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THE EFFECT OF DMSA ADDITION ON THE PERFORMANCE

OF THIOSULFATE LEACHING OF GOLD

S. Hume1, J. Shepherd2*, E. Guerra3, Y. Choi4

1
Chemistry and Biochemistry Department
Laurentian University.
Sudbury ON CANADA P3E 2C6
sa_hume@laurentian.ca
2
Associate Professor. Chemistry and Biochemistry Department
Laurentian University
Sudbury ON CANADA P3E 2C6
jshepherd@laurentian.ca
3
Associate Professor, Bharti School of Engineering
Laurentian University
Sudbury ON CANADA P3E 2C6
4
Sr. Manager, Hydrometallurgy & Environment, Strategic Technology Solutions.
Barrick Gold Corporation
BCE Place, Brookfiled Place,
TD Trust Tower, Suite 3700, 161 Bay Street. P.O. Box 212.
Toronto ON CANADA M5J 2S1

ABSTRACT

Meso-2,3-dimercaptosuccinic acid(DMSA) was studied as an additive for thiosulfate leaching of

gold. DMSA was added to solutionscomposed of either sodium thiosulfate or calcium thiosulfate and the
solutions were tested for their ability to leach pure gold samples as well as a calcined gold ore from Barrick
Gold Corp. Results showed prolonged leaching of pure gold samples when DMSA was added at a
concentration of 5µM; however, higher concentrations were shown to inhibit leaching. Differential
capacitance measurements of the interface indicated that DMSA adsorbed as a defective monolayer on the
surface of gold at low concentrations and formed a more compact monolayer with increased concentration.
It is proposed that a concentration of 5µM DMSA produces a defectivemonolayer on the surface that still
allowsthe transport of oxidants to the underling metal while inhibiting the formation of polysulfide passive
layers that arise fromdecomposed thiosulfate.The 5µM DMSA/CaS 2 O 3 system was also studied using
calcined ore. Results showed that the initial leaching rates in the presence of DMSA are lower than those
obtained in thiosulfate alone. However, after 10h, prolonged leaching is again observed when DMSA is
included.

KEYWORDS

Gold Leaching, Thiosulfate Leaching, Organic Additive, meso-2,3-dimercaptosuccinic acid, DMSA

