Hydrometallurgy 143 (2014) 12–22

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

Effect of minerals on the stability of gold in copper ammoniacal

thiosulfate solutions — The role of copper, silver and polythionates
M.G. Aylmore a,⁎, D.M. Muir a,1, W.P. Staunton b
a
CSIRO Minerals, PO Box 90, Bentley 6982, Australia
b
Western Australian School of Mines, Curtin University, GPO Box U1987, Perth 6845, Australia

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

Article history: The effect of some typical oxide and sulfide minerals, as well as activated carbon, on synthetic gold thiosulfate
Received 30 July 2013 leach solutions was examined. The presences of pyrite and goethite in a synthetic ore slurry have a significant ef-
Received in revised form 20 November 2013 fect on the adsorption and stability of gold, silver, copper and polythionates in ammoniacal thiosulfate solutions.
Accepted 3 December 2013
Adsorption of tetrathionate in particular leads to significant gold and silver losses. The adsorption of copper on
Available online 13 January 2014
mineral surfaces inhibited gold and silver losses, even in the presence of tetrathionate. However, goethite was
Keywords:
found to strongly adsorb copper(II). It is concluded that gold extraction from natural ores is lower than that ob-
Thiosulfate tained with cyanide, partly as a result of sorption or precipitation reactions. Furthermore, the presence of silver in
Gold solution catalyses the precipitation of a mixed copper/silver/gold sulfide in ammoniacal thiosulfate solutions con-
Silver taining tetrathionate.
Polythionates © 2014 Elsevier B.V. All rights reserved.
Pregrobbing

1. Introduction of thiosulfate degradation products such as tetrathionate, sulfide and

With increasing regulatory scrutiny of new gold projects and a low-
ering of what are considered acceptable levels of cyanide discharges,
world industry attention has focused on ammoniacal thiosulfate as
a relatively cheap and non-toxic reagent alternative to cyanide for
leaching gold ores. The establishment of an economic and environmen-
tally acceptable option for extracting gold without the use of cyanide
would seem highly desirable, and in some cases, essential.
Previous research has shown that by maintaining sufficient concen-
trations of thiosulfate, ammonia, copper and oxygen in the leach solu-
tion under suitable Eh and pH conditions gold can be readily extracted
with modest reagent consumption (Aylmore and Muir, 2001a, 2001b;
Li et al., 1996; Molleman and Dreisinger, 2002; Muir and Aylmore,
2002; Wan, 1997). Despite considerable research into the optimum
conditions for gold dissolution by thiosulfate, the maximum gold
extractions generally obtained remain some 5–25% less than those
achieved using cyanide.
In addition, the levels of reagent concentrations for effective
leaching rates in ores are normally at least 50 times greater than that
used in the cyanide leaching system. Furthermore, extending leaching
times in an attempt to increase gold extraction can result in the loss of
gold from solution, due to the formation of increased concentrations
⁎ Corresponding author at: Tenova Mining & Minerals (Australia) Pty Ltd, 2/93
Francisco Street, Belmont, WA 6104, Australia. Tel.: +61 8 9365 9447.
E-mail addresses: mark.aylmore@tenova.com (M.G. Aylmore),
w.staunton@curtin.edu.au (W.P. Staunton).
1
Deceased.
trithionate. This ultimately reduces the effectiveness of thiosulfate as
an alternative lixiviant to cyanide for leaching gold. There have been
extensive studies investigating additives to enhance gold and silver
leaching, some beneficial and others detrimental (Alonso-Gomez and
Lapidus, 2008, 2009; Feng and van Deventer, 2010a, 2010b, 2010c,
2011a, 2011b; Jeffrey et al., 2008; Xia and Yen, 2005, 2008). These addi-
tives either affect the residual copper(II) concentration and Eh, modify
surface reactions with gold by catalytic action and/or prevent the forma-
tion of or remove passivating layers on gold surfaces (Senanayake,
2013).
Whilst thiosulfate leaching is currently attractive for carbonaceous
ores, a number of issues and problems must be resolved before a general
process can be demonstrated as practical and economic for typical
oxidised gold ores (Muir and Aylmore, 2005).
The main reasons for lower gold extraction in thiosulfate compared
with cyanide systems undoubtedly include precipitation or adsorption
of species from solution associated with particular minerals in the ore
(Muir and Aylmore, 2002). This paper describes a systematic study of
the effects of selected oxide and sulfide minerals as well as activated
carbon on the thiosulfate leaching system. In particular, gold adsorption
and stability, the effect of copper, silver and polythionates are exam-
ined. This work was carried out under the auspices of the industry
funded AMIRA P420 Gold Processing Technology project.
Although carbon has a low affinity for Au(S2O3)3− 2 (Gallagher, 1989)
activated carbon has a high specific surface area relative to other min-
erals and could still reduce gold recoveries by sorption. Activated carbon
has been identified as having similar properties to that of ‘preg-robs’
gold from cyanide solutions in carbonaceous ores (Ibrado and

