Hydrometallurgy 175 (2018) 367–375

Contents lists available at ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

The effect of pyrite particle size on the electrochemical dissolution of gold T

during cyanidation
⁎
Ahmet Deniz Basa, Faïçal Larachia, , Patrick Laflammeb
a
Department of Chemical Engineering, Laval University, Québec G1V 0A6, Canada
b
COREM Research Center, 1180 Rue de la Minéralogie, Québec G1N 1X7, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Pyrite is considered as the most common sulphide mineral that carries gold in refractory gold ores. In these ores,
Gold pyrite can be found in different particle sizes. Following flotation process, the flotation tailings is sent to the
Pyrite cyanidation circuit for gold extraction that may contain appreciable amounts of pyrite. Until now, the effect of
Particle size pyrite on gold dissolution was reported to be either positive or negative in the open literature. This current
Leaching
research examines the effect of particle size and amount of pyrite on gold dissolution in a packed bed leach
Passivation
reactor (PBLR). Electrochemical characterization as a function of pyrite particle size on gold dissolution was
Electrochemical dissolution
tested. It was found that pyrite (4 g) has positive galvanic effect on gold dissolution especially in the presence of
fine particles, −106 μm (i.e., 54% Au in the absence of pyrite vs. 95% with +20–53 μm pyrite). On the other
hand, gold dissolution showed a sharp decrease when particle size was coarser than +106 μm. Highest gold
extraction, 98%, was achieved when gold particles are in contact with +75–106 μm pyrite particles. When the
pyrite amount was doubled (8 g of +75–106 μm), gold dissolution was decreased to 35% due to the partial
passivation of gold. If the pyrite amount were reduced by half (2 g of +75–106 μm), gold dissolution increased
by 30% as compared to the case without pyrite. Different scenarios were also considered regarding to activation
and passivation of gold. For instance, when gold was split and dispersed equally within the pyrite layer and
within the adjacent quartz layer, gold dissolution was found to be around 35%, suggesting a negative effect of
released species from pyrite. Cyclic voltammetry and potentiodynamic polarization findings are in line with the
cyanide leaching results. The shift in open circuit potential in presence of pyrite is in support of observed leach
kinetics. SEM-EDS results have confirmed the decrease in gold dissolution in the presence of coarse particles.
These findings have revealed that pyrite particle size and its amount have significant impact on gold dissolution.

1. Introduction sulphide minerals on gold dissolution has extensively been studied in

Due to the rapid depletion of free-milling types of gold ores, it is
accepted worldwide that there is an increasing trend in the treatment of
refractory sulphidic gold ores (Adams, 2016). Refractoriness is a term
generally used to express the reason(s) of poor or low gold extractions
(La Brooy et al., 1994). Since the majority of gold ores are associated
with sulphides, then it is critical to examine its influence on gold dis-
solution. Dissolution kinetics of gold may be reduced/slowed down in
some conditions, and if so, passivation and galvanic interaction phe-
nomena are considered as potentially significant factors (Lorenzen and
van Deventer, 1992; Mrkusic and Paynter, 1970).
In cyanide solutions, sulphide minerals are to some extent soluble
thus, there will possibly be some soluble species present in the leaching
solution. It is generally accepted that the presence of such species re-
sults in high consumption of cyanide and oxygen. The influence of
the literature (Fink and Putnam, 1950; Weichselbaum et al., 1989;
Deschênes et al., 1998; Dai and Jeffrey, 2006). Weichselbaum et al.
(1989) found that the addition of trace amounts of sodium sulphide to
the cyanide solution dramatically reduced gold leaching. This phe-
nomenon was attributed to the formation of a passive layer of Au2S on
the gold surface. Lorenzen and van Deventer (1992) obtained similar
results on gold dissolution in the presence of reactive sulphide minerals.
Liu and Yen (1995) conducted a systematic study of the kinetics of gold
dissolution in the presence of various sulphide minerals in both air-
saturated and oxygen-enriched systems. Their results demonstrated that
the leaching behaviour of gold in the presence of sulphide minerals
depended strongly on both the solubility of the sulphides and the
oxygen concentration in the solution.
Gold is mainly associated with sulphide minerals, in particular with
pyrite, arsenopyrite, and sphalerite (Flatt and Woods, 1995). Among

⁎
Corresponding author.
E-mail address: Faical.Larachi@gch.ulaval.ca (F. Larachi).

https://doi.org/10.1016/j.hydromet.2017.12.016
Received 17 October 2017; Received in revised form 8 December 2017; Accepted 20 December 2017
Available online 20 December 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

