Minerals Engineering 130 (2019) 48–56

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

The effect of flotation collectors on the electrochemical dissolution of gold T

during cyanidation
⁎
Ahmet Deniz Bas , Faïçal Larachi
Department of Chemical Engineering, Laval University, Québec G1V 0A6, Canada

A R T I C LE I N FO A B S T R A C T

Keywords: Gold-bearing ores, especially the sulphidic ones, are often treated by flotation prior to cyanidation. Following
Gold flotation process, the flotation concentrate or tailings are redirected to the cyanidation circuit for gold extraction
Leaching that may contain appreciable amounts of collector used in flotation, and also remained sulfide minerals, i.e.,
Collector predominantly pyrite. This current research examines the effect of collector on gold leaching by conditioning
Pyrite
gold prior to cyanidation and direct addition in cyanidation in a packed bed leach reactor. Effects of pyrite, and
Passivation
Electrochemical dissolution
solid-liquid separation on gold leaching and its electrochemical behaviour in presence of collector were also
investigated. It was found that conditioning of gold with Aerophine 3418A in absence of pyrite has a detrimental
effect especially on leach kinetics of gold since it adsorbs onto gold and decreases its further dissolution. In
presence of pyrite, a significant improvement was obtained in gold leaching due to the positive galvanic in-
teractions. These findings suggest that although collector adsorption adversely affects gold leaching, i.e., partial
passivation, yet galvanic interactions could continue to enhance its extraction. Following conditioning, solid-
liquid separation prior to cyanidation is shown to moderately increasing gold leaching by up to 10%. When
Aerophine 3418A was added directly during cyanidation, gold leaching showed a slight increase in absence of
pyrite. Conversely, in presence of pyrite, a significant increase in gold leaching was observed. Moreover, if
collector was added after the first one hour of cyanidation, gold leaching kinetics was enhanced. Cyclic vol-
tammetry tests within open circuit potential findings support the cyanide leaching results. SEM-EDS analysis of
leach residues has demonstrated that there is less amount of gold in the residue both when pyrite is present and
collector is added directly. XPS analyses have confirmed the presence of metallic gold in leach residues. These
results have revealed the effect of Aerophine 3418A on gold leaching is different when it is directly added than
that of conditioning and the positive galvanic effect of pyrite occurs even in the presence of collector.

1. Introduction concentration by flotation is often required before chemical pre-treat-

Gold occurs among a large variety of minerals (Harris, 1990),
mostly in its zero-valent native metallic form but also as gold metal
alloys (Chryssoulis and Cabri, 1990; Dunne, 2016). Gold particles in an
ore deposit may vary in size from large nuggets to tiny particles en-
claved within sulfide minerals, in particular associated with pyrite,
containing trace to minor levels of gold (Flatt and Woods, 1995;
Thomas, 1997). A refractory pyritic ore typically contains different
types of pyrite with various gold concentrations (Ketcham et al., 1993).
It is nowadays acknowledged that there is an increasing trend towards
treatment of refractory sulphidic gold ores as a result of rarefaction of
free-milling gold ores (Adams, 2016).
Presence of small-sized gold particles locked up within the sulfides
results in unacceptably poor gold extractions and for which
ment either by roasting, bio-oxidation or pressure oxidation to liberate
the gold for subsequent cyanidation (Marsden and House, 2006). For
instance, it has been experimentally observed that a sulfide bulk con-
centrate could be produced by froth flotation using potassium ethyl-
xanthate as collector for gold and silver recoveries from a refractory ore
(Celep et al., 2010). The flotation recovery of free gold is largely af-
fected by physical constraints such as shape and size of the particles as
it is generally accepted that gold particles finer than ca. 150 µm can be
floated with conventional collectors such as xanthates, dithiopho-
sphates, mercaptobenzothiazole or phosphine-based collectors
(Bulatovic, 1997; Teague et al., 1998).
Subsequent to base-metal flotation from gold-bearing sulphur/sili-
cate ores, the flotation concentrate is sent to cyanidation circuits for
gold extraction. Flotation is also an alternative process for the

⁎
Corresponding author current address: COREM, 1180 rue de la Minéralogie, G1N 1X7 Québec, Canada.
E-mail addresses: ahmet-deniz.bas.1@ulaval.ca, ahmet-deniz.bas@corem.qc.ca (A.D. Bas).

