MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW

2016, VOL. 37, NO. 6, 385–411

http://dx.doi.org/10.1080/08827508.2016.1218872

A Review of Ammoniacal Thiosulfate Leaching of Gold: An Update Useful for Further

Research in Non-cyanide Gold Lixiviants
X. M. Zhang and G. Senanayake
Chemical & Metallurgical Engineering & Chemistry, School of Engineering and Information Technology, Murdoch University, Murdoch, Perth,
WA, Australia

ABSTRACT KEYWORDS
This literature review provides an update of ammoniacal thiosulfate as a potential lixiviant of gold, the Ammonia; copper(II); gold;
history of thiosulfate leaching and recent progress on thiosulfate leaching of gold, as well as the leaching; thiosulfate
production, oxidation, and stabilization of thiosulfate. The leaching results of different types of gold
ores including oxide, sulfide, carbonaceous, and refractory ores/concentrates and the fundamentals
relevant to the oxidation of pure gold are summarized. The factors affecting gold leaching such as pH,
temperature, and oxidants in leaching solutions, reagent concentrations, and foreign ions are presented
to update the current understanding on gold dissolution in a Cu(II)-NH3-S2O32-system.

1. Introduction for the recovery of precious metals from a copper sulfide ore.
Subsequently, studies on leaching different kinds of gold ores
Over the past two to three decades, there are over 500 refer-
using ammoniacal thiosulfate lixiviant have been carried out
ences that appear related to the application of alternative
in many countries (Perez, and Galaviz, 1987; Zhang and Li,
lixiviants to cyanide for leaching gold (Aylmore, 2005).
1987; Zipperian et al., 1988; Langhans et al., 1992; Murthy and
Researchers have investigated at least 15 alternative gold lixi-
Prasad, 1996; Wan, 1997; Yen et al., 1998; Aylmore, 2001;
viants, which can be divided into three categories according to
Feng and van Deventer, 2001, 2007a, 2007b, 2007c; Ji et al.,
different leaching conditions, oxidants, and ligands (Sparrow
2003; Ficeriova et al., 2005; Tanriverdi et al., 2005). Research
and Woodcock, 1995): (i) Under low acidic or low basic
activities have been focused on investigating the effect of
conditions (pH 5–9), suitable lixiviants include thiosulfate,
physico-chemical factors such as pH, concentration of
halogens, bromocyanide, bromine, iodine, sulfurous acid, or
reagents, and temperature on overall gold dissolution and
bisulfite, and natural organic acids; (ii) Under alkaline condi-
recovery from different types of ores (Bagdasaryan, 1983;
tions (usually at pH > 10), effective lixiviants include cyanide,
Michel and Frenay, 1990; Chen et al., 1993; Gong et al.,
ammonia-cyanide, ammonia, sodium sulfide, and nitriles,
1993; Jiang et al., 1993a, 1993b, 1993c; Sullivan and Kohl,
with oxygen or sulfur as oxidants; (iii) Under acidic condi-
1997; Breuer and Jeffrey, 2000b; Jeffrey, 2001).
tions (pH < 3), lixiviants include thiourea, thiocyanate, aqua
A plant based on the Kerley patent (1981, 1983) had been
regia, hypochlorite, chlorine, ferric, or cupric as oxidants.
built in Mexico using thiosulfate to leach gold, but it did not
Despite the research interest in non-cyanide gold lixiviants,
operate successfully (Gong and Hu, 1990). Perez and Galaviz
many alternative non-cyanide gold processes are still at the
(1987) pointed out that the plant could be successful by leaching
early stages of development. Table 1 shows the various lixi-
at pH 10–10.5 rather than at pH 8, to avoid the problem of
viants, for gold dissolution, reaction conditions, and refer-
dissolution of iron. Newmont Gold Company set up a pilot plant
ences. The stability of gold(I)/(III) complexes with different
for heap leaching of carbonaceous preg-robbing ores using thio-
ligands is a key factor in determining the use of a particular
sulfate (Wan et al., 1994; Wan and LeVier, 2003). Much higher
lixiviant system (Senanayake, 2004a, 2004b).
gold recoveries were achieved than with cyanide, due to the
The dissolution of gold and silver in thiosulfate media has
inability of the carbonaceous material to adsorb gold thiosulfate.
been recognized for over a century. The first report on the use
Nicol and O’Malley (2001, 2002), Ji et al. (2003), and West-Sells
of thiosulfate for precious metal recovery dates back to 1905
et al. (2003) evaluated the effectiveness of anion exchange resins
in a method known as von Patera’s process. In this process,
for the recovery of gold from the thiosulfate leach liquors and
ammonia-thiosulfate was used for the recovery of gold from
pulps. The separation and recovery of gold from leach solutions
an ore subjected to a chloridizing roast (Flett et al., 1983; Yen
using ion exchange resins and carbon, solvent extraction, and
et al., 1998; Aylmore and Muir, 2001a, 2001b). Following this,
cementation have been discussed by Nicol and O’Malley (2001,
many decades have passed without much progress on gold
2002), Grosse et al. (2003), Hiskey and Lee (2003), Kejun et al.
leaching with thiosulfate. In 1979, Berezowski and Sefton
(2003), Choo and Jeffrey (2004), and Navarro et al. (2004, 2006).
(1979) renewed interest in the use of ammonium thiosulfate

CONTACT G. Senanayake G.Senanayake@murdoch.edu.au Chemical & Metallurgical Engineering & Chemistry, School of Engineering and Information
Technology, Murdoch University, 90 South Street, Murdoch, Perth, WA 6150, Australia.
© 2016 Taylor & Francis
386 X. M. ZHANG AND G. SENANAYAKE

Table 1. Gold lixiviants, conditions, and references.