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INTRODUCTION

In the process of recovering gold from ore, cyanide is the common industrial choice for alixiviant
due to its high leaching rates and specificity for gold. However, there are growing environmental,
economic and industrial concerns about the use of cyanide. For example, the toxicity of cyanide has led to
significant regulations on its transport, use and treatment before discharge (Mudder&Botz, 2004).
Furthermore, an increasing percentage of gold deposits are found in ores that cannot be economically
exploited by cyanide leaching. These ores may be high in copper content resulting in high consumption of
cyanide, contain gold that is encapsulated within host minerals that do not dissolve,or they may be high in
preg-robbing carbonaceous materials. These latter ores have been termed preg-robbing,because the
carbonaceous material adsorbs the gold cyanide complex resulting in the majority of the gold reporting to
the tailings instead of the leach solution (Marsden & House, 2006; Schmitz et al., 2001).
These problems and concerns have led to the search for alternative lixiviants for gold leaching
including thiosulfate, thiocyanate, thiourea and chlorine (Hilson & Monhemius, 2006). Of these
alternatives, thiosulfate is promising due to its low toxicity and high specificity for gold. Furthermore, the
gold thiosulfate complex does not adsorb onto carbon (Abbruzzese et al., 1995) making it suitable as a
lixiviant for preg-robbing ores. For instance, ammoniacal thiosulfate has been studied as a lixiviant for a
carbonaceous ore with recoveries of over 90%, which is comparable to the extraction typically achieved
with cyanidation of non-refractory ores (Schmitz et al., 2001). However, this study used a high volume of
leaching solution and a concentration of 400 mM thiosulfate, which is not economically viable for
industrial use.A catalystmay be used with the thiosulfate system to achieve leaching rates that are similar to
those with cyanide (Jeffrey et al., 2001). The most commonly used catalyst is Cu(II) which is reduced to
Cu(I) on the gold surface and increases the anodic current density at the interface thereby increasing the
rate of gold oxidation (Breuer & Jeffery, 2002). Zhang and Nicol (2005) investigated the effect of adding
Cu(II) to thiosulfate leaching solutions and found that the addition of 5 mM Cu ions increased the rate gold
dissolution from 2.07 x 10-12mol cm-2 s-1to 6.5 x 10-12mol cm-2 s-1, when working with 0.2 M Na 2 S 2 O 3 at
pH 12, 25°C, and applying a potential of 0.3 V. In addition, ammonia is frequently added because it can
stabilize Cu(II) in solution. Since ammonia is also a weaker lixiviant for gold than thiosulfate, it can, itself,
act as a catalyst even in the absence of Cu (Senanayake, 2005). The combination of ammonia and Cu(II) in
solution allows the oxidation of gold to proceed through the following reactions(Abbruzzese et al., 1995;
Breuer & Jeffrey, 2002; Feng & van Deventer, 2011a; Muir &Aylmore, 2004):
5−
𝐴𝐴𝐴𝐴 + 5𝑆𝑆2 𝑂𝑂32− + 𝐶𝐶𝐶𝐶(𝑁𝑁𝐻𝐻3 )2+ 3−
4 → 𝐴𝐴𝐴𝐴(𝑆𝑆2 𝑂𝑂3 )2 + 4𝑁𝑁𝑁𝑁3 + 𝐶𝐶𝐶𝐶(𝑆𝑆2 𝑂𝑂3 )3 (1)

where Cu(I) is then re-oxidized to Cu(II) by oxygen through (Abbruzzese et al., 1995; Aylmore, 2001):
1
2𝐶𝐶𝐶𝐶(𝑆𝑆2 𝑂𝑂3 )5− 2+ − 2−
3 + 8𝑁𝑁𝑁𝑁3 + 𝑂𝑂2 + 𝐻𝐻2 𝑂𝑂 → 2𝐶𝐶𝐶𝐶(𝑁𝑁𝑁𝑁3 )4 + 2𝑂𝑂𝑂𝑂 + 6𝑆𝑆2 𝑂𝑂3 (2)
2

The addition of ammonia stabilizes the Cu(II) catalyst by the formation of stable Cu(II) amine complexes,
preventing the formation of Cu(OH) 2 , which has the potential to passivate the surface of gold (Marsden &
House, 2006). Ammonia is additionally beneficial because it maintains a high pH in solution, which can
help limit the decomposition of thiosulfate. At low pH,thiosulfate becomes unstable and converts into
tetrathionate, elemental sulfur and/or sulfide (Baron et al., 2013).
The use of the Cu(II) catalyst provides thiosulfate leaching rates that are comparable to cyanide;
however, Cu(II) also oxidizes thiosulfate resulting in a decrease in the concentration of the lixiviant itself
and a decrease in leaching rates over time(Breuer & Jeffery, 2002). Furthermore, the oxidation of
thiosulfate increases with higher concentrations of copper (Molleman&Dreisinger, 2002). As such, high
copper concentrations result in high rates of thiosulfate consumption with only small gains in leaching
compared to lower concentrations (Lampinen et al., 2015). Another problem associated with thiosulfate
oxidation is that it proceeds through a series of reactions whose products (Jeffrey et al., 2008) can adsorb
on the gold surface and form a passivating layer that interferes with the mass transport of the oxidants to
the surface of the gold (Breuer & Jeffery, 2003; Feng & van Deventer, 2007; Zhang & Nicol, 2003). This
passivating layer has been studied using surface enhanced Raman spectroscopy (SERS) and it was found to
be primarily composed of monoatomic sulfur (Mirza et al., 2015).