https://doi.org/10.1016/j.mineng.2018.10.003
Received 31 July 2018; Received in revised form 27 September 2018; Accepted 2 October 2018
Available online 12 October 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
A.D. Bas, F. Larachi
Electrolyte Outlet
Quartz
Sintered glass
filtered disc
Au + Pyrite
(a)
Electrolyte Inlet
Fig. 1. Schematic illustration of the packed-bed leach reactor (PBLR) setup filled with gold (Au), pyrite (Py), and quartz (Qtz): (a) Au + Pyr //Qtz; (b) Au + Qtz.
treatment of copper bearing gold ores prior to cyanidation of the flo-
tation tailings for maximizing gold recovery (Forrest et al., 2001;
Bulatovic, 2010). Salarirad and Behnamfard (2010) showed that the
presence of flotation and dewatering reagents in the leaching solution
has a detrimental effect on the gold cyanidation process. Besides gold
oxidative complexation, the surviving flotation collectors are also
known to imply other parasitic anodic collector oxidations such as the
well documented oxidation of xanthate to dixanthogen (Monte et al.,
1997; Dunne, 2016). These collectors could adsorb onto mineral sur-
faces turning the minerals into hydrophobic ones. Dixanthogen may
form on gold surfaces either by application of an imposed potential or
by the mixed potential prevailing in a pulp that involves the reduction
of oxygen. Finkelstein (1972) reported that thiol-type collectors such as
xanthates or dithiophosphates can be strongly adsorbed onto gold, thus
rendering the surface passive and retarding the anodic dissolution
process. It can be deduced that charge-transfer chemisorption of xan-
thate occurs on gold surfaces with subsequent oxidation of xanthate to
dixanthogen via a chemisorbed xanthate intermediate (Woods et al.,
1998). Phosphine-based collectors, such as aerophine 3418A, have also
found applications in the flotation of gold and silver sulfides, and also in
the treatment of copper-gold ores (Mingione, 1990; Bulatovic, 2010;
Guo et al., 2016). Aerophine 3418A is also being used in industrial
operations, e.g., Laiva gold mine of Nordic Mines AB in Finland, Kittila
gold mine of Agnico Eagle in Finland, El Cajón deposit of Scorpion
Mining in Mexico, Brasil Mineração operation of Kinross Gold Cor-
poration. The use of collector combinations is also a common practice.
Acarkan et al. (2010) reported that combining Aero 208 (350 g/t) +
Aerophine 3418A (350 g/t) resulted in a significant improvement in
gold recovery as compared to the use of individual collectors. In spite
that various electrochemical approaches are available to help gaining
insights on the electrochemical interactions between mineral and col-
lector, it has been reported that the electrochemical studies of thiol-
base collector interactions using mineral electrodes suffer a number of
disadvantages some of which may be overcome by using pure metal
electrodes (Woods et al., 2000).
The effect of collectors on the dissolution of gold with regard to
activation and passivation during cyanidation has hitherto not received
much attention, although the literature is copious with studies dealing
with the flotation of gold ores. Thus, the objectives of this study are: (i)
to examine the influence of Aerophine 3418A collector on gold dis-
solution either in presence or absence of pyrite by conditioning prior to
cyanide leaching; (ii) to test the effect of Aerophine 3418A by direct
49
Minerals Engineering 130 (2019) 48–56
Electrolyte Outlet
Qtz
Au
Py
(b)
Electrolyte Inlet
addition in cyanide leaching; (iii) to characterize its electrochemical
behaviour; and (iv) to provide an alternative explanation for the
slowdown of the gold leach rate supported by surface characterization
studies. These tests have been carried out in a packed-bed leach reactor
(PBLR) to decouple and quantify the individual contributions of passi-
vation phenomena and galvanic interactions on gold dissolution. It is
also important to note that when gold leaching was studied in slurries
containing sulfide mineral particles and gold/silver powder, permanent
galvanic contacts between gold and minerals particles, as in actual ores,
were virtually impossible to achieve. Readers interested in the com-
parative behaviours of gold leaching in the traditional slurry config-
uration and the packed bed leach reactors can refer to our previous
publications (Azizi et al., 2011, 2012, 2013). One of the worth re-
minding features of PBLR is its ability to “artificially” emulate large
ensembles of microscopic contacts which stem from partially liberated
gold inclusions within pyrite granular environments. More details about
the features of PBLR can be found elsewhere (Bas et al., 2018).
2. Experimental
2.1. Materials
Sodium cyanide (NaCN) with purity > 98% was obtained from
Sigma-Aldrich Canada. Aerophine 3418A collector was obtained from
Solvay Cytec Canada Inc. 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. The aqu-
eous solutions (100 mL) were prepared using distilled water.
Pure gold powder (P80 = 39 μm, 99.998%) was purchased from Alfa
Aesar USA. Pyrite obtained from Wards Minerals in the form of cm-size
bits was ground and sieved before its use in the cyanidation tests. In this
current study, pyrite particle sieved size of +75–106 µm only was
considered since it yielded the maximum gold recovery during cyani-
dation (Bas et al., 2018). X-ray fluorescence (XRF) analyses showed that
the sample contains 44.8% Fe, 51.4% S, and 0.45% SiO2. Unless
otherwise specified, 50 mg Au and 4 g pyrite (Py) were used in the
leaching tests, and the rest of the reactor volume was completed using a
segregated quartz (Qtz) layer (P80 ≤ 149 μm, Sigma Aldrich, Canada) as
illustrated in Fig. 1a. Mineral interlayer separation between PBLR
compartments was ensured by using a sintered glass filtered disc
(purchased from VWR) that has 20 mm diameter, and 3 mm thickness
to allow the options of either galvanically associating gold with pyrite
A.D. Bas, F. Larachi Minerals Engineering 130 (2019) 48–56