Other
Advantages:
Ligand/oxidant conditions Reference
Thiosulfate S2O32–/Cu(NH3)42+/O2 pH > 9.0 Wan (1997) (i) Thiosulfate has very low toxicity and has been used as
Bromocyanide CN–/BrCN pH = 7 Dorr and Bosqui (1950) a fertilizer for many years due to its relatively low
Bromine Br2 /Br– Pesic et al. (1992)
Iodine I–/I2 pH < 11 Qi and Hiskey (1991) impact on the environment.
Sulfite SO32– pH > 7 Touro and Wiewiorowski (ii) The common thiosulfate salts (Na+, K+, NH4+, and
Bacteria and natural amino acids pH = 9.5,
(1992)
Rapson (1982)
Ca2+) are biodegradable, and considered non-hazar-
30°C dous by Work Safe Australia (NOHSC, 1999). They
Glycine and hydrogen peroxide pH = 11, Oraby and Eksteen (2015) are not considered to be dangerous substances by
23–60°C
Cyanide CN–/O2 pH > 10 Nagy et al. (1966) European Standards (Langhans et al., 1992).
and (iii) Thiosulfate has the potential to treat a wide variety of
aeration gold ores, such as high copper ores, carbonaceous
Ammonia/cyanide O2/Cu(CN)3(NH3)22– alkaline Zheng et al. (1995); Muir
(2011) ores, and manganese-containing ores.
Copper(II)/ammonia Cu(NH3)42+ t > 150°C Meng and Han (1993); (iv) Among the non-cyanide lixiviants, thiosulfate has
Han (2001) accomplished high gold recoveries and fast leaching
Nitriles/malononitrile O2 CH2(CN)2 pH = 9.5– Sandgren et al. (1993)
12 rates (Cao et al., 1992).
Thiourea NH2CSNH2/ Fe(III) pH = 1–2 Hiskey (1981, 1988); Lan (v) Thiosulfate can be generated in situ at low cost.
et al. (1993)
Thiocyanate SCN–/Fe(III) pH = 1–3 Barbosa-Filho and
Monhemius (1994a, Disadvantages:
1994b, 1994c)
–
Chlorine (aqueous) Cl /Cl2 Putnam (1944)
Aqua regia HCl/HNO3 Hiskey and Atluri (1988) (i) The thiosulfate processes require a solid–liquid
separation stage in order to recover relatively high
concentrations of unconsumed reagents.
(ii) The degradation of thiosulfate will increase reagent cost,
Some research activities have focused more on the reaction while the degradation products (oxy-sulfur anions) have
mechanism and in-pulp processes for recovery of gold using lower detrimental effects on the leaching and recovery process.
reagent concentrations to minimize cost, for example, in heap- (iii) Thiosulfate leaching involves ammonia, a volatile and
leaching operations (Wan and LeVier, 2003). Researchers have noxious reagent that can easily escape from open
addressed some issues related to speciation of Au(I)/(III), Cu(I)/ leaching vessels and contaminate the surroundings
(II), and polythionates (Aylmore and Muir, 2001a, 2001b; Ritchie (Grosse et al., 2003).
et al., 2001; Molleman and Dreisinger, 2002; Muir and Aylmore, (iv) One of the main methods for recovery of gold from
2002; Senanayake et al., 2003; Perera and Senanayake, 2004; thiosulfate solution is resin in pulp; this method is
Senanayake, 2004a, 2004b, 2004c, 2005d; Zhang et al., 2004a, still under investigation (Nicol and O’Malley, 2001,
2008). The interest in the use of non-ammoniacal thiosulfate 2002; West-sells et al., 2003).
and amino acids for gold leaching is also growing (Choi et al., (v) Thiosulfate processing involves complex gold-cop-
2013; Ji et al., 2003; Eksteen and Oraby, 2015; Oraby and Eksteen, per-sulfur chemistry.
2015; Sitando et al., 2015). Two reviews presented a comparison of (vi) Alternative gold lixiviants, including thiosulfate, are
different non-cyanide lixiviant systems on the basis of the types of applied at concentrations 50–100 times those required
oxidant, process conditions, applications, current status, occupa- for cyanidation and, thus, needs techniques such as
tional health and safety issues, as well as environmental concerns reverse osmosis to produce lixiviant-free clean water
(Ritchie et al., 2001; Aylmore, 2005). Some of the important for recycle to the comminution circuit (Choi and La
aspects are summarized in Table 2. Out of all the processes Brooy, 2014).
available, thiosulfate and chloride leaching appear to be the most
favorable to replace cyanide (Aylmore, 2005). Ritchie et al. (2001) The intention of this article is to (i) present an update the
concluded that thiosulfate is the most promising alternative to ammoniacal thiosulfate leaching of gold, (ii) discuss the gold-
cyanide for the recovery of gold from ores. The advantages and copper-thiosulfate speciation, (iii) summarize the reactions
disadvantages of thiosulfate leaching of gold are listed below. involved in the production, oxidation, and stabilization of

Table 2. Relevant properties of lixiviants.

Lixiviant Stability of complex Oxygen as oxidant Chemical stability OHS Effect on environment Developmental stage Low cost
Cyanide + + 0 – – + +
Thiosulfate 0 – – + + 0 +
Hydrosulfide + – – 0 0 – +
Ammonia 0 –* 0 0 0 – +
Chloride – –* + + + – +
Thiourea 0 – – 0 0 0 0
Thiocyanate + – + – – 0 0
Sulfite 0 – – 0 + – +
Bromide - – + 0 0 – –
Iodide 0 – 0 + 0 – –
*Only at elevated temperatures under pressure leach conditions; Ritchie et al. (2001).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 387