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Other important factors in thiosulfate leaching include the choice of thiosulfate salt and the
temperature at which leaching takes place. It has been shown that CaS 2 O 3 is most aggressive at leaching
gold in sulfide ores, followed by ammonium thiosulfate, and then sodium thiosulfate (Feng & van
Deventer, 2010a). In this regard, leaching of a gold electrode with the different thiosulfate salts showed no
significant difference in the open circuit potential (ocp), but the use of calcium thiosulfate was associated
with an increase in the corrosion current density (Nicol et al., 2014). Elevated temperatures havealso been
shown to increase both the oxidation of gold and thiosulfate, resulting in an increase in leaching rates at the
cost of higher thiosulfate consumption (Marsden & House, 2006).
The problems of thiosulfate consumption and passivation of the gold surface are the major
limitations in using this lixiviant system. To reduce these problems, additives such as complexing agents
and surface active agents (Senanayake, 2012) have been studied. For example, there have been studies on
the effects of adding ethylenediaminetetraacetic acid (EDTA; Feng &van Deventer, 2010b),
carboxymethyl cellulose (CMC; Feng & van Deventer 2011b; Yang et al., 2015), humic acid and
carboxymethyl starch (CMS; Yang et al., 2015) as well as various amino acids (Feng & van Deventer
2011a). It has been proposed that EDTA acts to complex the Cu(II) ion which lowers the amount of free
Cu(II) in solution. This decreases the oxidation of thiosulfate, hence resulting in lower thiosulfate
consumption and a decrease in the formation of passivation products. CMC, on the other hand, was shown
to adsorb on the gold surface and disrupt the adsorption of polysulfide passivation products (Feng & van
Deventer, 2011b) but at higher concentrations the CMC formed increasingly solid layers that would begin
to inhibit transport processesat the gold surface resulting in lower leaching rates.
Alkylthiolscan bind with gold to form both defective and compact monolayers on the surface
(Love et al., 2005; Vericat et al., 2010).Therefore, it may be possible to use alkylthiol or
organosulfurcompounds with an appropriate terminal group to form a defective monolayer on gold that
may prove effective in preventing the formation of a passivating layer on its surface during thiosulfate
leaching.For example, thiourea addition has been shown to increase the instantaneous rate of gold leaching
(Chandra & Jeffery, 2004). Similarly, in our previous study (Uceda et al., 2013),meso-2,3-
dimercaptosuccinic acid (DMSA) was examined as a potential lixiviant for gold due to its ability to adsorb
to the surface (Mei Niu et al., 2006) as well as its ability to etch gold when it undergoes oxidative
desorption from the surface (Smith et al., 2011). Furthermore, DMSA is relatively non-toxic, having been
shown to be an effective antidote for gold-thiosulfate poisoning (Basinger et al., 1985). In our previous
study,DMSA was shown to be effective in improving the initial leaching rates when added at low
concentrations to a simple thiosulfate system consisting of 65mM Na 2 S 2 O 3 and 1mM NaOH at room
temperature (Uceda et al., 2013). In this present study, we further the analysis of DMSA addition to
thiosulfate systems and we examine the effect of DMSA on the leaching of a gold electrodeover longer
time periods (16h) and at 50oC using different thiosulfate systems. Furthermore, we further explore the
effect of DMSA on the leaching of calcined sulfide ore from Barrick Gold Corp.

EXPERIMENTAL

Leaching Studies

All leaching studies were performed at the open circuit potential. In every test, the solution was
stirred in order to improve the mass transport of oxidants to the gold surface, and the temperature was
maintainedat 50°C throughout the experiment. A condenser was used in all studies to limit evaporation of
the leaching solution while leaving the leach solution open to the atmosphere.Samples/aliquots of the leach
solution were kept in the fridge in order to minimize the degradation of the thiosulfate complex and
analyzed for gold content within a period of 1 week. The samples were analyzed for gold content without
further treatment.