0304-386X/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2013.12.001
 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22
Fuerstenau, 1992). Evidence of the influence of some minerals on gold
and silver dissolution rate has been presented in the literature particu-
larly for pyrite and haematite (e.g. Feng and van Deventer, 2002;
Zhang and Jeffrey, 2008). However, the study on the stability of gold
and silver in ammoniacal thiosulfate solutions in the presence of min-
erals is limited.
2. Experimental
Particular oxide and sulfide minerals were chosen as representative
of those commonly present in gold ores and mixed with finely ground
quartz to produce a synthetic ore. The minerals investigated, together
with the values for their specific surface areas and the mixtures with
quartz used are indicated in Table 1. The compositions chosen lie within
the range normally associated with natural ores.
Unless stated otherwise the synthetic leach solution contained
2−
0.4 M NH3/NH+ 4 and 0.05 M S2O3 , at pH 9.5 with the addition of
10 mg/L Au and 5 mg/L Ag. The reagent concentrations were chosen
based on prior work, thermodynamic analyses of gold leaching and spe-
ciation diagrams (Aylmore and Muir, 2001a, 2001b; Li et al., 1996; Wan,
1997). Fundamental aspects of gold and silver leaching with ammonia-
cal thiosulfate were also considered (Aylmore and Rae, 2001; Breuer
and Jeffrey, 2000; Breuer et al., 2001; Jeffrey, 2001; Jeffrey et al.,
2001a, 2001b). Stock solutions of reagents and precious metals were ad-
justed to pH 9.5. Experiments were performed by bottle rolling 600 mL
solutions containing 400 g of mineral sorbents. A blank was also run to
confirm that no loss occurred due to adsorption on the surface of the
bottles. Sub-samples were taken at 0.5, 2 and 5 h. The experiments
were carried out at ambient temperature regulated in the laboratory
at around 15 °C. The experiments where possible were grouped to elim-
inate the impact of temperature variations on the test results.
The polythionate concentrations for experiments containing
polythionates were determined by High Performance Liquid Chromato-
graphic (HPLC) technique. Chromatographic separations of thiosulfate
and polythionates were performed using an eluent of 0.005 M
tetrabutyl-ammonium hydroxide, 0.005 M perchlorate and 0.005 M
ammonia at a pH of 8.0. The HPLC equipment consisted of a Waters
C18 Guard-Pak (5.0 × 6.0 mm ID) guard column and a Waters Nova
Pak C18 column (150 × 3.9 mm ID) analytical chromatographic column
connected to a diode array detector to measure the different solution
species. Analytical grade sodium thiosulfate and sodium tetrathionate
were obtained from BDH Pty Ltd. Sodium trithionate was synthesised
from sodium thiosulfate and hydrogen peroxide following the method
outlined by Kelly and Wood (1994).
Comparisons were made between the loss of reagents and stability
of precious metals in solution for individual mineral components. Data
from these experiments were used to quantify the extent to which min-
eral components ‘preg-robbed’ gold and silver contributed to the loss of
reagents from solution. Duplicate experiments were conducted on
many of the tests with only average results reported, due to the stan-
dard deviations of all the tests being within 3%. In all figures in this
paper the gold and silver losses have been expressed as mg per
kilogramme of mineral to gauge the adsorption capacity of some min-
erals under conditions typically used in leaching. Under the gold and
Table 1
Mineral components examined.
Mineral Surface area Quartz Mineral Percentage
(m2/g) component component of mineral
(g) (g) in mixture
Kaolinite 18.17 300 100 25%
Activated carbon 872 380 20 5%
Pyrite 3.53 380 20 5%
Chalcopyrite 0.39 380 20 5%
Goethite 13.3 300 100 25%
13
silver solution concentrations and mineral quantities used, a 100% loss
of gold and silver in the presence of kaolinite or goethite is equivalent
to 60 and 30 mg/kgmineral respectively. Whereas in the case for pyrite
and activated carbon tests a 100% loss of gold and silver is equivalent
to 300 and 150 mg/kgmineral respectively. In later tests where the silver
concentration was doubled from 5 mg/L to 10 mg/L the values for gold
apply.
3. Results and discussion
3.1. Role of mineral surfaces
3.1.1. Effect of minerals on gold and silver adsorption
Equilibrium adsorption isotherms for gold and silver on pyrite, chal-
copyrite and activated carbon in copper-free ammoniacal thiosulfate
leach solutions are shown in Fig. 1. Each showed essentially linear
plots of gold and silver loading versus equilibrium concentration and
demonstrates significant preg-robbing capability. Activated carbon ex-
hibited the highest preg-robbing ability since its specific surface area
is significantly higher than other minerals (Table 1). However, based
on surface area measurement, the gold loading per unit area is smaller
(0.0001 mg/m2) than that observed for chalcopyrite (0.084 mg/m2)
and pyrite (0.0093 mg/m2) in an ammoniacal thiosulfate solution con-
taining 10 mg/L of gold.
In comparison, the sesquioxide minerals did not readily adsorb gold
and silver under the conditions used. Since Au(S2O3)2− 2 is a large linear
anion, it has been considered that it would be difficult for this species
to coordinate specifically with goethite surface hydroxyl groups
(Machesky et al., 1991; Ran et al., 2002). A similar conclusion also
holds for kaolinite.
3.1.2. Effect of ammonia and thiosulfate concentrations on the adsorption of
gold and silver
Fig. 2 shows the observed gold and silver concentrations lost to the
minerals after bottle rolling in copper ammoniacal thiosulfate solutions
for 2 h under different NH3/NH+ 4 and thiosulfate concentrations.
Generally the stability of gold and silver in solution was unaffected
by reducing the ammonia concentration to 0.1 M in the presence of
0.05 M thiosulfate. In contrast Navarro et al. (2006) observed that ad-
sorption of gold on the carbon increased with increasing ammonium hy-
droxide concentration up to 0.6 M and then remained constant, whilst
the effect of ammonium hydroxide concentration was less significant
at longer reaction times. They also observed that gold adsorption rate in-
creased with increasing initial thiosulfate concentration, but decreased
with extended length of time at higher thiosulfate concentrations.
In the presence of pyrite, significant gold and silver (N 80%) reported
to the mineral, and solution concentrations decreased when the ammo-
nia concentration was below 0.4 M. Feng and van Deventer (2001) also
found that preg-robbing of gold thiosulfate occurred on a range of
sesquioxide and sulfide mineral surfaces when ammonia in solutions
was below ~0.5 M — but in their case no free thiosulfate was present.
In the presence of pyrite, a thiosulfate concentration of around
0.05 M was required to reduce preg-robbing of gold and silver from
0.4 M NH3/NH+ 4 solution at pH 9.5. In contrast, results obtained by
Feng and van Deventer (2002) indicated that in an oxygen-deficient sys-
tem, a thiosulfate concentration of 0.5 M was required to eliminate
preg-robbing completely in a solution containing 0.5 M ammonia. The
lower levels of adsorption on goethite and kaolinite (~2% adsorption of
gold and silver from solution) appear to be similarly affected by thiosul-
fate concentration — though the results with goethite need further clar-
ification. Overall there was a limited reagent concentration range over
which precious metals were stable in ammoniacal thiosulfate solutions
at pH 9.5. To prevent precious metal loss onto sesquioxide minerals,
2−
reagent concentrations N0.2 M NH+ 4 /NH3 and ≥ 0.05 M S2O3 are
+ 2−
required. Pyrite requires ≥0.4 M NH4 /NH3 and ≥0.05 M S2O3 whilst
activated carbon requires N 0.1 M NH+ 2−
4 /NH3 and N 0.05 M S2O3 .
14 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22