thiosulfate, and (iv) review factors affecting the leaching of gold Gold reacts with ammoniacal thiosulfate in the presence of
in the pure form or as ores/concentrates of different origin. copper(II) as an oxidant, (Eq 3). Meanwhile, copper(II) also
reacts with thiosulfate, (Eq. 4). This leads to a series of stable
or metastable sulfur-oxygen species, for example, tetrathio-
2. Gold–copper–sulfur species and electrode
nate, pentathionate, trithionate, sulfite, and sulfate, which
potentials
could affect the kinetics of gold leaching (Naito et al., 1970;
2.1. Stability constants of gold(I)/(III) complex species Byerley et al., 1973b, 1975; Breuer and Jeffrey, 2003b; Chu
et al., 2003).
The lixiviant systems listed in Table 1 show mixed-ligand sys-
tems such as ammonia–thiosulfate, ammonia–cyanide, and Au þ CuðNH3 Þ4 2þ þ 2S2 O3 2
ammonia–chloride. Table 3 lists the stability constants (βn) for ¼ AuðS2 O3 Þ2 3 þ CuðNH3 Þ2 þ þ 2NH3 (3)
selected Au(I) and Au(III) complexes and standard reduction
potentials at 25°C. Some standard reduction potentials listed in
Table 3 were calculated from β values using Eqs. 1 or 2, where L 2CuðNH3 Þ4 2þ þ 8S2 O3 2 ¼ 2CuðS2 O3 Þ3 5 þ 8NH3
is ligand, E°{Au+/Au} = 1.69 V and E°{Au3+/Au} = 1.50 V þ S4 O6 2 (4)
(Schmid and Curley-Fiorino, 1975).
Thus, the chemistry of the thiosulfate leaching and recov-
Eo fAuðI ÞL2 =Aug ¼ Eo f
Auþ =Aug ð0:059=1Þlog β2 (1) ery of gold has been described as very complex by a number
E fAuðIII ÞL4 =Aug ¼ Eo Au3þ =Au  ð0:059=3Þlog β4
o
(2) of authors (Fung and Glastonbury, 1975; Abbruzzese et al.,
1995; Abulimit et al., 1999; Breuer and Jeffrey, 2000b;
Molleman and Dreisinger, 2002; Muir and Aylmore, 2005).
Gold(I) cyanide is the most stable complex with β2 ≈ 1038. Gold(I) This is due to the mixed ammonia-thiosulfate-hydroxide
sulfide/hydrosulfide complexes are also very stable, with βn ≈ ligand system, which affects Cu(II)-Cu(I)-Au(I) speciation,
1030–1033, followed by thiosulfate complexes. The reported values and the polythionates formed during thiosulfate degradation
of stability constants for gold(I) diammine and gold(I) dithiosul- (Byerley et al., 1973b; Aylmore and Muir, 2001a, 2001b;
fate vary within a large range of β2 = 1013–1026 and β2 = 1024–1028 Molleman and Dreisinger, 2002; Chu et al., 2003; Grosse
respectively, and reflect the difficulties in measuring these quan- et al., 2003; Senanayake, 2004a, 2004b, 2004c; Black, 2006).
tities. Studies based on linear free energy correlations and half The mixed complexes and polythionates affect the thermody-
wave potential measurements have shown that the most accepta- namics and kinetics of the leaching, separation, and recovery
ble values are β2 {Au(NH3)2+} = 1013 and β2 {Au(S2O3)23–} = 1024 stages of gold.
(Aylmore, 2001; Hindmarsh and Nicol, 2001; Senanayake et al., There are many chemical and physical factors that affect
2003; Perera and Senanayake, 2004). the kinetics of gold leaching in thiosulfate media: (i) con-
centration of reagents, (ii) pH, (iii) temperature, (iv) ionic
2.2. Major reactions strength, (v) dissolved oxygen, and (vi) background salts. A
number of reaction schemes and mechanisms for gold
oxidation by ammoniacal copper(II) thiosulfate have been
Table 3. Stability constants of selected Au(I) and Au(III) complexes and corre- put forward, with little agreement among the different
sponding standard reduction potentials.
research groups (Gong et al., 1993; Jiang et al., 1993a;
log log E°Au(I)/Au(0)
Gold species (β2) (β4) (V at 25°C) pH References
Breuer and Jeffrey, 2000b). A more detailed understanding
Au(CN)2– 38.3 –0.67 > 10 Smith and Martell (1976)
of the mechanism of gold leaching by ammoniacal thiosul-
Au(CN)4– 56 0.40m Nicol et al. (1987) fate would help the development of ammoniacal or non-
Au(HS)2– 32.8 –0.25m Webster (1986) ammoniacal processes to treat different types of gold ores.
Au2(HS)2S2– 72.9 –0.46m Webster (1986)
Au(S2O3)23– 28 0.038m 8–11 Sullivan and kohl (1997) The key to understanding the reaction mechanism is a
26 0.15 Hiskey and Atluri (1988) detailed study of the thermodynamics and kinetics of gold
24 0.274 Smith and Martell (1976)
Au(NH3)2+ 26 0.16 > 9 Wang (1992)
oxidation in these solutions.
19 0.57 Hiskey and Atluri (1988)
13 0.92m > 9 Hancock et al. (1974);
Senanayake et al. (2003) 2.3. Gold and copper species
Au(NH3)43+ 59 0.33 Hiskey and Atluri (1988)
Au(CS(NH2)2)+ 22 0.38 Hiskey and Atluri (1988) Electrochemical measurements including electrode poten-
AuI2– 18.6 0.59m < 4 Smith and Martell (1976)
AuI4– 47.6 0.56 Marsden and House tials (EH) have revealed useful information regarding the
(1992) reactions involved in the thiosulfate leaching of gold. For
Au(SCN)2– 17.1 0.66 < 3 Smith and Martell (1976) example, Zhu et al. (1994b) and Chen et al. (1996) inves-
Au(SCN)4– 10 0.64 1–3 Smith and Martell (1976)
AuH(SO3)2 2–
15.4 0.78m 5–7 Smith and Martell (1976) tigated the dissolution of gold in aqueous thiosulfate solu-
AuBr2– 12 0.98m < 4 Smith and Martell (1976) tions using voltammetry and electrochemical impedance
AuBr4– 32 0.85 Marsden and House
(1992)
spectra. They established that the anodic voltametric
AuCl2– 9.1 1.15m < 4 Smith and Martell (1976) response of a gold electrode in thiosulfate solutions
AuCl4– 25.6 1.00 < 4 Wang (1992) includes the oxidation of thiosulfate. Zhuchkov and
Au(NH3)(S2O3)– 20 Perera and Senanayake
(2004) Bubeyev (1990, 1994) pointed out that the dissolution of
m
Calculated from β values with Eq. 1 or Eq. 2. gold in thiosulfate solutions could be limited by the rate of
388 X. M. ZHANG AND G. SENANAYAKE
chemical dissolution of a passive surface film, possibly a
hydrated oxide. Jeffrey (2001) studied the leaching of silver
and gold-silver alloy in copper(II) ammonia-thiosulfate
solutions using a rotating electrochemical quartz crystal
microbalance and suggested that the initial rate of gold-
silver alloy was limited by a surface chemical reaction.
Zhang and Nicol (2003) conducted an electrochemical
study of the dissolution of gold in thiosulfate solutions.
They found that thiosulfate ions undergo oxidative decom-
position leaving a sulfur-like film on the surface of gold,
which inhibits the rate of dissolution of gold and results in
a low anodic current efficiency for the dissolution of gold.
The potential–pH (EH-pH) and species distribution dia-
grams can be used to clarify the predominant chemical species
under different EH-pH conditions or reagent concentrations.
Efforts to construct accurate EH-pH diagrams for the gold-
ammonia-thiosulfate system are hampered due to inconsisten-
cies in published data for the stability constants (β) of the
relevant complex species. For example, the reported values of
β for the complex Au(NH3)2+ differ by several orders of mag-
nitude (Table 3). The published EH-pH diagrams (Li et al.,
1966; Zipperian et al., 1988) with erroneous values of β indicate
that Au(NH3)2+ is more stable than Au(S2O3)23– in solutions of
pH > 9. However, there is experimental evidence to suggest that
Au(S2O3)23– is more stable than Au(NH3)2+ under such con-
ditions. Li et al. (1966) measured the rest potentials of a gold
electrode rotated in solutions of Na2S2O3 or (NH4)2S2O3 and
showed that the predominant species is Au(S2O3)23– rather
than Au(NH3)2+. Zhang et al., (2004a) studied dissolution
kinetics in oxygenated ammoniacal thiosulfate solutions, and
found that the predominant gold(I) species based on the mea-
sured potentials on gold electrode is gold-thiosulfate complex
(Au(S2O3)23–). Nicol and O’Malley (2001) also showed that Au
(S2O3)23– loaded onto anion-exchange resins could not be
eluted with concentrated ammonia solutions. Stability con-
stants calculated from thermodynamic data also show that β2
of Au(S2O3)23– is several orders of magnitude larger than that
of Au(NH3)2+ (Chen et al., 1993; Perera and Senanayake, 2004).
The latter is formed only at high concentration ratios of [NH3]/
[S2O32–] > 105 (Perera and Senanayake, 2004).
Wang (1992) constructed EH-pH diagrams for the Cu-
NH3-S2O32– system and Au-NH3-S2O32– system at low
reagent concentration. Aylmore and Muir (2001a, 2001b),
Molleman and Dreisinger (2002), Wan and LeVier (2003),
and Muir and Aylmore (2004) have also predicted EH-pH
diagrams for this system. Wan (1997) assumed the existence
of Au(NH3)S2O3–, although it has not been shown in pub-
lished EH-pH or species distribution diagrams (Aylmore and
Muir, 2001a, 2001b) due to the lack of reliable thermody-
namic data (Table 3). The reaction of ammoniacal copper(II)
with thiosulfate ions produces copper(I) and sulfur species
(Eq. 4). This has added to the complexity of the construction
of reliable EH-pH diagrams and elucidation of the gold oxida-
tion mechanism. For example, studies by Black (2006) con-
firmed the existence of mixed Cu(I)-NH3-S2O32– complexes
in typical thiosulfate leach liquors. Perera et al. (2005) studied
the Au(I)-SO32–-S2O32- system using Raman spectroscopy and
detected two mixed-ligand species, Au(S2O3)(SO3)3– and Au
(S2O3)(SO3)25–.
Nevertheless, typical reactions taking place under a given
set of experimental conditions can be predicted from pub-
lished EH-pH and species distribution diagrams of the copper
(II)-copper(I) system. For example, the following important
points have been noted by Aylmore and Muir (2001a):
(i) If pH is greater than 10, copper oxides could pre-
cipitate from solution.
(ii) The value of pH depends on the concentration ratio
of [NH3]/[NH4+], and pH 9–9.5 is the range in
which copper(II) ammine complex is most stable.
(iii) The equilibrium between copper(II) and copper(I)
influences EH, with a high Cu(II)/Cu(I) ratio giving a
high value of EH.
(iv) An appropriate concentration ratio of ammonia/
thiosulfate is needed in order to stabilize the copper
ions in both the Cu(I) and Cu(II) states and to
maintain the availability of Cu(II) for further reac-
tion with gold (Eq. 3).
(v) The leaching potential should be kept within 0.1–0.5
V for stable Au(S2O3)23- species because at potentials
lower than 0.1 V, gold cannot be leached, and copper
will precipitate out as a sulfide. A potential higher
than 1.0 V will form Au(NH3)43+ species.
(vi) At low ammonia concentrations, ([NH3] < 0.1 M)
and a ratio of [S2O32–] /[NH3] > 1, gold thiosulfate is
the dominant species and will change to gold dia-
mmine with an increase in the concentration of
ammonia, so high pH values favor the formation of
Au(NH3)2+.
(vii) If both thiosulfate and ammonia are low (0.1 M), the
two complexes Cu(S2O3)23- and Cu(S2O3)35– are
stable over the pH range 2–10. Copper(II) tetraam-
mine and copper(II) triammine can only be formed
at around pH 10. At very low copper concentrations,
copper(II) hydroxide will precipitate at pH > 10.5.
3. Production, oxidation, and stabilization of
thiosulfate
3.1. Sulfur species
The S2O32– ion is a structural analogy of SO42– ion with one
oxygen atom replaced by a sulfur atom (Hiskey and Atluri,
1988). The central sulfur atom has a nominal oxidation state
of +6 and the adjoining sulfur has an oxidation state of –2.
Thus, its structure can be represented by [S=SO3]2–, where the
chemical properties are dominated by the sulfide-like sulfur
atom, which imparts reducing properties, strong complex
tendencies, and sulfide-forming capabilities (Hiskey and
Atluri, 1988).
In copper(II)-ammonia-thiosulfate solutions, a series of
stable and metastable sulfur-oxygen species (Table 4) may be
formed in solution (Byerley et al., 1973a, 1973b; Wan, 1997;
Aylmore and Muir, 2001a, 2001b; Molleman and Dreisinger,
2002; Muir and Aylmore, 2005). Some of these species are
shown in the form of an EH-pH diagram for the metastable
S-H2O system (Aylmore and Muir, 2001a), which indicate
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 389

