Minerals Engineering xxx (xxxx) xxxxxx

Contents lists available at ScienceDirect

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

Galvanic interaction of grinding media with arsenopyrite and pyrite and its
eect on gold cyanide leaching

A. Rabieh, J.J. Eksteen , B. Albijanic
Department of Mining Engineering and Metallurgical Engineering, Western Australian 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

Keywords: Galvanic interactions between dierent types of grinding media and arsenopyrite and pyrite, during the grinding
Grinding media was quantied and the eect of galvanic interactions on gold cyanide leaching was investigated. The synthetic
Gold cyanidation ores were prepared by mixing arsenopyrite or pyrite with clean gravity gold concentrate and quartz. In the
Arsenopyrite presence of arsenopyrite, the results showed that when the grinding of the ore was performed using the 30%
Pyrite
chromium or ceramic grinding media, the gold leaching was more ecient than that when the forged steel
Galvanic interaction
media was used. Based upon the measurement, it was suggested that the galvanic interactions between the
forged steel grinding media and sulde minerals resulted in the formation of more iron hydroxide than that
when the 30% chromium or ceramic grinding media was used. As a result, free cyanide was converted to
ferrocyanide thereby lowering the cyanide available for the gold leaching. Additionally, the galvanic interactions
also reduced the dissolved oxygen content and thus cyanide gold leaching was more dicult particularly at the
early stages of the leaching process because the dissolved oxygen is required to dissolve gold. In contrast, when
the grinding was performed with the 30% chromium or ceramic media, a very small amount of free cyanide was
converted into by-products. Cyanide gold leaching was the most ecient when the 30% chromium media was
used during the grinding of the ore for both pyrite and arsenopyrite. In addition, in the presence of pyrite, due to
the lower galvanic current between pyrite and grinding media in comparison with arsenopyrite, the amount of
iron hydroxide was lower, and thus more free cyanide was available for the gold extraction. These results
indicated that more gold was extracted in the presence of pyrite rather than the arsenopyrite for a given media
type used. More precisely, in the presence of pyrite, when the 21% chromium grinding media was used, 70% of
gold was extracted while it was 60% in the case of arsenopyrite in 24 h. The selection of grinding media appears
to be signicant when cyanide reagent consumption is evaluated.

1. Introduction
Galvanic interactions between grinding media and sulde minerals
during grinding not only increase the corrosion of grinding media but
also can have a negative eect on downstream operations such as o-
tation of galena (Cullinan et al., 1999; Peng et al., 2003), pyrrhotite
(Adam and Iwasaki, 1984; Natarajan et al., 1984; Hodgson and Agar,
1988; Pozzo et al., 1990), sphalerite (Vathsala and Natarajan, 1989)
and chalcopyrite (Ahn and Gebhardt, 1991; Grano et al., 1994; Yuan
et al., 1996; Peng et al., 2003). The driving force for these interactions
is the dierence in open circuit potential of grinding media and sulde
minerals. Sulde minerals electrochemically interact with steel
grinding media which can increase the corrosion of steel grinding
media. It was found that the higher the electrochemically active
grinding media, the less the otation recovery of sulde minerals
(Adam and Iwasaki, 1984; Martin et al., 1991; Subrahmanyam and
Forssberg, 1993; Peng et al., 2003; Greet et al., 2004). Furthermore, it
was observed that the grinding media with less electrochemically ac-
tivity such as stainless steel and chromium grinding media may produce
higher otation recoveries of sulde minerals (Forssberg et al., 1988;
Cullinan et al., 1999). However, Rabieh et al. (2016 and 2017a) showed
that the improved response with high chromium media is not guaran-
teed in all cases, as forged steel can perform marginally better prior to
otation as known for orogenic gold-bearing pyrite ores such as Ka-
nowna Belle in Western Australia. Meanwhile, the otation response is
seen as dependant on a number of factors, such as ore mineralogy,
process water chemistry, and grinding media metallurgy.
Although the inuence of grinding media on otation performance
of sulde minerals have been studied, the literature does not provide
any information about the inuence of galvanic interactions during
grinding on the cyanide gold leaching for the common gold associated
minerals such as pyrite and arsenopyrite. The objectives of this research

