Aylmore & Muir 2001

Minerals Engineering 2001 14(2)
THIOSULFATE LEACHING OF GOLD A REVIEW
MARK G AYLMORE AND DAVID M MUIR

CSIRO Division of Minerals, PO Box 90 Bentley WA 6982, Australia.
E-mail: [email protected]
(Received 26 May 2000 ;accepted 20 October 2000)
ABSTRACT
The ammoniacal thiosulfate leaching process for gold and silver extraction has been reviewed in terms of
leaching mechanism, thermodynamics, thiosulfate stability, and gold recovery options. The application to
different ore types and process options have also been discussed.
The thiosulfate leaching process it catalysed by copper and has several advantages over the conventional
cyanidation process. Thiosulfate leaching can be considered a non-toxic process, the gold dissolution
rates can be faster than conventional cyanidation and, due to the decreased interference of foreign
cations, high gold recoveries can be obtained from the thiosulfate leaching of complex and carbonaceoustype ores. In addition, thiosulfate can be cheaper than cyanide.
The chemistry of the ammonia-thiosulfate - copper system is complicated due to the simultaneous
presence of complexing ligands such as ammonia and thiosulfate, the Cu(II)-Cu(I) redox couple and the
stability of thiosulfate in solution. However, by maintaining suitable concentrations of thiosulfate,
ammonia, copper and oxygen in the leach solution, and consequently, suitable Eh and pH conditions,
thiosulfate leaching can be made practical.
Generally the thiosulfate leaching conditions reported in the literature are severe with high reagent
consumption. Further investigations are required on leaching under low reagent concentrations over
extended periods where reagent consumption is low. For high grade ores or refractory sulfide ores where
some pretreatment processing is required to liberate gold, the in-situ generation of thiosulfate should be
investigated in more detail. This may lessen thiosulfate consumption and liberate more gold through the
oxidation of host sulfide minerals.
Cementation (or metal displacement), resins and to a limited extent, activated carbon can be used to
recovery gold from thiosulfate solutions. The use of resins to recover gold from solution appears to show
some promise, however more work is required to develop suitable elution and recovery methods, and
greater selectivity over copper.
While difficulties remain to be overcome, thiosulfate leaching has considerable potential as an effective
and less hazardous procedure for gold and silver extraction from auriferous ores.
Keywords
Gold ores, Precious metal ores, Hydrometallurgy, Leaching, Extractive metallurgy
INTRODUCTION
Considerable attention has been given to alternatives to the use of the conventional cyanidation/carbon in pulp
process to extract gold from gold ores. Interest in the use of non-cyanide methods for the dissolution of gold
arises from concerns regarding the toxicity of cyanide and the inability of cyanide solution to effectively leach
carbonaceous or complex ores. Sparrow and Woodcock (1995) have provided a summary review on non-cyanide
lixiviants for leaching of gold.
In addition to cyanide being hazardous, metal cyanide species derived from cyanide leaching (e.g. copper
cyanide) and other cyanide species end up in the tailings dam. This can lead to environmental problems where
cyanide pollutants reach the water table and cause destruction of animal life. This is a major problem where
residential areas are developing closer to the plant sites.
An alternative approach is to use thiosulfate to leach gold from ores. Thiosulfate is considered a non-toxic
alternative to cyanide and can leach gold faster than cyanide.
In the conventional cyanide process, the recovery of gold and silver from ores is hindered by a variety of metal
impurities like copper, arsenic, antimony, zinc and nickel, since these consume either cyanide or oxygen.
Leaching by thiosulfate decreases interference from these foreign cations. In fact the presence of copper in the
ore can be utilised directly in the leaching process.
High consumption of reagents and the lack of a cheap process for recovering gold have made thiosulfate leaching
uneconomical to date, in comparison with cyanide leaching. Consequently the process has not been widely used
on a commercial scale.
The following is a review of the ammoniacal thiosulfate leaching process. It covers the leaching mechanism,
thermodynamics, thiosulfate stability, and possible gold recovery processes. The application to different ore
types is also discussed. The discussion is largely restricted to ambient leaching conditions with limited reference
made to elevated temperature and pressure conditions where appropriate.
Development history
The recovery of precious metals using thiosulfate was first proposed early in the 1900s (White, 1900). In a
process known as the Von Patera process, gold and silver ores were first subjected to a chloridising roast and
then leached with thiosulfate. Silver-rich sulfide ores in South America were leached for many years prior to
World War II with thiosulfate after a chloridising roast (Flett et al., 1983). A similar treatment was also carried
out at the LaColorado Mine at Sonora in Mexico (Von Michaelis, 1987). However, it was not until the late
1970s that an application to recover precious metals from copper-bearing metal sulfides concentrates and
pressure leach residues was developed employing ammonium thiosulfate and patented by Berezowsky and Kerry
(Hiskey and Atluri, 1988). During this period, studies were also carried out in the former Soviet Union (e.g. TerArakeyan et al., 1984). It was demonstrated that copper ions in solution could speed up the dissolution of gold.
Early research tended to concentrate on leaching at high temperatures and pressures to prevent copper sulfide and
sulfur layers from forming on gold particles thus preventing their leaching.
Berezowsky and Sefton (1979) revived interest in thiosulfate leaching by developing an atmospheric ammoniacal
thiosulfate leach process to recover gold and silver from residues of the ammonia oxidation leaching of sulfide
copper concentrates
More recent work has concentrated on understanding and improving the atmospheric ammoniacal thiosulfate
leach process. Extensive studies on the kinetics and mechanism of gold dissolution by thiosulfate have been
carried out by the Chinese and Japanese (e.g. Tozawa et al., 1981; Jiang et al., 1993).
Qian and Jiexue (1989) reported that a large plant had been built in Mexico using thiosulfate based on the Kerley
(1981, 1983) patents but could not be run successfully. Although these authors do not provide a reference to the
Mexican operation, they state that a subsequent patent by Perez (1987) claimed that the plant would have been
successful if run at pH 10.0-10.5 rather than pH 8 to avoid the problem observed with dissolution of iron from
milling media.
Heap leaching of carbonaceous preg-robbing ores using thiosulfate, has been the only industrial application in
recent years established by Newmont Gold Co. (Wan et al., 1994). Unlike gold cyanide, gold thiosulfate does not
adsorb on carbonaceous material and much higher gold recoveries can be achieved.
Conventional uses of thiosulfate

Its major industrial uses include the removal of excess chlorine in paper and textile bleaching, the preparation of
matches, the preservation of soap and as a chemical reagent.
Thiosulfate can be used as an antidote to cyanide and arsenic poisoning. It has been used to treat parasitic skin
disorders such as ringworm (Meyer, 1977). Ammonium thiosulfate has been used as a fertilizer for soils low in
sulfur for many decades. Environmentally it has distinct advantages over cyanide due to its low toxicity and
beneficial nature as a fertilizer. High concentrations of ammonium thiosulfate into water courses would, however
exasperate the common problem of excess nutrients and algae growth in rivers and lakes.
Although the price varies with location, sodium cyanide costs about US$2.00 per kilogram, whereas ammonium
thiosulfate costs about US$0.10 per kilogram. Therefore, providing reagent consumption is not high, thiosulfate
can be cheaper than cyanide.
GOLD DISSOLUTION IN THIOSULFATE LEACHING UNDER AMBIENT CONDITIONS
The chemistry of the ammonia-thiosulfate - copper system is complicated due to the simultaneous presence of
complexing ligands such as ammonia and thiosulfate, the Cu(II)-Cu(I) redox couple and the possibility of
oxidative decomposition reactions of thiosulfate involving the formation of tetrathionate and other additional
sulfur compounds (Umetsu and Tosawa, 1972; Kerley, 1981).
For clarity, the different components in the thiosulfate leaching system are discussed separately.
Thiosulfate leaching
In alkaline or near neutral solution of thiosulfate, gold dissolves slowly in the presence of a mild oxidant (White,
1905). The dissolution of the gold can be described as follows where oxygen is the oxidant and thiosulfate the
ligand.
4 Au + 8 S2O32- + O2 + 2H2O = 4[Au(S2O3)2]3- + 4 OHTwo thiosulfate complexes of gold are known to form and these are Au(S 2O3)- and Au(S2O3)23- with the latter
complex being the most stable (Johnson and Davis 1973).
Alkaline solutions must be used to prevent the decomposition of thiosulfate at low pH. This has the added
advantage of minimising the solubility of impurities, in particular iron compounds as discussed later. Once
formed, the thiosulfate complex is extremely stable. The stability constants for thiosulfate in comparison with
various other gold complexes are shown in Table 1.
TABLE 1 Stability constants for gold complexes
Gold species
Au(CN)2Au(SCN)2Au(SCN)4AuCl4Au(NH3)2+
Stability Log K*
Reference
38.3
Smith and Martell, 1989
16.98
10
25.6
Wang 1992
26
Wang 1992
13
Hancock et al., 1974&
3Au(S2O3)2
26.5
IUPAC, 1993
28
Sullivan and Kohl, 1997
&
*Temperature 25C, calculated from linear free energy relationship; Ionic strength = 1.0
Effect of ammonia
In the absence of ammonia, gold dissolution by thiosulfate is passivated by the build up of sulfur coatings as a
result of decomposition of thiosulfate on the gold surface (Pedraza et al., 1988; Jiang et al., 1993; Chen et al.,
1993). It is suggested that ammonia prevents gold passivation by being preferentially adsorbed on gold surfaces
over thiosulfate thus bringing gold into solution as an ammine complex (Jiang et al., 1993; Chen et al., 1996).

Ammonia reacts with gold ions forming gold ammonia complex ions that are then substituted by thiosulfate ions
(Chen et al., 1993).
The ammine complex is converted to thiosulfate complex as shown below
Au(NH3)2+ + 2S2O32- = Au(S2O3)23- + 2NH3
Although the dissolution of gold is thermodynamically feasible in ammoniacal solutions, kinetic experiments
have shown that gold is essentially not leached in ammonical solutions at room temperature (Meng and Han,
1993). Gold dissolution in ammonia solutions is observed only at temperatures above 80C.
The major role of ammonia in the thiosulfate system is to stabilise copper (II) as discussed below. However, the
presence of ammonia hinders the dissolution of iron oxides, silica, silicates and carbonates, the most common
gangue minerals found in gold bearing ores (Abbruzzese et al., 1995).
Effect of copper
The catalytic action of copper ions in promoting gold dissolution in thiosulfate solutions was first reported by
Tyurin and Kakowsky. (1960). Copper ions in solution can speed up the dissolution of gold by 18 to 20 times
(Ter-Arakeyan et al., 1984). In ammoniacal solutions and at temperatures below 60C, Cu(NH3)42+ is reported to
form (Tozawa et al., 1981). Gold dissolution can occur by using copper as the oxidant, rather than oxygen, as
follows
Au + Cu(NH3)42+ = Au(NH3)2+ + Cu(NH3)2+
The redox equilibrium between the cuprous-cupric couple in ammoniacal solution and thiosulfate is represented
by the following reaction (Garrel et al., 1965; Abbruzzese et al., 1995; Wan, 1997)
2Cu(S2O3)35- + 8NH3 + 1/2O2 + H2O = 2Cu(NH3)42+ + 2OH- + 6S2O32The role of copper(II) ions in the oxidation of metallic gold to aurous Au+ ion is shown in the following reaction
Au + 5S2O32- + Cu(NH3)42+ -> Au(S2O3) 23- + 4NH3 + Cu(S2O3)35The reported increase in dissolution of gold in copper thiosulfate solutions containing ammonia has been
attributed to the formation of copper (II) ammine complexes. This suggestion is supported by electrochemical
studies carried out by Chen et al. (1996). The copper catalytic process is described in more detail later.
In addition to the above processes, some thiosulfate degradation to tetrathionate occurs. The oxidation reaction,
which is promoted by copper (II) ion, is shown as follows
2Cu(NH3)42+ + 8S2O32- = 2Cu(S2O3)35- + S4O62- + 8NH3
Consequently, the concentration of copper (II) ion present in the leaching solution is an important factor in
thiosulfate stability and reagent management. The reduction of Cu (II) by thiosulfate ions is extremely rapid in a
pure aqueous solution but in the presence of ammonia the reduction reaction is slower and is dependent on the
ammonia concentration.
Effect of oxygen
Oxygen or some other oxidant is required to convert copper (I) to copper (II) for further gold leaching.
The most detailed work on the role of oxygen in ammoniacal thiosulfate systems containing copper (II) was
carried out by Byerley et al., (1973ab,1975). Depending upon the amount of oxygen dissolved in solution, rapid
oxidation of Cu(I) to Cu(II) occurs with some oxidation of thiosulfate to give sulfate and trithionate.
The oxidation of thiosulfate in aqueous solution by molecular oxygen, under ambient conditions of temperature
and pressure, is known to be extremely slow and only occurs when copper (II) ions and ammonia are present
(Naito et al., 1970).
In the absence of oxygen and under alkaline conditions, copper (II) ions in aqueous ammonia solution oxidise
thiosulfate ions initially to tetrathionate ions, the latter then undergoes a disproportionation reaction to yield
trithionate and thiosulfate ions. This reaction is catalysed by the presence of thiosulfate ions.
At low potentials where oxidants are deficient, in stagnant solutions, or in solutions containing high copper, the
decomposition of thiosulfate leads to the precipitation of black copper sulfides. Hence the precipitation of copper
sulfides is related to the availability of oxygen in the system. The limited solubility of oxygen in solutions and
the slow reduction at the gold surface makes the use of oxygen without the copper catalytic reaction very slow,
resulting in low gold dissolution.
THERMODYNAMICS OF GOLD DISSOLUTION