Pyrite Chalcopyrite
200
200
Au
Au

Au/Ag lost (mg/kg)

Au/Ag lost (mg/kg)

Ag
150 150 Ag

100 100

50 50

0 0
0 10 20 30 40 0 10 20 30 40
Equilibrium concentration (mg/L) Equilibrium concentration (mg/L)

Activated carbon
600
Au
Au/Ag lost (mg/kg) 500
Ag
400

300

200

100

0
0 10 20 30 40
Equlibrium concentration (mg/L)

Fig. 1. Au and Ag isotherms for pyrite, chalcopyrite and activated carbon (conditions: 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , no Cu, pH 9.5).

3.1.3. Absorption of ammonia and thiosulfate on minerals Pyrite produced no apparent ammonia loss from solution. Thiosulfate
Adsorption of ammonia onto mineral surfaces was minimal with ap- loss in ammoniacal thiosulfate solutions associated with pyrite and acti-
proximately 1 g/kg on sesquioxide minerals and 2–5 g/kg on carbon. vated carbon was about 2–5 g/kg, whereas sesquioxide minerals

a
250 20
Au act carbon Au Kaolinite
Au/Ag lost onto minerals

Au/Ag lost onto minerals

Ag act carbon Ag Kaolinite

200 Au Goethite
Au Pyrite 15
Ag Goethite
(mg/kgmineral)

(mg/kgmineral)

Ag Pyrite
150
10
100

5
50

0 0
0 0.1 0.2 0.3 0.4 0.5 0 0.1 0.2 0.3 0.4 0.5
Ammonia/ammonium conc (mol/L) Ammonia/ammonium conc (mol/L)

b
250 20
Au act carbon Au Kaolinite
Au/Ag lost onto minerals

Au/Ag lost onto minerals

Ag act carbon Ag Kaolinite

200
Au Pyrite 15 Au Goethite
Ag Pyrite Ag Goethite
(mg/kgmineral)

(mg/kgmineral)

150
10
100

5
50

0 0
0 0.02 0.04 0.06 0 0.02 0.04 0.06
Thiosulfate conc (mol/L) Thiosulfate conc (mol/L)

Fig. 2. Effect of (a) ammonia/ammonium and (b) thiosulfate concentration on gold and silver stability in ammoniacal thiosulfate solutions for different minerals (Au 10 mg/L; 5 mg/L Ag;
0.05 M S2O2− 3 , pH 9.5, after 2 h).
 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22 15

Copper (II) adsorption Copper (I) adsorption

1000 act. carbon 1000

Cu lost (mg/kgmineral)

Cu lost (mg/kgmineral)
goethite
800 goethite 800

600 600
kaolinite
400 400 act. carbon
200 200
kaolinite
0 0
0 50 100 150 0 50 100 150 200 250
Equilibrium concentration (mg/L) Equilibrium concentration (mg/L)

Fig. 3. Cu(II) and Cu(I) isotherms for goethite, kaolinite and activated carbon (conditions: Cu(II) in 0.4 M NH+ 2−
4 /NH3; or Cu(I) in 0.05 M S2O3 , pH 9.5).

produced no measurable loss. No trend between thiosulfate concentra-
tion and its loss could be accurately ascertained. The adsorption of
polythionates is discussed later.
3.2. Role of copper
3.2.1. Effect of minerals on the adsorption of copper in solution
In dilute ammoniacal thiosulfate solutions, Cu(II) is rapidly reduced
by thiosulfate to Cu(I) and an equilibrium ratio of Cu(II):Cu(I) is
established that depends upon the relative concentrations of ammonia,
thiosulfate and dissolved oxygen. Adsorption isotherms for the separate
minerals bottle rolled in solutions containing either Cu(I) added as cu-
prous chloride in a 0.05 M thiosulfate solution, or Cu(II) added as cop-
per sulfate in a 0.4 M ammoniacal solution are shown in Fig. 3.
Generally, oxide minerals have a preference for Cu(II) adsorption
over Cu(I) with higher copper losses being associated with activated
carbon, goethite and kaolinite. In the Cu(I) thiosulfate solution, kaolinite
loads around 70 mg Cu/kg (0.0042 mg/m2), corresponding to a cation
exchange of 1.1 meq/kg whereas in equilibrium with 8 mg/L Cu(II) solu-
tion, goethite loaded 700 mg Cu/kg. The depletion of Cu(II) from solu-
tion through strong adsorption on iron oxides like goethite would
undoubtedly reduce the effectiveness of copper as an oxidant in the
gold dissolution process.
Clearly lower copper losses from solution are possible by maintain-
ing the majority of copper in solution as Cu(I) by adjustment of the am-
moniacal thiosulfate concentrations. However, some Cu(II) is required
to catalyse the gold dissolution process.
3.2.2. Effect of copper(II) and copper(I) on gold and silver adsorption
Fig. 4 shows that both Cu(II) and Cu(I) significantly reduced gold and
silver adsorption on minerals when N16 mg/L Cu was added. The addi-
tion of copper reduced gold loss to activated carbon from 100 mg/kg to
80 mg/kg, and gold loss to pyrite from 120 to 20 mg/kg. However the
small gold loss to both goethite and kaolinite increased slightly to
5 mg/kg (~2%) with increased copper concentration. Overall, in addi-
tion to catalysing the leaching of gold, the adsorption of Cu(I) and
Cu(II) onto mineral surfaces appears to compete and minimise gold
and silver losses from solution.
3.3. Role of polythionates (tetrathionate and trithionate)
Polythionates are produced in ammoniacal thiosulfate through reac-
tions between copper(II) and oxygen and thiosulfate (Li et al., 1996).
However, polythionate analysis of solutions bottle rolled with pyrite
and carbon indicated that up to 0.002 M tetrathionate was present
after 5 h. Feng and van Deventer (2002) and Zhang and Jeffrey (2008)

a Gold Silver
140 140
Au lost onto minerals

Ag lost onto minerals

120 120
(mg/kgmineral)