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

http://dx.doi.org/10.1016/j.mineng.2017.10.018
Received 15 August 2017; Received in revised form 16 October 2017; Accepted 24 October 2017
0892-6875/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Rabieh, A., Minerals Engineering (2017), http://dx.doi.org/10.1016/j.mineng.2017.10.018
A. Rabieh et al.
are: (i) to quantify the galvanic interactions between grinding media
and arsenopyrite and pyrite based on their electrochemical behaviour
during grinding, (ii) to investigate the inuence of grinding media type
on cyanide gold leaching in the presence of arsenopyrite and pyrite and
(iii) to propose a model which can explain the correlation between
oxidized iron and galvanic currents. Conversely, it would also be im-
portant to investigate to which extent post-grind cyanidation can serve
as a diagnostic tool to infer the extent of galvanic interactions during
the grind. This work extends previous research by the authors (Rabieh
et al. (2017b), which investigated the interactions between grinding
media and pyrrhotite on cyanide leaching of gold from ores containing
2% gold-bearing pyrrhotite. As pyrrhotite is a highly reactive iron
sulde it signicantly amplied the grinding media-ore interaction and
the eects on cyanide leaching of gold was highly signicant. This
paper investigates, using a similar approach as followed by Rabieh et al.
(2017b), the interactions of grinding media with the less reactive ar-
senopyrite and least reactive (of the iron sulde minerals) pyrite, both
of which are common gold-bearing, or gold-associated minerals.
2. Materials and methods
2.1. Synthetic ore
Two synthetic ores were obtained by mixing 12 g of arsenopyrite
(99% FeAsS and 1% SiO2) or pyrite (98% FeS2 and 2% SiO2), 0.5 g of
the gravity gold concentrate (6% gold from Knelson concentrator ana-
lysed by re assay), and 587.5 g of quartz (99.5 % purity). Therefore,
the synthetic gold ores had 2% arsenopyrite or 2% pyrite and 50 ppm
gold. Table 1 shows the XRD analysis of the gold concentrate.
2.2. Grinding system
The feed ore was ground to a 80% pass size (P80) of 75 m by wet
grinding at 34% w/w solids in the grinding system as explained in our
previous work (Rabieh et al., 2017b). The grinding time to achieve the
desired particle size distribution was 80 min for all type of grinding
media, and the only dierence was the speed of the mill which was 42,
38, 38 and 46 RPM for forged steel, 21% chromium, 30% chromium
and ceramic, respectively. The pulp chemical conditions (pH, Eh, and
dissolved oxygen) during the grinding of the ore samples was recorded
for each minute. Additionally, every 20 min around 35 mL of the slurry
was collected for the EDTA iron extraction and dissolved sulfur mea-
surements. The dissolved sulfur measurements were performed using
high performance liquid chromatography (HPLC); SO42 ions were the
only detected sulfur species.
2.3. Cyanide leaching procedure
After the grinding, the mill discharge was transferred into a 3 L glass
Table 1
Mineralogical analysis of the gold concentrate.
Mineral Mass (%)
Clinochlore 6
Talk <1
Biotite 27
Muscovite 25
Amphibole 1 All in-situ mill electrochemistry measurements were performed
Clinopyroxene 3
Rutile 1
Albite 3 AFTP1) provided by Pine Research Instrumentation. It should be noted
Alpha quartz 22
Calcite <1
Dolomite - ankerite 4
Malachite 4
Magnetite 3 L KCl as a reference electrode and a platinum wire as a counter elec-
2
Minerals Engineering xxx (xxxx) xxxxxx
reactor, mechanically agitated along with a sucient quantity of Perth
tap water to generate slurry samples at 22% (w/w) pulp solid ratio.
Around 12 mL of caustic soda solution (1 M NaOH) was added into the
slurry in order to maintain a pH of approximately 10.5, and then mixed
for another 5 min; then the solid sodium cyanide was added to the
slurry in order to keep cyanide solution concentrate at 500 ppm. During
the leaching process, approximately 20 mL of the slurry samples were
collected after 2, 4, 6, and 24 h. These samples were ltered to analyse
the solution for gold content by atomic absorption (AAS) technique,
cyanide speciation by high performance liquid chromatography
(HPLC), and solution cyanide strength by silver nitrate titration.
2.4. Determination of iron hydroxide content by EDTA
The amount of extractable iron in the samples taken from the mill
slurry (every 20 min) was analysed by an ethylene diamine tetra acetic
acid (EDTA) extraction method. In this method, a 250 mL of 3 wt% of
EDTA solution at pH of 7.5 was prepared and transferred into a la-
boratory leaching vessel with a magnetic stirrer and purged with ni-
trogen for 5 min to remove the dissolved oxygen. The mill slurry sam-
ples (25 ml) were then added to the leaching vessel. The experiments
were carried out for 5 min by purging with nitrogen. The slurry was
then ltered through a 0.2 m millipore membrane, and the solution
was analysed by inductively-coupled plasma optical emission spectro-
metry (ICP-OES) for iron content, and then the amount of iron in the
aqueous phase was calculated.
2.5. Electrodes preparation and voltammetry apparatus
2.5.1. Grinding media electrodes preparation
Two types of grinding media (i.e. forged steel and 30% chromium)
were used to make the working electrodes. A grinding media sample
was cut to the size of 15 15 3 mm to ll a Teon tube. The elec-
trode was connected to a screw by a conductive epoxy resin, and non-
conductive epoxy was used to ll in between the Teon tube and
electrodes for isolation. Before each experiment, the electrode surface
was gently polished by a set of polishing discs and alumina slurries. The
chemical composition of dierent grinding media types used in this
project explained in our previous research (Rabieh et al., 2017b).
2.5.2. Sulde mineral electrodes preparation
The carbon paste-pyrite or arsenopyrite electrodes were prepared by
thoroughly mixing 4 g of graphite powder with 3 g of pure arsenopyrite
or pyrite mineral and 3 g of paran oil. The carbon paste-minerals was
packed into the hole of the electrode body and polished. The exposed
surface area of the mineral electrode was 0.071 cm2. It should be noted
that the carbon paste electrode was used for the electrochemistry study
of sulde minerals by a number of researchers such as Gerlach and
Kuezeci (1983), Lu et al. (2000), Cruz et al. (2005), and Urbano et al.
(2007). For further details about the carbon paste electrochemistry the
reader is referred to work published by Lazaro et al. (1995) and Sauber
and Dixon (2011).
2.5.3. In-situ mill electrochemistry
using a WaveNow Potentiostat/Galvanostat system (Model number:
that the potentiostat electrodes were placed inside the mill. The three-
electrode setup consisted of the grinding media electrode or carbon
paste-mineral electrode as the working electrode, an Ag/AgCl in 3 mol/
trode.
A. Rabieh et al. Minerals Engineering xxx (xxxx) xxxxxx