others, pyrite is known as the most common sulphide mineral that
carries significant amounts of gold, to the point where solid-solution
gold may become the principal form of gold in the ore and pyrite its
chief carrier (Thomas, 1997). A refractory pyritic ore typically contains
different types of pyrite with various gold concentrations (Ketcham
et al., 1993).
A number of studies have investigated the galvanic interaction be-
tween gold and pyrite as a function of leaching parameters such as
cyanide concentration, pH, dissolved oxygen, and agitation rate (Azizi
et al., 2011; Huai et al., 2017; Lorenzen and van Deventer, 1992) and
the galvanic interaction between gold and pyrite occurs and enhances
the dissolution of gold at the initial stage, followed by the passivation of
iron oxides (Aghamirian and Yen, 2005; Azizi et al., 2010; Lorenzen
and van Deventer, 1992). Aghamirian and Yen (2005) employed po-
tentiodynamic polarization tests in one container and found that pyrite
and pyrrhotite showed positive effect on the leaching of gold which is
not in agreement with the previous findings (Paul, 1984; Lorenzen and
van Deventer, 1992). These results show that the influence of pyrite on
gold dissolution still receives much attention.
Following the base-metal flotation of gold-bearing ores, such as in
sulphur/silicate bearing minerals, the flotation tailings are sent to cy-
anidation circuit to extract gold. This flotation residue could contain
some amounts of pyrite with a particle sizes defined for the flotation
circuit, and this may play an important role on the cyanidation process.
Until now, the effect of pyrite with different size fractions on gold
dissolution with regard to activation and passivation during cyanida-
tion has not received much attention. Hence, the objectives of this study
are: (i) to examine the influence of particle size of pyrite on gold dis-
solution; (ii) to test the quantitative effect of pyrite on the leaching of
gold which represents the practical conditions of some of the gold with
base metal ore deposit; (iii) to characterise its electrochemical beha-
viour; and (iv) to provide an alternative explanation for the slowdown
in the gold leach rate supported by surface characterization studies.
These tests have been carried out in packed-bed leach reactor (PBLR) to
decouple and quantify the individual contributions of passivation
phenomena and galvanic interactions on gold dissolution (Table 1). It is
important to underline the fact that liquid-solid mass transfer coeffi-
cients with similar-size particles, whether being present in a fixed bed
–such as the present mini-reactor cell– or in a conventional slurry re-
actor –as in actual cyanidation slurry agitated tanks or sparged bubble
columns–, must behave in a qualitatively similar fashion by virtue of
the convective flows in action in both reactor geometries. In addition,
should the imposed flow rates in the PBLR correspond, hydro-
dynamically speaking, to liquid interstitial velocities matching the
particle-liquid slip velocities in slurry configuration then similar figures
must prevail for both mass transfer coefficients. Another worth re-
minding feature of this PBLR is its ability to “artificially” emulate large
ensembles of microscopic contacts which stem from partially liberated
gold inclusions within pyrite granular environments. This is rendered
possible with the PBLR tool without recourse to microscopic/nano-
scopic costly instrumentation to assess microscopic solid-state phe-
nomena while being representative of the industrial bulk leach condi-
tions.
2. Experimental
2.1. Materials
Sodium cyanide (NaCN) with a purity of > 98% was obtained from
Sigma-Aldrich Canada. The solution medium (100 mL) was prepared
using distilled water. Leaching tests were conducted in 30 mM NaCN
electrolyte solutions saturated with oxygen at 0.1 MPa, and NaOH
(Fisher Scientific Canada) adjusted pH to 11 ± 0.01.
Pure gold powder (P80 = 39 μm, 99.998%) was purchased from
Alfa Aesar USA. Pyrite was obtained from Wards Minerals and was
reduced in COREM Research Centre down to the following size frac-
tions: + 20–53 μm, +53–75 μm, +75–106 μm, + 106–150 μm,
+ 150–212 μm and + 212 μm. X-ray fluorescence (XRF) analyses
showed that the sample contains 44.8% Fe, 51.4% S, and 0.45% SiO2.
Unless otherwise reported, 50 mg Au and 4 g pyrite (Py) were used in
leaching tests, and the rest of the reactor volume was segregated (//) by
quartz (Qtz). Different scenarios such as half Au + Pyrite // half Au
+ Quartz were also considered. Sintered glass filtered disc that has
20 mm diameter, and 3 mm thickness was purchased from VWR. This
was used to have two compartments, i.e., segregating Au from pyrite.
2.2. Cyanidation test procedure
Leaching tests were performed in a 250 mL glass container by a
continuous circulation of 100 mL of leach solution with a peristaltic
pump through PBLR (cylindrical working section 25 mm H, 15 mm I.D.)
with a constant flow rate of 10.4 mL/min. The solution was agitated at
300 rpm with a magnetic bar (4 cm long and 1 cm in diameter) during
tests. Leach solution was fed upwardly from the bottom in order to
avoid the channeling of the feed solution in the reactor and to maximize
residence time of the cyanide solution in the mineral layer (Fig. 1).
Instead of air, pure oxygen gas was sparged through the container to
maintain a constant dissolved oxygen level (DO2 ~0.45 mM at 25 °C),
which was monitored by means of a dissolved oxygen probe (FOXY-
AL300 model from Ocean Optics), while pH of the feed solution was
maintained at 11 ± 0.01 using an Oakton 1000 series pH-meter. The
concentration of CN− in solution was monitored using Thermo Scien-
tific Orion 9606BNWP Cyanide Ion-Selective Electrode. Sodium cyanide
was added to maintain the concentration of free cyanide at the pre-
determined level over the leaching period. Leach solution was sampled
at predetermined intervals over 24 h.
At the termination of cyanidation, leach residues were collected and
dried in oven at 105 °C for characterization studies (explained in

Table 1
Strategy adapted to examine the effect of pyrite regarding the activation and passivation of gold.

Tests Objectives & explanation

• Au + Qtz (No Pyr) ✓ Dissolution profile of Au in absence of pyrite.