Thermodynamic calculations can help to clarify the observed experimental processes described above.
Zipperian et al (1988) constructed a series of Eh-pH diagrams to identify the predominant species that exist in
metal-ammonia-thiosulfate-water systems for high reagent concentrations (>1M). For low reagent
concentrations, Wang (1992) assumed the presence of AuNH 3S2O3- ions in constructing Eh-pH diagrams
although the existence of AuNH3S2O3- has not been confirmed experimentally. However at low reagent
concentrations it could be expected since the stability constants of Au(NH 3)2+ and Au(S2O3)23- complexes coould
be similar (see Table1).
The Eh-pH and speciation diagrams for ammoniacal thiosulfate and copper system, for high and low
concentrations of ammonia and thiosulfate are shown in the following Figures. The diagrams represent the
typical range of leaching conditions used. Construction of Eh-pH and speciation diagrams was carried out using
Outokumpu HSC Chemistry for Windows (Roine, 1994) and MINEQL+ software (Schecher and McAvoy,
1998). Thermodynamic data was obtained from Smith et al (1998) and is listed in Table 2.
TABLE 2 Free energies of formation (kJ/mol) for copper ammonical thiosulfate species
Species
S
S5O62-(a)
S3O62-(a)
S2O62-(a)
SO32-(a)
HS2O3-(a)
H2S(a)
HS-(a)
H2SO3(a)
H2S2O3(a)
H2S2O4(a)
HSO3-(a)
HS2O4-(a)
S2-(a)
S22-(a)
S32-(a)
S42-(a)
S52-(a)
S2O32-(a)
S2O42-(a)
S2O82-(a)
S4O62-(a)
NH3(a)
NH4+(a)
G298
(kJ/mol)
0
-956.0
-958.0
-966.0
-486.5
-541.8
-27.3
12.6
-537.9
-543.5
-436.3
-527.7
-434.2
91.9
79.7
73.8
69.4
66.1
-532.2
-600.6
-1115.0
-1040.4
-26.7
-79.5
Ag
AgO
AgOH
Ag2O3
Ag2O
Ag2S
Ag2+(a)
Ag+(a)
AgO-(a)
Ag(S2O3)35-(a)
Ag(S2O3)23-(a)
Ag(S2O3) -(a)
Ag(NH3) +(a)
Ag(NH3)2+(a)
G298
(kJ/mol)
0
10.9
-92.0
87.0
-10.8
-40.5
268.2
77.2
-23.0
-1598.3
-1058.6
-506.3
31.8
-17.5
Au
AuO2
Au(OH)3
Au2O3
Au+(a)
Au3+(a)
H3AuO3(a)
Au(S2O3)23-(a)
Au(NH3)43+(a)
Au(NH3)2+(a)
AuO33-(a)
HAuO32-(a)
H2AuO32-(a)
0.0
200.8
-290.0
163.2
163.2
433.5
-258.6
-1050.2
64.4
-41.4 or 35.7
-24.3
-115.5
-191.6
Species
Species
Cu
CuO
Cu2O
Cu(OH)2
CuS
Cu2S
Cu2+(a)
Cu+(a)
Cu(S2O3)35-(a)
Cu(S2O3)23-(a)
Cu(S2O3) -(a)
Cu(NH3) +(a)
Cu(NH3) 2+(a)
Cu(NH3)22+(a)
Cu(NH3)32+(a)
Cu(NH3)42+(a)
CuO22-(a)
HCuO2-(a)
G298
(kJ/mol)
0
-127.194
-146.356
-356.895
-48.953
-86.1904
64.978
50.208
-1624.65
-1084.07
-540.991
-10.293
14.477
-32.259
-73.212
-112.968
-181.167
-256.981
Increase in dissolution of gold in copper thiosulfate solutions containing ammonia is attributed to the
stabilisation of the oxidant Cu(II) by ammonia by forming copper (II) ammine complexes. Therefore the
conditions need to be chosen where both copper (II) ammine complex and gold dissolution occur.
It is clear in both Eh-pH conditions illustrated (Figures 1 and 2) that high pH values should be avoided since
copper will be removed from the leach solution as oxides. In addition, potential influences the equilibrium
between copper (I) and copper (II) ions. At high potentials ammonia copper (II) complexes exist, whereas at low
potentials copper (I) thiosulfate complexes exist.

Decreasing the ammonia, thiosulfate and copper (II) concentrations significantly narrows the region of stability
of Cu(NH3)42+ and Cu(S2O3)35-, and expands the stability region of CuO, Cu2O and Cu2S.
As the concentrations of thiosulfate, copper and ammonia change the stability regions of gold species change
slightly. It should be noted that the pH values change significantly, with change in the concentration of either
thiosulfate or ammonia. If the potentials in a copper - ammoniacal thiosulfate system are too low, gold remains
undissolved over the whole pH range from 0-14. In addition, copper in solution will precipitate out as a sulfide.
Eh (Volts)
2.0
Cu+2 (aq)
1.5
CuO
Cu(NH3)4+2 (aq)
1.0
CuO
0.5
Cu(S2O3)3-5 (aq)
0.0
Cu2O
CuS
-0.5
Cu2S
-1.0
Cu
-1.5
-2.0
4
10
12
14
pH
(a)
Eh (Volts)
2.0
Au(NH3)4+3 (aq)
1.5
1.0
{Au(NH3)2+(aq)}
Au(S2O3)2-3 (aq)
0.5
0.0
-0.5
Au
-1.0
-1.5
-2.0
4
10
12
14
pH
(b)
Fig 1 Eh-pH diagram at high reagent concentrations for (a) Cu-NH3-S2O32- system and (b) Au-NH3-S2O32system (conditions: 5x10-4M Au; 1MS2O32-;1M NH3/NH4+, 0.05M Cu2+). The dotted line marks the
stability region of Au(NH3)2+ where the stability constant log K= 26.0 (see Table II). The shaded region
is the predominance area for Au(S2O3)23- where stability constants are based on linear free energy
calculations (Hancock et al., 1974).
Eh (Volts)
2.0
Cu(NH3)4+2 (aq)
1.5
Cu+2 (aq)
CuO
1.0
CuO
0.5
Cu(S2O3)3-5 (aq)
0.0
CuS
Cu2O
Cu2S
-0.5
-1.0
Cu
-1.5
-2.0
4
10
12
14
pH
(a)
Eh (Volts)
2.0
Au(NH3)4+3 (aq)
1.5
AuO2
1.0
Au(S2O3)2-3 (aq)
0.5
{Au(NH3)2+(aq)}
0.0
-0.5
Au
-1.0
-1.5
-2.0
4
10
12
14
pH
(b)
Fig 2 Eh-pH diagram at low reagent concentrations for (a) Cu-NH3-S2O32- system and (b) Au-NH3-S2O32- system
(conditions: 5x10-4M Au; 0.1M S2O32-; 0.1M NH3/NH4+, 5x10-4M Cu2+). The dotted line marks the
stability region of Au(NH3)2+ where the stability constant log K= 26.0 (see Table II). The shaded region
is the predominance area for Au(S2O3)23- where stability constants are based on linear free energy
calculations (Hancock et al., 1974).
Eh-pH diagrams of Au-NH3 - S systems (Figures 1b and 2b) and species distribution diagrams (Figure 3) in
aqueous solution indicate that under certain conditions gold could be present in solution as [Au(NH 3)2]+ rather
than as [Au(S2O3)2]3- (Zipperian et al., 1988). The gold (I) thiosulfate complex is the most stable species in the
leaching system up to pH 8.5 or below 0.01M NH 4+. Above this pH, when NH4+ converts to NH3 and when the
ammonia concentration exceeds 0.1M, the predominate gold compound is gold (I) diammine complex (Zipperian
et al., 1988) (designated (a) in Figure 3).
5.00E-05
Au(S2O3)23-
Au(NH3)2+
Concentration (M)
4.00E-05
3.00E-05
(b)
(a)
2.00E-05
1.00E-05
0.00E+00
-3
-2
-1
Log [NH3] (M)
Fig 3 Distribution of gold species at different ammonia concentrations (0.1M S 2O32-, 5x10-5M Au, pH 9.5,
Eh=0.250V) with stability constant for Au(NH3)2+ at (a) Log K = 28 and (b) log K = 13.
However measurements at pH >9 have shown that gold rest potentials change with thiosulfate concentration
rather than with ammonia concentration (Wan, 1997). This suggests that the predominant gold species is
Au(S2O3)23- rather than Au(NH3)2+. The variation between thermodynamics and electrochemical studies may be
attributed to the high activation energy for Au(NH 3)2+ formation (Meng and Han, 1993). In addition, predicted
stability constants based on linear free energy relationship between silver (I) and gold (I) (Hancock et al., 1974)
derive a lower stability constant for Au(NH3)2+ than that for Au(S2O3)23- . Based on these calculations a much
higher concentration of ammonia is required to stabilised Au(NH 3)2+ (designated (b) in Figure 3) and Au(S2O3)23exists over the whole pH range under conditions examined in Figures 1b and 2b (shaded area).
Eh-pH diagrams can be used to show the predominant species under different potentials and pH conditions.
However, speciation diagrams are required to characterise the distribution of various Cu-NH3-S2O32- species coexisting in solution.
The copper species distributions for high and low reagent concentrations at fixed Eh are shown in Figures 4a and
b respectively. It can be seen that to leach gold under low reagent conditions only a narrow pH region around pH
9.5 to 10.0 exists where copper ammonia complex is stable without the precipitation of copper (II) oxide,
tenorite. At high reagent concentrations a broader pH range is available.
Increasing the potential (e.g. with O2) but keeping all reagent concentrations constant results in the reduction in
Cu(S2O3)35- and an increase in Cu(NH3)42+ in the solution (Figures 5a and b). At low NH 3-S2O32--Cu2+
concentrations in solution, other copper ammonia and thiosulfate complexes are stable which can have a
significant effect on thiosulfate stability and leaching properties. Byerley et al., (1973) reported the role of the
10