Table 4. Sulfur–oxygen species and oxidation states of sulfur. Table 5. Summary of reactions and conditions for thiosulfate regeneration.
Species Name Oxidation state Reactions (References) Conditions Eq. No.
S2– Sulfide –2 SO2 (aq) + H2O = 2H+ + SO32– 70–80°C 5
S° Sulfur 0 SO32– + S° = S2O32– 6
S6O62– Hexathionate +1.7 (Dreisinger, 1998; Aylmore, 2001)
S2O32– Thiosulfate +2 4S° + 6OH– = 2S2– + S2O32- + 3H2O Phase transfer catalysis 7
S5O62– Pentathionate +2 (x–1)S° + S2– = Sx2– (Zhu et al., 1994a)
S4O62– Tetrathionate +2.5 2SO32– + 2HS–+ O2= 2S2O32– + 2OH– Heated 8
S2O42– Dithionite +3 (Kerley, 1981)
S3O62– Trithionate +3.3 Na2S5 + 1.5O2= Na2S2O3 + 3S° Partial oxidation 9
S2O52– Disulfite +4 (Chen et al., 1996)
SO32– Sulfite +4 2Na2S + 4SO2 + Na2CO3 = 3Na2S2O3 + CO2 pH: 6.4–7.0 10
S2O62– Dithionate +5 (Chen et al., 1996)
S2O72– Disulfate +6 2Na2S2 + 3O2 = 2Na2S2O3 70–80°C 11
SO42– Sulfate +6 (Chen et al., 1996)

that HS–, S2–, S2O32–, SO32–, S2O62–, and S4O62- exist, along
with S2O32–, which occupies a narrow elongated stability field
from pH 4–14 and EH –0.6 V to 0.2 V. Tetrathionate S4O62- is
located in a large area and seems to be the most stable species
in acidic solutions. Sulfite (SO32–) and dithionate (S2O62–)
ions also have stability regions larger than thiosulfate
(S2O32–), depending on EH and pH.
cost, but also leads to the formation of sulfides, which passi-
vate gold and retard the leaching rate (Wan, 1997). Therefore,
it is important to consider the possible degradation reactions
of thiosulfate in the presence of the two oxidants, oxygen and
copper(II).