Fig. 1. Pulp chemical properties during grinding of gold in the presence of (a) arsenopyrite and (b) pyrite as a function of grinding time.

3. Results and discussion the slurry, and this explains why the dissolved oxygen content slightly
decreased.
3.1. Grinding On the surface of a sulde mineral:

1/2 O2 + H2 O+ 2e 2(OH) K1 = 3.687 1013 (1)

3.1.1. Pulp chemistry
The pulp chemistry properties during the grinding of the gold-ar- Steel media oxidation:
senopyrite or gold-pyrite synthetic ores with four dierent grinding
media are given in Fig. 1. As seen in Fig. 1, the changes from the 30% Fe Fe2 + + 2e K2 = 6.598 1013 (2)
chromium and ceramic to the forged steel grinding media resulted in a
Fe Fe3 + + 3e K3 = 1.025 103 (3)
systematic reduction in the pulp potential. This may be explained by the
galvanic interactions between the forged steel media and sulde mi- Hydrolysis:
nerals, which cause the increase in the hydroxide ion production as
Fe2 + + 2H2 O Fe(OH)2 + 2H+ K 4 = 2.534 1012 (4)
shown in Eq. (1). A list (Eqs. 17) of the electrochemical reactions that
may occur on the surface of sulde minerals (cathodic reaction, Eq. (1)) Fe3 + + 3H2 O Fe(OH)3 + 3H+ K5 = 3.654 105 (5)
and grinding media (i.e. anodic reaction (Eqs. (2) and (3)) and hydro-
lysis of Fe 2+and Fe 3+ (Eqs. (4) and (5))) is provided below. In addi- Arsenopyrite and pyrite oxidation:
tion to galvanic interactions, arsenopyrite and pyrite surfaces oxidize
(Marsden and House, 2009); the oxidation of arsenopyrite and pyrite in 2FeAsS + 7O2 + 8H2 O= 2Fe(OH)3 + 2H3 AsO4 + 4H+ + 2SO24 K6
neutral and alkaline solutions can be explained by Eq. (6) and (7). =1 10308 (6)
It should be noted that pyrite can be slightly oxidized (see Eq. (7)).
This implies that pyrite may consume a small amount of the oxygen in 4FeS2 + 15O2 + 14H2 O 4Fe(OH)3 + 16H+ + 8SO24 K7 = 1 10308
(7)