triammine copper (II) complex rather than the tetraammine copper (II) complex in the oxidation of thiosulfate to
tetrathionate. In addition, only a small Eh range is available for maintaining copper ammonia complex in
solution.
Increasing total ammonia concentration but keeping the other reagent concentrations, pH and Eh constant,
increases the stability region of the Cu(NH3)42+ complex (6a and b), whereas increasing the thiosulfate
concentration ions increases the stability region of the Cu(S 2O3)35- complex (Figures 7a and b).
Under the conditions used, copper concentration has a much more pronounced effect on the stability regions of
copper species where Cu(S2O3)35-, becomes more stable over the Cu(NH3)42+ complex for both high and low
NH3-S2O32--Cu2+ concentrations in solution (Figures 8a and b). In addition, precipitation of tenorite occurs with
increased copper concentration in solution. It would appear that a higher ammonia to thiosulfate concentration
would be required to achieve a higher Cu(NH3)42+ concentration in solution over Cu(S2O3)35- (see Figure 6).
However, high Cu(NH3)42+ concentrations in solution will also result in higher losses of thiosulfate through its
conversion to tetrathionate.
It has been reported that significantly increasing the copper concentration can result in the precipitation of the
mixed copper(II)-copper(I) species Na[Cu(NH3)4. Cu(S2O3)2]. The addition of copper sulfate can result in the
precipitation of copper (I) thiosulfate and oxidation of thiosulfate to tetrathionate (Flett et al., 1983).
No inhibition of gold dissolution in thiosulfate solutions by excessive ammonia (0-2M) occurs in the absence of
copper (Chen et al., 1996). This precludes the widely held assumption that hydroxide ions in high concentration
that are produced by excessive ammonia, inhibit gold dissolution.
Regeneration of the copper (II) to sustain the catalytic reaction is an important feature of the leaching reaction
and so the concentration ratio of ammonia to thiosulfate has to be maintained so that copper can easily transfer
between the Cu(II) and Cu(I) states. For effective gold dissolution at high reagent concentrations, Zipperian et
al., (1988) determined that an oxidation potential of 150-200mV with reference to standard hydrogen electrode
(SHE) is required at pH 10. Eh-pH diagrams constructed here suggest a higher oxidation potential of 250mV is
required. At lower reagent concentrations the optimum Eh appears the same, but the pH range is smaller.
11
5.00E-02
Cu(S2O3)35-
Tenorite
Concentration (M)
4.00E-02
Cu(NH3)42+
3.00E-02
Cu(S2O3)
2.00E-02
1.00E-02
Cu(S2O3)23-
Cu(OH)4-
0.00E+00
0
10
12
14
pH
Fig 4a Distribution of copper species at different pH conditions for high reagent concentrations (1M S 2O32-, 1M
NH3, 0.05M Cu, Eh=0.250V).
5.00E-04
Cu(S2O3)-
Tenorite
Concentration (M)
4.00E-04
Cu(S2O3)35-
3.00E-04
2.00E-04
Cu(S2O3)231.00E-04
Cu(OH)4-
Cu(NH3)42+
Cu(NH3)32+
Cu(OH)3-
0.00E+00
0
10
12
14
pH
Fig 4b Distribution of copper species at different pH conditions for low reagent concentrations (0.1M S 2O32-,
0.1M NH3, 5x10-4M Cu, Eh=0.250V).
12
5.00E-02
Cu(NH3)42+
Cu(S2O3)35-
Concentration (M)
4.00E-02
3.00E-02
2.00E-02
1.00E-02
Cu(S2O3)23-
Cu(NH3)32+
0.00E+00
0
0.1
0.2
0.3
0.4
0.5
0.6
Eh (V)
Fig 5a Distribution of copper species at different Eh conditions for high reagent concentrations (1M S2O32-, 1M
NH3, 0.05M Cu, pH=10.0).
5.00E-04
Tenorite
4.00E-04
Concentration (M)
Cu(S2O3)353.00E-04
Cu(NH3)42+
2.00E-04
Cu(S2O3)231.00E-04
Cu(NH3)32+
Cu(S2O3)0.00E+00
0
0.1
0.2
0.3
0.4
0.5
0.6
Eh (V)
Fig 5b Distribution of copper species at different Eh conditions for low reagent concentrations (0.1M S 2O32-,
0.1M NH3, 5x10-4M Cu, pH 10.0).
13
5.00E-02
Cu(NH3)42+
Cu(S2O3)35-
Concentration (M)
4.00E-02
3.00E-02
2.00E-02
1.00E-02
Cu(NH3)32+
Cu(S2O3)23-
0.00E+00
0
Total NH3 conc (M)
Fig 6a Distribution of copper species at different NH3 conditions for high reagent concentrations (1M S2O32-,
0.05M Cu, pH 10.0, Eh=0.250V). At pH 10.0 less than half the total ammonia is present as ammonium.
5.00E-04
Cu(NH3)42+
4.00E-04
Concentration (M)
Cu(S2O3)353.00E-04
2.00E-04
Cu(S2O3)23-
Cu(NH3)2+
1.00E-04
Cu(S2O3)Cu(NH3)32+
0.00E+00
0
0.2
0.4
0.6
0.8
Total NH3 conc (M)
Fig 6b Distribution of copper species at different NH 3 conditions for low reagent concentrations (0.1M S2O32-,
5x10-4M Cu, pH 10.0, Eh=0.250V). At pH 10.0 less than half the total ammonia is present as
ammonium.
14
5.00E-02
Cu(NH3)42+
Cu(S2O3)35-
Concentration (M)
4.00E-02
3.00E-02
2.00E-02
Cu(NH3)32+
1.00E-02
Cu(S2O3)230.00E+00
0
S2O32-
conc (M)
Fig 7a Distribution of copper species at different S2O32-conditions for high reagent concentrations (1M NH3,
0.05M Cu, pH=10.0, Eh=0.250V).
5.00E-04
Tenorite
Cu(S2O3)35-
Concentration (M)
4.00E-04
3.00E-04
2.00E-04
Cu(S2O3)23Cu(NH3)42+
Cu(NH3)32+
1.00E-04
Cu(S2O3)-
0.00E+00
0
0.2
0.4
S2O32-
0.6
0.8
conc (M)
Fig 7b Distribution of copper species at different S 2O32-conditions for low reagent concentrations (0.1M NH 3,
5x10-4M Cu, pH 10.0, Eh=0.250V).
15
0.80
0.70
Tenorite
Concentration (M)
0.60
0.50
0.40
0.30
0.20
Cu(NH3)42+
Cu(S2O3)35-
0.10
Cu(NH3)22+
Cu(S2O3)230.00
0
0.2
0.4
0.6
2+
Cu
0.8
Conc (M)
Fig 8a Distribution of copper species at different Cu2+ conditions for high reagent concentrations (1M S2O32-,
1M NH3, pH 10.0, Eh=0.250V).
0.0010
0.0009
Tenorite
Concentration (M)
0.0008
0.0007
Cu(S2O3)35-
0.0006
0.0005
0.0004
0.0003
Cu(S2O3)23-
0.0002
Cu(S2O3)2-
Cu(NH3)42+
0.0001
Cu(NH3)32+
0.0000
0
0.002
0.004
0.006
2+
Cu
0.008
0.01
Conc (M)
Fig 8b Distribution of copper species at different Cu2+ conditions for low reagent concentrations (0.1M S2O32-,
0.1M NH3, pH 10.0, Eh=0.250V).
16
THE ELECTROCHEMICAL-CATALYTIC MECHANISM OF GOLD LEACHING

The electrochemical-catalytic mechanism that is proposed to identify the leaching of gold with ammoniacal
thiosulfate is illustrated in Figure 9.
S2O32Gold surface
Anodic area
Au(S2O3)23-
Au=Au + e
Au+ + 2S2O32- = Au(S2O3)23-
Au
Cu(NH3)42 + S2O32e
+ O2
OH-
Cu(S2O3)35- + NH3
Cathodic area
Cu(NH3)42+ + e = Cu(NH3)2+ + 2NH3
Cu(NH3)2+ + 3S2O32- = Cu(S2O3)35- + 2NH3
+ S2O32Cu(NH3)2+ + 2NH3
2Cu(NH3)42+ + 8S2O32- = 2Cu(S2O3)35- + S4O62- + 8NH3
Fig 9 The model of electrochemical catalytic mechanism of ammoniacal thiosulfate leaching of gold.
Thiosulfate ions react with Au+ ions on the anodic surface of gold and enter the solution to form Au(S2O3)23-. The
Cu(NH3)42+ present in solution acquires electrons on the cathodic portion of the gold surface and is directly
reduced to Cu(NH3)2+. In the presence of S2O32-, Cu(NH3)2+ converts to Cu(S2O3)35- ions. The Cu(S2O3)35- species
in solution is then oxidised into Cu(NH3)42+ with oxygen (Wan, 1997). Likewise, the Cu(NH3)2+ species, if
present in solution, is oxidised into Cu(NH3)42+ with oxygen (Jiang et al., 1993). The predominant cathodic
reaction will depend upon the relative concentrations of the species in solution.
The mechanism is further complicated by the oxidation of some thiosulfate to tetrathionate. In the absence of
oxygen and pH>10, copper (II) ions in aqueous ammonia solution oxidise thiosulfate ions to tetrathionate ions.
Over a extended period of time, tetrathionate can further disproportionate to yield trithionate and thiosulfate ions.
The suggested mechanism from kinetic studies of the reaction indicates that substitution of thiosulfate ion into
the co-ordination sphere of ammine copper (II) complex occurs. At pH >10 , the copper(II) ammine species are
reported as existing in equilibrium with significant concentrations of hydroxo-species. Therefore, in addition to
tetra-ammine, some tri-ammine copper (II) species co-exist. An electron-transfer from the thiosulfate to the
copper (II) ion, occurring in the intermediate tri-ammine copper(II)-thiosulfate complex, gives rise to copper (I)
and S2O32- ions, which in turn dimerise to tetrathionate ions (Byerley et al., 1973).
17

The formation of tetrathionate from thiosulfate ions using Cu(NH 3)42+ or Cu(NH3)32+ as oxidants can be
demonstrated by examining the relevant redox potentials for the systems. The calculated redox potentials from
G and stability constants are shown in Table 3.
TABLE 3 Redox potentials for copper ammonia and thiosulfate complexes
Couple
Cu(NH3)42+/ Cu(S2O3)35Cu(NH3)42+/ Cu(S2O3)23Cu(NH3)32+/ Cu(S2O3)35Cu(NH3)32+/ Cu(S2O3)23S2O32/S4O62-
Redox potential (V)

0.22
0.14
0.36
0.27
0.12
It can be seen that redox potentials both for Cu(NH3)42+/ Cu(S2O3)35- and Cu(NH3)42+/ Cu(S2O3)25- are greater
than that for S2O32/S4O62 .
In the presence of oxygen, the Eh rises and rapid oxidation of Cu(I) to Cu(II) occurs with further oxidation of
thiosulfate to sulfate and trithionate, depending upon the amount of oxygen dissolved in solution. Detailed
kinetic studies undertaken by Byerley et al, (1973) suggested a mechanism in which O2 and thiosulfate become
associated with ammine-thiosulfato-copper (II) species and form sulfate and trithionate ions in solution. In this
role O2 assists in electron transfer between S2O32- and Cu(II).
Clearly only sufficient O2 necessary to oxidise Cu(I) to Cu(II) is required to prevent the significant loss of
thiosulfate from solution.
Regeneration of the copper (II) to sustain the catalytic reaction is an important feature of the leaching reaction
and so the concentration ratio of ammonia to thiosulfate has to be maintained.
In principal, ammonia and cupric ions are not consumed and the reagent replenishment is limited to thiosulfate.
Loss of some ammonia from the leaching solution is unavoidable but can be reduced providing the pH and
aeration are properly maintained.
Tao et al (1993) and Michel and Frenay (1996) have evaluated by electrochemical means, a similar mechanism
of gold oxidation and cupric complex reduction process as described above.
Gong et al (1993) divided the leaching of gold in a copper-ammonia-thiosulfate system into a two stage reaction.
The first stage is controlled by the interface reaction as described above. The second is a diffusion process of
reaction through a layer of decomposed products. They suggested that the kinetics of leaching gold from an
auriferous pyrite concentrate could be controlled by a corrosion reaction of ammonia-thiosulfate-copper system
on pyrite. However no other workers have reported a corrosion process
18
DISSOLUTION OF SILVER BY THIOSULFATE LEACHING