• Au + Pyr (+ 20–53 μm) // Qtz
• Au + Pyr (+ 53–75 μm) // Qtz
• Au + Pyr (+ 75–106 μm) // Qtz
• Au + Pyr (+ 106–150 μm) // Qtz
• Au + Pyr (+ 150–212 μm) // Qtz
• Au + Pyr (+ 150–212 μm) // Qtz
• Au + excess Pyr (8 g) // Qtz
• Au + Pyr (2 g) // Qtz
• half Au + Pyr (4 g) // half Au + Qtz
• Pyr (4 g) // Au + Qtz
✓ Packed-bed leach reactor (PBLR) was entirely filled with mix of Au (50 mg) and quartz (Qtz).
Objective: investigate the effect of pyrite particle size on gold dissolution and the galvanic interactions between gold and pyrite.
✓ Mix of Au and Pyrite (Pyr) samples placed in lower part of PBLR, and Qtz was in upper part. Tests with 4 g of Pyr.
✓ According to results, pyrite particle size of + 75–106 μm was considered for further investigation as it yielded maximum gold
dissolution.
Objective: test the effect of pyrite amount on gold dissolution.
✓ Amount of pyrite (8 g) doubled and halved (2 g).
✓ Amount of Au split and dispersed equally with Pyr and Qtz powders in segregated parts of PBLR.
Objective: examine passivation effect during gold leaching.

368
A.D. Bas et al.
Electrolyte Outlet Electrolyte Outlet
Quartz
Qtz
Au Sintered glass
filtered disc
Py
Au + Pyrite
(a) (b)
Electrolyte Inlet Electrolyte Inlet
Electrolyte Outlet
Au + Quartz
Sintered glass
filtered disc
Pyrite
(c)
Electrolyte Inlet
Section 2.4). Metal analysis (Au and Fe) was performed by Atomic
Absorption Spectroscopy (Perkin Elmer AAnalyst 800). Microwave
Plasma-Atomic Emission Spectrometer (4100 MP-AES by Agilent
Technologies) was also considered since it is a recent methodology that
is especially suitable for the detection of gold, even at low concentra-
tions (Shareder et al., 2011).
2.3. Electrode preparation and electrochemical test procedure
Pure gold powder or mixture of pure gold and pyrite was mixed
with graphite powder (to increase the conductivity) 3:1 and with few
drops of silicone oil, for binding, till a paste was obtained. Graphite
powder, which has a particle size of < 45 μm, and a 99% purity, was
obtained from Sigma-Aldrich. The mixture was manually homogenized
during 30 min. Then, it was mechanically pressed at 20 tons to have
uniform sample surface. After that, disc electrodes were kept under
nitrogen atmosphere over a night. Then, these electrodes were con-
nected with an insulated copper wire, cast in acrylic resin. Pure gold or
mixture of pure gold and pyrite disc electrode with a surface area of
2.54 cm2 was considered as working electrode, platinum as counter
electrode, and Ag/AgCl, KClsat as reference electrode, and all potentials
here were reported vs. standard hydrogen electrode (SHE). Working
electrode was first polished with a fine (MicroCut® 100 Grit Soft) pol-
ishing paper and then rinsed with distilled water. Then, it was in-
troduced in aqua-regia for 10 s to clean the surface, washed with dis-
tilled water and ethanol, and finally rinsed with distilled water again to
assure reproducibility (Kirk et al., 1978).
Electrochemical studies were performed using a potentios-
tat–galvanostat (model VSP-27 from Bio-Logic SA) and the EC-Lab
369
Hydrometallurgy 175 (2018) 367–375
Fig. 1. Schematic illustration of the packed-bed leach re-
actor (PBLR) setup filled with gold (Au), pyrite (Py), and
quartz (Qtz). (a) Au + Pyrite // Quartz; (b) Au
+ Quartz // Au + Pyrite; (c) Pyrite // Au + Quartz.
half Au + Quartz
Sintered glass
filtered disc
half Au + Pyrite
software. Cyclic voltammetry (CV) tests were carried out in 0.03 M
NaCN solution at a scan rate of 10 mV/s. First, electrodes were allowed
to stay at open circuit potential (OCP) during 30 min for stabilization.
CV studies were conducted between −1 V and 1.4 V values and steady-
state cycle was considered. Potentiodynamic cathodic polarization tests
were performed in presence of oxygen and cyanide. First, electrodes
were allowed to stay at open circuit potential (OCP) during 30 min for
stabilization. Cathodic polarization tests were performed by scanning
from −900 mV to Ecorr, and the corrosion current (icorr) was estimated
by considering the cathodic Tafel slope, only extrapolating to OCP. A
scan rate of 0.166 mV/s was selected based on the polarization stan-
dards (ASTM Standard G 5-94, 2006). Electrochemical tests were per-
formed in replicates to ensure the reproducibility.
2.4. Characterization of gold leach residues
The residues of cyanide leaching tests were subjected to Scanning
Electron Microscopy (SEM) (JEOL 840-A) coupled with Energy-dis-
persive X-ray spectroscopy (EDS) to detect the residual gold. X-ray
photoelectron spectroscopy (XPS) analysis was also conducted for
characterization. XPS results were collected using an AXIS-ULTRA in-
strument by Kratos (UK). The X-ray source is a monochromatic Al
source operated at 300 watts. Detection of the photoelectrons is per-
formed with an 8-channel detector. Electrostatic charge appearing on
the electrically insulating samples under X-ray irradiation is neutralized
with the integrated very low energy electron flood gun, the parameters
of which are set to optimize energy resolution and counting rate. Survey
scan is recorded with pass energy of 160 eV and a step size of 1 eV, and
these were used for elemental analysis and apparent concentrations
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