3
A. Rabieh et al.
3.1.2. EDTA and dissolved sulfur measurements during grinding
The samples collected every 20 min during the grinding of the gold-
arsenopyrite or gold-pyrite synthetic ores with four dierent grinding
media were analysed by EDTA iron extraction technique. It should be
noted that the EDTA-extracted iron originate from the oxidation of
grinding media and sulde minerals. Therefore, the amount of EDTA
iron extraction can be shown as:
QEDTA for Iron = QFe from media oxidation + QFe from sulfide minerals (8)
Arsenopyrite and pyrite was probably oxidized according to the
reactions shown in Eqs. (6) and (7). As can be seen in Eqs. (6) and (7),
the amount of dissolved sulfur is equal and twice to the EDTA-ex-
tractable iron formed from arsenopyrite and pyrite oxidation respec-
tively. Therefore, the oxidation of forged steel media can be described
by Eqs. (11) and (12):
QFe from arsenopyrite oxidation = QSO4 (9)
QFe from pyrite oxidation = 1/2QSO4 (10)
Arsenopyrite:QFe from media oxidation = Q EDTA for IronQ SO4 (11)
Pyrite:QFe from media oxidation = Q EDTA for Iron1/2Q SO4 (12)
Fig. 2 shows the amount of iron hydroxide in the slurries as a
function of grinding time and grinding media. As seen in Fig. 2, the
amount of iron hydroxide produced in the slurries decreased in the
following order: forged steel media > 21% chromium media > 30%
chromium media > ceramic media. It implies that the amount of
produced iron hydroxide strongly depends on the type of the grinding
media. In addition, in the case of gold-arsenopyrite grinding, the
amount of EDTA-extractable iron oxidation products is higher than the
gold-pyrite grinding. The reason for this higher the electrochemical
activity of the arsenopyrite rather than the pyrite.
Fig. 3 shows the amount of dissolved sulfur in the slurry as a
function of various grinding media and grinding time. Relative to iron
oxidation products, the amount of dissolved sulfur was small regardless
of the type of the grinding media and sulde minerals. It is important to
highlight that arsenopyrite oxidation did not change the amount of iron
hydroxide in the slurries even though arsenopyrite have oxidized sig-
nicantly; the reason was that the ore contained a small amount of
arsenopyrite (2%). These results are in agreement with the results ob-
tained by Huang and Grano (2005). However, it should be mentioned
that Huang and Grano (2005) conducted the experiments with much
higher concentrations of arsenopyrite and pyrite. This is an important
dierence as it would inuence the overall reduction/oxidation equi-
librium in the mill. For instance, in their results, a higher concentration
of dissolved sulfur during grinding was observed which was very low in
this study.
In the presence of arsenopyrite, the calculated amounts of iron hy-
droxide due to the oxidation of grinding media is shown in Fig. 4a. The
forged steel media produced a higher amount of iron hydroxide in
4
Minerals Engineering xxx (xxxx) xxxxxx
comparison with the 30% chromium and ceramic media. Given that the
amount of dissolved sulfur was negligible, it can be deduced that the
EDTA-extractable iron in the slurries mainly originated from the
grinding media oxidation. Even though the ceramic media is non-con-
ductive, this media showed iron oxidation products due to the metallic
mill shell (which is the same in all the tests). One would expect some
galvanic interactions between the inner wall of the mill and sulde
minerals, as the inner wall of the mill is made of steel. The mill di-
mensions and shell internal surface area and grinding media surface
areas are given in Rabieh et al. (2017b). It has a smaller surface area
than the area associated with the grinding media, but it will nonetheless
have a background inuence irrespective of the grinding media used. In
in the case of pyrite (see Fig. 4b), a similar observation was seen.
However, due to the lower galvanic current between pyrite and
grinding media in comparison with arsenopyrite, the amount of iron
hydroxide was lower.
3.2. Cyanide gold leaching
3.2.1. Pulp chemical properties
Free cyanide was added to dissolve gold (Eq. (13)). However, free
cyanide reacts with other species available in the mill discharge. More
precisely, the free cyanide is consumed by iron hydroxide as presented
in Eq. (14) (Marsden and House, 2009). The free cyanide also reacts
with arsenopyrite and pyrite according to Eqs. 1517 (Yannopoulos,
1991):
4Au + 8CN + O2 + 2H2 O 4Au(CN)2 + 4OH K10 = 5.618 106
(13)
Fe(OH)3 + 6CN + e Fe(CN)64 + 3OH K11 = 6.660 1018 (14)
4FeAsS + 28CN + 5O2 + 2H2 O AsO33 + 4Fe(CN)64 + 4SCN
+ 4H+ K12 = 1 10308 (15)
2FeS2 + 9CN + 1/2O2 + H2 O FeS + Fe(CN)64 + 3SCN
+ 2OH K13 = 2.37 1076 (16)
2FeS + 2CN + 3/2O2 + 3H2 O 2SCN + 2Fe(OH)3 K14
= 1.71 10114 (17)
It should be noted that the presence of iron hydroxide can be ex-
plained by Eqs. 47.
Fig. 5 shows that the Eh-pH diagram for the Fe-S-As-CN-H2O system
at 25 C (Marsden and House, 2009). The diagram was obtained for
dissolved iron, arsenic, and sulfur species of 104 M and a free cyanide
concentration of 103 M. Given that the pulp pH was between 10.5 and
11.5 as well as the pulp Eh was between 0.3 and 1 V vs SHE during
the leaching experiments in this work, ferrocyanide (Fe(CN)64) was
the most dominant ion. The formation of ferrocyanide can be explained
Fig. 2. The amount of EDTA extractable iron during
grinding of gold in the presence of (a) arsenopyrite and
(b) pyrite as a function of grinding time.
A. Rabieh et al. Minerals Engineering xxx (xxxx) xxxxxx