The Eh-pH diagrams for the ammoniacal thiosulfate and silver system, for high and low concentrations of
ammonia and thiosulfate are shown in Figure 10. Silver combines preferentially with thiosulfate, while silver
ammonia complexes are only stable at low thiosulfate concentrations (Figure 11). Flett et al. (1983) observed
better recovery of silver in the absence of ammonia. Zipperian et al (1988) observed that at higher reagent
concentrations, the concentration of both ammonia and copper (II) in solution affected silver extraction. The EhpH diagram indicates similar potentials are required to leach silver to that required for gold dissolution. If the
potential is too low, silver will remain undissolved or precipitates as a silver sulfide (Ag 2S) over the whole pH
range from 0-14. At high potentials and pH values, silver oxide (Ag2O3) precipitates.
The leaching mechanism for silver metal by ammoniacal thiosulfate solutions with copper is similar to that of
gold where an oxidant is necessary (Lukomskaya et al., 1984; Zipperian et al., 1988). However the leaching
mechanism of silver sulfide is reported to occur by the substitution of copper for silver in the sulfide matrix with
silver complexing with thiosulfate in solution as follows (Briones and Lapidus, 1998):
2Cu+ + Ag2S 2Ag+ + Cu2S (chalcocite) + 4S2O32- 2Ag(S2O3)23Cu2+ + Ag2S 2Ag+ + CuS (covellite) + 4S2O32- 2Ag(S2O3)23Silver leaching was found to increase with increasing copper and thiosulfate concentrations, and to decrease with
increments of ammonia concentration. This reaction is also controlled by optimising the ammonia/thiosulfate
ratio.
The presence of silver also increases the dissolution of gold at least 6 times more than that of pure gold reacting
with thiosulfate solution (Webster, 1986). In addition, electrum alloys (64 at% Ag) dissolve faster than pure gold.
In terms of leaching kinetics, gold leaches faster than silver. This is most probably associated with the thiosulfate
leaching mechanism being different. In addition, Zipperian et al. (1988) reported silver extraction more sensitive
to changes in reagent concentration than gold extraction.
19

Eh (Volts)
2.0
1.8
Ag2O3
1.6
Ag(S2O3)23-(aq)
1.4
1.2
1.0
Ag(S2O3)35(aq)
0.8
0.6
0.4
0.2
0.0
-0.2
Ag2S
-0.4
Ag
-0.6
Ag
-0.8
-1.0
0
10
12
14
pH
(a)
Eh (Volts)
2.0
1.8
1.6
Ag2O3
1.4
Ag(S2O3)23-(aq)
1.2
1.0
0.8
Ag(S2O3)35-(aq)
0.6
0.4
0.2
0.0
-0.2
Ag2S
-0.4
-0.6
Ag
Ag
-0.8
-1.0
0
10
12
14
pH
(b)
Fig 10 Eh-pH diagram for the silver, thiosulfate and ammonia systems (a) High reagent concentrations 5X10 -4m
Ag; 1MS2O32-;1M NH3/NH4+and (b) low reagent concentrations 5X10-4m Ag; 0.1MS2O32-;0.1M NH3
20
5.00E-04
Concentration (M)
4.00E-04
Ag(S2O3)35-
3.00E-04
2.00E-04
Ag(S2O3)231.00E-04
Ag(NH3)2+
0.00E+00
-6
-5
-4
-3
-2
-1
Log [NH3] (M)
(a)
5.00E-04
Ag(NH3)2+
4.00E-04
Concentration (M)
Ag(S2O3)35-
Ag(S2O3)23Ag(S2O3)-
3.00E-04
2.00E-04
1.00E-04
0.00E+00
-6
-5
-4
-3
log
-2
[S2O32-]
-1
(M)
(b)
Fig 11 Distribution of silver species in the silver, thiosulfate and ammonia systems (5X10 -4m Ag; 0.1MS2O32-;
0.1M NH3,pH 9.5, Eh 0.250V) with varying (a) ammonia and (b) thiosulfate concentrations.
21

STABILITY OF THIOSULFATE
One of the major problems in thiosulfate leaching is the high consumption of thiosulfate during gold leaching.
High consumption of thiosulfate is mainly caused by its decomposition in solution, or through its loss to tailings
by adsorption onto solids. Zipperian et al., (1988) reported a loss of up to 50% of thiosulfate in ammoniacal
thiosulfate solutions containing copper.
Thiosulfate is a metastable anion that tends to readily undergo chemical decomposition in aqueous solutions. The
factors that influence the stability of thiosulfate are the concentration and pH of solutions, the presence of certain
metals, the presence of sulfur metabolising bacteria, and exposure to ultraviolet light (Dhawale, 1993). Dilute
solutions of thiosulfate (<0.01M) decompose more rapidly than concentrated solutions (>0.1M). Thiosulfate
solutions prepared in freshly boiled, double-distilled water or distilled water are very stable if stored in an air
tight bottle.
Figure 12 presents the Eh-pH diagram for the metastable S-H2O system (Kametani and Aoki, 1976; Osseo-Arare,
1989). The thermodynamically stable species (i.e. HSO4- and SO42-) are omitted from consideration to reveal the
metastability domain of species such as thiosulfate (S2O32-), tetrathionate (S4O62-) and sulfite (SO3-).
Under alkali conditions, a number of metastable sulfur species, such as sulfite (SO 32-), thiosulfate (S2O32-),
polythionates (SnO62-. 2<n<6) and polysulfides (Sn2-) are found to occur. The sulfurwater system is more
complicated than the metal-water systems because sulfur is mulitvalent and easily forms sulfur chains and
colloidal precipitates. Thermodynamically sulfate is more stable under the leaching conditions.
It can be seen that S2O32- is located in a narrow elongated stability field in the neutral to basic pH region. To
maintain thiosulfate in solution at ambient conditions, the solution would have to be maintained within this
region. Once formed, the metal thiosulfate complexes are stable over a larger pH-Eh range as observed earlier in
Eh-pH diagrams.
Eh (Volts)
2.0
S - H2O - System at 25.00 C
1.8
1.6
1.4
S2O82- (aq)
1.2
1.0
0.8
H2SO3 (aq)
0.6
S4O62- (aq)
0.4
0.2
S2O62- (aq)
0.0
S2O32- (aq)
-0.2
-0.4
H2S(aq)
-0.6
SO32- (aq)
HS- (aq)
S2-
-0.8
-1.0
-2
10
12
14
16
pH
Fig 12 Eh-pH diagram for the metastable S-H2O system {S} = 1.0 M. The S-H2O system without thiosulfate is
superimposed to show an increase in tetrathionate (S4O62-) domain.
22

Under oxidising conditions, thiosulfate will be oxidised to sulfate or tetrathionate:
S2O32- + O2 + 2H2O = 2SO42- + 4H+
2S2O32- + 1/2O2 + H2O = S4O62- + 4OHor disproportionates into sulfate and elemental sulfur:
2S2O32- + H2O = 2SO42- + 4S + OHor disproportionates into sulfite and sulfide ion:
3S2O32- + 6OH- = 4SO32- + 2S2- + 3H2O
S2O32- = SO32- + S0
depending upon the conditions.
Thermodynamically, thiosulfate oxidises to tetrathionate between a pH range of 4 to 6. Otherwise thiosulfate
oxidises to other sulfur species, such as S2O62- or SO32-. In the presence of copper and ammonia, however some
thiosulfate oxidises to tetrathionate at pH 8 to 10 (see Table 3). The oxidative degradation of thiosulfate to
tetrathionate is promoted by the cupric ion (Hemmati et al., 1989, Byerley et al., 1973ab, 1975). Thus the
amount of cupric ion addition, or the concentration of cupric ions is an important factor in thiosulfate stability
and reagent management.
Under non-oxidising conditions some thiosulfate (~62.5%) can be regenerated slowly from the decomposition of
tetrathionate to higher or lower polythionate ions through the formation of trithionate ions (Naito et al., 1970;
Byerley et al., 1973). The reaction is highly catalysed by the presence of thiosulfate ions according to the
reaction scheme:
S4O62- + S2O32- S5O62- + SO32SO32- + S4O62- S3O62- + S2O32S5O62- + 3OH- 5/2S2O32- + 3/2H2O
--------------------------------------------------------------2S4O62- + 3OH- 5/2S2O32- + S3O62- + 3/2H2O
In ammoniacal thiosulfate leaching of gold, increasing the concentration of thiosulfate in solution results in an
increase in thiosulfate consumption (Cao et al., 1992). Efforts have been made to reduce consumption by
reducing the concentration of thiosulfate in solution and leaching for extended periods (e.g. 24 hours) (Cao et al.,
1992). Alternatively, sulfite and sulfate have been added to the leaching solution to stabilise the thiosulfate as
described below.
Effect of sulfite
The presence of sulfite inhibits the decomposition of thiosulfate (Kerley , 1981,1983).
An equilibrium reaction occurs in the thiosulfate liquor as represented by the following equation (Hemmati et al.,
1989)
SO32- + S0 = 3S2O32The presence of sulfite ions is claimed to prevent the formation of any free sulfide ion and the precipitation of
gold or silver from solution. Maintaining a level of 0.05% has been found to stabilise thiosulfate (Kerley, 1983)
but this will also lower the Eh of the solution and reduce Cu(II) in solution. It has also been shown that sulfite is
oxidised by copper (II) ion to sulfate and dithionate depending upon the reaction conditions
Manganese containing ores have a high requirement for sulfite ion because of the oxidising capability of various
manganese compounds (Kerley, 1981). In addition high concentrations of oxygen and/or copper in solution will
decompose sulfite to sulfate. Kerley (1983) observed that the addition of sulfite to reduce strongly oxidising
mineral components in the ore increased gold recovery from about 5.8% to 84.5%.
23
Effect of sulfate
Jiexue and Qian (1991) and Hu and Gong (1991) claimed that gold could be extracted from sulfide ores with
thiosulfate-sulfate instead of thiosulfate-sulfite solutions. They found that the loss of thiosulfate could be reduced
and the gold extraction increased by adding sulfate to the solution. They suggested that the following reaction
takes place:
SO42- + S2- + H2O = S2O32- + 2OHHowever this is most unlikely as sulfate is very stable.
Sulfate ions are unreactive in ammoniacal thiosulfate leaching system, but are also a decomposition product of
thiosulfate. A build up adversely affects the activity of the solution. The addition of lime has been recommended
if such a buildup of sulfate does occur. The lime reacts with the sulfate ions to precipitate gypsum.
EFFECT OF OTHER CATIONS IN SOLUTIONS

In general, leaching gold by thiosulfate permits a decreased interference from foreign cations in comparison with
the conventional cyanidation method. However, Perez (1987) reported that at pH levels lower than 8.0, metallic
iron (from grinding media) and iron salts dissolve in solution resulting in a decrease in gold dissolution. The
ferric ion is reduced to a ferrous ion and the thiosulfate ions are oxidised to tetrathionate ions (Perez and Galaviz,
1987). Tetrathionate has no lixivating action on gold or silver.
The dissolution of copper present in the ore can be used directly in the leaching process as described above.
Moderate concentrations of cobalt, nickel, and manganese can also be in solution at temperatures above
ambience in ammonium thiosulfate solutions. However, at pH values greater than 10 they are generally in low
concentrations (Niinae et al, 1996).
PASSIVATION OF GOLD
Early work at higher concentrations of reagents reported the precipitation of copper sulfide and the promotion of
the oxidation of thiosulfate to tetrathionate. Clearly, the formation of CuS and sulfur layers on gold particles will
hinder their dissolution.
Bagdasaryan et al. (1983) and Pedraza et al. (1988) observed a sulfur layer as well as copper sulfide in a
thiosulfate-copper sulfate system. Both elemental and sulfide sulfur can be provided by the decomposition of
thiosulfate in alkaline solution.
Electrochemical impedence spectral studies have shown that gold passivation can occur in the absence of copper
(MacDonald, 1990). The appearance of an inductive arc in the potential range of gold dissolution in sodium
thiosulfate solution is assigned to the passivation of the gold electrode accompanying its dissolution. The belief
is that elemental sulfur may be formed preventing thiosulfate from diffusing to the gold surface and hence,
inhibiting the gold dissolution. The elemental sulfur coating is formed either by the adsorption of elemental
sulfur, or by the oxidation of sulfide ion on the gold surface.
The passivation of gold can be prevented with the presence of ammonia, adjustment of Eh-pH conditions and the
presence of O2 as described earlier.
EFFECT OF TEMPERATURE ON THIOSULFATE LEACHING