Leaching Pure Gold in Sodium Thiosulfate based Leach Solutions

These studies were performed on pure gold using a solution composed of 100 mM
Na 2 S 2 O 3 (Na 2 S 2 O 3 ·5H 2 O, Fisher Scientific, 100.4%), 1 mM NaOH(Sigma-Aldrich, >98%), and 1 mM
CuSO 4 (CuSO 4 ·5H 2 O, Fisher Scientific, 100.1%). The solution also contained 0, 1, 5, or 15 µM DMSA

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(linear formula HO 2 CCH(SH)CH(SH)CO 2 H, Sigma-Aldrich, >98%). The gold sample was prepared by
melting gold wire (Alfa Aesar, 0.5mm diameter, 99.9985%) with a propane torch to form a molten sphere
at the end of the wire. This was subsequently quenched in ultra-pure water (Millipore, 18.2 MΩ cm) to
solidify the metal into a polycrystalline bead. The bead was then mounted in an epoxy resin (LECO long-
cure epoxy kit) and a circular face was exposed by grinding with a belt sander. The face was further
polished using finer grades of sandpaper and finally polished to a mirror finish using 6, 3, and 1 micron
diamond polishing suspensions (Buehler, Metadi® Supreme). This provided a sample with a controlled
surface area of 0.027 cm2. Between each leaching experiment, the surface of the metal was cleaned by
polishing it to a mirror finish using 1 micron diamond polishing suspension. Solutions were analysed using
ICP-MS with a Perkin Elmer ELAN 6000 to determine the concentration of gold leached. Standard curves
were prepared using a gold standard (Fluka, 1002 ± 4 mg L-1) at 0.5, 1, 2, and 5 ppb in the same matrix as
the electrolyte.

Leaching Pure Gold in Calcium Thiosulfate based Leach Solutions

These studies were performed on pure gold using a leaching solution composed of 100 mM
CaS 2 O 3 , 1 mM CuSO 4 and either 0 of 5 µM DMSA and the pH was adjusted to an intial value of 8 using
NaOH. Calcium thiosulfate (20-30% wt. CaS 2 O 3 ) was provided by Barrick Gold Corp. Analysis of the
calcium thiosulfate based samples with ICP-MS was found to result in fouling of the mass spectrometer.
As a result, these solution samples were analyzed for gold using flame atomic absorption
spectrophotometry (AAS; Perkin Elmer Model 3110). Because this method is unable to detect gold at the
ppb level,more concentrated gold solutions were generated by increasing the area of the gold surface to
3.45 cm2 using alooselycoiled section of gold wire. The gold wire was cleaned by flame annealing between
each leaching study.All other factors were the same as for the previous experiment.

Leaching a Calcinated Sulfide Ore in Calcium Thiosulfate

The final leaching study was performed using calcined sulfide gold from Barrick Gold Corp. The
leaching solution was composed of 100 mM CaS 2 O 3 , 0.5 mM CuSO 4 and either 0 of 5 µM DMSA and the
pH was adjusted to 8 using NaOH. Approximately 100 g of gold ore was used to form a slurry with the
leaching solution at a pulp density of 35% wt. solids. The experiments were conducted in a 500 mL glass
flask. Prior to adding thiosulfate, the ore was first mixed with ultra-pure water and stirred for 24 hours,
while the pH was adjusted with NaOH and carefully monitored using a pH electrode (Thermo Scientific
Orion 9156DJWP Double Junction pH Electrode) and pH meter (Thermo Scientific Orion Star series). The
pH was adjusted to a value of 8, at which point the other components of the electrolyte were added to
initiate leaching and obtain the pulp density described above. Leaching was conducted at a temperature of
50oC over 24 hours. Aliquots were extracted at intermediate intervals. The slurry was stirred with a PTFE
impeller at 350 rpm in order to maintain a homogenous mixture with off-bottom suspension of the ore.
Samples were extracted through vinyl tubing attached to a 20mL syringe and filtered:first with a Buchner
funnel and Whatman grade 1 filter paper, and then using a plastic Luer-Lock syringe to draw up the filtrate
and filtering a second time using Fisherbrand™ 0.45µm PTFE syringe filter. At the end of the leaching
experiment the remaining slurry was filtered with a 0.45 µm VWR® Vacuum Filtration System and the
filter-cake was rinsed with ultra-pure water then dried and weighed.