3.3. Oxidation of thiosulfate by oxygen

3.2. Production of thiosulfate
2–
Thiosulfate is produced from sulfite (SO3 ), polysulfide
(Sn2–), and elemental sulfur (S°), or polythionate (SnOm2–),
according to the reactions listed in Table 5. Zhu et al. (1994a)
reported that the disproportionation of elemental sulfur in
ammonia media produces thiosulfate and polysulfide through
phase transfer catalysis (Eq. 7). Thiosulfate can also be gener-
ated by oxidation of polysulfides Sn2–, n = 2, 3, 4,. . . (Chen
et al., 1996) (Eqs. 9–11).
Thiosulfate ions are metastable and tend to undergo che-
mical decomposition in aqueous solutions. The stability of
thiosulfate ions is affected by a number of factors (Dhawale,
1993; Deschenes, 1998; Aylmore and Muir, 2001a, 2001b;
Molleman and Dreisinger, 2002), which include:
(i) The water purity; freshly prepared thiosulfate with
double-distilled water is very stable if stored in an
airtight bottle.
(ii) The concentration of thiosulfate; diluted solutions
(< 0.01 M) decompose more rapidly than concen-
trated solutions (> 0.1 M).
(iii) The pH of the solution.
(iv) The presence of certain metals or alloys.
(v) The presence of sulfur metabolizing bacteria.
(vi) The presence of microorganisms and redox
catalysts.
(vii) The presence of oxygen.
(viii) Exposure to ultraviolet light.
(ix) The presence of sulfite.
The high consumption of thiosulfate, when added as
sodium thiosulfate or ammonium thiosulfate during gold
leaching, is one of the major problems in thiosulfate pro-
cesses. Thiosulfate degradation in leach liquors can occur as
a result of oxidation by oxygen, copper(II), or both. The
degradation of thiosulfate not only results in higher reagent
A 5% (w/w) solution of thiosulfate has a pH of 6.0–8.4 at 25°C
and is very stable at normal pressures and temperatures. Rolia
and Chakrabarti (1982) reported that under sterile laboratory
conditions at pH 7, solutions of thiosulfate and polythionates
can be aerated over four months, with less than 10% change in
the concentrations. Jiang et al. (1996) reported that thiosulfate
solutions stirred for 24 hr at pH 6–12 lost less than 1%
thiosulfate due to oxidation. Zhang (2008) conducted experi-
ments on the oxidation of thiosulfate by oxygen ([O2] = 0.75
mM) in ammonia-thiosulfate solutions at pH 9.3. He found
that there was no detectable decomposition of thiosulfate in
the first hour and 6% of thiosulfate decomposed in 5 hr. This
demonstrated that the aerobic oxidation of thiosulfate is a
very slow process.
In oxygen-ammonia-thiosulfate solutions, the decomposi-
tion of thiosulfate as shown in Eq. 12 was found to be a first-
order reaction with respect to thiosulfate concentration (Fung
and Glastonbury, 1975). Thiosulfate was also oxidized by
molecular oxygen in alkaline solutions in the temperature
range 75°C–87°C (Rolia and Chakrabarti, 1982), and the
final product was sulfate.
S2 O3 2 þ O2 þ H2 O þ 2NH3 ¼ 2SO3 2 þ 2NH4 þ (12)
þ
S2 O3 þ2O2 þ H2 O ¼ 2SO4 þ 2H
2 2
(13)
S2 O3 2 þ2O2 þ 2OH  ¼ 2SO4 2 þ H2 O (14)
Similar results were obtained at 100°C under air pressures
of 980 kPa (Gluud, 1921). The rate of oxidation of thiosulfate
under pressure was increased by increasing pH, concentration
of thiosulfate, oxygen pressure, and temperature (Rolia and
Chakrabarti, 1982). Moreover, thiosulfate can degrade to form
sulfate and sulfur in solutions of low pH (< 9), or sulfate and
bisulfide in solutions of high pH (> 9) as shown by Eqs. 15
and 16 (Dreisinger, 1998).
3S2 O3 2 þ 2H þ ¼ 4S0 þ 2SO4 2
þ H2 O pH < 9 ðvery slowÞ (15)
390 X. M. ZHANG AND G. SENANAYAKE
S2 O3 2 þ OH  ¼ HS þ SO4 2 pH > 9 ðvery slowÞ (16)
3.4. Oxidation of thiosulfate by copper(II)
In copper(II)-ammonia-thiosulfate solutions, thiosulfate
decomposition can include oxidation or reduction. The half
cell reactions can be described as follows, where the final
product is sulfate, elemental sulfur, or copper sulfides (Wan,
1997).
Oxidation:
2S2 O3 2 ¼ S4 O6 2 þ 2e (17)
S4 O6 2
þ 10H2 O ¼ 4SO4 2 þ 20H þ þ 14e (18)
Reduction:
CuðII Þ þ S2 O3 2 þ 6H þ þ 6e ¼ S þ CuS þ 3H2 O (19)
2CuðI Þ þ S2 O3 2 þ 6H þ þ 6e ¼ S þ Cu2 S þ 3H2 O (20)
In aqueous ammonia solutions without oxygen, copper(II)
initially oxidizes the thiosulfate to tetrathionate ions (Byerley
et al., 1973b). The exact speciation of Cu(I)/(II) complexes and
the ionic charges are not shown in Eq. 21 due to the involve-
ment of a number of different complexes of Cu(II) and Cu(I)
shown in published Eh-pH and speciation diagrams (Aylmore
and Muir, 2001a, 2001b) as well as mixed complexes of Cu(II)-
NH3-S2O32– (Byerley et al., 1973b) and Cu(I)-NH3-S2O32–
(Black et al., 2003; Black, 2006), which are generally not
shown in Eh-pH diagrams. Subsequently, tetrathionate ions
undergo alkaline hydrolysis to trithionate and thiosulfate by
raising the pH value to 11 (Fava and Bresadola, 1955; Foss and
Kringlebotn, 1961; Naito et al., 1970; Zhang and Dresinger,
2002; Muir and Aylmore, 2005). The rate of oxidation is
dependent on reagent concentration and pH. The overall reac-
tion of Eqs. 21 and 22 is given by Eq. 23:
2CuðII Þ þ 2S2 O3 2 ¼ S4 O6 2 þ 2CuðI Þ (21)
2
4S4 O6 þ 6OH  ¼ 5S2 O3 2 þ 2S3 O6 2 þ 3H2 O (22)
8CuðII Þ þ 3S2 O3 2 þ 6OH 
¼ 8CuðI Þ þ 2S3 O6 2 þ 3H2 O (23)
In the case of non-ammoniacal solutions in which thiosul-
fate is not present in large excess, or in which copper(II) is in
excess, the fast redox reaction (Eq. 21) is followed by slower
side reactions that result in the formation of Cu, Cu2S, and
SO42– (Rabai and Epstein, 1992):
2CuðI Þ ¼ CuðII Þ þ Cuð0Þ (24)
2CuðII Þ þ S2 O3 2 þ H2 O þ 2e
¼ Cu2 S þ SO4 2 þ 2H þ (25)
The rate of thiosulfate decomposition is proportional to the
concentration of copper(II) and thiosulfate. The presence of
ammonium sulfate and the increase in ammonia concentration
results in increased stability of thiosulfate. However, an increase in
temperature accelerates the decomposition of thiosulfate by Cu(II)
(Fung and Glastonbury, 1975). Senanayake (2004c) revisited lit-
erature data to show that (i) the oxidation of thiosulfate takes place
via mixed complexes Cu(NH3)2(S2O3) and Cu(NH3)2(S2O3)22–,
(ii) gold dissolution in the copper(II)-ammonia-thiosulfate system
show first-order dependence with respect to copper(II) and
thiosulfate, (iii) rate is relatively less affected by ammonia and
hydroxide concentration, and (iv) rate becomes zero order with
respect to these reagents at higher copper(II) and thiosulfate
concentration.
3.5. Oxidation of thiosulfate by oxygenated copper(II)
The reaction between Cu(II) and S2O32– is catalyzed by the
presence of oxygen. The rate of thiosulfate oxidation in the
presence of oxygen is at least 40 times greater than that in the
absence of oxygen (Byerley et al., 1973a). Increased oxygen
percentage in air or gas flow can:
(i) rapidly oxidize copper(I) to copper(II) (Eq. 26),
(ii) make the direct reaction between copper(II) and
S2O32- continuous (Eq 21),
(iii) increase the rate of copper(II) reduction by thiosul-
fate to copper(I), and
(iv) rapidly oxidize thiosulfate (Breuer and Jeffrey,
2003a).
2CuðI Þ þ 0:5O2 þ H2 O ¼ 2CuðII Þ þ 2OH  ðfastÞ (26)
Wensveen and Nicol (2005) investigated the kinetics of the
copper-catalyzed oxidation of thiosulfate in ammoniacal solu-
tions, and pointed out that copper(I) thiosulfate complexes are
very slowly oxidized while the copper(I) diammine complex is
rapidly oxidized to copper(II) state by dissolved oxygen. The
initial rapid oxidation of thiosulfate by copper(II) leads to a
pseudo steady-state condition. The concentration of copper(I)
in the pseudo steady-state condition is relatively constant.
Thus, the measured rate of oxidation of copper(I) by oxygen
can be used to predict the rate of oxidation of thiosulfate.
Byerley et al. (1975) suggested a reaction mechanism invol-
ving a Cu(II)-O2-S2O32– complex as an intermediate, where
the oxygen molecule is axially associated with the metal centre
of the complex. This was proposed to cause an increase in the
rate of oxidation of thiosulfate in the presence of oxygen.
Experimental evidence also suggests the involvement of
S2O52– ion in the process of copper(II) catalyzed oxidation
of thiosulfate (Byerley et. al. 1973a). Table 6 is a summary of
decomposition reactions of thiosulfate. It can be seen that
thiosulfate can be changed to sulfur, sulfide, sulfite, sulfate,
or trithionate in alkaline solution, and sulfate is the most
stable species. In neutral or acid solutions, thiosulfate is likely
to be converted to tetrathionate or sulfite and elemental
sulfur. Clearly, the mechanism and decomposition pathway
of thiosulfate species is complex and not yet well understood
(Muir and Aylmore, 2005).
3.6. Stabilization of thiosulfate
The high consumption of thiosulfate during gold leaching is a
major problem, highlighting the importance of stabilization of
thiosulfate in leaching solutions. Table 7 lists a series of
reactions showing the formation of thiosulfate from various
sulfur species. Two patents were assigned to Kerley (1981,
1983) for the addition of sulfite ions to control the stability
of thiosulfate solutions during the leaching reaction,
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 391