Higher gold and silver dissolution rates have been reported at temperatures in the range of 40-60C (Berezowsky
and Weir, 1989; Qian and Jiexue, 1989; Hemmati et al., 1989;Tozawa et al., 1981; Zipperian et al., 1988). In
contrast, Abbruzzese et al. (1995) found in their studies that increasing temperature decreased gold recoveries by
20%. They ascribed this result to passivation by cupric sulfide formed by the thermal reaction between Cu(II)
ions and thiosulfate as follows :
Cu2+ + S2O32- + H2O = CuS + SO42- + OH-
24

However, the decrease may have been caused by loss of ammonia from solution at higher temperature
destabilising the Eh-pH leaching conditions. Such problems may have been overcome by the addition of sulfite
as described above.
Temperatures above 60C make it difficult to maintain ammonium hydroxide in solution (Kerley, 1981). In
addition heating a large quantity of material would not be practical unless the ore had been previously treated in
some way at elevated temperatures.
AUTOCLAVE LEACHING OF GOLD

To overcome problems associated with passivation of gold through the formation of sulfur and copper sulfide
layers on gold particles during thiosulfate leaching, most work in the early days was carried out at elevated
temperatures and pressures in autoclaves. At temperatures above 100C the layer of elemental sulfur that is
formed by the oxidation of thiosulfate can be redissolved:
4S + 6OH- S2O32- + 2S2- + 3H2O
Thiosulfate is regenerated in alkaline solutions, whereas sulfur is reprecipitated in acidic solutions. TerArakelyan et al. (1984) noted that ammonium sulfate promotes the oxidation and dissolution of the sulfide layer
on the surface of gold only at elevated temperatures and oxygen pressures.
LEACHING WITH POLYSULFIDE

In addition to thiosulfate, polysulfides will also be present during leaching. These can be produced from the
disproportionation of elemental sulfur or thiosulfate decomposition.
Investigations into the use of polysulfides to leach gold has been carried out by Chen et al., (1996). From
electrochemical studies carried out on a gold electrode in polysulfide solutions, gold dissolution occurred as a
result of absorption of polysulfide on its surface, accompanied by the oxidation of polysulfide as follows:
Anode: Au/Sx2- AuS- + (x-1)S0 + eAu/Sx2- Au/Sx + 2eCathode: S0 +2e- S2The cathode reaction indicates that the elemental sulfur acts as an oxidant for gold dissolution. Thus gold can be
leached in polysulfide solution without the addition of any oxidant. Chen et al. (1996) reported at 50C, 90%
gold extraction from a sulfide concentrate without the addition of an oxidant. However, a relatively high
polysulfide concentration (>2M) is required for high gold extraction.
In mixtures of thiosulfate and polysulfides, the polysulfides only act as a lixivant when no oxidant is present. In
the presence of copper, which is required as the oxidant in thiosulfate leaching, polysulfides precipitate with
copper to form CuS.
GENERATION OF THIOSULFATE IN SITU

As thiosulfate systems can be economically unacceptable due to high reagent consumption, several authors have
investigated the possibility of generating thiosulfate in-situ.
Thiosulfate and polysulfides can be produced by the disproportion of elemental sulfur with OH - ions in
ammoniacal solution through a phase transfer catalysis (Deng et al., 1984) or from hydrated lime solution with
sulfur (Zhang et al., 1993) as follows
4 S0 + OH- S2O32- + 2S2- + 3H2O
Sulfide ions are then able to form polysulfides with elemental sulfur as follows
S2- + S0x-1 = Sx2-.
25
and dissolve gold as described above.

However, thiosulfate degrades with time to sulfate and sulfide.
Zhang et al (1993) using the Lime Sulfur Synthetic Solution (LSSS) method obtained gold recoveries over a two
stage process of 99% for a high lead sulfide concentrate and nickel-copper matte residue respectively.
Thiosulfate can also be produced by the reaction of hydrogen sulfide on aqueous solutions of sulfites:
2HS- + 4HSO3- = 3S2O32- + 3H2O
or by boiling aqueous solutions of metal sulfite with elemental sulfur
Na2SO3 + S = Na2S2O3
In this method, a slurry of sodium sulfite is digested with an excess of sulfur to produce thiosulfate. The sodium
sulfite slurry is prepared by passing sulfur dioxide through soda ash solution.
Oxidation of polysulfides generates thiosulfate as follows (Greenwood et al, 1984):
Na2S5 + 3/2 O2 = Na2S2O3 + 3S
Kerley (1983) described a method of generating thiosulfate by the following reaction:
2NH3 + SO2 + S + H2O (NH4)2S2O3
Ammonia can be recycled while elemental sulfur and sulfur dioxide gas is added in sufficient amounts to make
thiosulfate. The reaction proceeds very slowly and so an excess of sulfur is required. Free ammonia should
always be present to avoid acid conditions. Sulfur dioxide gas is readily dissolved in water at pH<2. By
increasing the pH, sulfur dioxide forms sulfite as follows
2NH3
SO2(aq) + H2O = H+ + HSO32- H2O + SO32- + 2NH4+

In the presence of sulfur, thiosulfate is produced as follows
3H2O + 4SO32- +2S = 3S2O32- +6OHUsing this method Kerley (1983) was able to recovery 90% silver from a 16oz/t Ag grade ore containing 10.5%
manganese.
Thiosulfate formation and complexing with gold has been observed in natural and particularly in supergene
enivronments (Bowell et al., 1993; Benedetti and Boulegue, 1991; Kucha et al., 1994). In alkaline solutions,
pyrite oxidation proceeds through the intermediate tetrathionate ion (at pH 6-7) and thiosulfate ions (pH >7).
Goldhaber (1983) showed that sulfate is directly formed by pyrite oxidation only at pH < 6. The breakdown of
meta-stable thiosulfate to sulfate is delayed by an induction period, the duration of which increases with
alkalinity (Rolla and Chakrabarti, 1982). However, the concentration of thiosulfate in solutions is low. No doubt
certain sulfur-oxidising enzymes and bacteria may increase thiosulfate concentrations initially (Lakin et al.,
1974, Webster, 1986).
Cao et al (1992) tried to generate thiosulfate in-situ by leaching a copper-gold ore in ammonia solution. No
thiosulfate was present but up to 22% gold was recovered as a result of gold-copper-ammonia complexes being
formed.
It has been reported that significant amounts of thiosulfate can form during ammoniacal pressure oxidation
leaching of complex copper-nickel-cobalt sulfide concentrates (Forward et al., 1955).
26
DECOMPOSITION OF SULFIDES IN THIOSULFATE LEACH SOLUTION

From X-ray powder diffraction studies Qian and Cao (1993) observed less pyrite present in thiosulfate leached
residues than in the original ore. They concluded that a ammonia-thiosulfate solution containing copper, leaches
pyrite by a corrosive process. Scanning electron microscopy showed clear scarring on pyrite leached grains.
These authors also observed some dissolution of chalcopyrite in the residues.
Copper sulfide minerals, other than chalcopyrite, also dissolve readily in aerated thiosulfate leach solution,
particularly when ammonia is in solution.
THIOSULFATE LEACHING OF ORES

Table 4 shows a summary from selected literature of the various thiosulfate leaching conditions that have been
used. After initial studies around 1980, renewed interest occurred in the 1990s. Most work has been carried out
on complex ores containing high copper, carbonaceous ores or ores containing high concentrations of lead, zinc
or manganese. The gold dissolution rates and percentage recovery will vary depending on the deportment of gold
in the ores. A wide range of conditions appear to have been used, including relatively severe conditions,
compared with those used in the cyanidation process.
The gold concentration in the ore has varied from between 1 and 62 g/ton. The addition of copper has varied
from 0.001 to 0.1 mol/L, whereas ammonia concentration has varied from 0.1 to 6 mol/L and thiosulfate
concentration from 0.1 to 2 mol/L. The pH conditions are all alkaline with most leaches carried out at near pH 910. Generally the leaching time has been over a relatively short period of a few hours. Reagent consumption
appears to be lower where reagent concentrations are low and the ore leached over longer periods of time.
The patents taken out that refer to thiosulfate leaching are listed in Table 5. With the exception of Yen et al.
(1998), recent papers and patents use much more dilute reagent concentrations and low Cu2+ concentrations in
order to minimise thiosulfate oxidation.
27
TABLE 4 List of conditions used in literature

Tozawa et al , 1981
Kerley, 1981,1983
Block-Bolten and Torma
1985, 1986
Zipperian et al , 1988
Ore type
Gold plates
2Gold (g/ton) Temperature pO2 (kPa) Retention (hrs) S2O3 (M)

99.99%
65
100
3
0.5
sulfide
2% Mn
Zn-Pb sulfide flotation
1.75
22.5g/t Ag,0.7%Zn,0.5% Pb
Rhyolite ore
3
7g/Kg MnO2
Carbonaceous
14.74
2.5% org C
Oxidised ore
4.78
0.05% Cu,
0.048% MnO2
50.4
3.19% Cu
Pb-Zn sulfide
1.75
22.5g/tAg, 0.44% Cu, 0.68% Zn, 0.54% Pb
Sulfide conc
62
3% Cu
Oxidised ore
1.65
0.02% Cu
Carbonaceous
2.4
1.4% C, 1.0% S
Gold ore
51.6
NH3 (M)
1
Cu2+ (M)
0.04
SO32-(M)
-
pH
-
%Recovery Consumption
18%
2%
4g/L
2%
7-9
95
4Kg/t
21-50
air 2L/min
0.125-0.5
0.75
7-9
90
45 Ib/t
50
atm
0.1
10
90%
50%
35
103
0.71
0.15
0.22
10.5
73%
15-19%
30-65
atm
1-22%
1.36-8.86%
0.05-2%
1%
93.9
40 Kg/t
40
1L/min
1-2
0.016
95.6
21-70
atm
0.125-0.5
6.9-8.5
95%
60
atm
1-2
0.2-0.3
2-4
0.047
10-10.5
95
4.8 Kg/t
ambient
atm
48
0.2
0.09
0.001
11
90
2kg/t
ambient
atm
12-25 days
0.1-0.2
0.1
60ppm
9.2-10
25
atm
0.1
8.5-10.5
80
3.2
ambient
atm
15g/l
added to pH 9.5
0.5g/l
0.5g/l
9.5-10.0
80
3-7
55
atm
0.02-0.1
2000ppm
500ppm
0.01-.05
7-8.7
70-85
7.26
ambient
atm
24
0.4
0.2
0.03
11
90
Wan, 1997
Gold-copper ore
1.4g/t Ag, 0.3% Cu
Sulfide carbonaceous
1-3
ambient
atm
Wan and Brierley, 1997
Carbonaceous sulfide
1-3
ambient
atm
91-116days
0.1
0.1
0.005
50.7-65.7
5.2-8.4
Yen et al , 1998,1999
Gold copper ores

~0.36% Cu
Pressure oxidised sulfide ore
7.2-7.9
ambient
atm
24
0.5
0.1
10
95-97
30kg/t
2.5
45-55
atm
12
0.03-0.05
7.5-7.7
80-85
Hemmati et al , 1989
Caixia and Qiang, 1991
Hu and Gong, 1991
Murthy, 1991
Cao et al. , 1992
Langhans et al , 1992
Wan et al , 1994
Abbruzzese et al , 1995
Groudev et al , 1996
Marchbank et al , 1996
Yen et al ,1996
Thomas et al , 1998
Bacteria leached ore