Differential Capacitance Measurements

Differential capacitance studies were performed in a customized glass cell with a separate
chamber for the saturated calomel reference electrode (SCE). This arrangement ensured a chloride free
electrolyte. Prior to each investigation the cell was washed in a heated acid bath of 50:50 (v:v) nitric
acid:sulfuric acid then rinsed in ultra-pure water. The cell was then filled with a NaOH solution and left
overnight to neutralize any acid that had leached into the glassware and the cell was rinsed again using
ultra-pure water before running the experiments. All studies were performed using a VoltaLab® PGP 201
potentiostat/galvanostatand a Stanford Research Systems® SR530 dual phase lock-in
amplifier.Capacitance was measured by imposing a sinusoidal voltage (25Hz and 5mV rms, output from

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the SR530) onto a linear potential ramp and collecting the in-phase and out-of-phase components of the
current. It is important to note that these studies were performed in the absence of thiosulfate so that no
leaching occured during these experiments. As such, the measured currents were used to calculate
capacitance assuming a series RC circuit model for the interface as described in a previous study (Lemay
& Shepherd, 2008).The working electrode was a gold bead and the counter electrodewasa platinum
coil.Before the electrode was transferred into the electrochemical cell for capacitance measurements, it was
first modified with a layer of DMSA. For this, a stock solution of 137 mM sodium hydroxide and 2.45 mM
DMSA was diluted to contain 15 µM, 5 µM, and 1 µM DMSA. The bead electrode was then introduced
into these solutions for an incubation time of 10 min to allow for the adsorption of DMSA on the surface.
The modified electrode was then transferred to the electrochemical cell composed of 250 mM KOH
(Sigma-Aldrich, 99.99%). The electrolyte was purged of oxygen by passing a stream of argon gas (Praxair,
ultra high purity) through the electrolyte for 10 min. A stream of argon was maintained above the surface
of the electrolyte for the duration of the experiments to minimize the amount of oxygen re-dissolving in the
electrolyte.Between studies,the gold electrode was cleaned by flame annealing in a propane flame.

RESULTS AND DISCUSSION

Influence of DMSA on Thiosulfate Leaching of Pure Gold Samples

The influence of DMSA on thiosulfate leaching was initially studied by exposing pure gold
samples (of known area) to a stirred leach solution at 50oC for a period of time and then quantifying the
total amount of gold in solution per unit area of the original sample. All leach solutions additionally
contained 1 mM NaOH, and 1 mM CuSO 4 . This rendered a solution with an initial pH of 8 but we note
that the pH was closer to 6 at the end of the experiment. The results of this study are presented in Figure 1.

Figure 1 - Total gold in solution after leaching pure gold samples at the ocp in a solution of either 100mM
Na 2 S 2 O 3 (blue bars and red bars) or 100 mM CaS 2 O 3 (green bars). Each electrolyte additionally contained
1mM CuSO 4 ,1 mM NaOH and 0, 1, 5, or 15 µM DMSA, in a system that was open to atmosphere, stirred
and maintained at 50oC. Solution analysis was performed with ICP-MS for Na 2 S 2 O 3 solutions or flame
AAS for CaS 2 O 3 solutions and converted into µg of gold per unit area of the gold sample. The error bars
represent the standard deviation on 3 independent trials and the inset represents the ocp measured for the
CaS 2 O 3 system over 3 hours.