Fig. 3. The amount of dissolved sulfur in slurry during

grinding of gold in the presence of (a) arsenopyrite and
(b) pyrite as a function of grinding time.

by Eqs. 1416.
Fig. 6 shows the changes of pulp chemical variables (pH, DO, and
Eh) during the cyanide gold leaching in the presence of arsenopyrite
and pyrite. The amount of iron hydroxide was higher when the forged
steel or 21% chromium grinding media were used than that when the
ceramic or 30% chromium grinding media were used. For that reason,
using of the forged steel or 21% chromium media resulted in the pro-
duction of a strong reducing environment during the rst hours of
leaching process probably due to the reaction between iron hydroxide
and free cyanide (see Eq. (14)). It is important to highlight that free
cyanide was consumed by iron hydroxide which is especially important
when the forged steel or 21% chromium media were used (Eq. (14)).
Additionally, when the forged steel or 21% chromium grinding media
were employed in the rst hours of leaching, hydroxide ion is produced;
therefore, the pulp pH increased to 11.4 until the free cyanide or iron
hydroxide were consumed.

3.2.2. Cyanide gold leaching performance

The inuence of grinding media on the cyanide gold leaching in the
presence of arsenopyrite or pyrite is shown in Fig. 7. In the presence of
arsenopyrite, when the ceramic or 30% chromium grinding media was
employed, the gold dissolution was the highest due to the lowest gal-
vanic interaction. The consequences of the galvanic interactions were
the forged steel media oxidation and thus iron hydroxide was generated
in the slurries (see. Fig. 4). Iron hydroxide has been precipitated on gold
surfaces, causing (in addition to the lower available cyanide due to
cyanide consumption) a low gold extraction. Furthermore, a signicant
amount of the free cyanide (60%) converted to ferrocyanide (see Fig. 8
and Eq. (14)) which could not dissolve gold. Fig. 7 also shows that the
gold extraction in the presence of arsenopyrite was the highest (i.e.
75%) when the ceramic or 30% chromium media was used. One of the
Fig. 5. EhpH diagram for the FeSAs-CNH2O system at 25 C (Marsden and House,
2009).
possible explanations for the reduced gold extraction could be a certain
consumption of the free cyanide. Precisely, 5.5% of the free cyanide
was converted to ferrocyanide and 1.2% of the free cyanide was con-
verted to thiocyanate. In addition to the consumption of the free cya-
nide, the passivation of gold grains by arsenopyrite have also reduced
the gold extraction. For that reason, the gold leaching mechanism is
probably aected by galvanic interactions, cyanide consumption and
gold passivation.

Fig. 4. The amount of iron oxidized from media during

grinding of gold in the presence of (a) arsenopyrite and
(b) pyrite as a function of grinding time.

5
A. Rabieh et al.
Fig. 6. Pulp chemical conditions during cyanide leaching of gold in the presence of (a) arsenopyrite and (b) pyrite as a function of leaching time.
In the presence of pyrite, due to the lower galvanic current between
pyrite and grinding media in comparison with arsenopyrite, the amount
of iron hydroxide was lower and thus more free cyanide was available
for gold extraction. It means that more gold was extracted in the pre-
sence of pyrite than the arsenopyrite. More precisely, in the case of
pyrite, when the 21% chromium grinding media was used, 70% of gold
was extracted while it was 60% in the case of arsenopyrite.
6
Minerals Engineering xxx (xxxx) xxxxxx
3.2.3. Cyanide speciation during gold leaching
The solution samples collected during the leaching of gold in the
presence of arsenopyrite and pyrite (at 2, 4, 6, and 24 h) were analysed
by HPLC for cyanide speciation to show how the grinding media and
sulde minerals can aect the cyanide speciation. As can be seen in
Fig. 8a, in the presence of arsenopyrite, when the forged steel or 21%
chromium media were used, around 60% of the free cyanide was
Fig. 7. Eect of grinding media on gold-leaching in the
presence of (a) arsenopyrite and (b) pyrite.
A. Rabieh et al.
consumed to form ferrocyanide (see Eq. (14)). For that reason, gold
cyanide leaching was less ecient when the forged steel or 21%
chromium media were used. It should be noted that a small amount
(around 1.2%) of free cyanide was converted to thiocyanate due to the
reaction of arsenopyrite with free cyanide (see Fig. 8). By contrast,
when the ceramic and 30% chromium media were used, only 5.5% of
free cyanide was converted to ferrocyanide because the amount of
produced iron hydroxide during grinding with the ceramic media was
insignicant. The amount of converted free cyanide to thiocyanate was
also negligible. As a result, when the ceramic or 30% chromium media
were used, the cyanide remained mostly unreacted (thus free) and thus
cyanide gold leaching was more ecient than that when the grinding
was performed with the forged steel or 21% chromium grinding media.
However, in the presence of pyrite (see Fig. 8b), due to the lower
galvanic interaction between pyrite and grinding media, the amount of
iron hydroxide was lower. Therefore, less free cyanide was decomposed
to formed ferrocyanide.
7
Minerals Engineering xxx (xxxx) xxxxxx
Fig. 8. The amount of free cyanide, ferrocyanide
and thiocyanate during leaching in the presence
of (a) arsenopyrite and (b) pyrite as a function of
leaching time.
3.3. Electrochemical properties of grinding media and arsenopyrite during
grinding
3.3.1. Open circuit potentials (OCP)
Open circuit potentials determines the behaviour of grinding media
and sulde minerals in galvanic couples when exposed to the same
environment (Huang and Grano 2005). The open circuit potentials of
the grinding media (i.e. forged steel or 30% chromium) and the ar-
senopyrite and pyrite electrodes were measured in-situ of mill. Fig. 10
shows the open circuit potentials of the forged steel, 30% chromium
grinding media and sulde minerals (arsenopyrite and pyrite) elec-
trodes during grinding of the gold-arsenopyrite and gold pyrite syn-
thetic ores. During grinding of the gold-arsenopyrite ore, forged steel
grinding media electrode showed much lower open circuit potential
than the arsenopyrite electrode, demonstrating that the forged steel
behaved as anode with regards to arsenopyrite. A similar observation
was seen in the case of the 30% chromium grinding media electrode.
However, the 30% chromium grinding media electrode had slightly
A. Rabieh et al. Minerals Engineering xxx (xxxx) xxxxxx