15.2 g/t,0.14%Cu,0.91%S
Sulfide carbonaceous
~500-1000ppm 10-100ppm 0.01-0.05
28
TABLE 5 Patents on thiosulfate leaching

Authors
Title
Patent No
Kerley, Jr 1981
Kerley, Jr, 1983
Perez and Galaviz, 1987
Recovery of precious metals from difficult ores

Recovery of precious metals from difficult ores
Method for recovery of precious metals from difficult ores
with copper-ammonium thiosulfate
Recovery of precious metals from metal sulfides
US 4,269,622
US 4,369,061
US 4,654,078
Hydrometallurgical process for the recovery of precious

metals values from precious metal ores with thiosulfate
lixiviant
Gold recovery from refractory carbonaceous ores by
pressure oxidation and thiosulfate leaching
Process for recovering gold from oxide-based refractory
ores
Gold recovery from refractory carbonaceous ores by
pressure oxidation, thiosulfate leaching and resin-in-pulp
US 5,354,359
Genik-Sas-Berezowsky;
et al 1978
Wan et al., 1994
Marchbank et al., 1996

Pappas (1997)
Thomas et al., 1998
US 4,070,182:
US 5,536,297
UK GB 2,310,424 A
US 5,785,736
Leaching copper containing ore

The presence of reactive copper in auriferous ore is well known to cause high reagent consumption
using the conventional cyanide method. The advantages of using ammoniacal thiosulfate containing
copper to treat such ore has been investigated. Genik-Sas-Berekowski (1978) patented a technique for
the use of ammonia thiosulfate as a secondary leach for the recovery of silver and gold in conjunction
with a hydrometallurgical process for the recovery of copper from copper bearing sulfide ores.
Chalcopyrite ores containing gold were leached in ammonium sulfate with an O 2 over-pressure of 20
psi before treatment with 65-130 g/L of ammonium thiosulfate within pH values of 8.5 to 9.5. In some
cases high gold and silver recoveries (90%) were observed. However, the method did not take into
account the instability of thiosulfate and the time related instability causing loss of recovery of gold.
Kerley (1981, 1983) described a process in which ores which are difficult-to-treat by the conventional
method were treated by lixiviation in ammonia thiosulfate solutions containing copper to extract gold
and silver. Sulfite ions were provided by adding ammonium sulfite or ammonium bisulfite to the
leaching solution in order to minimise the oxidation of thiosulfate. The pH recommended was at least
7.5 or higher.
Perez and Galaviz (1987) modified Kerleys process to inhibit Fe3+ oxidation of thiosulfate (and
possibly Cu2+ cementation) caused by the dissolution of metallic iron from grinding media present in
the treated ore. Their process involved treating copper containing gold ore with copper ammonium
thiosulfate in which the pH of the lixiviating solution was maintained at a minimum of 9.5. Copper
cement was then used in a subsequent precipitation process on which the gold and silver was
precipitated without causing precipitation of copper from the lixiviant solution. Trial runs on a pilot
plant scale were carried out at LaColorada, in the State of Senora, Mexico.
The pilot plant layout that existed at LaColorada is shown in Figure 13. The ore was ground to increase
the amount of surface area of the ore exposed to the lixiviating solution. Before milling, copper
ammonium thiosulfate and water were added to the ore until the concentration required was obtained.
Anhydrous ammonia was added to the copper ammonium thiosulfate to maintain the pH at a level of at
least 9.5. After grinding to approximately 200 mesh, the viscosity of the slurry was lowered by adding
more water and ammonium thiosulfate to bring the solids in the slurry to 40%. This also lowered the
pH to around 8 or 9. An agitator step was then performed to increase reagent contact with gold and
silver. After agitating for about 1.5 hours, the slurry went to a thickening tank and the pregnant solution
was removed to another agitator tank. Copper cement from a container was fed into the agitator tank to
precipitate the gold and silver from solution which settled in the settling tank. The gold and silver
precipitate was then collected and the spent solution reused. High gold recoveries were obtained, but
there is no mention of reagent consumption.
29
NH3
Fine ore
Bin
Cu(NH3)42+ (NH4)2(S2O3)
Ball Mill
Water + (NH4)2S2O3
Agitator
Tank
Pregnant
solution
Thickener
SO2
to
lower
pH
Filtration
Agitator
Tank
Copper
cement
Tailings
Settling
Tank
Precious
Metal
Precipitate
Fig 13
Flow chart of pilot plant layout that existed at LaColorada, in the State of Senora, Mexico
(after Perez and Galaviz, 1987).
Cao et al (1992) reported a low thiosulfate but high ammonia concentration leaching system that has
the potential to be economic for treating sulfide gold ores. Over 95% gold was extracted from
auriferous sulfide ore containing high copper (62g/t Au and 3.1% Cu). The conditions used were 0.2-
30

0.3M (NH4)2S2O3, 3 g/L Cu2+, 2-4M NH4OH, 0.5-0.8M (NH4)2SO4, at 60C for 1-2 hours aeration.
However this work has only been carried out under laboratory conditions, and losses of thiosulfate and
ammonia were not reported.
An evaluation of the potential of heap leaching, or in-situ copper catalysed thiosulfate leaching of low
grade ore was carried out by Langhans et al (1992). The work concentrated on investigating the
feasibility of using thiosulfate under long term leaching conditions and at lower reagent concentrations.
From 48 hour leaching tests they obtained 83% gold extraction with a consumption of 0.4 kg/t of
thiosulfate at 0.2M S2O32-, 0.00625M SO32-, 0.001M Cu(II) and 0.09M NH3. However the leaching
studies were conducted on low grade oxidised ore with traces of sulfides.
Preg robbing type ores
The presence of carbon in an active form will adsorb gold that has dissolved in the conventional
cyanide process, thus robbing the lixiviant. This process is known as preg-robbing. By virtue of the
fact that gold thiosulfate adsorption on to carbon is low, thiosulfate leaching of carbonaceous ores is
potentially economical, therefore attracting significant industry research.
Hemmati et al. (1989) investigated the thiosulfate leaching of gold from carbonaceous ore that
contained 2.5% organic carbon. The optimum conditions for gold extraction were found to be 35C and
103 kPa oxygen over pressure, pH 10.5, 3M NH 3 with a lixiviant containing 0.71M (NH4)2S2O3, 0.15M
CuSO4 and 0.1M (NH4)2SO3. Extraction of gold was 73% in 4 hours compared with only 10%
observed using cyanide over 24 hours.
In the case of low-grade carbonaceous ores, they can be processed without pretreatment by heap
leaching with thiosulfate. However, ores containing high sulfide concentrations require at least partial
oxidation prior to thiosulfate leaching.
Newmont Gold Co patented a microbial innoculation/agglomeration process for rapid initiation of biooxidation of refractory ores in heaps followed by thiosulfate leaching to avoid the preg-robbing activity
of carbonaceous matter (Brierley and Hill, 1993, Wan et al., 1994; Wan and Brierley, 1997). The work
was carried out in trials on both laboratory and pilot plant scale experiments. The process consists of
growing a dense cell suspension of the naturally occuring iron-oxidising bacteria Thiobacillus
ferrooxidans and Leptospirillum ferrooxidans and then adding this bacterial culture to the ore as the
heap is formed. The distribution of bacteria throughout the heap is achieved with noticeable
agglomeration of the fine ore particles. The effluents from the heaps are collected in either a tank or
pond and recirculated to the top of the heap. The progress of the biooxidation pretreatment process is
monitored by measuring pH, Eh and Fe2+/Fe3+ ions in solution. After bio-oxidation, an agglomeration
/neutralisation step is carried out to neutralise the acidic ore for leaching with thiosulfate under alkaline
conditions. This is achieved by washing the heap in water to displace soluble acid and iron salts. The
washed heap is further neutralised by blending in lime or soda ash.
A schematic diagram of the heap leach process used by Newmont Gold Co during the thiosulfate
leaching stage is shown Figure 14. After passing through the heap, the pregnant lixiviant solution is
recovered at the bottom of the heap and recirculated, either continuously or intermittently. After the
precious metals values are recovered from the lixiviant solution by precipitation, the solution is
recirculated to the static heap. Using this method Wan et al., (1994) obtained gold recoveries as high as
70% whereas the conventional cyanidation process resulted in only about 20% (Wan and Brierley,
1997). They recommended a leach solution with pH between 9.2-10.0, 0.1-0.2M (NH4)2S2O3 and/or
Na2S2O3, at least 0.1M ammonia and up to 60ppm of Cu(NH3)42+ to act as a catalyst for gold oxidation.
31
Heap
Ammonium
Thiosulfate
Cu2+
NH3
Ammonium
Thiosulfate
Precious
Metal
Recovery
system
Pregnant
Lixiviant
Solution
Storage
Pump
Fig 14 A schematic diagram of a gold and silver leaching and recovery process for static heaps using
thiosulfate (after Wan et al., 1994).
A similar process was also developed by Pappas (1997) for treating carbonaceous oxide ores.
An alternative to bacterial oxidation as a pretreatment of sulfide rich carbonaceous ores, is to fine mill
the ore prior to thiosulfate leaching (Wan et al., 1994). A schematic diagram illustrating such a process
is shown in Figure 15. Finely ground carbonaceous ore is initially slurried with water, thiosulfate,
copper sulfate and ammonia in a slurry preparation unit. Each reagent is added in appropriate quantities
to obtain the right pH and oxidising concentration conducive to gold extraction. During the process,
stripped thiosulfate lixiviant is pumped from the precious metal recovery unit into the slurry
preparation unit thus reducing the amount of extra reagents and water required to maintain the desired
conditions for leaching. The ground slurry is transferred to a heat exchanger where the temperature can
be increased to about 45C to improve gold extraction. The slurry is then passed to a stirred tank
reactor where the extraction of gold by the thiosulfate lixiviant takes place. After the appropriate
contact interval, lixiviated ore slurry is transferred from the stirred tank reactor to a conventional
separator where the separator overflow is the pregnant thiosulfate lixiviant and the underflow is the
leached residue. The leached residue is transferred to the tailings and the precious metal in the pregnant
solution is recovered by means of precipitation. The retention time for the whole process is governed
by the composition of the ore and its particle size.
32
Ground
Carbonaceous ore
NH3
Water
Sulfur
Pretreatment
Copper
sulfate
Slurry
Preparation
Thiosulfate
Heat
Exchanger
Stirred
Tank
Reactor
Separator
Precious
Metal
Recovery
Fig 15 Major steps in a gold and silver leaching and recovery process for finely ground ore material
using thiosulfate (after Wan et al., 1994).
Barrick Co. have also patented a process for recovering gold from an ore having a combination of
refractory sulfide and carbonaceous material using pressure oxidation followed by thiosulfate leaching
(Marchbank et al., 1996). The oxidised ore slurry was mixed with thiosulfate solution maintained at a
pH between 7 and 8.7. The preferred lixiviant was ammonium thiosulfate (0.025-0.1M) with a
residence time of 60-240 minutes at temperatures between 45-55C. The cupric ion concentration was
kept in the range of 5-50ppm. Sufficient ammonia was added to maintain the copper in solution with a
minimum molar ratio of 4:1 NH3:Cu. To reduce thiosulfate consumption, 0.01-0.05M sulfite was
added in the form of sodium metabisulfite or through additions of sulfur dioxide gas. About 70-75%
gold was extracted from the ore.
Recently the Barrick Gold Corporation patented a combined pressure oxidation, thiosulfate and resinin-pulp process for treatment of refractory gold ores (Figure 16) (Thomas et al., 1998). In this process
ore is ground to a size with about 65-85% passing 200 mesh and thickened to about 40-50% solids.
Sodium carbonate is added to ensure that pressure oxidation is carried out under alkaline conditions
and Cl- is added to improve the kinetics and to facilitate oxidation. The ore which is pressure oxidised,
leaves the autoclave at about 35% solids and is directed to a leaching operation where it is contacted
with ammonium thiosulfate (5g/L) and copper sulfate (25ppm Cu). The slurry of gold-bearing leachate
and solid residue leaving the leaching circuit contains in the range of 1-5ppm gold and is directed to a
Resin-in-pulp (RIP) circuit where gold and copper are loaded onto a strong base resin to about 1-5Kg/t
Au and about 10-25 kg/t Cu. Copper is eluted from the resin using ammonia thiosulfate (200g/L) and
gold is eluted using potassium thiocyanate (200g/L). The copper-bearing eluate is returned to the
leaching circuit while the gold eluate is either electrowon or precipitated. Clearly the resin is not
selective for gold, and loads both Au and Cu in proportion to their concentration in solution. This
approach is therefore applicable only to copper-free ores using low levels of Cu(NH3)42+ as a catalyst.
33