Conditioning

Au+Qtz and Au+Pyr //Qtz samples were conditioned with Aerophine 3418A collector during 1 h.
Samples were filtered, dried and subjected to cyanide leaching tests in PBLR.
Tests were performed either in absence or presence of pyrite (Pyr, +75-106 μm).

Direct addition

Aerophine 3418A collector was directly added at the onset of leaching test.
Regarding activation and passivation, in some tests collector was added after 1 h.
Tests were performed either in the presence or absence of pyrite.

Electrochemical
characterization
Open-circuit potential and cyclic voltammtery tests have been employed.
Anodic dissolution was examined.

Surface
characterization
SEM-EDS and XPS studies have been considered.
Detect corrosion product(s) and/or surface film(s) leading to partial passivation of surface.

Fig. 2. Strategy adopted to examine the effect of collector on gold cyanidation in absence and presence of pyrite (in this study, only +75–106 µm pyrite fraction was
used).

(Fig. 1a) or, on the contrary, eliminating gold-pyrite contacts (Fig. 1b)
(Bas et al., 2018).
2.2. Conditioning and cyanidation test procedures
A systematic study was adopted to examine the influence of flota-
tion collector on gold leaching (Fig. 2). Conditioning tests lasting 1 h
were performed in a 250 mL glass container with a 100 mL of cyanide-
free solution containing Aerophine 3418A at pH 9 adjusted with NaOH.
A 100 g/ton Aerophine 3418A was chosen as an average concentration
based on previous studies (Acarkan et al., 2010). Following con-
ditioning of the Au + Qtz or Au + Pyr//Qtz samples, a solid-liquid
separation (SLS) using filtration was optionally enabled (or not) to
approach industrial flotation modus operandi. Then, the sample was
subjected to cyanide leaching tests. During conditioning, the con-
centration of collector was monitored by SMA-FL Fluorescence Flow
Cell by FIAlab Instruments (USA). This fiber optic cell utilizes a fiber
optic line to send an excitation light through a fused silica window into
a 2-mm inner-diameter sample compartment. Emitted energy is col-
lected by a second fiber, oriented at 90° that connects to a spectro-
meter/detector configured for fluorescence. The flow cell is available in
chemically inert Black Ultem. The windows are removable for cleaning
or replacement to another material with different optical properties.
Each cell includes 1 mm thick UV grade Fused Silica windows, a hard,
non-corrosive, chemically resistant material that also has a high UV
through IR transmission (260 nm through 2000 nm) (FIALab Maunal,
2.1).
Leaching tests were performed in a closed loop by continuous cir-
culation of 100 mL leach solution from a glass container through PBLR
(cylindrical working section 25 mm H, 15 mm I.D.) using a peristaltic
pump at a constant flow rate of 10.4 mL/min. The recirculating solution
in the glass container was agitated at 300 rpm with a magnetic bar
(4 cm long and 1 cm in diameter) during the cyanidation tests. Leach
solution was fed upwardly through the PBLR in order to prevent
channeling of the feed solution in the reactor and to maximize re-
sidence time of the cyanide solution by ensuring circulation of the latter
across the entire porous volume left within 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 as measured using an Oakton 1000 series pH-
meter. The concentration of CN− in solution was monitored using
Thermo Scientific Orion 9606BNWP Cyanide Ion-Selective Electrode.
Sodium cyanide was added to maintain the concentration of free cya-
nide at the predetermined level over the leaching period. Leach solution
was sampled at predetermined intervals over 24 h reaction horizons
(Bas et al., 2018).
At the termination of cyanidation, leach residues were collected and
dried in oven at 105 °C for characterization studies (explained in
Section 2.4). Metal analyses (Au and Fe) were 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, pyrite powder or mixture of pure gold and pyrite
was mixed with graphite powder –to increase conductivity– in 3:1 mass
ratio and with few drops of silicone oil binder till pastes were obtained.
Graphite powder, which has a particle size of < 45 µm, and a 99%
purity, was purchased from Sigma-Aldrich. The mixture was manually
homogenized during 30 min. Then, it was mechanically pressed at 20
tons and cut to yield uniform-surface disc electrode specimens. These
latter were kept overnight under nitrogen atmosphere. These electrodes
were then connected with an insulated copper wire cast in acrylic resin.
Gold-, pyrite- or gold-pyrite loaded disc electrodes with a surface area
of 2.54 cm2 were tested as working electrodes together with platinum
counter-electrode and Ag/AgCl, KClsat reference electrode. All poten-
tials here were expressed versus the standard hydrogen electrode (SHE).