(mg/kgmineral)

100 activated carbon

100
80 80
60 60
pyrite
40 40 pyrite
20 20 activated carbon
goethite kaolinite goethite kaolinite
0 0
0 20 40 60 80 0 20 40 60 80
Cu (II) Conc. (mg/L) Cu (II) Conc. (mg/L)

b 140 140
Ag lost onto minerals
Au lost onto minerals

120 pyrite 120

(mg/kgmineral)
(mg/kgmineral)

100 100 pyrite

activated carbon
80 80
60 60
40 40
20 20 activated carbon
goethite
kaolinite 0 goethite kaolinite
0
0 20 40 60 80 0 20 40 60 80
Cu (I) Conc. (mg/L) Cu (I) Conc. (mg/L)

Fig. 4. Effect of (a) Cu(II) and (b) Cu(I) on gold and silver adsorption on minerals (conditions: Au 10 mg/L; 5 mg/L Ag; 0.4 M NH+
4 /NH3, pH 9.5, after 2 h).
16 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22

have reported that pyrite catalyses thiosulfate oxidation. Unfortunately Gold

180
there is no published literature on the effects of polythionates on
the stability of gold and silver in solution and on the adsorption of 160
polythionates on mineral components.

Au lost onto minerals

140 activated carbon

(mg/kgmineral)
120
3.3.1. Polythionate adsorption isotherms
Adsorption isotherms for tetrathionate from copper-free leach solu- 100
tion onto individual mineral components are shown in Fig. 5. The 80 pyrite
continuous decomposition of tetrathionate under alkaline conditions
60
results in some analytical uncertainty, with resultant spread of data.
kaolinite
Furthermore the equilibrium concentration of tetrathionate in the pres- 40
ence of pyrite increased with time, presumably due to the catalysed 20
degradation of thiosulfate adsorbed on pyrite and surface oxidation of Goethite
0
pyrite surface (Feng and van Deventer, 2002, 2005, 2006; Zhang and 0 2 4 6
Jeffrey, 2008). Nevertheless the data reveal trends, and clearly there is Time (hrs)
a linear relationship between tetrathionate lost from solution and equi-
librium concentration. The amount lost, attributed to mineral adsorp- Silver
tion, is small on sesquioxide minerals compared with that on 180
activated carbon and pyrite. In typical leach solutions containing 160
1–2 g/L tetrathionate, goethite adsorbs about 2 g/kg, whilst activated

Ag lost onto minerals

140
carbon adsorbs about 40 g/kg and pyrite about 100 g/kg.

(mg/kgmineral)
By contrast, no significant loss of trithionate was observed, which in- 120
dicates that trithionate behaves like thiosulfate — rather than like 100 activated carbon
tetrathionate.
80

3.3.2. Effect of tetrathionate on gold and silver stability 60 pyrite

Fig. 6 illustrates the extent of gold and silver losses to different min- 40
erals from copper-free ammoniacal thiosulfate solutions containing kaolinite
20
~1 g/L (0.005 M) tetrathionate over a 5-hour period. In all solutions a Goethite
reddish pink precipitate was observed after 0.5 h. Energy dispersive 0
0 2 4 6
X-ray analysis of the precipitated solid under a scanning electron micro-
Time (hrs)
scope showed it was a mixed silver/gold sulfide (approx. 30% Ag, 30%
Au, 40% S). After 5 h the uptake of gold and silver onto kaolinite and Fig. 6. Gold and silver uptake on minerals from ammoniacal thiosulfate solution contain-
goethite was 50 mg/kg and 25 mg/kg respectively. This corresponds ing 1 g/L (0.005 M) tetrathionate and with 10 mg/L Au or Ag (conditions: 0.4 M NH+ 4 /

to about 90% loss of gold and silver from solution. Even a tetrathionate NH3; 0.05 M S2O2− 3 , no Cu, pH 9.5).
Tetrathionate lost from solution
Tetrathionate lost from solution

20 90
80 Activated
70 carbon
15
(g/kgmineral)
(g/kgmineral)

60
kaolinite 50
10
40
30
5 goethite 20
10
0 0
0.0 2.0 4.0 6.0 0.0 1.0 2.0 3.0 4.0
Equilibrium concentration (g/L) Equilibrium concentration (g/L)
Tetrathionate lost from solution

160
140
Pyrite
120
(g/kgmineral)

100
80
60
40
20
0
0.0 0.5 1.0 1.5 2.0 2.5
Equilibrium concentration (g/L)

Fig. 5. Tetrathionate isotherms on kaolinite, goethite, activated carbon and pyrite analysed at different times (♦ 0.5 h, ■ 2 h, ▲ 5 h), (conditions: 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , no Cu,
pH 9.5).
 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22 17

concentration as low as 0.5 g/L (0.0025 M) was effective in ‘preg- et al., 2000; Miura and Koh, 1983; Muir et al., 2001; Rolla and
robbing’ gold and silver from solution. Chakrabarti, 1982; Zhang and Dreisinger, 2002):
Overall, gold and silver losses increased with time with decomposi-
2− 2− −
tion of tetrathionate. Our work has also shown that gold and silver 3S4 O6 þ 3:5O2 þ H2 O → 4S3 O6 þ 2OH ð1Þ
losses increased with increased tetrathionate concentrations. Conse-
quently the concentration of tetrathionate during the thiosulfate 2− − 2− 2−
4S4 O6 þ 6OH → 5S2 O3 þ 2S3 O6 þ 3H2 O ð2Þ
leaching process should be kept low or preferably eliminated to prevent
some gold and silver precipitating from solution. 2− − 2− . 2− . 2−
10S4 O6 þ 34OH →13S2 O3 þ 122 SO3 þ 17H2 O þ 4 S :
3 3