higher open circuit potential than the forged steel grinding media
electrode. In the case of pyrite electrode, similar results were obtained;
the only dierence was that the pyrite electrode had higher potential in
comparison with the arsenopyrite electrode. As can be seen in Fig. 9,
the potentials of grinding media and minerals electrodes decreased in
the following order:
Forged steel > 30% chromium > arsenopyrite > pyrite.
It means that pyrite is the least electrochemically active mineral. As
a result, grinding of pyrite resulted in the lowest galvanic current and
thus a small amount of produced iron hydroxide.
Similar observation was seen in the results obtained by Huang and
Grano (2005, 2006). The only dierence is that Huang and Grano
(2005) only studied the behaviour of the forges steel media.

3.3.2. Polarization curves

Fig. 9. Open circuit potentials of forged steel, 30% chromium, arsenopyrite and pyrite
electrodes during grinding of gold-arsenopyrite and gold-pyrite synthetic ores as a
function of time.
Due to the dierence in open circuit potentials of grinding media
and sulde minerals, a galvanic interaction occur during grinding
(Huang and Grano 2005). In this study, the galvanic current between
grinding media and sulde minerals (arsenopyrite and pyrite) was de-
termined from polarization curves of the electrodes. Polarization curves
of the grinding media (forged steel or 30% chromium) and sulde
mineral electrodes (arsenopyrite and pyrite) during grinding of the
gold-arsenopyrite and gold-pyrite synthetic ores with the forged steel
and 30% chromium media are shown in Figs. 10 and 11. The dash line
shows the galvanic current for the grinding media-sulde minerals
couple. It can be seen from Figs. 10 and 11 that the forged steel-ar-
senopyrite couple had a signicantly higher galvanic current than the
30% chromium-arsenopyrite couple; the presence of chromium in the
grinding media reduced the galvanic current between the grinding
media and sulde minerals. Comparison of the galvanic currents of the
couples, the following order may be given:

Fig. 10. Polarization curve of grinding media and arsenopyrite at dierent grinding times. Measured times at (a) 20 min; (b) 40 min; (c) 60 min; (d) 80 min.