100 10

90

80
8

NaCN consumption, kg/t

70
Au extraction, %

60
6
50

40
Au+Qtz (No Pyrite)
30 Au+Pyrite (+20-53 µm)//Qtz 4
Au+Pyrite (+53-75 µm)//Qtz
Au+Pyrite (+75-106 µm)//Qtz
20
Au+Pyrite (+106-150 µm)//Qtz
Au+Pyrite (+150-212 µm)//Qtz
10 Au+Pyrite (+150-212 µm)//Qtz 2
Au+Pyrite (+212 µm)//Qtz
0
0 4 8 12 16 20 24
Time, h 0
No Pyrite Pyrite Pyrite Pyrite Pyrite Pyrite
Fig. 2. The effect of pyrite particle size on the cyanide leaching of Au (%). (+20-53 µm) (+53-75 µm) (+75-106 µm) (+150-212 µm) (+212 µm)

calculations.
3. Results and discussion
3.1. Influence of pyrite particle size on gold dissolution
The effect of particle size of pyrite on gold dissolution was examined
in PBLR (Fig. 2). The lower part of the PBLR was filled with a mixture of
pure gold powder and pyrite, while the upper part was filled with
quartz. A sintered glass filtered disc was used to have two separate
compartments. The extraction of gold in the absence of pyrite resulted
in 55% after 24 h of cyanide leaching.
In the presence of pyrite with fine particle sizes, gold extraction
showed an increasing trend. This increase is attributed to the positive
galvanic interaction between gold and pyrite (Habashi, 2013;
Aghamirian and Yen, 2005). The highest gold extraction, i.e., 98%, was
obtained in the presence of pyrite with a particle size of +75–106 μm.
It is obvious that the leach kinetics is also faster at this pyrite size
fraction. In general, the initial 12 h seems to be optimal since only a 3%
increase, as an average, was achieved over the subsequent 12 h. How-
ever, gold extraction decreased around 51% when pyrite particle size
was coarser than the + 75–106 μm fraction. The lowest gold extraction
was obtained when the pyrite particle size was the coarsest, + 212 μm.
It can be deduced that the increase in gold leaching with fine pyrite
particles could be linked to the enhanced surface area, and to the gal-
vanic interaction.
Gold extraction results were found to be reproducible within re-
plicates analyzed by AAS. Due to the difference in pyrite size and low
gold concentration in PBLR, MP-AES was also considered for Au ana-
lysis for comparison and reliability of findings (Table 2). MP-AES reads
almost the same Au extractions, just only a 3% higher Au than that of
AAS at coarser pyrite particle sizes. This slight difference is completely
normal due to the operational differences between these tools.
It is essential and critical to monitor and maintain the cyanide
concentration in the solution during cyanidation. In this case, NaCN
consumption was considered based on the used sample, mixture of gold
Fig. 3. The effect of pyrite particle size on NaCN consumption (kg/ton ore).
and pyrite (Fig. 3). Cyanide consumption was greatly enhanced in
presence of pyrite. Increasing pyrite particle size from + 20 μm to
− 106 μm resulted in an increase in the cyanide consumption. At
+ 75–106 μm pyrite particle size, NaCN consumption was found to be
8.5 kg/ton ore, and it was decreased by 9% at coarser pyrite size,
+ 212 μm. Gold leaching results (Fig. 2) are in accordance with the
cyanide consumption.
The dissolution profile of Fe in the solution is given in Fig. 4. It has
been found that the highest Fe dissolution was obtained at fine pyrite
particle size, + 20–53 μm. This finding is attributed to the increase in
the surface area at fine sizes. Accordingly, dissolved Fe decreased at
coarser pyrite fractions, which is in line with the cyanide consumption.
3.2. Interpretation of leaching results
It has been found that gold dissolution increased in presence of fine
pyrite particles (−106 μm), whereas decreased in presence of coarse
pyrite particles (+106 μm). Then, a systematic study has been con-
sidered to reach a better understanding regarding to passivation and
dissolution of gold at the optimal pyrite particle size (+ 75–106 μm)
where gold leaching was the highest. In this manner, different scenarios
and effect of pyrite amount were considered (Fig. 5).
When using the +75–106 μm pyrite size fraction and reducing the
amount by half (2 g), the extraction of gold was increased by 30% if
compared to the case with no pyrite. However, it resulted in lower gold
extraction than that of 4 g pyrite. This increase in presence of pyrite is
in line with the positive galvanic interactions. On the other hand, when
pyrite amount was doubled (8 g), gold extraction showed a sharp de-
crease (from 98% to 44%). It can be deduced that high amount of pyrite
has negative effect on gold dissolution, leading to the partial passiva-
tion of gold.
To have a better understanding on the passivation phenomenon of
gold, pyrite was dispersed in the lower part of the PBLR, and the gold
particles and quartz were mixed together in the upper part (Fig. 6). The
leaching kinetics was found to be slow as compared to other

Table 2
Comparison of Au dissolution by AAS and MP-AES after 6 h and 24 h of cyanide leaching.