The blue and red bars represent the amount of gold leached from solutions containing 100 mM
Na 2 S 2 O 3 over short (1.5 h) and long (16 h) leaching times, respectively. The green bars represent a long-
term leaching study (16 h) from a 100 mM CaS 2 O 3 solution. Over 1.5 hours of leaching in Na 2 S 2 O 3 (blue
bars), there appears to be minimal influence from DMSA and the amount of gold leached is always below
2 µg cm-2 on average with the smallest amount noted for 15 µM DMSA. This trend indicates that the initial
leaching performance is slightly reduced by the presence of the additive; an observation that is most
notable at higher concentrations. However, a new trend emerges during prolonged leaching with Na 2 S 2 O 3
solutions (red bars),where after 16 hours there is a clear increase in the amount of gold leached when 5 µM

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of DMSA is added. For this mixture, the average amount of gold in solution was near 6 µg cm-2 in
comparison to a value of just above 2 µg cm-2 in the absence DMSA. However, at a larger concentration of
15 µM DMSA a marked reduction in the amount of leached gold is noted after 16 h again suggesting that
high levels of DMSA inhibit gold leaching. While the results with 5 µM DMSA in Na 2 S 2 O 3 solutions do
show a higher amount of gold leached on average, we note that the error bars (standard deviation over
three independent trials) are large and an ANOVA test rendered a p-value of 0.14. As such, there is some
variability in the process, however, when a similar study was performed using 100 mM CaS 2 O 3 the same
trend emerges between 0 and 5 µM DMSA over a leaching time of 16 h and we conclude that the addition
of 5 µM DMSA to thiosulfate leaching solutions results in a higher average of gold leached over a period
of 16 h Moreover, we can infer that DMSA is as effective at improving leaching performance for calcium
thiosulfate as for sodium thiosulfate under the conditions of this experiment.
These results could be explained by variations in the extent of DMSA adsorption on the gold
surface. When 5 µM DMSA is included in solution, it may adsorb on the surface as a defective monolayer
that still allows for the transport of oxidants to the gold interface. Under this condition, the initial leaching
performance may be slightly impeded by the presence of the adsorbed additive. This argument is supported
by the ocp values provided in the inset of Figure 1. Over the first 2 hours of leaching, the open circuit
potential in the presence of DMSA is more negative (less oxidizing) than in the absence of DMSA. This
could result in slower initial leach rates between 0 and 2 h. However, after a longer period, the trends in the
ocp merge and thedistribution of DMSA on the gold surface may act to block sites where undesired side-
reactions would irreversibly foul the gold surface, such those that that involve polythionates or elemental
sulfur. This could explain in the increased leaching performance over 16 h when 5 µM DMSA is present in
solution. However, at higher concentrations of DMSA, the surface coverage of the gold may increase so as
to severelylimit mass transport of thiosulfate to the gold surface. While it is known that DMSA monolayers
do not restrict electron transfer between ferri/ferro cyanide complexes (Mei Niu et al., 2006),this reaction is
a simple outer-sphere electron transfer reaction, and so is not an analogue to the more complex mechanism
of thiosulfate leaching of gold. This would explain the result in the decreased leaching performance when
15 mM DMSA is present in solution. These possibilities depend on the extent of DMSA adsorption on gold
and can be estimated using differential capacitance as described next.

Extent of DMSA Adsorption on Gold

Differential capacitance measurements were used to determine the extent that DMSA adsorbsonto
the metal surface as a function of its concentration in solution. In this approach the metal-solution interface
is modelled as a resistor and capacitor in series and if the diffuse part of the double layer is neglected, the
measured capacitance can be expressed as:
𝜀𝜀𝜀𝜀0
𝐶𝐶 = (4)
𝑑𝑑

where ε is the permittivity of free space and ε o is the permittivity of the adsorbed material. However, this
equation is most appropriate when a highly ordered or defect free monolayer is present at the surface. For
defective monolayers, the interface should be modelled as two capacitors in parallel; one representing
fractions of the surface coated by DMSA and the other representingfractions coated by the electrolyte. This
can be treated with the parallel plate capacitor model (Damaskin et al., 1971) given by:

𝐶𝐶 = 𝐶𝐶𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 (𝜃𝜃) + 𝐶𝐶𝑜𝑜 (1 − 𝜃𝜃) (5)