Table 6. Stoichiometry of oxidative and reductive decomposition of thiosulfate. Table 7. Stoichiometry of the stabilization reactions of thiosulfate.
Eq. Reactions (References) Conditions Eq. No.
Reactions (References) Conditions No SO42– + S2– + H2O = S2O32– + 2OH– Alkaline solution 37
S2O32– + O2 + H2O + 2NH3 = 2SO32– + 2NH4+ NH3 12 (Hu and Gong, 1991)
(Fung and Glastonbury, 1975) SO32– + 2OH– + S4O62– = S2O32– + SO42– + H2O pH 8 38
S2O32– + 2O2 + H2O = 2SO42– + 2H+ T = 75–85°C 13 (Kerley, 1981)
(Rolia and Chakrabarti, 1982) alkaline 4SO32– + 2S2– + 3H2O = 3S2O32–+ 6OH– Alkaline solution 39
S2O32– + 2O2 + 2OH– = 2SO42– + H2O Cu(NH3)42+ 14a (Gong and Hu, 1990; Kerley, 1981)
(Byerley et al., 1975) solution 4SO32– + 2HS– + H2O = 3S2O32– + 4OH– Alkaline solution 40
1.5S2O32– + O2 + 0.5H2O = S3O62– + OH– Cu(NH3)42+ 14b (Dreisinger, 1998; Li et al., 1995)
(Byerley et al., 1975) solution SO32– + S4O62– + HS– + OH– = 3S2O32– + H2O Alkaline solution 41
3S2O32– + 2H+ = 4S° + 2SO42– + H2O pH < 9 15 (Dreisinger, 1998)
(Dreisinger, 1998) SO32– + S4O62– = S2O32– + S3O62– 42
S2O32– + OH– = HS– + SO42– pH > 9 16 (Dreisinger, 1998)
(Dreisinger, 1998) 4SO32– + 2S+ 6H++ 4e = 3S2O32– + 3H2O Heated 43
2S2O32– = S4O62– + 2e Ammonia 17 (Perez and Galaviz, 1987)
(Wan, 1997) solution 2SO32– + 2HS–+ O2 = 2S2O32– + 2OH– 44
S4O62– + 10H2O = 4SO42– + 20H+ + 14e Ammonia 18 (Kerley, 1981)
(Wan, 1997; Byerley et al., 1973a, 1973b, 1975) solution 2S4O62– + 3OH– = 2.5S2O32– + S3O62– + 1.5H2O pH = 11.5 45
Cu(II) + S2O32– + 6H+ + 6e = S + CuS + 3H2O Ammonia 19 (Naito et al., 1970)
(Wan, 1997) solution S3O62– + 2OH– = S2O32–+ SO42– + H2O pH = 11.5 46
2Cu(I) + S2O32– + 6H+ + 6e = S + Cu2S +3H2O Ammonia 20 (Naito et al., 1970)
(Wan, 1997) solution 2S3O62– + 6OH–+ 2O2= S2O32– + 4SO42– + 3H2O pH = 13 47
2Cu(II) + 2S2O32– = S4O62– + 2Cu(I) Alkaline 21 (Naito et al., 1970)
(Byerley et al., 1973a, 1973b) 2S5O62– + 6OH– = 5S2O32– + 3H2O pH = 13 48
4S4O62– + 6OH–= 5S2O32– + 2S3O62– + 3H2O pH = 11.5 22 (Naito et al., 1970)
(Naito et al., 1970) 3S4O62– + 10OH– + 2.5O2 = [NH3] > 2M 49
8Cu(II) + 3S2O32– + 6OH–= 8Cu(I) + 2S3O62– + 3H2O Alkaline 23 4S2O32– + 4SO42– + 5H2O
(Byerley et al., 1973a, 1973b) (Naito et al., 1970)
2Cu(I) = Cu(II) + Cu Excess copper(II) 24 3S4O62– + 6OH– + 2.5O2 + 4NH3 = [NH3] > 2M no air 50
2Cu(II)+ S2O32– + H2O+ 2e= Cu2S + SO42– + 2H+ 25 4S2O32– + 4SO3NH2– + 5H2O
(Rabai and Epstein, 1992; non-ammonia system) (Naito et al., 1970)
2Cu(I) + 0.5O2 + H2O = 2Cu(II) + 2OH– Oxygen 26 4S4O62– + 10OH– = 7S2O32– + 2SO42– + 5H2O [NH3] > 2M no air 51
(Byerley et al., 1973a, 1973b) (Naito et al., 1970)
2S2O32– + 0.5O2 + 2H+ = S4O62– + H2O pH = 7 27 4S4O62– + 8OH– + 2NH3 = [NH3] > 2M no air 52
(Dreisinger, 1998) 7S2O32– + 2SO3NH2– + 5H2O
S2O32– + S3O62– + H+ = S4O62– + HSO3– pH ≤ 7 28 (Naito et al., 1970)
(Naito et al., 1970) Noet: e represents e–
S2O32– + H+ = S + HSO3– pH ≤ 7 29
(Naito et al., 1970; Huang et al., 1998)
S2O32– = S + SO32– 30
(Dreisinger, 1998)
3S2O32– + 6OH– = 4SO32– + 2S2– + 3H2O Alkaline 31 Gong and Hu (1990) reported that the presence of sulfide
(Huang et al., 1998) in solution would be advantageous for the stabilization of
2Cu(NH3)42+ + 8(S2O3)2– = 2Cu(S2O3)35– + 8NH3 + Alkaline 32 thiosulfate (Eq. 39 in Table 7). They recommended a mini-
S4O62–
(Chu et al., 2003) mum pH of 9.5 for the copper(II) ammonia thiosulfate system
Cu(II) + S2O32–+ 2OH– = CuS + SO42– + H2O Hot solution 33 to stabilize thiosulfate. However, some experimental results
(Fung and Glastonbury, 1975) contradict this suggestion. For example, Molleman and
2S2O32–+ H2O + 0.5O2 = S4O62– + 2OH– Cu(NH3)42+ 34
(Byerley et al., 1975; Naito et al., 1970) solution Dreisinger (2002) investigated the treatment of copper-gold
Noet: e represents e– ores by ammonia thiosulfate, but did not observe that sulfite
and sulfate improved the stability of thiosulfate.
Hu and Gong (1991) used sulfate instead of sulfite in gold
leaching to reduce the loss of thiosulfate. As the sulfate was not
according to Eq. 38 in Table 7. Some other benefits of the consumed during leaching, they suggested the reaction in Eq.
addition of sulfite are listed below: 37 (Table 7) as a mechanism that would avoid reagent con-
sumption. However, Aylmore and Muir (2001a) doubted this
(i) Sulfite ions can react with sulfide ions in solution, reaction (Eq. 37), because SO42– is very stable. Thiosulfate
preventing the precipitation of metal sulfides as oxidation by copper(II) occurs via mixed complexes such as
shown in Eq. 40 in Table 7 (Li et al., 1995). Cu(NH3)3(S2O3)° (Byerley et al., 1973b). Studies by Chandra
(ii) As described by Perez and Galaviz (1987) in their and Jeffrey (2004) and Wensveen and Nicol (2005) showed that
patent, an excess of sulfite may prevent the precipita- the addition of sulfate retarded the reaction of copper(II) with
tion of sulfur according to Eq. 43 in Table 7. thiosulfate as well as the oxidation of gold by copper(II) due to
(iii) Sulfite is an unstable substance that can be oxidized the formation of Cu(NH3)p(SO4)°. Based on kinetic studies,
to sulfate during leaching: Wensveen and Nicol (2005) confirmed the formation of an
intermediate mixed ammine/thiosulfate copper(II) complex.
SO3 2 þ 0:5O2 ¼ SO4 2 (35)
(iv) The addition of SO32-
to stabilize S2O3 does not 2–
4. Leaching of gold
reduce reagent consumption, rather, the loss of thio-
sulfate in leaching solution is replaced by the loss of The thiosulfate system has been used to leach gold from differ-
sulfite due to the reaction shown in Eq. 35. ent types of ores/concentrates as listed in Tables 8 and 9.
392 X. M. ZHANG AND G. SENANAYAKE

Table 8. Different types of ores/concentrates used in thiosulfate leaching.
Ore type Symbol in Tables 9 and 10
Oxidized ore (O1)–(O4)
Sulfide ore (S1)–(S6)
Sulfide concentrate (SC)
Carbonaceous ore (C1)–(C6)
Refractory ore (R1)–(R2)
Chalcopyrite ore (Cha)
Rhyolite ore (Rh)
Gold (bearing) ore (G1)–(G4)
Note: See Table 10 for references.
The gold ores or concentrates used in batch leaching experi-
ments had different mineralogy, gold grade, and chemical
composition, so the optimum leaching conditions were also
different (Table 10). A summary is presented below:
(i) For most ores, the optimum concentrations were:
thiosulfate 0.1–1.0 M, copper(II) < 0.1 M, ammonia
0.1–3.0 M at pH 9–10.5 and temperatures up to 60°C.
(ii) For a mild refractory ore, the optimum reagent con-
centrations have been reported as 0.05 M Cu(II),
0.5 M Na2S2O3, and 6 M NH3 (Yen et al., 1998).
(iii) The optimum reagent concentrations for a chalcopyr-
ite concentrate have been reported as 0.05 M Cu(II)
and 0.3 M Na2S2O3 at pH = 10 (Navarro et al., 2002),
which gave 94% extraction after 15 hr.
(iv) In the case of a carbonaceous ore, the optimum
reagent concentrations were 0.05 M Cu(II), 0.71 M
S2O32–, and 3 M NH3 at pH 10.5 (Hemmati, 1987),
which gave a gold extraction of 73%.
(v) In the case of pressure oxidized sulfide gold concen-
trate, 89% gold extraction was achieved with the
leaching solutions of 0.2 M S2O32–, 0.2 M NH3, and
0.1 g/L Cu(II), and continuous aeration of 0.2 L/min,
leaching time 6 hr (Lampinen et al., 2015).
4.1. Oxide ores
Langhans et al. (1992) claimed that copper-catalyzed thiosul-
fate leaching might be competitive with conventional cyanida-
tion methods for heap, dump, and in-situ leaching. They
carried out statistically designed experiments to determine
the optimum leaching conditions for minimum thiosulfate
consumption and maximum gold extraction (O1 in Tables 9
and 10). The leaching rate was slow due to low reagent con-
centration, resulting in only 83% gold extraction, with 0.4 kg
S2O32– consumed per ton of ore. In comparison, standard
cyanidation gave 86% gold extraction with 0.21 kg CN– con-
sumed per ton of ore. Navarro et al. (2002) also showed that
leaching of gold from a sulfide concentrate using ammonium
thiosulfate at pH 10–11 gave faster gold extraction than stan-
dard cyanidation. Ji and Yu (1991) studied gold extraction from
refractory deeply oxidized mud ore and reported a higher gold
recovery of 93.9% under optimum conditions (O2 in Table 10).
Li and Kuang (1998) investigated the leaching of gold from an
oxide ore and showed that the extraction of gold increased 15%
when the concentration of sodium chloride added was
increased from 0.2 M to 1.0 M (O3 in Table 10). In a study,
Xia and Yen (2005) extracted 92% of gold from a gold-bearing
silicate ore within 3 hr using a solution of 0.2 M ammonium
thiosulfate, 0.9 M ammonia, 30–300 mg/L copper(II), and 8.6
mg/L dissolved oxygen at pH 10.3.
Zhang et al. (2005) studied a new iron(III)/EDTA/thiosul-
fate-thiourea lixiviant system using electrochemical and
kinetic methods. The iron(III)-EDTA complex is an effective
oxidant for the thiosulfate-thiourea leaching system; it has a
low reactivity with thiosulfate due to complexation of Fe(III)
with EDTA. Thiourea is a co-ligand/catalyst for gold oxida-
tion. The addition of thiourea to the new lixiviant system can
significantly enhance the anodic oxidation of gold. The iron
(III)/EDTA/thiosulfate-thiourea lixiviant system can leach