Sample name 6h 24 h

AAS MP-AES AAS MP-AES

Au + No pyrite 47.1 ± 4.7% 45.3 ± 3.2% 54.1 ± 6.1% 51.2 ± 4.5%

Au + Pyrite (+ 53–75 μm) 63.0 ± 3.9% 65.4 ± 4.1% 90.9 ± 2.6% 87.7 ± 3.3%
Au + Pyrite (+ 75–106 μm) 87.3 ± 5.3% 91.9 ± 2.8% 98.7 ± 1.2% 96.5 ± 4.2%
Au + Pyrite (+ 212 μm) 37.6 ± 6.1% 42.6 ± 3.6% 42.1 ± 3.6% 46.8 ± 4.7%

370
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

Fig. 4. The effect of pyrite particle size on the dissolution

3.5
of Fe (× 10− 5 g/4 g).

3.0
Dissolved Fe, x10-5g / 4 g

2.5

2.0

1.5

1.0

0.5

0.0
Au+No Pyrite Au+Pyrite Au+Pyrite Au+Pyrite Au+Pyrite Au+Pyrite Au+Pyrite
(+20-53 µm) (+53-75 µm) (+75-106 µm) (+106-150 µm) (+150-212 µm) (+212 µm)

100 in the anodic dissolution. However, when coarse pyrite particles were
90 used, the lesser negative OCP was tantamount to a nobler instance for
Au. This finding might explain the positive galvanic interaction effect
80
the finer the pyrite particles.
70 The shift/change in the dissolution potential of gold during leaching
Au extraction, %

60
50
40
30
20
10
0 Au+Pyrite (2g) (+75-106 µm)//Qtz
0 4 8 12
Time, h
Fig. 5. The effect of amount of pyrite on Au extraction, %.
experiments, and a 34% of gold was extracted. This decrease could be
linked to the released species from pyrite that had detrimental effect on
gold dissolution. This finding suggests the partial passivation of gold by
pyrite-issued soluble species.
A legitimate question to be asked concerns “which one between
galvanic interaction and passivation has a dominant effect on gold
dissolution?” For this purpose, half of gold was dispersed with pyrite in
the lower part, and the other half was dispersed within the quartz upper
part. In this case, gold dissolution was found to be ~34%. This result is
very close when gold was entirely dispersed only within the quartz
upper part with pyrite left alone in the lower part. Although same gold
extractions were obtained in both cases, initial leaching kinetics was
faster when gold was equally dispersed in both parts. This finding
suggests that although galvanic interaction has positive impact on gold
dissolution, passivation by the release species is detrimental to cyani-
dation of gold.
3.3. Electrochemical characterization of pyrite particle size on gold
dissolution
The change in the open circuit potential (OCP) of gold is helpful as
to have an idea about the active behaviour of gold dissolution. Note
that the OCP also corresponds to the corrosion/dissolution or leaching
potential. The change in corrosion potential of electrodes is shown at
the end of leaching (after 24 h) in Table 3. The dissolution potential of
gold electrode in the absence of pyrite was found to be −0.39 V/SHE.
In presence of fine pyrite particles, the dissolution potential was shifted
to more negative potential up to −0.47 V, suggesting the enhancement
has been reported in the literature. For instance, Lorenzen and van
Deventer (1992) found that the dissolution potential of gold shifted to
less negative/active values with a concurrent decrease in dissolution
current when gold is pulped in sulphide minerals slurries, and this was
linked to a retarding effect on the gold dissolution rate.
Au+Qtz (No Pyrite)
Since the dissolution of gold is an electrochemical reaction, its
Au+Pyrite (+75-106 µm)//Qtz dissolution behaviour can readily be studied by means of electro-
half Au+Pyrite (+75-106 µm)//half Au+Qtz
Au+excess Pyrite (8 g) (+75-106 µm)//Qtz chemical methods. In this manner, cyclic voltammetry (CV) tests on
Pyrite (+75-106 µm)//Au+Qtz
gold dissolution as a function of pyrite particle size was tested (Fig. 7).
16 20 24 The presence of pyrite, + 20–106 μm, has led to an increase in current
density suggesting a better dissolution. When coarser pyrite particle
size, + 106 μm, was used, a sharp decrease was observed in terms of
current density suggesting the decrease in dissolution profile of elec-
trode. This finding is in agreement with the cyanide leaching results.
The oscillations observed in cyclic voltammetry could be linked to the
repeated formation and dissolution of unstable corrosion products on
the electrode surface (Fig. 7). This oscillatory behaviour can occur
during both anodic and cathodic processes, but it is generally accepted
that this is mainly related to the anodic polarization of metals and the
instability of the corrosion products leading to partial passivation
(Jayasekera et al., 1996).
Estimation of gold corrosion rate by electrochemical tests is a sub-
ject of debate in the literature. The pioneering work in gold electro-
chemistry by Kudryk and Kellogg (1954) and Cerovic et al. (2005)
considered the intersection of cathodic and anodic curves for the cal-
culation of the gold leach rate. However, recent studies by Dai and
Breuer (2013), and Bas et al. (2016, 2017) reported that considering the
intersection locus might be misleading since it is unrepresentative of
practical conditions, and there is a potential passive behaviour in the
anodic curve. Bas et al. (2016) considered only cathodic Tafel slope
extrapolation to the open circuit potential, as a new approach, which
was found to be representative of the conventional cyanidation.
The dissolution (corrosion) rate of gold was estimated by extra-
polation of the cathodic Tafel slope to open circuit potential (Fig. 8). It
is worth noting that, due to the difficulty in the Tafel extrapolation, two
recommended rules as follows are carefully considered in this study: i)
the extrapolation should start at least 50–100 mV away from Ecorr, and
(ii) at least one of the branches of the polarization curve (cathodic or
anodic) should exhibit Tafel trend over at least one decade of current
density (Kelly et al., 2002). However, in this study, it should be un-
derlined that a completed decade is partially observed for some curves.
It is important to note that, although the slopes are similar, the level of