8
A. Rabieh et al.
Fig. 11. Polarization curve of grinding media and pyrite at dierent grinding times. Measured times at (a) 20 min; (b) 40 min; (c) 60 min; (d) 80 min.
Forged steel-arsenopyrite > forged steel-pyrite > 30% chromium-
arsenopyrite > 30% chromium-pyrite.
3.4. Correlation between oxidized iron and galvanic currents
Fig. 12 shows that there is a linear relationship between the gal-
vanic currents for the sulde mineral-grinding media couple and the
amount of iron oxidation in the mill discharge after grinding of the
gold-arsenopyrite and gold-pyrite synthetic ore. It means that in the
presence of arsenopyrite (Fig. 12a), the higher the galvanic current
between the grinding media and arsenopyrite, the greater the degree of
oxidation of the grinding media (i.e. the amount of EDTA extractable
iron produced). It can be seen that the coecient of galvanic current
with the forged steel grinding media is around two times higher than
that with the 30% chromium grinding media, which correlates with the
information provided by the polarization curves. A similar observation
9
Minerals Engineering xxx (xxxx) xxxxxx
was seen in the case of pyrite (Fig. 12b). However, in the presence of
pyrite, due to the lower galvanic current between pyrite and grinding
media, the amount of iron hydroxide were lower in comparison with
arsenopyrite. Therefore, the lower coecient can be observed.
The linear relationship between the galvanic currents and the
amount of iron oxidation in the mill discharge was also obtained using
the mathematical model derived by Huang and Grano (2006). The
model is given in Eq. (18):
AMd
QFe (t) = Q0 /t grind + IgAMd
nF (18)
where Q Fe (t) is the total amount of oxidized iron in the mill discharge;
Q0 represents the iron hydroxide identied on the surface of grinding
media and the mineral samples before grinding of the ore; tgrind is the
grinding time; AMd is the surface area of the grinding media; n re-
presents the number of moles of electrons transferred per mole of iron;
IgAMd is the average galvanic current; F is the Faraday constant i.e.
Fig. 12. Correlation between the oxidation of grinding
media and galvanic current between (a) arsenopyrite
or (b) pyrite and grinding media.
A. Rabieh et al.
96,500 C/mol. The model assumes that the sulde mineral oxidation
does not change signicantly the total amount of oxidized iron in the
mill discharge. This assumption is experimentally also validated in this
study. Namely, the amount of dissolved sulfur was negligible (see
Fig. 3) and thus sulde minerals oxidation did not change the amount
of iron hydroxide in the mill discharge even though arsenopyrite have
oxidized signicantly; the reason is that the ore had a small amount of
arsenopyrite (2%).
4. Conclusions
In this paper, the inuence of the grinding media on cyanide gold
leaching in the presence of arsenopyrite and pyrite was investigated.
The oxidation of grinding media was quantied using EDTA extraction
method and dissolved sulfur measurements while cyanide species was
determined using high-performance liquid chromatography. The fol-
lowing results have been observed:
i. Pulp chemistry data revealed that grinding with forged steel
grinding media resulted in a greater reducing environment in
comparison with the 30% chromium and ceramic grinding media
due to the galvanic interactions between the forged steel media and
sulde minerals. The degree of oxidation of forged steel media was
the highest while the opposite is true in the case of the ceramic
grinding media as conrmed with EDTA extraction and dissolved
sulfur measurements. The degree of oxidation of grinding media
also depends on the type of the ore. Specically, when grinding was
performed with the same grinding media, the amount of produced
iron hydroxide decreased in the following order: arsenopyrite
ore > pyrite ore. The reason for this is that arsenopyrite is more
electrochemically active than the pyrite.
ii. The gold extraction data showed that when the ceramic or 30%
chromium grinding media were used, cyanide gold leaching was
very ecient because the free cyanide almost did not decompose
and relatively oxidising conditions were maintained in the pulp
during grinding and directly afterwards during cyanidation. In
contrast, when the forged media was used, the cyanide gold
leaching was the lowest.
iii. Cyanide speciation by HPLC showed that when the forged steel or
21% chromium media were used, generated iron hydroxide reacts
with free cyanide, resulting in the consumption of the free cyanide
to form ferrocyanide which cannot dissolve gold. When the grinding
was conducted in the presence of the forged media, the decom-
position of the free cyanide decreased in the following order: ar-
senopyrite ore > pyrite ore.
iv. In many ways, the 30% chromium media behaved more like the
ceramic media than like the 21% chromium media with regards to
the downstream impacts on leaching.
Acknowledgement
Financial support from the AMIRA International P420F Project and
the member companies (Vega Industries, AngloGold Ashanti, Australian