50
A.D. Bas, F. Larachi Minerals Engineering 130 (2019) 48–56

The working electrodes were first polished with a fine (MicroCut® 100 Table 1
Grit Soft) polishing paper and then rinsed with distilled water. Then, Comparison of Au dissolution (%) by AAS and MP-AES after 6 h and 24 h of
they were briefly immersed in aqua regia for 10 s to clean the surface cyanide leaching.
before successively rinsing with distilled water, ethanol, and with dis- 6h 24 h
tilled water again for reproducibility purposes (Kirk et al., 1978).
Electrochemical studies were performed using a potentios- Sample name AAS MP-AES AAS MP-AES
tat–galvanostat (model VSP-27 from Bio-Logic SA) and the EC-Lab
Au + Qtz 47.1 ± 2.2 45.3 ± 1.4 57.3 ± 3.4 59.2 ± 2.6
software. Cyclic voltammetry (CV) tests were carried out in 30 mM C-condition, Au + Qtz 29.8 ± 1.2 27.2 ± 0.9 54.8 ± 1.8 56.3 ± 2.0
NaCN solution at a 10 mV/s scan rate. First, the electrodes were C-condition (No SLS), 21.1 ± 0.4 24.2 ± 1.1 49.3 ± 2.1 51.8 ± 1.9
maintained at open circuit potential (OCP) during 30 min for stabili- Au + Qtz
Au + Pyr //Qtz 87.2 ± 4.5 91.2 ± 2.5 98.8 ± 1.2 96.5 ± 3.1
zation. CV studies were conducted between −1 V and 1.4 V values and
C-condition, Au + Pyr 42.4 ± 1.8 45.2 ± 2.3 60.2 ± 2.3 57.4 ± 2.1
steady-state cycle was considered. Potentiodynamic cathodic polariza- //Qtz
tion tests were performed in presence of oxygen and cyanide. Likewise, C-condition (No SLS), 40.3 ± 1.7 42.2 ± 1.6 52.3 ± 1.4 55.8 ± 2.0
electrodes were kept at open circuit potential (OCP) during 30 min for Au + Pyr //Qtz
stabilization. A scan rate of 0.166 mV/s was selected based on the po-
larization standards (ASTM Standard G 5-94, 2006). Electrochemical
tests were performed in replicates to ensure reproducibility. over the 24 h. However, when a similar pyrite-free gold-quartz mixture
was conditioned with Aerophine 3418A during 1 h (referring to “C-
condition, Au + Qtz” in Fig. 3) and then recovered by filtration (cf. SLS
2.4. Characterization of gold leach residues procedure described above in Section 2.1) before to be exposed to cy-
anide leaching for 24 h, gold extraction led to a lower recovery of 55%
To detect residual gold particles, the solid residues of cyanide with a slower leach kinetics (Fig. 3). This decrease could be explained
leaching tests were subjected to Scanning Electron Microscopy (SEM) by the adsorption of collector onto the gold surfaces resulting in a
(JEOL 840-A) coupled with Energy-dispersive X-ray spectroscopy (EDS) slowdown of gold leaching kinetics. Conversely, skipping the solid-li-
and X-ray photoelectron spectroscopy (XPS) analysis. XPS results were quid separation (SLS) step while everything else was kept identical,
collected using an AXIS-ULTRA instrument by Kratos (UK). The X-ray gold leaching led to a slightly lower recovery of 50% (Fig. 3). This
source is a monochromatic Al source operated at 300 W. Detection of finding indicates that filtration is almost inoperative in terms of col-
the photoelectrons is performed with an 8-channel detector. lector desorption from gold surfaces with SLS step marginally im-
Electrostatic charge appearing on the electrically insulating samples proving gold leaching.
under X-ray irradiation is neutralized with integrated very-low energy Au leaching results by AAS were found to be reproducible within
electron flood gun, the parameters of which are set to optimize energy replicates. MP-AES was also considered for Au analysis for comparison
resolution and counting rate. Survey scan is recorded with pass energy and to ensure the reliability of results since the sample might contain
of 160 eV and a step size of 1 eV, and these were used for elemental ions which are potentially detrimental to gold speciation especially at
analysis and apparent concentrations calculations (Bas et al., 2018). low concentration of Au in PBLR (Table 1). As seen, these two different
methods confirm the leaching results. Only a very slight difference was
3. Results and discussion observed, which is fairly reasonable due to the operational differences
between these two analytical tools.
3.1. Effect of Aerophine 3418A conditioning prior to gold cyanidation Another series of leaching tests was carried out with a mixture of
gold powder and sieved pyrite fraction placed at the PBLR bottom while
The influence of gold ore conditioning by flotation collector prior to the latter the upper part was filled with quartz. A sintered glass filtered
gold cyanidation was examined using PBLR gold dissolution tests disc was used to have the two layers as separate compartments (Fig. 1).
(Fig. 3). In absence of pyrite –i.e., Au mixed with quartz only (Fig. 1b)– Gold leaching, in presence of pyrite and without conditioning, soared to
while skipping the collector conditioning step, a 57% of Au was leached 98% recovery (Fig. 3) unlike the 57% in absence of pyrite. This increase
is attributed to the positive galvanic interactions between gold and
100 pyrite (Habashi, 2013; Aghamirian and Yen, 2005). Interestingly, if the
90 gold-pyrite powdery mixture was conditioned with a collector solution
prior to cyanidation while skipping the SLS step, gold leaching was
80
dramatically decreased, i.e., by 45% (Fig. 3). In industrial practice, SLS,
70 e.g., through filtration, is an essential step before routing the flotation
Au extraction, %