371
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

Fig. 6. Schematic illustration of the strategy adapted to

examine the influence of pyrite particle size on gold cya-
nidation.

Table 3 -0.2
1-Au+No Pyrite
Open Circuit Potential (OCP) (V/SHE) of electrodes after 24 h of leaching. 2-Au+Pyrite (+75-106 µm)
-0.3 3-Au+Pyrite (+106-150 µm)
4-Au+Pyrite (+212 µm)
Corrosion potential (V/SHE)
-0.4
Potential, E vs V/SHE

Electrode type End of leaching (after 24 h)

-0.5
Au + Quartz (No Pyrite) − 0.39 ± 4.3%
Au + Pyrite (+ 20–53 μm) // Quartz − 0.42 ± 3.6% -0.6
Au + Pyrite (+ 53–75 μm) // Quartz − 0.44 ± 5.8%
Au + Pyrite (+ 75–106 μm) // Quartz − 0.47 ± 5.7% -0.7 1
Au + Pyrite (+ 106–150 μm) // Quartz − 0.38 ± 6.9% 3
Au + Pyrite (+ 150–212 μm) // Quartz − 0.37 ± 5.4%
-0.8
Au + Pyrite (+ 212 μm) // Quartz − 0.36 ± 5.5% 2
-0.9 4

4.5 -1.0
Au+No Pyrite
Au+Pyrite (+20-53 µm) -1.8 -1.5 -1.2 -0.9 -0.6 -0.3 0.0 0.3
Au+Pyrite (+53-75 µm) Log I, mA/cm2
3.5 Au+Pyrite (+75-106 µm)
Au+Pyrite (+106-150 µm)
Fig. 8. Potentiodynamic cathodic polarization of electrodes as a function of pyrite par-
Current density, mA/cm2

Au+Pyrite (150-212 µm)

2.5 Au+Pyrite (+212 µm) ticle size (1: Au + No Pyrite; 2: Au + Pyrite (75–106 μm) // Quartz; 3: Au + Pyrite
(+ 106–150 μm) // Quartz; 4: Au + Pyrite (+ 212 μm) // Quartz.

1.5
Table 4
Corrosion (dissolution) rate of electrodes (obtained from cathodic polarization curves,
0.5 Fig. 8).

Electrode type Corrosion current Corrosion rate of electrode

-0.5 (μA/cm2) (× 10− 6 mol m− 2 s− 1)

Au + Quartz (No Pyrite) 184 9.53 ± 4.3%

-1.5 Au + Pyrite (+ 75- 194 10.10 ± 5.7%
-1.2 -0.9 -0.6 -0.3 0.0 0.3 0.6 0.9 1.2 1.5 106 μm) // Quartz
Potential, E vs V/SHE Au + Pyrite (+ 106- 19 0.98 ± 6.9%
150 μm) // Quartz
Fig. 7. Electrochemical characterization of the effect of pyrite particle size. Au + Pyrite (+ 212 μm) // 18.5 0.95 ± 5.5%
Quartz

372
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

Au
Py

Py

Au

Fig. 9. SEM-EDS images of leach residues, light white particle is gold, grey particle is pyrite, and black particle is silica: (a) Au + Quartz (No Pyrite); (b, c) Au + Pyrite (75–106 μm) //
Qtz.

the open circuit potential plays a significant role in the determination of
the leach rate of gold.
It was found that a higher corrosion current, i.e., corrosion rate, was
obtained in the case of finer pyrite particles (+75–106 μm), whereas
the corrosion current obeyed a decreasing trend the coarser the pyrite
particles (+106–150 and + 212 μm) (Table 4, and Fig. 8). These
findings are in accordance with those obtained in conventional cyani-
dation (Fig. 2) and cyclic voltammetry (Fig. 7) results. The corrosion
rate obtained in presence of pyrite represents the dissolution behaviour
of electrode, i.e., gold and other metals as well. By this extrapolation,
the corrosion rate of gold with quartz particles in the absence of pyrite
was found to be 9.53 × 10− 6 ± 4.3% ± mol m− 2 s− 1, and this was
increased by 5% in presence of fine pyrite particles suggesting a posi-
tive galvanic effect on the dissolution.
3.4. Characterization of cyanide leach residues
Fig. 9(a, c) and Fig. 10(a, d) illustrate the SEM-EDS images of leach
residues of (Fig. 9a) Au + Quartz (No Pyrite); (Fig. 9b, c) Au + Pyrite
(75–106 μ) // Quartz; (Fig. 10a, b) Au + Pyrite (+ 212 μm) // Quartz.
In the absence of pyrite (Fig. 9a), there is enough un-leached gold
leftover trapped within the quartz layer. Very high amount of gold was
found in the leach residue in the presence of coarse pyrite particles,
+ 212 μ (Fig. 10a, b), compared with that of the fine pyrite particles,