WhereC DMSA represents the capacitance of a monolayer of DMSA, C o represents the capacitance in the
absence of DMSA and θ represents the fractional coverage of the organic material on the surface and can
range from 0 to 1. Since C DMSA is less than C o one can expect that the measured capacitance of the
interface will decrease as more DMSA is adsorbed. This approach has been used to characterize the
adsorption of organic materials and is typically performed in 250mM KOH (Barlow & Burgess, 2007;
Laredo et al., 2007; Lemay & Shepherd, 2008; Smith et al., 2011). We used this approach and conditioned
a gold bead electrode in a solution containing 0, 1, 5, or 15 µM DMSA for 10 min to allow DMSA to form

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a crude layer on the surface. The electrode was then removed from this solution and placed in an
electrochemical cell that contained250mM KOH and the capacitance was measured over the potential
range shown in Figure 2.

Figure 2 - Differential capacitance scans of a gold bead electrode in 250 mM KOH after conditioning the
electrode in solutions containing 0, 1, 5, or 15 µM DMSA for 10 minutes. Scans were run using a gold
bead electrode that was flame annealed between each conditioning. The sweep rate was 25 mVs-1 and the
capacitance was measured using a 5 mV rms perturbation at 25Hz. Capacitance was calculated assuming
the interface can be modelled as a series RC circuit. It is important to note that thiosulfate was not present
in these studies. This ensured that leaching did not occur during the adsorption characterization.

In the absence of DMSA (black line) the metal is void of all thiol and the bare/uncoated electrode can be
scanned between 0 and -1.4 V vs SCE. This scan is in good agreement with other reports in the literature
(Stolar et al., 2015) and the curve can be used as a reference capacitance in the absence of DMSA. When
DMSA is present on the surface, the potential scan was limited to 0 and -0.100 V vs SCE in order to
prevent desorption of the DMSA molecules. The capacitance values can then be compared within this
narrow region of potential. As seen in Figure 2, increasing concentrations of DMSA in the incubating
solution result in a general decrease in capacitance. From this data, it is clear that a more complete
monolayer of DMSA is formed on the surface of gold as the concentration of DMSA increases. In
combination with the previous results, this data further supports the notion that DMSA is forming a
monolayer on the surface of the gold to some extent. Since the capacitance is intermediate when 5µM
DMSA is used, it may be defective enough to allow transport of oxidants to the gold surface while
interfering with the build-up of polythionate passivation products thereby improving the overall leaching
performance. Moreover, 1 µM DMSA may be too defective and 15 µM DMSA may be too compact to
allow for the same mechanism. However, we can only speculate on this mechanism until we have
spectroscopic evidence of the presence or absence of polythionate products on the surface. Even so, this
hypothesis is supported by the data thus far. From the collected results, it appears that 5µM DMSA may be
suitable as an additive for gold leaching in thiosulfate solutions. This was tested next using a calcined gold
ore from Barrick Gold.

Leaching of a CalcinedGold Ore

We have initiated a final investigation wherewe examine the influence of DMSA on the calcium
thiosulfate leaching of a calcinedgold ore (Barrick Gold Corp.). For this experiment, a homogeneous 35%
ore slurry was used with an industrially relevant solution of 100 mM CaS 2 O 3 , and 0.5mM CuSO 4 . The pH
of the slurry was adjusted to pH 8.5 and maintained at this value for the duration of the experiment. The
slurry was leachedin a solution without DMSA, and in another one which contained 5 µM DMSA. Each
leaching study was performed over a 24h period and aliquots of the solution were extracted at various
times. The amount of gold in each aliquot was determined using flame AAS and converted to grams of
gold extracted per tonne of ore. A fire assay (Barrick Gold Corp.) was performed on 3 unleached samples
and revealed a gold content of 10.3 ± 0.5 g t-1for this particular ore. This value was used to express the

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percent of gold leached. Preliminary results are presented in Figure 3 for the 0 µM DMSA (blue bars) and
5 µM DMSA (red bars) samples respectively.