NAOH/NACL
or
Na2CO3/NaCl
Steam
O2 H2O
NH4+
(NH4)2S2O3
Ore
CuSO4
Autoclave
Pressure
Oxidation
Grinding
Leach
Water
Treatment
RIP
Resin
Ammonium
Thiosulfate
Liquid
optional
Cu/(NH4)S2O3
Cu Elution
Liquid/
Solid
Separation
Au Elution
Water
Potassium
Thiocyanate
Solids
Tailings
Disposal
Electrowinning
or
Precipitation
Fig 16 Flow sheet illustrating the pressure oxidation, thiosulfate and resin in pulp recovery process for
refractory gold ores (after Thomas et al., 1998)
Manganese containing ore

Kerley (1981,1983) used ammoniacal thiosulfate to leach gold and silver from an ore containing 2%
manganese. He used a solution containing 18% (NH4)2S2O3, 3% (NH4)2SO3, 2% NH4OH and 4g/L Cu.
Although gold and silver recoveries were high, reagent consumption was 4 kg/t (NH 4)2 S2O3 , 3 kg/t
(NH4)2SO3 and 0.5 kg/t Cu. Manganese type ores containing precious metal ores have a high
consumption rate of sulfite with the following reaction taking place
MnO2 + 2(NH4)2SO3 + 2H2O MnS2O6 + 4NH4OH
34

Lead- Zinc sulfide ore
Gold and silver extraction from low grade lead and zinc sulfide flotation tailings was investigated by
Murthy (1991). Thiosulfate leaching at 50 resulted in 95% gold extraction. Block-Bolten and Torma
(1985, 1986) obtained high gold recovery (90%) from a lead-zinc sulfide flotation tailings using a two
step counter current leaching process. The counter current leaching process consisted of the fresh
tailings being in contact with pre-used leach solution and the pre-leached tailings receiving the fresh
leachant. Compared with cyanide heap leaching, the thiosulfate process required only about 1 hour to
achieve 90% gold recovery using up to 0.5M thiosulfate whereas cyanide required at least 24 hours to
extract 50% of the gold. While results are favourable for thiosulfate leaching, experiments were carried
out on a laboratory scale and high gold extraction required a temperature of 50 C.
35
RECOVERY OF GOLD FROM THIOSULFATE LEACHED ORE

Most research has been concerned with the extraction of gold with thiosulfate and only limited work
has been carried out on the process of recovering gold from solution. In general precipitation methods
have been considered for clarified leach solutions particularly heap leaching, whilst carbon and resins
have been considered for adsorption from slurries.
Precipitation methods
Gold and silver in copper-ammonia thiosulfate solutions can be precipitated out of clarified solution by
the addition of finely divided copper metal (Perez and Galaviz, 1987), zinc metal (Berezowsky and
Sefton, 1979; Panayoto et al., 1994), iron metal (Jiexue and Qian 1989), aluminium metal or soluble
sulfides (Kerley, 1983).
The reduction of metals from solution is a result of charge-transfer reactions. The reaction of gold
recovery by zinc cementation in the presence of ammonia can be represented in the following
reactions:
2 Au(S2O3)23- + 2Zn0 + 4NH3 = 2 Auo + 2 S2O32- + Zn(S2O3)22- + Zn(NH3)42+
Berezowsky and Sefton (1979) observed high consumption of zinc by cupric ion in the thiosulfate
solution and appreciable amounts of zinc and copper in the cement product.
The reaction for the precipitation by zinc can be expressed in the following reaction:
Cu(S2O3)22- + Zn0 = Zn(S2O3)22- +Cu0
Increasing the copper ions (such as copper sulfate) in solution can reduce the amount of unreacted zinc
remaining with the gold (Wan et al., 1993). However, cementation of copper results in low grades of
gold. A suitable reductant such as sulfur dioxide can be used to reduce the cupric form to cuprous prior
to zinc dust cementation. This reduces the amount of copper co-precipitating with gold.
In the Merrill-Crowe zinc cementation process used in cyanide lixiviation systems, de-aeration of the
filtered pregnant solution prior to cementation is one of the most important factors for efficient gold
recovery. The presence of oxygen passivates the surface of the zinc and also causes re-dissolution of
the gold precipitate. This results in an excessive consumption of zinc and incomplete recovery of gold.
In this application the presence of copper as well as air results in high zinc consumption. Furthermore
significant dissolved gold is left in the filtered tailings.
Jiexue and Qian (1989) claimed that the use of iron powder prevented the problems observed with the
precipitation of gold using the zinc method. However, it is expected that copper would also precipitate
with iron.
Detailed kinetic studies by Guerra and Dreisinger (1999) observed that increased temperature (3050C) and a higher pH/ammonia concentration enhanced cementation performance, whereas the
presence of sulfite and copper ions in solution negatively affected cementation performance. In
addition they observed that measurement of changes in solution potential cannot be used to indicate the
progress of the gold cementation reaction since measured solution potential is dominated by the mixed
potential of side-reactions.
Sodium borohydride can also be used as an efficient agent for reducing gold and silver in clarified
acidic solutions of thiosulfate at room temperature. The Au(I) ion is reduced to metallic gold in the
form of very fine crystals. A complete reduction of gold in thiosulfate solutions can occur with a
sodium borohydride to gold molar ratio of 0.625 at a pH of 6 over a one hour time period (Awadalla
and Ritcey, 1991,1993; Groves and Blackman 1995). However, the presence of ferrous ion, cobalt,
nickel or in particular, copper in solution decrease the efficiency of borohydride to reduce gold because
of extensive co-precipitation of other metals. Most work has been adapted to thiourea leaching rather
than thiosulfate.
36
Gold recovery has also been achieved by sparging or pressurising gold thiosulfate solutions with
hydrogen (Deschenes and Ritcey, 1990). It is inferred, although no evidence was given, that thiosulfate
is not lost.
Finally dissolved gold and silver has been recovered by the addition of a sulfide solution with
regeneration of thiosulfate (Kerley, 1981; Flett et al., 1983):
Ag2S2O3 + (NH4)2S Ag2S + (NH4)2S2O3
Solvent extraction techniques
In general solvent extraction can only be applied to clarified solutions containing relatively high
concentrations of gold and silver. Nevertheless there have been significant efforts at finding suitable
extractants.
Alkyl phosphorus esters
Solvent extraction with alkyl phosphorus esters on gold thiosulfate solutions show high gold recoveries
in alkaline conditions with increased gold recoveries being observed with increased concentrations of
thiosulfate (Zhao et al., 1997). In sodium thiosulfate solution, the extraction reaction using tributyl
phosphate (TBP) can be represented as:
iNa+ + 2Au(S2O3)23- + OH- + mTBP = NaiAu2(S2O3)2-3(OH).mTBP
Where m=1.5-2.5
Recovery of gold was lower with aromatic hydrocarbons than with aliphatic hydrocarbon diluents.
The presence of ammonia and higher concentrations of TBP improved gold recoveries due to the
formation of hydrogen bonds between ammonia and TBP (iNa iAu2(S2O3)3(OH)NH3)2.nTBP, where
n=6-9).
Primary, secondary and tertiary amines
Primary amine (R1R2CHNH2. where R1+R2 = C18-22), secondary amine DNA (dionylamine) and tertiary
amine TOA (trioctylamine) were tested for the extraction of gold from thiosulfate solutions (Zhao et
al., 1998a,b). The extraction capacity decreased in the order of primary>secondary>tertiary amine. It is
suggested that the species extracted by amines from alkaline solutions is different to that from acid
solutions. The extraction reaction of Au(S2O3)22- by primary amines is proposed as follows:
Au(S2O3)23- + 3H+ + 3RNH2 = (RNH3)3Au(S2O3)2
and in ammoniacal thiosulfate solution:
NH4+ + Au(S2O3)23- + 2RNH3+ = NH4(RNH3)2Au(S2O3)2
In general the separation of gold from silver, copper, zinc and nickel in thiosulfate solutions by primary
amines is difficult. However, the addition of ammonia into the thiosulfate solution increased the
difference between the extraction of gold and other metals from the solution leading to good
separation.
Activated carbon adsorption
Activated carbon is preferred for gold recovery from cyanide solutions because it can be added to the
pulp and avoids soluble losses in tailings. Unfortunately it has a low affinity for Au(S 2O3)23- (Gallagher
et al., 1989).
37

Jiexue and Qian (1989) recorded a 30% recovery of gold thiosulfate on activated carbon. For
thiosulfate leached slurries containing up to 16 mg/L of gold, Abbruzzese et al., (1995) observed an
increase in gold recovery from 22% to 43% when the carbon concentration was increased from 5g/L to
60g/L. They also claimed to have achieved a 95% gold recovery after six hours. However increasing
the carbon concentration (120 g/L) resulted in a decrease in gold recovery. Yen et al. (1998) observed
similar gold recoveries of 95% in thiosulfate solutions containing 60g/L of carbon at pH 11 after 6
hours. However the gold loading on carbon at these concentrations was too low to be considered
practical or economic.
The reason for the low loading of gold onto carbon from thiosulfate system is uncertain. It has been
suggested that it could be related to the relatively high negative charge of the complex, steric
limitations due to its molecular structure, or specific interactions of the ligand group with carbon active
sites.
The potentials for the reduction of five gold complexes to gold metal from a solution containing gold at
10-5 M given by McDougall and Fleming (1987) are shown in Table 6.
TABLE 6 Potentials for the reduction of gold complexes to gold metal from a solution
containing gold at 10-5 M
Ligand
Thiourea
Thiocyanate
Thiosulfate
Chloride
Cyanide
Ligand
Concentration
(M)
10-1
10-2
10-1
10-2
10-1
10-2
10-1
10-2
10-1
10-2
E0
(versus SCE)
(V)
0.11
0.11
0.47
0.47
-0.21
-0.21
0.76
0.76
-0.79
-0.79
E
(versus SCE)
(V)
-0.07
0.05
0.30
0.42
-0.47
-0.27
0.64
0.65
-0.85
-0.73
Combination of the above electrode potential for gold thiosulfate with the reduction potential of
activated carbon (-0.14 versus SCE) gives a negative reduction potential for the gold thiosulfate species
adsorbed onto activated carbon. Thermodynamically, therefore, the gold thiosulfate complex is stable
and will not be reduced during adsorption. Adsorption may be expected to occur via the same
mechanism as the adsorption of the aurocyanide complex onto activated carbon, that is, by ion pairing.
To circumvent the problem of low loading/low affinity for Au(S 2O3)23-, gold can be adsorbed from a
thiosulfate solution by carbon after adding a small amount of cyanide to the system (Lulham and
Lindsay, 1991). The solution is treated with at least a stoichiometric amount of cyanide ions and the
resultant gold cyanide complex is adsorbed on to carbon or a resin. The gold loaded adsorbent is then
subjected to stripping to recover adsorbed gold. It was claimed that selective recovery of gold can be
achieved from thiosulfate feed solution containing other metal ions in solution such as silver, copper
and zinc and 95-97% gold recovery was reported by this method.
Resins
Most anion exchange resins would not be expected to effectively adsorb gold thiosulfate complexes
because thiosulfate is an effective eluant for stripping gold from loaded resins. In general, studies have
found that gold and silver can only be adsorbed on anion exchange at very dilute thiosulfate
concentrations (Wan et al., 1993) and is inhibited by the presence of tetrathionate, a decomposition
product of thiosulfate. (OMalley, Pers. Comm., PhD student, Murdoch University)
However, Thomas et al (1998) claimed to have achieved almost full recovery of gold and silver using
strong base resins.
38