Table 9. Chemical composition of different types of starting material used in thiosulfate leaching*.
Composition g/t Composition (%)
Ore type Particle size S:L Au Ag Corg Cu Fe Si Stot Al As Ca Zn Mg Mn Pb
O1 –100 mesh 1:1 480 570 0.11 0.02 3.13 39.0 1.12 3.00 0.07
O2 4.75 12.5 3.25 73.6 4.1 <0.005 0.13
O3 1:10 7.0
S1 90% <200 mesh 1:6 62 60 0.42 3.19 28.9 38.0 20.6 5.8 0.39 0.1 0.28 0.048 <0.03
S1 1.75 22.5 0.4 11.1 9.8 0.7 5 0.25
S2 50.4 0.42 3.19 28.9 37.95 20.6 5.75 0.39 0.1 0.28 0.048 <0.03
S3 94.6 24 0.20 31.9 30.7 2.64 1.96 0.022 0.829 0.073 0.004
S4 66% <200 mesh 5.0 – – 0.22 14.7 0.002
SC 170 353 0.9 20 5.5 44 0.12 3.6 4.1
C1 50% <200 mesh 8.67 – 0.02 >7 Major Major – Major – 3.0 0.02 <0.01
C2 –100 mesh 13.4 2.5
C3 <1.9 cm 1.46–3.17 0.78–1.35 0.67–2.42 0.78–1.35 2.5 0.14 5.6 0.036 2.4 0.19 0.026
C4 9–10 1.51 0.005 3.8 51.8 0.39 9.8 0.043 12.6 0.017 2.6 0.01
C5 80% <200 mesh 1:1.5 6.79 7.35 0.004 1.35 1.22 1.97 0.06 0.028
C6 80% <75 μM 9:11 8.3 0.2 1.77 0.61 2.24 0.11 1.60 0.085 7.66 0.016 0.86 0.020
R1 65% <74 μM 1:1.2 7.92 3.06 <0.25 0.37 7.6 5.62
R2 72% <44 μM 1:3 84.3 13.6 0.1 31.25 37.96 1.03 5.97 0.55 1.55 0.72
Cha 95 235 3.7 40.4 6.9 1.5
Rh 3 113 0.7
G1 1.28 0.73
G2 51.6 1
G3 146 293 6.20 39.2 5.85 41.1 0.25 0.39 0.25 0.29 0.46
G4 153 443 4.71 40.9 4.23 38.4 0.24 0.54 0.84 0.32 0.26
Note: See Table 10 for references.
S:L = solid:liquid ratio; Corg. %: percentage of organic carbon from carbonaceous matter.
*Most ores studied have low copper except S1, S2, G3, G4.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 393

Table 10. Maximum gold leaching under optimum conditions.

Ore type (Reference) T (°C) pH NH3 (M) Na2SO3 (mM) Retention time (h) Cu(II) (mM) Na2S2O3 (M) %Gold leached
O1 (Langhans et al., 1992) Amb 0.09 6.25 48 1 0.2 83
O2 (Ji and Yu, 1991) 60 1.68 79 2 78 0.64 93.9
O3 (Li and Kuang, 1998) 50 0.5 1 M NaCl 2 – 0.8 96
O4 (Zhang et al., 2005) Amb ≈7 – – 48 – 0.3 98t
S1 (Cao et al., 1992) 60 10.2 3 – 2 47 0.2 97.7
S2 (Gong and Hu, 1990) 40 1.8–2.2 100 1.5 16 0.8–1.0 95
S3 (Aylmore, 2001) Amb 10.2 4 – 48 50 0.8 90
S4 (Bhaduri, 1987) 35 10–11 1.0 90 2 32 0.19 80
S5 (Block-Bolten et al., 1985) 37 – 1 – 0.5 NM 0.5 82
S6 (Lampinen et al., 2015) 30 ≈10 0.2 – 6 1.5 200 89
SC (Ficeriova et al., 2005) 70 6 1.0 – 1 40 0.5 99
C1 (Bhaduri, 1987) 60 10–11 1.0 224 1.5 64 0.27 75
C2 (Hemmati, 1987) 35 10.5 3.0 100 2 50 0.9 73
C3 (Wan and Brierley, 1997) Amb 9 0.1 – 60 days 0.5 0.1 62
C4 (Ji et al., 2003) 60 11 0 – 3 0 0.1 80
R1 (Yen et al., 1998) Amb 10.2 6 – 24 100 0.5 95
Cha (Navarro et al., 2002) Amb 10 1 – 15 50 0.3 90
Rh (Zipperian et al., 1988) 50 10 4 – 1–2 0.1 2.66 70
G1 (Chai, 1997) 60 10.5 2 0.8 M SO42– 2.5 0.12 0.287 > 93.5
G2 (Abbruzzese et al., 1995) 25 8.5–10.5 4 3 100 2 80
R2 (Xu et al., 2015) 25 10 1 80 mM HA* 4 30 300 81.4
R2 (Xu et al., 2015) 25 10 1 0 4 30 300 72.7
Amb: ambient; (O1)–(O5): oxidized ore; (S1)–(S6): sulfide ore; (SC): sulfide concentration;
(C1)–(C4): carbonaceous ore; (R1)–(R2): refractory ore; (Cha): chalcopyrite ore;
(Rh): rhyolite ore; (G1) and (G2): gold (bearing) ore; NM: not mentioned.
t
10 mM thiourea and 3 mM Fe-EDTA.
*HA is sodium humic acid.