3.3.3. Effect of trithionate on gold and silver stability
For comparison, Fig. 7 illustrates the extent of gold and silver losses
onto different minerals from copper-free ammoniacal thiosulfate solu-
tions containing ~1 g/L (0.005 M) trithionate over a 5-hour period.
Overall, the loss of gold and silver from solution was found to be un-
changed with time in the presence of trithionate for all the minerals ex-
amined. With the exception of pyrite, there were no significant changes
in gold and silver concentrations in the presence of the minerals after
the first half-hour. Losses in the presence of activated carbon are associ-
ated with direct adsorption. The significant loss of gold and silver in the
presence of pyrite is similar to that found in the absence of trithionate
where no copper is present (see Fig. 4a), and is attributed to strong
chemi-adsorption of gold and silver onto the pyrite surface.
3.3.4. Mechanism of precipitation
The mechanisms and pathways for the decomposition of
tetrathionate species depend upon Eh and pH but are not well under-
stood. The following simplified reactions have been proposed in the liter-
ature for oxygen and alkaline decomposition of tetrathionate (Fleming
Gold
180
160 pyrite
Au lost onto minerals
ð3Þ
Fundamental studies on the kinetics of decomposition of
tetrathionate, trithionate and thiosulfate in alkaline solution (Rolla
and Chakrabarti, 1982; Zhang and Dreisinger, 2002) have shown that
tetrathionate can be readily decomposed to thiosulfate and trithionate
by raising the pH. On the other hand work by Miura and Koh (1983) in-
dicated that tetrathionate decomposed to thiosulfate and sulfite ions to-
gether with some sulfide ion. Oxidation of tetrathionate with oxygen to
trithionate also occurs (Aylmore and Rae, 2001; Fleming et al., 2000).
Trithionate is more stable than higher order polythionates, requiring
higher pH or temperature to effect decomposition (Fleming et al.,
2000; Muir et al., 2001).
Addition of sulfide ion is reported to quantitatively precipitate gold
and silver from solution (Fleming et al., 2000; West-Sells and Hackl,
2005). At the Eh values observed in this work (250–300 mV vs SHE),
the formation of sulfide ions would not be expected. However, adsorp-
tion and decomposition of tetrathionate may take place on mineral sur-
faces at lower Eh when the rate of oxygen consumption by the absorbed
decomposing tetrathionate exceeds the rate of oxygen mass transfer
from solution. This could produce sulfide ions on the mineral surface
and facilitate gold–silver sulfide precipitation.
3.3.5. Role of copper on gold and silver stability in the presence
of polythionates
The effects of copper on the stability of gold and silver in ammonia-

140 cal thiosulfate solution containing ~ 1 g/L trithionate or tetrathionate

(mg/kgmineral)

120 are shown in Fig. 8. Generally copper had little effect in the presence
activated carbon
100 of trithionate, with gold losses observed similar to those in ammoniacal
thiosulfate solutions containing copper without trithionate (see Fig. 4)
80 or trithionate without copper (Fig. 7). However, the addition of copper
60 reduced the loss of silver.
40 The addition of copper significantly reduced gold and silver losses in
Goethite the presence of tetrathionate (comparing Fig. 8b with Fig. 6). Gold loss
20
to activated carbon was reduced from 80 g/t to 30 g/t, and losses to py-
0 kaolinite rite were also reduced. It is proposed that the presence of copper either
0 2 4 6 competes with gold and silver for sites on the mineral surface, or main-
Time (hrs) tains potentials near the mineral surfaces sufficiently high to prevent
mixed sulfide precipitation.
Silver
180
3.4. Effect of silver on gold loss
160
Ag lost onto minerals

140 The presence of silver has been shown to be beneficial in increasing

(mg/kgmineral)

120 the rate of gold dissolution in thiosulfate leach solutions (Zhang et al.,
100 2008). Higher silver grade in oxide ores causes a higher extraction of
pyrite both gold and silver in copper ammoniacal thiosulfate solutions (Muir
80 and Aylmore, 2004, 2005). The effect of silver on gold losses on goethite
60 and pyrite from copper-free ammoniacal thiosulfate containing 1 g/L
activated carbon (0.005 M) tetrathionate is illustrated in Fig. 9. In both cases, the pres-
40
ence of silver in solution resulted in 40% gold loss after approximately
20 Goethite kaolinite 1 h, whereas without silver, the gold was stable. The molar ratio of
0 gold to silver lost from solution in the presence of tetrathionate was
0 2 4 6
1.0 until the silver concentration in solution dropped to 3 mg/L. There-
Time (hrs) after, the molar ratio of gold to silver lost was 0.7.
Fig. 7. Gold and silver uptake on minerals from ammoniacal thiosulfate solution contain-
As shown in Fig. 10, the amount of gold lost over a 5-hour period is
ing ~1 g/L (0.005 M) trithionate and with 10 mg/L Au or Ag (conditions: 0.4 M NH+4 /NH3;
proportional to the loss of silver irrespective of the mineral in the pres-
0.05 M S2O2−3 , no Cu, pH 9.5). ence of tetrathionate. However, activated carbon exhibited a different
18 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22

a Trithionate present 140

Goethite
140

Au/Ag lost onto mineral

Au/Ag lost onto minerals

Au - koalinite Ag - koalinite 120 Au/Ag - Ag

120 Au - goethite Ag - goethite Au/Ag - Au

(mg/kgmineral)
100
(mg/kgmineral)