tailings or overflow pulps to the cyanidation circuit. Hence, when the

60
conditioned Au-pyrite mixture sample was preventively filtered, Au
50 leaching exhibited a slight increase to 60% (Fig. 3).
To gain further understanding on the effect of collector, its con-
40
centration was monitored by UV during 1 h of conditioning. A typical
30 calibration between the solution UV absorbance and collector con-
20 Au+Qtz centration revealed a linear behaviour for the Aerophine solution,
C-condition, Au+Qtz
C-condition (No SLS), Au+Qtz
y = 0.0009x + 0.05 (Fig. 4a).
10 Au+Pyr //Qtz Depletion of Aerophine 3418A from the solution as a function of
C-condition, Au+Pyr //Qtz

0
C-condition (No SLS), Au+Pyr //Qtz conditioning time upon contacting with gold-pyrite powdery mixture is
0 4 8 12 16 20 24 illustrated in terms of collapsing UV spectra in Fig. 4b. After 1 h con-
Time, h ditioning, nearly 50% of collector vanished from the solution sug-
Fig. 3. Effect of Aerophine 3418A collector (100 g/t) conditioning on cyanide gesting likely collector adsorption events onto gold surfaces. Alteration
leaching of Au (%) (C-condition: conditioning of Au with collector; SLS: solid- of gold bare surfaces with strongly bound collectors is coherent with the
liquid separation) (solution saturated at pure O2 atmospheric pressure, mag- negative impact on gold leaching kinetics of the conditioning step,
netic agitation at 300 rpm, 30 mM NaCN) (Tests for black (O) and blue (X) whether for pyrite-free gold or for gold-pyrite mixture including or not
symbols taken from Bas et al. (2018)). an SLS step (Fig. 3).

51
A.D. Bas, F. Larachi Minerals Engineering 130 (2019) 48–56

0.35 4.0
(a)
0.3 3.5
Au+Qtz
C-condition
0.25 y = 0.0009x + 0.05 (No SLS),
3.0

Dissolved Fe, x10-5g / 4 g

Au+Pyr //Qtz
Absorbance

0.2 C-condition,
2.5 Au+Pyr //Qtz

0.15
2.0

0.1
1.5

0.05
1.0

0
0 50 100 150 200 250 300 350 0.5
Concentration of Aerophine 3418A, g/ton
0.0

0.20 Fig. 6. The effect of collector conditioning (C-condition) on the dissolution of

(b) Fe (×10−5 g/4 g).

0.15 0 min cyanidation (Fig. 5).