Gold Reagents, Barrick Gold Corporation, Gekko Systems, Lhoist,
Newcrest Mining, Newmont Asia Pacic, Northern Star Resources,
Orica Australia, CRC ORE and Pionera) is gratefully acknowledged.
10
Minerals Engineering xxx (xxxx) xxxxxx
References
Adam, K., Iwasaki, I., 1984. Grinding mediasulde mineral interaction and its eect on
otation. In: S. P., S., Woods, R. (Eds.), Proceedings of the International Symposium
on Electrochemistry in Mineral and Metal Processing, Pennington, N.J., 6680.
Ahn, J.H., Gebhardt, J.E., 1991. Eect of grinding media chalcopyrite interaction on the
self-induced otation of chalcopyrite. Int. J. Miner. Process. 33 (14), 243262.
Cruz, R., Luna-Snchez, R.M., Lapidus, G.T., Gonzlez, I., Monroy, M., 2005. An experi-
mental strategy to determine galvanic interactions aecting the reactivity of sulde
mineral concentrates. Hydrometallurgy 78 (34), 198208.
Cullinan, V.J., Grano, S.R., Greet, C.J., Johnson, N.W., Ralston, J., 1999. Investigating
ne galena recovery problems in the lead circuit of Mount Isa Mines Lead/Zinc
Concentrator, part 1: grinding media eects. Miner. Eng. 147163.
Forssberg, E., Sundberg, S., Hongxin, Z., 1988. Inuence of dierent grinding methods on
oatability. Int. J. Miner. Process. 22 (14), 183192.
Gerlach, J., Kuezeci, E., 1983. Application of carbon paste electrodes to elucidate hy-
drometallurgical dissolution processes with special regard to chalcocite and covellite.
Hydrometallurgy 11, 345361.
Grano, S.R., Wong, P.L.M., Skinner, W., Johnson, N.W., Ralston, J., 1994. The eect of
autogenous and ball mill grinding on the chemical environment and otation of the
copper ore of mount Isa Mines Limited, Australia. In: Castro, S., Alvarez, J. (Eds.), IV
Meeting of the Southern Hemisphere on Mineral Technology: and III Latin American
Congress on Froth Flotation, 351388.
Greet, C.J., Small, G.L., Steinier, P., Grano, S.R., 2004. The Magotteaux MillR: in-
vestigating the eect of grinding media on pulp chemistry and otation performance.
Miner. Eng. 17 (78), 891896.
Hodgson, M., Agar, G.E., 1988. The INCO-voltammetric cell: a new approach to otation
modelling. Int. J. Miner. Process. 24 (12), 2745.
Huang, G., Grano, S., 2005. Galvanic interaction of grinding media with pyrite and its
eect on otation. Miner. Eng. 18 (2005), 11521163.
Huang, G., Grano, S., 2006. Galvanic interaction between grinding media and arseno-
pyrite and its eect on otation. Part I. Quantifying galvanic interaction during
grinding. Int. J. Miner. Process. 78 (2006), 182197.
Lazaro, I., Martinez-Medina, N., Rodriguez, I., Arce, E., Gonzalez, I., 1995. The use of
carbon paste electrodes with non-conducting binder for the study of minerals: chal-
copyrite. Hydrometallurgy 38 (3), 277287.
Lu, Z.Y., Jerey, M.I., Lawson, F., 2000. An electrochemical study of the eect of chloride
ions on the dissolution of chalcopyrite in acidic solutions. Hydrometallurgy 56 (2),
145155.
Marsden, J.O., House, C.I., 2009. The Chemistry of Gold Extraction. Ellis Horwood,
Chichester, England.
Martin, C.J., McIvor, R.E., Finch, J.A., Rao, S.R., 1991. Review of the eect of grinding
media on otation of sulphide minerals. Miner. Eng. 4 (2), 121132.
Natarajan, K.A., Riemer, S.C., Iwasaki, I., 1984. Inuence of pyrrhotite on the corrosive
wear of grinding balls in magnetite ore grinding. Int. J. Miner. Process. 13 (1), 7381.
Peng, Y., Grano, S., Fornasiero, D., Ralston, J., 2003. Control of grinding conditions in the
otation of galena and its separation from pyrite. Int. J. Miner. Process. 70 (14),
6782.
Pozzo, R.L., Malicsi, A.S., Iwasaki, I., 1990. Pyritepyrrhotitegrinding media contact and
its eect on otation. Miner. Metallurg. Process. 2, 1621.
Rabieh, A., Albijanic, B., Eksteen, J.J., 2016. A review of the eects of grinding media and
chemical conditions on the otation of pyrite in refractory gold operations. Miner.
Eng. 94, 2128.
Rabieh, A., Eksteen, J.J., Albijanic, B., 2017a. Inuence of grinding media and water
quality on otation performance of gold bearing pyrite. Miner. Eng. 112, 6876.
Rabieh, A., Eksteen, J.J., Albijanic, B., 2017b. Eect of grinding media on cyanide
leaching of gold in the presence of pyrrhotite. Hydrometallurgy 173, 115124.
Sauber, M., Dixon, D.G., 2011. Electrochemical study of leached chalcopyrite using solid
paran-based carbon paste electrodes. Hydrometallurgy 110 (14), 112.
Subrahmanyam, T.V., Forssberg, K.S.E., 1993. Mineral solutioninterface chemistry in
minerals engineering. Miner. Eng. 6 (5), 439454.
Urbano, G., Melendez, A., Reyes, V., Veloz, M., Gonzalez, I., 2007. Galvanic interactions
between galenasphalerite and their reactivity. Int. J. Miner. Process. 82 (3),
148155.
Vathsala, Natarajan, K.A., 1989. Some electrochemical aspects of grinding media corro-
sion and sphalerite otation. Int. J. Miner. Process. 26 (34), 193203.
Yannopoulos, John C., 1991. The Extractive Metallurgy of Gold. Springer, US, pp. 296.
Yuan, X.M., Palsson, B.I., Forssberg, K.S.E., 1996. Flotation of a complex sulphide ore: II.
Inuence of grinding environments on Cu/Fe sulphide selectivity and pulp chemistry.
Int. J. Miner. Process. 46 (34), 181204.