100 Au - act carbon Ag - act carbon Au

Au - pyrite Ag - pyrite 80
80
60
60
40 40

20 20

0 0
0 2 4 6 0 2 4 6
Time (hrs) Time (Hrs)

b Tetrathionate present Pyrite

140
140

Au/Ag lost onto mineral

120 Au/Ag - Ag
Au/Ag lost onto minerals

Au - koalinite Ag - koalinite
120 Au/Ag - Au

(mg/kgmineral)
Au - goethite Ag - goethite 100
(mg/kgmineral)

100 Au - act carbon Ag - act carbon Au

Au - pyrite Ag - pyrite 80
80
60
60
40 40

20 20

0 0
0 2 4 6 0 2 4 6
Time (hrs) Time (Hrs)

Fig. 8. Gold and silver losses from ammoniacal thiosulfate solutions with 32 mg/L Cu(II) Fig. 9. Effect of silver on gold losses onto goethite and pyrite from copper-free ammoniacal
addition in the presence of (a) ~1 g/L (0.005 M) trithionate and (b) ~1 g/L (0.005 M) thiosulfate solutions containing ~1 g/L (0.005 M) tetrathionate (Au/Ag — solutions con-
tetrathionate (conditions: 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , pH 9.5). taining both Au and Ag; Au — solutions containing Au only), (conditions: 0.4 M NH4+/
NH3; 0.05 M S2O2− 3 , pH 9.5).

curve and took up ~100 mg Au/kg. It appears that both adsorption and
precipitation are significant on activated carbon. Clearly the presence of
silver catalyses the precipitation of gold as a mixed sulfide in the pres-
ence of tetrathionate. This is in accord with the results from Breuer
et al. (2001) who showed that at low Eh, silver reduces the over-
potential for gold deposition and produces a gold/silver alloy from am-
moniacal thiosulfate solutions.
3.5. Sulfite addition to remove tetrathionate
The impact of the addition of sulfite to remove tetrathionate on the
stability of precious metals was examined. The benefits of adding sulfite
during thiosulfate leaching has been reported in the literature (Fleming
et al., 2000; Ji et al., 2003; Kerley, 1983). Tetrathionate is decomposed by
sulfite under neutral or alkaline conditions according to the reaction:
was also found to be independent of trithionate concentration examined
(0.005 to 0.01 M). The loss of some gold and silver without tetrathionate
is related to some other gold preg-robbing mechanism.
Trithionate concentration appeared to be the same or lower where
sulfite was present. The lower concentration of trithionate in some solu-
tions in the presence of sulfite is unclear.
3.5.2. Effect of sulfite on precious metal stability in ammoniacal thiosulfate
solutions
Fig. 12 shows the effect of the addition of 0.005 M sulfite to an aurif-
erous ammoniacal thiosulfate solution containing 0.01 M trithionate.
30
Au lost from solution

2− 2− 2− 2−
S4 O6 þ SO3 → S2 O3 þ S3 O6 : ð4Þ
(moles x10-6)

20

3.5.1. Effect of sulfite on gold and silver stability in the presence of minerals
A comparison between the stability of precious metals in the pres-
ence of minerals in ammoniacal thiosulfate solutions containing
10
trithionate with and without sulfite was made and the results for goe-
thite and pyrite are shown in Fig. 11. Gold and silver concentrations in
solution are plotted on the left hand side with their corresponding con-
centration of polythionates plotted on the right hand side. In all exper-
iments sulfite removed tetrathionate where it was present in solution. 0
0 10 20 30
Sulfite addition partially reduced precious metal loss to goethite and
significantly reduced precious metal loss to pyrite. Sulfite had no effect
Ag lost from solution (moles x10-6)
on precious metal loss to kaolinite or activated carbon. Fig. 10. Relationship between gold and silver losses on minerals in ammoniacal thiosulfate
Sulfite eliminated tetrathionate, which was causing precious metal containing ~1 g/L (0.005 M) tetrathionate (♦ kaolinite, ■ goethite, ▲ pyrite, ✖ activated
precipitation to pyrite. The preg-robbing of gold and silver by pyrite carbon) (conditions: 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , no Cu, pH 9.5).
 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22 19

Goethite 0.01M trithionate Goethite 0.01M trithionate

Concentration in solution
20 0.0140

Precious metal loss

18
0.0120
16

(mg/kggoethite)
14 0.0100

(mol/L)
Au
12 0.0080
Ag
10 Au
8 0.0060 trithionate - no sulfite
Ag
6 tetrathionate - no sulfite
0.0040 trithionate - with sulfite
4 tetrathionate - with sulfite
2 0.0020
0 0.0000
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time (hrs) Time (Hrs)

Pyrite 0.005M trithionate Pyrite 0.005M trithionate

Concentration in solution
300 0.0140
Precious metal loss

250 0.0120
(mg/kgpyrite)

0.0100 trithionate - no sulfite

200

(mol/L)
Au tetrathionate - no sulfite
Ag 0.0080 trithionate - sulfite
150 Au tetrathionate - sulfite
0.0060
Ag
100
0.0040
50 0.0020
0 0.0000
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time (hrs) Time (Hrs)

Fig. 11. Effect of sulfite addition on gold and silver, and polythionates in copper free ammoniacal thiosulfate solutions containing 0.01 M or 0.005 M trithionate in the presence of goethite
and pyrite (symbols: closed — no sulfite; open — sulfite) (Au 10 mg/L; 10 mg/L Ag; 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , no Cu, pH 9.5).