The solution content in terms of dissolved Fe is shown in Fig. 6.
Absorbance

30 min
Mirroring the finding for cyanide consumption for gold-pyrite mixture,
Decreasing concentration

40 min
0.10 the highest Fe dissolution was obtained if the collector conditioning
50 min
step was totally skipped. On the contrary, implementing a conditioning
60 min
step followed by a solid-liquid separation (SLS) step translated in 25%
0.05 less dissolved iron in the solution. A decrease by a mere 11% of leached
iron from pyrite would have been achieved if SLS step was skipped after
conditioning (Fig. 6). The present findings do not support the intuitive
0.00
expectation that homogeneous iron-coordinated collector organome-
185 190 195 200 205 210 215 220 225 tallic complexes would have contributed in the build-up of more dis-
Wavelength solved iron. Quite the contrary, the presence of collector, in conjunction
Fig. 4. (a) Linearity for absorbance and Aerophine concentration in solution;
or not with SLS step, did not appear to promote iron dissolution.
(b) UV monitoring Aerophine 3418A depletion in the conditioning step of gold- However, in light of the gold dissolution profiles (Fig. 3), less dissolved
pyrite mixture. iron would be stoichiometrically compatible with less gold leaching
presumably because of equally sorption-active pyrite surfaces vis-à-vis
10
the Aerophine collector itself.

Au+Pyr //Qtz C-condition C-condition,

(No SLS), Au+Pyr //Qtz
8 Au+Pyr //Qtz 3.2. Effect of Aerophine 3418A direct addition on gold cyanidation
NaCN consumption, kg/t

It has been found that gold dissolution increased in presence of

6 pyrite but decreased with collector conditioning prior to cyanidation.
Then, a systematic approach has been considered to reach a better
understanding regarding passivation and dissolution of gold at the
4 optimal pyrite particle size (+75–106 µm) where gold leaching was the
highest (Bas et al., 2018). In this manner, different scenarios were
considered (Fig. 7).
2 In absence of pyrite and no conditioning, when Aerophine 3418A
C-condition C-condition,
(No SLS), Au+Qtz was added directly into the solution at the onset of cyanidation, Au
Au+Qtz
Au+Qtz
leaching was found to be slower as compared to the case without col-
0 lector addition. However, at the end of 24 h, Au recoveries were found
Fig. 5. The effect of collector conditioning on NaCN consumption (kg/ton ore). to be similar. On the other hand, in presence of pyrite when collector
was added (referring to “C-addition, Au + Pyr //Qtz” in Fig. 7), a sig-
nificant increase was observed in gold leaching. This result suggests
In addition to the above-monitored conditions and cyanidation
that pyrite has a positive effect on gold leaching due to galvanic in-
variables, it is of tantamount importance to monitor and maintain the
teractions even in the presence of collector.
cyanide concentration in the solution during cyanidation. Cyanide
The legitimate question as to which extent the effect of collector on
consumption in absence of pyrite was found to be very minor (Fig. 5)
gold dissolution differs when added in cyanide solution or during the
which is expectable and in line with the gold leaching stoichiometry
conditioning step is worth addressing. For this purpose, Aerophine
obtained for this condition (Fig. 3). When pyrite-free gold powder was
3418A was added after the initial 1 h of cyanide leaching (Fig. 7). In
conditioned and filtered before cyanidation, cyanide consumption was
pyrite-free gold-quartz mixtures when the collector was added after
found to be more than (Fig. 5) in the case without conditioning. On the
initial 1 h cyanidation reaction, a palpable improvement was noted in
other hand, in the presence of pyrite, cyanide consumption was greatly
terms of gold leaching. A similar improvement was also noted in gold-
enhanced. In particular, cyanide consumption increased by 8.5% if the
pyrite mixtures. These findings suggest that the collector alters the
conditioning step with Aerophine 3418A was omitted prior to
surface of gold and decreases the potential negative effect of dissolved

