
of sulfide surface with iron hydroxide species. Therefore, this
grinding media is suitable for grinding of pyrite ores (Greet et al.,
2004; Chen et al., 2013). For example, Fig. 5 shows that when the
grinding was conducted in the absence of Cu2+, the flotation perfor-
mance of a single pure pyrite with the high chrome grinding media
was four times higher than that with the forged steel grinding
media.
5. Influence of gas atmosphere during grinding
Nitrogen gas purging can be used to remove oxygen from grind-
ing environment. The advantage of nitrogen gas purging is the
reduction of the corrosion rate of forged steel grinding media,
which was experimentally confirmed by measuring the galvanic
current (Adam et al., 1986). It should also be noted that nitrogen
gas purging minimizes the oxidation of pyrite. The influence of
purging gas on the galvanic current of pyrrhotite is presented in
Table 4, which shows that when the grinding was performed with
the mild steel media, the galvanic current in the presence of oxy-
gen was 12 times higher than that in the presence of nitrogen. This
effect is much less pronounced when the grinding is conducted
with austenitic and martensitic stainless steel. Another benefit of
nitrogen purging is the prevention of extensive oxidation of sulfide
minerals and media debris due to the reduction of the pulp poten-
tial. Although the influence of nitrogen purging on flotation perfor-
mance has been extensively studied, it has been rarely applied in
27
mining industry (Huang, 2005). For example, Simmons et al.
(1999) reported the beneficial effect of nitrogen purging on flota-
tion performance of the refractory gold ore at the Lone Tree Mine
Mild in Nevada.
steel In contrast to the nitrogen purging during wet grinding of ores,
12.00
the oxygen purging improves the galvanic interactions, which
11.00 increases the concentration of iron hydroxide species on the sur-
160.00 face of sulfide mineral, preventing the adsorption of xanthate ions.
For that reason, the floatability of sulfide minerals is significantly
depressed (Forssberg et al., 1988). Furthermore, the oxygen purg-
ing increases the pulp potential which causes the oxidation of sul-
fide minerals and grinding media debris (Yuan et al., 1996).
However, it has to be highlighted that a certain amount of oxygen
is needed to enable the adsorption of xanthate ions on the surface
of sulfide minerals (see Section 3.1).
6. Conclusions
This paper reviews the influence of the grinding conditions on
the flotation performance of pyrite, which is of great importance
in the gold mining industry. According to the literature reviewed,
the grinding conditions might activate or depress pyrite, depend-
ing on the complex interactions among ore mineralogy, grinding
media, addition of different reagents, and gas atmosphere during
grinding. Although this review contributes mostly a better under-
standing of chemical and electrochemical processes occurring dur-
ing grinding of refractory gold ores and their effect on flotation
recovery of pyrite, similar conclusions can be probably applied
for other ores. This review also reveals that there is insufficient
knowledge with regards to various refractory gold ores, and signif-
icant amounts of further work are needed to determine the influ-
ence of different grinding conditions on pyrite floatability.
7. Future work
Future work for various refractory gold ores should include:
(1) Investigation of the influence of added flotation reagents
(collectors and activators) before grinding stage on pyrite
floatability.
(2) Study of the addition of different corrosion inhibitors prior
to grinding stage on flotation performance of pyrite.
(3) Research about the influence of gas atmosphere during
grinding on pyrite floatability.
Acknowledgements
Financial support from the AMIRA International P420E Project
and the member companies (AngloGold Ashanti, Barrick, CSBP-
Australian Gold Reagents, Gekko Systems, Harmony, Kemix,
Magotteaux, Newcrest, Newmont, Norton Gold Fields, Orica, Rand-
gold, St Barbara, Tenova-Bateman) is gratefully acknowledged. The
authors would like to express particular gratitude to Dr Chris Greet
from Magotteaux for his reviews and valuable contributions.
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