373
A.D. Bas et al. Hydrometallurgy 175 (2018) 367–375

Fig. 10. SEM images of leach residues, light white parti-

cle = gold, grey particle = pyrite, and black particle = -
quartz; (a, b) Au + Pyrite (+ 212 μm) // Quartz; (c, d) half
Au + Pyrite (75–106 μm).
Au
Py
Si
Py
Au

Si Py

a b

Si

Py
Py
Py
Py Si

Au Py

c d

75–106 μm (Fig. 9b–c). Au in these leach residues were associated with
pyrite particles.
When half Au was dispersed with pyrite in the lower part, the leach
residue was also subjected to surface characterization. In this case, high
amount of gold was also found as it was obtained in the presence of
coarse particles (Fig. 10c, d). Un-leached gold in the residue was found
to accompany both pyrite and silica particles.
The leach residue of gold powder dispersed entirely within quartz
particles in absence of pyrite in PBLR was analyzed by XPS (Fig. 11).
Metallic Au and oxidized Au were detected by XPS in leach residue.
This finding supports the cyanidation results where only 54% of Au was
leached in this experiment.
It is important to underline that pyrite is the most common gold
sulphide bearing mineral in gold deposits. Most of the industrial op-
erations rely on flotation, and its tailings are treated by means of cya-
nide leaching for gold extraction. This residue could contain appreci-
able amounts of pyrite in different size fractions. Hence, this current
research shows the importance of electrochemical tests and
540
520
Au
Au+
500
480
CPS
characterization of leach residue that provide better insights on gold
dissolution as a function of pyrite particle size.
4. Conclusion
1. Cyanide leaching tests have revealed that pyrite has a positive
galvanic effect on gold dissolution. Highest gold dissolution, 98%, was
achieved at a pyrite particle size of + 75–106 μm. Coarser size fractions
of pyrite, + 106 μm, resulted in a significant decrease in gold dissolu-
tion, even lower than without pyrite.
1. Electrochemical characterization studies have shown that current
density increased in presence of fine pyrite particles, suggesting the
increase in its dissolution behaviour. This finding is in line with the
cyanidation results in PBLR. At coarser pyrite particles, gold dis-
solution commenced slowly and very late. Potentiodynamic
cathodic polarization curves support the cyanidation results.
2. When pyrite amount was doubled at the size distribution of
+75–106 μm (from 4 g to 8 g), gold extraction showed a significant
decrease (from 98 to 35%). When pyrite amount was halved (from
4 g to 2 g), gold extraction was increased as compared to the case
without pyrite (from 54 to 83%), suggesting the positive galvanic
interaction on gold dissolution.
3. SEM-EDS analysis of leach residues have confirmed that when fine
pyrite particles, +75–106 μm, were used, there is very less amount
of gold in the residue. On the other hand, it was significantly in-

creased when pyrite particle size was coarser, + 212 μm. Also, it can
460
be deduced that there is more pyrite in the residue at coarser size
440 while gold is surrounded by pyrite particles.
4. When half of Au was dispersed within pyrite lower part, and half
420 within quartz upper part of the PBLR, gold dissolution was also
decreased. A similar trend was also obtained when pyrite was dis-
400 persed in the lower part, and Au and silica were mixed in upper part.
This finding suggests that the dissolved species have negative effect,
380
82 83 84 85 86 87 88 89 90 91 92 93 leading to poor gold extractions due to the partial passivation of
Binding Energy (eV) gold.

Fig. 11. XPS analysis of the leach residue of gold powder dispersed within quartz in
absence of pyrite.