A strong base resin consisting of a quaternary amine attached to a polymer backbone (e.g. polystyrene
beads) is preferred rather than a weak base resin. This is because weak base resins generally require a
pH of less than 8 and do not have the same capacity as strong resins. In addition, strong bases are more
widely available. Suitable resins include all commerical strong base resins of either type I
(triethylamine functional groups) or type II (triethyl ethanolamine functional groups). To facilitate
screening, macroporous resins with beads of at least 0.8mm in average diameter are preferred. Specific
strong base ion exchange resins for use are listed in Table 7.
Table 7: Suggested resins for gold thiosulfate adsorption (after Thomas et al., 1998)
Resin
Dowex M-41
Dowex MSA-1
Amberlite IRA-904
Amberlite IRA-910
Lewatit M-600, MP 500
Gel-type resin 21K
Type
Type I
Type II
Type I
Type II
Manufacture
Dow chemical
Dow chemical
Rohm&Haas
Rohm&Haas
Bayer
Dow chemical
The gold-bearing lixiviant and solid residue are subjected to resin-in-pulp (RIP) or resin-in-leach (RIL)
which recovers both copper and gold.
A schematic diagram of the resin-in-pulp circuit as outlined by Thomas et al (1998) is shown in Figure
17. The RIP operation is carried out in a stirred tank reactor vessel, preferably in a Pachuca tank, which
is an air-agitated, conical bottom, solid-liquid mixing vessel in which the air is injected into the bottom
of the cone. The Pachuca system reduces resin bead breakage and improves dispersion of the resin
beads in the slurry compared with a mechanical agitator system. Between four to eight pachucas are
connected in series with a total residence time for pulp of about 12 hours. Alternatively the resin is
moved from stage to stage counter-currently to the pulp at a rate such that the retention time of the
resin is about two to three hours per stage.
Thomas et al (1998) found that higher gold recoveries were obtained by using very dilute thiosulfate
solutions at 45-55C and adding the resin to the pregnant solution containing the solid residue rather
than adding it to the pregnant solution after a liquid/solid separation step. The presence of the resin in
contact with both the pregnant solution and solid residue reduces degradation of gold thiosulfate and
thiosulfate reagent and reduces the adsorption of gold on the solids.
The pulp and barren lixiviant exiting during the final RIP stage are sent to tailings for further treatment
and reclaim. The loaded resin is sent to an elution stage where copper is eluted from the loaded resin by
washing with ammonia salt or a mixture containing 100-200 g/L of ammonium thiosulfate solution.
The eluate containing ammonium thiosulfate and copper (500-1500 ppm) together with about 10% of
the gold on the resin is then recycled to the leaching circuit.
After copper elution, a thiocyanate solution (100-200g/L) is used to elute gold from the resin. The
eluate is passed to a gold recovery process such as electro-winning whilst the resin is recycled to the
RIP circuit. Because the resin is returned in its SCN- form, it is not clear whether gold is taken up on to
the resin as the Au(SCN)2- complex.
39

Pulp
Cu/(NH4)2S2O3
Leach
Au and Cu
Bearing Resin
Cu
Elution
Ammonium
Thiosulfate
RIP
Au + Cu
Resin
Return
Potassium
Thiocyanate
Au Elution
Au - Bearing
Tails
And
Reclaim
Eluate to
Au recovery
Fig 17 Schematic diagram of resin-in-pulp circuit (after Thomas et al., 1998)
ELECTROWINNING
Some work has been carried out on electrowinning gold from thiosulfate solution. The main
electrochemical reaction occurring at the cathode surface is the reduction of the auro-thiosulfate
complex (Gallagher et al., 1989, Abbruzese et al., 1995). The electro reduction of gold thiosulfate to
gold is kinetically faster than the reduction of gold cyanide to gold (Sullivan and Kohl, 1997). Gold
thiosulfate is reduced at -0.15V vs SCE and is independent of pH for values above 4. But because of
the various oxidation and reduction reactions of S2O32- which occur at the anode and cathode,
electrowinning is not an attractive option for recovery of gold.
CONCLUSIONS
Interest in the use of non-cyanide methods for dissolution of gold is due to the increasing concern
regarding the toxicity of cyanide and the inability of cyanide solution to effectively leach carbonaceous
or complex ores.
Thiosulfate leaching can be considered as a non-toxic alternative to conventional cyanidation. Leaching
by thiosulfate permits a decreasing interference from cations such as lead, zinc, and copper. In some
cases the gold dissolution rates can be faster than for conventional cyanide treatment. The main
disadvantage of thiosulfate however, has been reagent consumption and the lack of a suitable gold
recovery method.
Thiosulfate in the presence of oxygen in solution can leach gold. However without the presence of
ammonia, passivation of gold occurs through the breakdown of thiosulfate to form sulfur coating on the
gold particles. Copper(II) is also required to significantly increase the rate of gold dissolution.
40

The chemistry of the ammonia-thiosulfate and copper system is complicated due to the simultaneous
presence of complexing ligands such as ammonia and thiosulfate and the Cu(II)-Cu(I) redox couple.
Oxidative decomposition reactions of thiosulfate occur which involve the formation of additional sulfur
compounds such as tetrathionate.
The leaching of gold or silver with ammoniacal thiosulfate can be described as an electrochemicalcatalytic mechanism. Thiosulfate ions react with Au ions formed at anodic sites on the gold surface.
Gold enters the solution to form Au(S2O3)23-. The Cu(NH3)42+ acquires electrons and is directly reduced
to Cu(NH3)2+ at cathodic sites on the gold surface. In the presence of S2O32-, an equilibrium exist
between Cu(NH3)2+ and Cu(S2O3)35- ions. Both the Cu(S2O3)35- and Cu(NH3)2+ species in solution are
then regenerated into Cu(NH3)42+ with oxygen.
The mechanism is further complicated by the oxidation of thiosulfate to tetrathionate. Both oxygen and
Cu(NH3)42+ oxidise thiosulfate ions to tetrathionate ions.
Efficient leaching is achieved by maintaining the appropriate concentrations of ammonia and
thiosulfate in solution with copper (II) acting as oxidant. Oxygen is required to maintain the required
Eh to leach gold and convert the reduced cuprous ion to the cupric state for further gold leaching.
Leaching should be carried out at pH values greater than 8.5 to allow free ammonia to be present to
complex copper (II) and reduce the interference of some foreign cations such as iron or manganese. For
effective gold dissolution an oxidation potential between 150-250mV with reference to standard
hydrogen electrode (SHE) is required (depending upon pH). At higher potentials there is significant
oxidation of thiosulfate to tetrathionate.
Higher gold and silver dissolution rates have been reported at temperatures in the range of 40-60C.
Most work has been carried out on complex gold ores containing high copper, carbonaceous ores or
ores containing high concentrations of lead, zinc or manganese. Relatively high concentrations of
thiosulfate, compared with those used in cyanide are generally used, but recent work favours low
concentrations of reagents around 0.1-0.2M thiosulfate and ammonia.
In ammoniacal thiosulfate leaching of gold, increasing the concentration of thiosulfate in solution
results in an increase in thiosulfate consumption. Efforts have been made to reduce consumption by
reducing the concentration of thiosulfate in solution and leaching for extended periods (e.g. 24 hours).
Alternatively, sulfite has been added to the leaching solution to stabilise the thiosulfate.
In the case of low-grade carbonaceous ores, processing by thiosulfate leaching without pretreatment by
heap leaching can be carried out. However, ores containing high sulfide concentrations require at least
partial oxidation prior to thiosulfate leaching. Several investigators have looked at the use of bacteria or
pressure leaching prior to thiosulfate leaching. Another possibility is to generate thiosulfate in-situ. The
stability field for thiosulfate is located in the neutral to basic pH region. Once thiosulfate has been
formed conditions can be readily adjusted for gold and silver leaching. In addition to thiosulfate,
polysulfides will also be present during leaching which provide another complexant for leaching gold
and silver.
While thermodynamic predictions can be made, research is required on detailing the reactions and
species involved in thiosulfate leaching of gold and silver in order to establish the optimum molar
ratios for ammonia, thiosulfate and copper. In addition, the oxygen concentration required in the
ammonical thiosulfate and copper systems to regenerate copper to the Cu(II) state requires
investigation.
Most research has been concerned with the extractability of gold with thiosulfate and only limited work
has been carried out on the process of recovering gold from solutions. Precipitation methods appear to
have been used the most and are relatively successful on clarified liquors. Alternative processes include
a reduction-precipitation process with stabilised alkali metal borohydrides, hydrogen sparging, use of
alkyl phosphorus esters, extraction using amines, addition of sulfide to solution, and electro winning to
remove gold from solution. However in most cases coprecipitation of copper occurs which gives a low
grade gold product or high reagent consumption. Activated carbon has a low affinity for Au(S 2O3)23-.
41

However, gold complex anions can be adsorbed from a thiosulfate solution by carbon after adding a
small amount of cyanide to the system.
The use of a strong base resin consisting of a quaternary amine attached to a polymer backbone has
been partially successful in resin-in-pulp studies. Unfortunately copper also loads on to the resin and
thiosulfate ion inhibits the loading of gold. More research into the selective adsorption or stripping of
gold is required.
The difficulties described here do not appear insurmountable given a detailed understanding of the
mechanism involved which should lead to an effective alternative and less toxic methodology for gold
extraction.
ACKNOWLEDGEMENTS
Advice on the construction of speciation diagrams by Dr Ewen Silvester is gratefully appreciated.
42
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Minerals Engineering 2001 14(2)

THIOSULFATE LEACHING OF GOLD A REVIEW

MARK G AYLMORE AND DAVID M MUIR

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Conventional uses of thiosulfate

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

THERMODYNAMICS OF GOLD DISSOLUTION

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Log [NH3] (M)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Total NH3 conc (M)

Total NH3 conc (M)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

THE ELECTROCHEMICAL-CATALYTIC MECHANISM OF GOLD LEACHING

2Cu(NH3)42+ + 8S2O32- = 2Cu(S2O3)35- + S4O62- + 8NH3

Minerals Engineering 2001 14(2)

Redox potential (V)

Minerals Engineering 2001 14(2)

DISSOLUTION OF SILVER BY THIOSULFATE LEACHING

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

Log [NH3] (M)

Minerals Engineering 2001 14(2)

S - H2O - System at 25.00 C

Minerals Engineering 2001 14(2)

Minerals Engineering 2001 14(2)

EFFECT OF OTHER CATIONS IN SOLUTIONS

EFFECT OF TEMPERATURE ON THIOSULFATE LEACHING

Minerals Engineering 2001 14(2)

AUTOCLAVE LEACHING OF GOLD

LEACHING WITH POLYSULFIDE

GENERATION OF THIOSULFATE IN SITU

Minerals Engineering 2001 14(2)

and dissolve gold as described above.

SO2(aq) + H2O = H+ + HSO32- H2O + SO32- + 2NH4+

Minerals Engineering 2001 14(2)

DECOMPOSITION OF SULFIDES IN THIOSULFATE LEACH SOLUTION

THIOSULFATE LEACHING OF ORES

Minerals Engineering 2001 14(2)

TABLE 4 List of conditions used in literature

2Gold (g/ton) Temperature pO2 (kPa) Retention (hrs) S2O3 (M)

Wan and Brierley, 1997

Gold copper ores

Bacteria leached ore

~500-1000ppm 10-100ppm 0.01-0.05

Minerals Engineering 2001 14(2)

TABLE 5 Patents on thiosulfate leaching