52
A.D. Bas, F. Larachi Minerals Engineering 130 (2019) 48–56

100 Table 2
90 Open Circuit Potential (OCP) (V/SHE) of electrodes after 24 h of leaching.

80 Electrode type Corrosion potential (V/SHE)

End of leaching (after 24 h)
70
Au extraction, %

Au + Qtz −0.39 ± 4.3%

60
50
40
30
20
10
0
0 4 8 12
Time h
Fig. 7. Effect of collector direct addition on Au extraction, % (C-addition: direct
addition of collector at the onset of cyanidation; C-addition after 1 h: collector
addition after first 1 h of cyanidation) (solution saturated at pure O2 atmo-
spheric pressure, magnetic agitation at 300 rpm, 30 mM NaCN) (Black (O) and
blue (X) symbols from Bas et al. (2018)). (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
species in solution. It can also be deduced that although similar gold
extraction levels were achieved for the gold-pyrite powder mixtures,
initial leaching kinetics was faster when Aerophine 3418A was added
after 1 h. This observation leans towards pyrite-aided galvanic inter-
action and collector adsorption are two competitive steps during cya-
nidation.
3.3. Electrochemical characterization of gold dissolution
Since the dissolution of gold is an electrochemical reaction, its
dissolution behaviour can readily be studied by means of electro-
chemical methods. In this manner, cyclic voltammetry (CV) tests on
gold dissolution as a function of collector and pyrite was tested (Fig. 8).
CV is one of the fundamental techniques used to characterize the in-
teractions between collector and gold surfaces (Groot et al., 2005).
Changes in the open circuit potential (OCP) of gold prove helpful to
unveil 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
5.5
1- Au+Qtz
2- Au+Pyr //Qtz
3- C-condition, Au+Pyr //Qtz
4.5 4- C-addition, Au+Qtz
5- C-addition, Au+Pyr //Qtz
Current density, mA/cm2
Au + Pyr //Qtz −0.47 ± 5.7%
C-condition, Au + Pyr //Qtz −0.30 ± 4.7%
C-addition, Au + Qtz −0.23 ± 3.8%
C-addition, Au + Pyr //Qtz −0.44 ± 5.1%
Au+Qtz
C-addition, Au+Qtz
C-addition after 1 h, Au+Qtz
of leaching (after 24 h) in Table 2. The dissolution potential of gold
Au+Pyr //Qtz electrode in the absence of pyrite was found to be −0.39 V/SHE. In
C-addition, Au+Pyr //Qtz
C-addition after 1 h, Au+Pyr //Qtz presence of pyrite particles, the dissolution potential was shifted to
16 20 24 more negative potential up to −0.47 V, suggesting enhancement in the
anodic dissolution. It was also observed that when the collector was
added in presence of pyrite, dissolution potential shifted to more ne-
gative potential. This finding is an indication for positive galvanic in-
teraction effect of pyrite which is in line with the leaching result
(Fig. 7).
The wavy profiles revealed in cyclic voltammetry could be linked to
the repeated formation and dissolution of unstable corrosion products
on the electrode surface (Fig. 8). 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 although this os-
cillatory behaviour could happen during both anodic and cathodic
processes (Jayasekera et al., 1996). The shift/change in the dissolution
potential of gold during leaching has also been discussed in the litera-
ture. 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 was pulped in
sulfide minerals slurries, and this was linked to a retarding effect on the
gold dissolution rate. It is important to note that although the slopes are
similar, the level of the open circuit potential plays a significant role in
the determination of the leach rate of gold.
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) in addition to that of Cerovic
et al. (2005) considered the intersection of cathodic and anodic curves
for the calculation of the gold leach rate. However, recent studies by
Dai and Breuer (2013), and Bas et al. (2016, 2017) reported that con-
sidering the intersection locus might be misleading since it is un-
representative of practical conditions, and there is a potential passive
behaviour in the anodic curve. Bas et al. (2016, 2017, and 2018) con-
sidered only cathodic Tafel slope extrapolation to the open circuit po-
tential which was found to be relatively representative of the conven-
tional cyanidation.
An attempt for estimation of leach rate by electrochemical method

3.5
was done by extrapolation of the cathodic Tafel slope to open circuit
2
potential. It is worth noting that due to the difficulty in the Tafel ex-
5 trapolation, two recommended rules as follows are carefully considered
2.5
in this study: (i) the extrapolation should start at least 50–100 mV away
1.5
from Ecorr, and (ii) at least one of the branches of the polarization curve
1 (cathodic or anodic) should exhibit Tafel trend over at least one decade
3
0.5
of current density (Kelly et al., 2002). However, in this study, it should
4 be underlined that a completed decade was not observed for curves,
-0.5
thus the rate estimation was not considered. In one of the key studies
relevant to the mechanism of flotation, Woods (1971) examined the
-1.5
oxidation of flotation collector, ethylxanthate, on gold, and reported
-1.2 -0.9 -0.6 -0.3 0.0 0.3 0.6 0.9 1.2 1.5 that Tafel slope obtained was insufficient for an accurate estimation.
Potential, E vs V/SHE

Fig. 8. Electrochemical characterization of the effect of Aerophine 3418A 3.4. Characterization of cyanide leach residues
(100 g/ton) on gold leaching (C-condition: conditioning of gold with collector
prior to cyanidation; C-addition: direct addition of collector at the onset of Characterization of leach residues was performed by SEM-EDS and
cyanidation) (solution saturated at pure O2 atmospheric pressure, magnetic XPS analysis. SEM-EDS analyses were presented as follows:
agitation at 300 rpm, 30 mM NaCN). Au + Quartz (Fig. 9a); Au + Pyrite //Qtz (Fig. 9b); C-condition,