374
A.D. Bas et al.
Acknowledgements
The authors would like to express their thanks and appreciation to
the Natural Sciences and Engineering Research Council of Canada
(NSERC) and Agnico Eagle, Barrick Gold Corporation, Camiro, Corem,
Glencore, IamGold, Niobec, and Teck for their financial support
through the R&D NSERC Grant Program. Laval University personnel
and colleagues, i.e., Prof. J. Bouchard (for cyanide ion probe), V. Dodier
(MP-AES analysis), Dr. A. Adnot (XPS analysis and fruitful discussion),
A. Ferland (SEM-EDS analysis), are gratefully acknowledged for their
help. Thanks are extended to COREM's personnel for kindly providing
the pyrite samples.
References
Adams, M.D., 2016. Gold Ore Processing: Project Development and Operations, Second
ed. Elsevier ISBN 978-0-444-63658-4.
Aghamirian, M.M., Yen, W.T., 2005. Mechanisms of galvanic interactions between gold
and sulfide minerals in cyanide solution. Min. Eng. 18, 393–407.
ASTM Standard G 5-94, 2006. Standard reference test method for making potentiostatic
and potentiodynamic anodic polarization measurements. In: Annual Book of ASTM
Standards. vol 03.02 ASTM International, West Conshohocken. PA.
Azizi, A., Petre, C.F., Olsen, C., Larachi, F., 2010. Electrochemical behavior of gold cya-
nidation in the presence of a sulfide-rich industrial ore versus its major constitutive
sulfide minerals. Hydrometallurgy 101, 108–119.
Azizi, A., Petre, C.F., Olsen, C., Larachi, F., 2011. Untangling galvanic and passivation
phenomena induced by sulfide minerals on precious metal leaching using a new
packed-bed electrochemical cyanidation reactor. Hydrometallurgy 107, 101–111.
Bas, A.D., Safizadeh, F., Ghali, E., Choi, Y., 2016. Leaching and electrochemical dis-
solution of gold in the presence of iron oxide minerals associated with roasted gold
ore. Hydrometallurgy 166, 143–153.
Bas, A.D., Ghali, E., Choi, Y., 2017. A review on electrochemical dissolution and passi-
vation of gold during cyanidation in presence of sulphides and oxides.
Hydrometallurgy 172, 30–44.
Cerovic, K., Hutchison, H., Sandenbergh, R.F., 2005. Kinetics of gold and a gold-10%
silver alloy dissolution in aqueous cyanide in the presence of lead. Min. Eng. 18,
585–590.
Dai, X., Breuer, P.L., 2013. Leaching and electrochemistry of gold, silver, and gold-silver
alloys in cyanide solutions: effect of oxidant and lead (II) ions. Hydrometallurgy 133,
139–148.
Dai, X., Jeffrey, M.I., 2006. The effect of sulphide minerals on the leaching of gold in
375
Hydrometallurgy 175 (2018) 367–375
aerated cyanide solutions. Hydrometallurgy 82, 118–125.
Deschênes, G., Rousseau, M., Tardif, J., Prud'homme, P.J.H., 1998. Effect of the compo-
sition of some sulphide minerals on cyanidation and use of lead nitrate and oxygen to
alleviate their impact. Hydrometallurgy 50 (3), 205–221.
Fink, C.G., Putnam, G.L., 1950. The action of sulphide ion and of metal salts on the
dissolution of gold in cyanide solutions. Trans. AIME 187, 952–955.
Flatt, J.R., Woods, R., 1995. A voltammetric investigation of the oxidation of pyrite in
nitric acid solutions: relation to treatment of refractory gold ores. J. Appl.
Electrochem. 25, 852–856.
Habashi, F., 2013. The role of pyrite in hydrometallurgical processes. Metallurgy 67,
96–98.
Huai, Y., Plackowski, C., Peng, Y., 2017. The surface properties of pyrite coupled with
gold in the presence of oxygen. Min. Eng. 111, 131–139.
Jayasekera, S., Avraamides, J., Ritchie, I.M., 1996. The electrochemical oxidation of gold
telluride (AuTe2) in perchloric acid solutions. Electrochim. Acta 41 (6), 879–885.
Kelly, R.G., Sculy, J.R., Shoesmith, D.W., Buchheit, R.G., 2002. Electrochemical
Techniques in Corrosion Science and Engineering. ISBN, 0203909135,
9780203909133. CRC Press.
Ketcham, V., O'Reilly, J., Vardill, W., 1993. The Lihir gold project; process plant design.
Miner. Eng. 6, 1037–1065.
Kirk, D.W., Foulkes, F.R., Graydon, W.F., 1978. A study of anodic dissolution of gold in
aqueous alkaline cyanide. J. Electrochem. Soc. 125, 1436–1443.
Kudryk, V., Kellogg, H.H., 1954. Mechanism and rate-controlling factors in the dissolu-
tion of gold in cyanide solutions. Trans. AIME J. Met. 6 (5), 541–548.
La Brooy, S.R., Linge, H.G., Walker, G.S., 1994. Review of gold extraction from ores.
Miner. Eng. 7 (10), 1213–1241.
Liu, G.Q., Yen, W.T., 1995. Effects of sulphide minerals and dissolved oxygen on the gold
and silver dissolution in cyanide solution. Min. Eng. 8, 111–123.
Lorenzen, L., van Deventer, J.S.J., 1992. Electrochemical interactions between gold and
its associated minerals during cyanidation. Hydrometallurgy 30, 177–194.
Mrkusic, D.P., Paynter, J., 1970. The Recovery of Gold From Sulphidic and Arsenical Ores
Mainly From the Barberton Area. National Institute for Metallurgy, Johannesburg
(Report 911).
Paul, R.L., 1984. The role of electrochemistry in the extraction of gold. J. Electroanal.
Chem. 168, 147–162.
Shareder, D., Vanclay, E., Hammer, M., Taylor, C., 2011. An innovative new plasma
source for elemental analysis using atomic spectroscopy. In: Gulf Coast Conference,
Galveston Island, TX, (October 11–12).
Thomas, K.G., 1997. Barrick and gold characterization by SIMS and related techniques.
In: Gillen, G., Lareau, R., Bennett, J., Stevie, J. (Eds.), Secondary Ion Mass
Spectroscopy (SIMS XI). J. Wiley & Sons, Chichester, pp. 793–797.
Weichselbaum, J., Tumilty, J.A., Schmidt, C.G., 1989. The effects of sulfide and lead on
the rate of gold cyanidation. In: Proceedings Aus.I.M.M. Annual Conference Perth/
Kalgoorlie. Australasian Institute of Mining and Metallurgy, Melbourne, pp. 221–224.