One half an hour after the addition of sulfite, 10% gold and silver were experimental period (closed symbols and solid line in the graph).
lost from solution as a precipitate (observed by the cloudiness of solu- Trithionate concentration appeared independent of sulfite and re-
tion). No further losses of precious metals were observed with time. A mained unchanged (polythionate graph).
sulfite-free ammoniacal thiosulfate solution containing trithionate Whilst sulfite can eliminate tetrathionate in solution thus pre-
showed gold and silver concentrations to be stable over the whole venting gold and silver precipitation by one mechanism, sulfite itself
can decompose and precipitate gold and silver from solution. Conse-
quently some control of the addition of sulfite to prevent tetrathionate
in solution and adequate aeration is required.
Precious metals in solution (mg/L)

Blank- Effect of sulfite on gold and silver loss

12.00 3.6. Recovery of preg robbed precious metals from mineral surfaces
10.00
To determine the gold preg robbing mechanisms and identify possi-
8.00 ble options for reversing gold and silver adsorption on mineral surfaces,
a four-stage elution process was carried out on minerals that were
6.00
bottle rolled in copper ammoniacal thiosulfate solutions containing pre-
4.00 Au cious metals. This elution method is a modification of that used by Feng
Addition of Ag and van Deventer (2001) in that resin was used as a method for remov-
2.00 sulfite Au - no sulfite ing adsorbed gold, silver and copper from mineral surfaces. In addition,
Ag - no sulfite
0.00 more dilute ammonia thiosulfate solutions were used. Furthermore
0.00 1.00 2.00 3.00 4.00 5.00 Feng and van Deventer (2001) only investigated gold in copper-free
Time (Hrs) ammoniacal thiosulfate solutions.
Polythionates The investigation was carried out by first bottle rolling mineral com-
2−
0.0140 ponents separately in 32 mg/L Cu, 0.4 M NH+ 4 /NH3, 0.05 M S2O3 ,
Polythionate concentration

0.0120 10 mg/L gold and 5 mg/L silver solution at pH 9.5 for 2 h under similar
conditions to those used in earlier experiments.
0.0100 After collecting the filtered solution the residue was then stirred
with water in a beaker for 0.5 h. The residual solids were then filtered
(mol/L)

0.0080 trithionate - no sulfite

tetrathionate - no sulfite and stirred with a 0.4 M NH+ 4 /NH3, 0.05 M S2O3
2−
solution for another
0.0060
trithionate - sulfite 0.5 h. A sub-sample was collected for analysis and 10 g/L of Amberlite
0.0040 tetrathionate - sulfite resin added to the rest of the slurry for a further 2 h. The resin was
then collected and the solution filtered from the solids. With the excep-
0.0020
tion of activated carbon, the residue was then leached with 500 mg/L of
0.0000 sodium cyanide at pH 10.0 for 0.5 h to remove any residual precious
0 1 2 3 4 5 6 metals and copper from solids. All filtered solutions and the final solids
Time (Hrs) were assayed for gold, silver and copper.
Fig. 12. Precious metal and polythionate concentrations in ammoniacal thiosulfate solu-
The residual gold, silver and copper on mineral surfaces after each
tions containing 0.01 M trithionate, with and without 0.005 M sulfite (conditions: treatment are shown in Fig. 13. For kaolinite and goethite, the water
10 mg/L Au, 10 mg/L Ag, 0.4 M NH+ 2−
4 /NH3; 0.05 M S2O3 , no Cu, pH 9.5). wash essentially eliminated 95% of the gold and silver residing after
20 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22

Residual gold on mineral surface Gold kaolin and none from quartz. They attributed the lack of elution of
80 gold to the viscosity of the slurry and only observed 90% of the gold elut-
70 pyrite ed following ammoniacal thiosulfate treatment. The presence of copper
60
quartz would undoubtedly compete and minimise gold and silver losses from
goethite
solution as described earlier in this paper. Consequently in these
50 act. Carbon
(mg/kg)

kaolinite
sesquioxide minerals any gold and silver that is absorbed on mineral
40 surfaces or is residual solution caught up in mineral grains is extractable.
30 For activated carbon, the water wash removed 66% of the gold and
20 55% of the silver entrapped. The ammonia thiosulfate wash and stronger
adsorption ability of resin were required to remove the balance of gold
10
and silver adsorbed on the carbon surface. No cyanide leach was carried
0 out as direct adsorption of residual gold as a cyanide complex on carbon
ll ter n in in ide id
. ro wa esi res res an sol would be expected.
B e fr ft Cy
O3 -b -a For pyrite, the water wash removed about 50% of the gold and 8% of
/S2 2O
3
2O
3
H4 /S /S the silver. Whilst ammonium thiosulfate solution was effective at re-
C u/N N H4 N H4 moving the majority of the silver, the rest of the gold remained on the
pyrite. Hence the behaviour of the majority of silver deposited in the
presence of pyrite is different to gold. Only with cyanide elution was
Silver
Residual silver on mineral surface

the gold and remaining silver removed from the pyrite surface. Evidence
30 of gold precipitation has been reported in the literature (e.g. Feng and
pyrite van Deventer, 2001) where gold adsorbs and precipitates as the metal
25 quartz at defect sites on the sulfide mineral surface. Pyrite also catalyses thio-
goethite
20 sulfate oxidation to produce tetrathionate and silver can catalyse and
(mg/kg)

act. Carbon
kaolinite precipitate along with gold as a mixed sulfide in the presence of
15 tetrathionate as described above. Unlike the other minerals, the removal
10 of silver during the ammoniacal thiosulfate and resin elution from pyrite
appears related to the copper removal.
5 Copper was not recovered from any mineral surfaces except for
quartz in the presence of a water wash and hence was strongly
0
adsorbed or precipitated. Around 35% was eluted in ammoniacal thio-
ll ter n in in ide id
. ro wa esi res res an sol sulfate solutions and a total of 70% recovered following the addition of
B e fr ft Cy
O3 -b -a resin. The copper recovery with both ammoniacal thiosulfate solution
/S2 2O
3
2O
3
H4 /S /S and resin can be attributed mainly to desorption reactions. However
Cu/N N H4 N H4
some redissolution of a copper sulfide precipitate with the ammoniacal
thiosulfate solution cannot be ruled out. Residual copper extracted by
cyanide for both goethite and pyrite (30%) is associated with precipita-
Residual copper on mineral surface