53
A.D. Bas, F. Larachi
Au
Py
Py
Au
Au
c
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; (b) Au + Pyrite //Qtz; (c) C-
condition, Au + Qtz; (d) C-condition, Au + Pyr //Qtz; (e) C-addition, Au + Pyr //Qtz (×200); (f) C-addition, Au + Pyr //Qtz (×2000).
Au + Qtz (Fig. 9c); C-condition, Au + Pyr //Qtz (Fig. 9d); C-addition,
Au + Pyr //Qtz (x200) (Fig. 9e); C-addition, Au + Pyr //Qtz (x2000)
(Fig. 9f).
In the absence of pyrite (Fig. 9a), there is enough un-leached gold
leftover trapped within the quartz layer (Bas et al., 2018) which is in
line with the incomplete gold leaching measured after 24 h (Fig. 3). As
observed, there is less gold in residue when the gold-pyrite mixture was
conditioned with collector (Fig. 9d) as compared to the case with no
pyrite (Fig. 9c). This can be also an indication that pyrite shows a po-
sitive effect on gold leaching due to galvanic interactions, as already
obtained in leaching results (Fig. 3).
The leach residues of the tests “C-condition, Au + Qtz (sample A)”,
“C-condition, Au + Pyr //Qtz (sample B)” and “C: C-addition, Au + Pyr
//Qtz (sample C)” in PBLR were analyzed by XPS. Metallic gold was
detected in three residue samples. Fe and S were detected in samples B
and C as pyrite. For instance, XPS analysis of the leach residue of “C-
condition, Au + Pyr //Qtz (sample B)” is presented (Fig. 10). It is im-
portant to underline that gold was associated with pyrite particles in the
leach residue of sample B according to the binding energies. This
finding can be linked to the negative effect of collector on gold dis-
solution, i.e., slowdown in gold leaching kinetics when conditioned
54
Minerals Engineering 130 (2019) 48–56
with collector.
4. Conclusion
1. Conditioning of gold with Aerophine 3418A in absence of pyrite has
a detrimental effect on the leach kinetics of gold since it enables
collector adsorption and decreases further the dissolution of gold. In
presence of pyrite, a significant improvement was obtained in gold
leaching. The positive effect of pyrite is ascribed to the well-estab-
lished aiding galvanic interactions during dissolution. However, our
findings suggest that although galvanic interactions promote gold
leaching, collector adsorption leads to poor gold extractions due to
partial passivation of gold surfaces.
2. Following conditioning, solid-liquid separation plays a moderate
helping role prior to cyanidation. The results have shown that the
collector adsorption onto gold has a detrimental effect and that an
additional separation step to get rid of the conditioning solution in
contact with the solids in the pulp does improve only marginally the
recovery of gold leaching.
3. When Aerophine 3418A was added directly in the cyanidation
medium, leach kinetics of gold (in absence of pyrite) was slower
A.D. Bas, F. Larachi
Au
Py
Py
Au
e f
Fig. 9. (continued)
Fig. 10. XPS analysis of the leach residue of gold powder in presence of pyrite
after 1 h conditioning with Aerophine 3418A (C-condition, Au + Pyr //Qtz
(sample B)).
than that without collector addition; however, almost similar gold
recoveries were obtained in both cases after of 24 h. In presence of
pyrite, a significant increase was observed. Moreover, if collector is
added after the first one hour of cyanidation, an enhancement was
observed in gold leaching kinetics. These results have revealed that
the positive galvanic effect of pyrite occurs even in the presence of
collector. Also, it can be deduced that the impact of Aerophine
3418A is different when it is directly added than that of con-
ditioning.
4. Cyclic voltammetry tests within open circuit potential findings have
confirmed the cyanide leaching results. Electrochemical findings
have also shown that the negative effect of collector and the positive
effect of pyrite on gold leaching.
5. SEM-EDS analysis of leach residues have demonstrated that there is
less amount of gold in the residue when both pyrite is present and
55
Minerals Engineering 130 (2019) 48–56
Py
Au
collector is directly added. XPS analyses have confirmed the pre-
sence of metallic gold, and iron in leach residues. It can be deduced
that gold in the residue was surrounded by pyrite particles when
gold and pyrite mixture was conditioned with collector before cy-
anidation. This could be linked to the partial passivation of gold
surface by collector adsorption, and that was also supported by UV
analyses monitoring the concentration of collector in solution.
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.
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