Figure 3 -Percent of gold leached from a calcined ore in a solution composed of 100mM CaS 2 O 3 + 0.5mM
CuSO 4 at pH 8.5 and 50ºC. The leach solution also contained 0µM DMSA (blue bars – single trial)and 5
µM DMSA (red bars – two trials). Error bars represent thestandarddeviation across 2 independent runs.

In Figure 3 it is clear that in the absence of DMSA, the percent of gold leached rises between 1 and 7h and
reaches a plateau near 65% after this point. With the addition of 5µM DMSA, the initial leaching between
0 and 7h shows reduced performance when compared to the data in the absence of DMSA. However,
beyond 7h of leaching, the trend does not plateau when using 5µM DMSA. Rather, the percent of gold
leached continues to increase even after 25h, in contrast to the trend observed in the absence of DMSA. In
fact, the percent of gold leached reaches an average value above 70% (over two trials) after 24 hours.
These results again indicate that the leaching of gold is prolonged in the presence of 5µM DMSA and is
consistent with the results obtained with pure gold samples previously described in this paper. These
results do show potential for DMSA to be used as an additive to thiosulfate leaching of gold. However, it
should be remembered that the results are preliminary and further trials are under way. Currently the data
in Figure 3 represent a single trial for 0 µM DMSA and 2 trials for 5µM DMSA. Also, we must consider
that while 5µM DMSA showed improved leaching for pure gold samples, the leaching of gold ore may
require a different amount of DMSA since the gold ores may contain other metals that could complex with
DMSA and reduce its efficiency. As such, higher concentrations of DMSA will be studied in future
experiments.

CONCLUSIONS

In this report we have demonstrated that the addition of 5µM DMSA can prolong the leaching of
pure gold samples in different thiosulfate solutions. This additive also shows potential improvement in the
prolonged leaching of acalcinedsulfidic gold ore. The improvement in the leaching of pure gold samples
was demonstrated in solutions of 100mM Na 2 S 2 O 3 as well as 100mM CaS 2 O 3 in moderately basic
conditions and with addition ofCu(II). In all cases, the solution was open to the environment and
maintained at 50ºC. Differential capacitance studies on a gold electrode preconditioned in varying
concentrations of DMSA indicated that DMSA forms a crude layer on the surface of the gold electrode and
the compactness of this layer increasesas the bulk DMSA concentration increases in the system. From
these results we propose that a layer of DMSA on the gold surface retards thiosulfate leaching of gold.
However, further evidence suggests that this layer may also mitigate irreversiblepassivation of gold that
would otherwise occur through deposition of sulfur species on the gold surface during prolonged leaching.
Higher bulk concentrations of DMSA result in more densely compacted layersof DMSA on the gold
surface, reducing the effectiveness of the additive. Future studies will focus on altering the experimental
set-up so that fire assays for the leached oremay be used to form a mass balance with the solution and the
ore. More studies will focus on leaching beyond 24 hours to determine if a plateau is reached with the
DMSA and if so at what gold concentration. AFM will also be used in order to further verify the formation
and quality of monolayers of DMSA on the surface of the gold. Another aspect to be investigated further is
whether or not DMSA may be chelating other metals in the slurry during ore leaching since DMSA has

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been demonstrated to be capable of chelating As(Aposhian et al., 1984) and Pb (Lee et al., 1995), and
Hg(Roels et al., 1991), both of which are commonly present in gold ore.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the Natural Sciences and Engineering Research Council of
Canada (NSERC), and Barrick Gold Corporation for financial support. Barrick Gold Corporation is also
acknowledged for approving this research for publication. The authors would also like to acknowledge Luc
Beaudet for his support and maintenance of the ICP-MS and Henry Ylitalo for his support of and
maintenance of the Flame-AA and Jack Biln of Barrick Gold for performing a fire assay analysis of the
ore.
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