Copper
tion reaction.
250 The presence of releached copper in solution following ammoniacal
pyrite thiosulfate elution can potentially leach any silver sulfide precipitate
200 quartz
following a substitution leaching mechanism for silver sulfide by copper
goethite
act. Carbon
ions proposed in the literature (Deutsch and Dreisinger, 2013; Flett
150
kaolinite et al., 1983).
(mg/kg)

100
4. Conclusions

50
This study has investigated the effects of copper, silver and
polythionates on the stability of gold on selected oxide and sulfide
0
minerals, as well as activated carbon, in the ammoniacal thiosulfate
l ter
rol res
in
res
in esi
n ide sol
id
leaching system. It is concluded that gold extraction from natural ores
3B
. wa ef ft r an
b a Cy
/S 2O 3- 3- in copper ammoniacal thiosulfate solutions is lower than that obtained
H4 2O 2O
/N 4/S 4/S with cyanide partly as a result of the following sorption or precipitation
Cu NH NH reactions:
Fig. 13. Residual gold, silver and copper in minerals after water, ammoniacal thiosulfate,
and resin addition and cyanide treatments.
1/ Tetrathionate, a product formed from the degradation of thiosulfate
and presence of silver has detrimental roles in destabilising both
gold and silver thiosulfate complexes in ammoniacal thiosulfate
solutions. Whilst the adsorption of ammonia, thiosulfate and
trithionate is insignificant, the adsorption of tetrathionate on mineral
the initial auriferous copper ammoniacal thiosulfate treatment. The surfaces leads to significant gold and silver losses where the presence
water eluted gold and silver from these minerals can be attributed to of silver in solution catalyses the precipitation of gold and silver as a
entrapment around mineral particles rather than adsorption. The appli- sulfide. It was shown that:
cation of ammonium thiosulfate solution followed by resin removed the
remaining gold and silver. Therefore around less than 5% of the gold and • The addition of sulfite eliminates tetrathionate and prevents the
silver can be attributed to physical adsorption. As expected no entrain- gold and silver precipitation reaction.
ment of gold and silver was observed for quartz. In contrast Feng and • No significant loss of gold and silver occurs in the presence of
van Deventer (2001) observed only 10% of the gold removed from trithionate, which is relatively stable in solution.
 M.G. Aylmore et al. / Hydrometallurgy 143 (2014) 12–22
2/ Copper adsorption onto mineral surfaces inhibits gold and silver
losses to the mineral surfaces, even in the presence of tetrathionate.
The outcomes are that:
• The presence of copper either competes with gold and silver for
sites on the mineral surfaces thereby reducing the precious metal
loading as in the case for activated carbon and clay minerals, or
the copper maintains potentials near the mineral surfaces suffi-
ciently high to prevent precipitation of precious metals.
• The preferential adsorption of copper on some minerals
(goethite ≫ kaolinite NNN pyrite) would deplete copper from so-
lution and would undoubtedly reduce the effectiveness of copper
in the gold dissolution process.
3/ The presence of pyrite and activated carbon has significant effects on
the stability of gold and silver in ammoniacal thiosulfate solutions as
a result of both sorption and precipitation reactions, whereas ad-
sorption of gold and silver on the minerals goethite and kaolinite is
low (~2%). Variations in surface area, particle size, habit and crystal-
linity on minerals would undoubtedly impact the degree of
pregrobbing. It was shown that:
• In a copper ammoniacal thiosulfate solution with polythionate for-
mation kept at a minimum, gold and silver thiosulfate complexes
are largely stable in solution in the presence of kaolinite, goethite
and quartz, and any precious metals entrapped can be readily re-
moved in a water wash.
• Pyrite enhances the production of tetrathionate from thiosul-
fate through catalytic oxidation of thiosulfate to tetrathionate
by pyrite. Silver can catalyse and precipitate along with gold
as a mixed sulfide in the presence of tetrathionate. In addition
gold/silver adsorbs and precipitates as the metal at defect
sites on the sulfide mineral surface. Whilst silver lost on pyrite
can be recovered through re-dissolution in copper ammonia
thiosulfate solution and ion exchange resin, gold and some sil-
ver precipitated on pyrite surface are not recoverable without
treatment with cyanide.
• Carbon normally only constitutes a small component of a carbo-
naceous ore and the quantities of reactive carbon with similar
properties to activated carbon are even smaller. The precious
metals lost in the presence of activated carbon are associated
with direct adsorption on carbon in ammoniacal thiosulfate so-
lution. Gold and silver adsorbed on the carbon surface can be
displaced by ion exchange resin which has a stronger affinity
for precious metal complexes.
Remedies to combat pregrobbing are as follows:
• The concentration of tetrathionate during the thiosulfate leaching
process should be kept low or preferably eliminated to prevent
some gold and silver precipitating from solution.
• The addition of sulfite can be used to react and eliminate tetrathionate
and prevent pregrobbing providing there is adequate aeration.
• Possible remedies such as the addition of phosphate in small quanti-
ties to suppress the catalysis of pyrite may have benefits (Alonso-
Gomez and Lapidus, 2009; Zhang and Jeffrey, 2008).
• Regulating the concentration of copper in solution could reduce pre-
cious metal loss, although the activity of copper needs to be controlled
to prevent detrimental effects on reagent consumption and the build-
up of polythionates.
• Keeping thiosulfate degradation to minimum and favouring conditions
where trithionate forms during leaching rather than tetrathionate can
reduce preg robbing.
• Using a suitable ion exchange resin to recover gold and silver thiosul-
fate complexes from solution.
21
Acknowledgements
The first author acknowledges the help and support of the late David
Muir in the early development of the thiosulfate programme at CSIRO.
The authors wish to thank industry sponsors of the AMIRA Project
P420 Gold Processing Technology project for their support and permis-
sion to publish this paper. The authors gratefully acknowledge that
financial support was provided by the Australian Government through
the Cooperative Research Centres Program.
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