more than 90% gold from oxide ores (Zhang et al., 2005; O4
in Table 10).
4.2. Sulfide ores
Cao et al. (1992) investigated the leaching of gold using a low
concentration of thiosulfate in solution and achieved 95% gold
extraction from auriferous sulfide ore (S1 in Tables 9 and 10).
For a gold concentrate of complex metal sulfides (G3 in Table 9),
the gold recovery was 96% at an optimum concentration ratio of
S2O32–/Cu(II) = 10–15 and S2O32–/SO32– = 4 (Zhang and Li,
1987). Gong and Hu (1990) also reported a higher gold extrac-
tion of 95% from a sulfide concentrate containing copper(II) (S2
in Table 9). They used a lower temperature of 40°C and lower
concentrations of copper(II) and ammonia, but a higher thio-
sulfate concentration (Table 10). The stripped ammonium thio-
sulfate solution was directly reused in this process. In carefully
controlled experimental conditions, aeration resulted in oxida-
tion of copper(I) to copper(II), with very low thiosulfate oxida-
tion. Molleman and Dreisinger (2002) showed that aeration is a
key control parameter during the leaching of a copper-gold ore
using ammonium thiosulfate. The surface aeration gave a slow
but higher gold recovery, with low thiosulfate degradation.
Forced aeration gave fast initial leach kinetics but lower final
gold extraction, with high thiosulfate degradation. Feng and van
Deventer (2007a, 2007b) also showed the beneficial effects of
oxygenation and low concentrations of sulfur species on gold
leaching from sulfide ores.
Aylmore (2001) reported a gold extraction of 90% from a
refractory gold-copper sulfide concentrate using ambient con-
ditions in a 48 hr leach. However, the reagent consumption
was high: thiosulfate 36–70 kg/t, ammonia 5 kg/t, copper 1–2
kg/t, after leaching for 24 hr (S-3 in Table 10). Ficeriova et al.
(2002) studied the leaching of gold from a mechanochemically
pre-treated Cu-Pb-Zn complex sulfide concentrate using
ammonium thiosulfate solution at pH 6–7 and an elevated
temperature of 60°C to 70°C. The particle size of “as-received”
sample, d50 = 25 µm, was reduced to d50 = 4.5 µm after an
energy input of 202 kWh/t. The corresponding gold recovery
varied from 54% to 85%. They suggested that the enhanced
gold recovery was due to the increase in surface area to about
2.5 m2/g. Ficeriova et al. (2005) also reported that it was
possible to achieve 99% Au recovery within 45 min for a
sulfide concentrate sample mechanically activated. Feng and
van Deventer (2007c) achieved a gold extraction close to 100%
from a sulfide ore after 48 hr, but this was decreased to 80% in
the presence of hematite due to enhanced thiosulfate degrada-
tion and gold passivation. Air injection also decreased gold
leaching due to accelerated thiosulfate decomposition (Feng
and van Deventer, 2007b). However, oxygen injection was
beneficial when it enhanced the dissolution of host sulfides,
releasing more gold from the sulfide matrices.
Feng and van Deventer (2010a) reported the effect of thiosul-
fate salts on ammoniacal thiosulfate leaching of pyrite concen-
trate. The concentrations of ammonia (0.5 M) was higher than
that of sodium/ammonium thiosulfate or calcium thiosulfate
(0.1–0.2 M).The gold extraction was slightly higher after 24 hr
leaching in the ammonium thiosulfate solution than in the cal-
cium thiosulfate solution, and both of them higher than sodium
thiosulfate solution. This is likely linked to the availability of free
ammonia and the stabilization of copper in solutions.
Lampinen et al. (2015) studied ammoniacal thiosulfate
leaching of pressure oxidized sulfide gold concentrate with
low reagent concentrations. They achieved 89% gold extrac-
tion with 0.2 M thiosulfate, 0.2 M ammonia, 0.1 g/L Cu(II),
temperature 30°C, and continuous aeration at 0.2 L/min over
6 hr. The concentrations of thiosulfate and copper after 6 hr
leaching were 0.19 M and 0.08 g/L; the reagent consumption
394 X. M. ZHANG AND G. SENANAYAKE
was low. Feng and van Deventer (2010b) reported that the
oxidative pre-treatment of sulfide gold ore can enhance the
thiosulfate leaching of gold; the sulfide minerals partially
decomposed in the pre-treatment process, exposing gold to
leaching solution.
4.3. Carbonaceous ores
Due to the high affinity of carbon towards the complex ion Au
(CN)2–, cyanidation cannot effectively leach gold from carbonac-
eous ores and therefore the carbonaceous matter is detrimental for
gold cyanidation (Senanayake, 2008). In contrast, carbonaceous
matter has a very low affinity for Au(S2O3)23- complex ions (Wan
and Brierley, 1997), so it is possible to leach gold from carbonac-
eous ore using a thiosulfate lixiviant. Newmont Gold developed a
bio-oxidation process for the pretreatment of low-grade carbonac-
eous-sulfidic refractory gold ore (C3 in Table 9), which cannot be
heap leached with cyanide. The bio-oxidation-thiosulfate-heap
process was successfully practiced on a pilot plant scale. A total
of 327,000 tons of carbonaceous-sulfidic ore, pre-treated using
bio-oxidation, was leached with ammonium thiosulfate. Wan and
Brierley (1997) also reported that the concentration ratio of
ammonia to thiosulfate should be kept within a certain range, so
that copper can easily transfer between the cupric and cuprous
state. In addition, a key factor for success was maintaining the
stability of the leaching system by controlling the solution pH and
redox potential (EH).
Feng and van Deventer (2001) studied preg-robbing phe-
nomena in gold leaching. They tested five ores (arsenopyrite,
chalcopyrite, pyrite, kaolin, and quartz) that were highly preg-
robbing with fast adsorption of gold cyanide. However, thio-
sulfate leaching greatly decreased or eliminated preg-robbing
in both mineral and gold ore systems. It was found that the
presence of lead(II) and zinc(II) ions could reduce preg-rob-
bing, whereas copper(II) ions could not. Hemmati (1987)
concluded that thiosulfate is chemically superior and econom-
ically more advantageous than cyanide because it was possible
to extract 73% of gold from a carbonaceous ore using ammo-
niacal thiosulfate under optimum conditions (C2 in Tables 9
and 10). West-Sells and Hackl (2005) conducted a thiosulfate
leach process for the treatment of carbonaceous gold ores (C6
in Table 9) at ambient temperature, and 70% and 78% gold
was extracted in 4 hr and 24 hr, respectively. All the dissolved
gold was recovered by precipitation with ammonium sulfide.
In most cases, thiosulfate leaching of carbonaceous ore was
carried out in a pressure autoclave at 50–60°C to increase
leaching kinetics and gold recovery. A US Patent (Thomas
et al., 1998) described gold recovery from refractory carbo-
naceous ores using pressure oxidation (oxygen pressure =
400–500 psia), followed by copper(II) (10–100 mg/L) and
thiosulfate (10–100 mM) leaching, where 75–85% gold was
recovered, compared with only 6% gold recovered by cyani-
dation. Schmitz et al. (2001) compared the results from
ammoniacal thiosulfate and sodium cyanide leaching of
preg-robbing Goldstrike ore and carbonaceous matter.
Regardless of the preg-robbing behavior of the parent ore, in
which about 60% of gold was encapsulated in sulfides, only
40% gold was extracted from non-autoclaved ores. A much
higher gold solubilization of 90% to 100% was reported from
autoclaved ores.
The ability of ammonia to cause health problems in the
workplace and of copper to cause excessive thiosulfate degra-
dation prompted Ji et al. (2003) to investigate a new lixiviant
system that consists only of oxygen and sodium thiosulfate,
without copper and ammonia. Experiments were performed
on highly preg-robbing carbonaceous ore in an autoclave. The
results showed 80% gold extraction at 60°C, 10 psig to 100
psig oxygen pressure, and 0.1 M thiosulfate in 3 hr (C4 in
Tables 9 and 10). Further analysis of the results reported by Ji
et al. (2003) could shed light on the role of copper(II), carbo-
nate, and sulfite ions (Senanayake, 2005c) and copper(II)-
thiosulfate-oxygen interactions (Senanayake, 2005f) on gold
leaching and thiosulfate degradation.
4.4. Refractory ores
Ores that do not prove economical for gold recovery with
conventional cyanidation are termed refractory (La Brooy
et al., 1994). Perez and Galaviz (1987) patented a method
for recovery of precious metals from refractory ores, such as
an ore containing manganese and/or copper, using a copper-
ammonia-thiosulfate solution. They claimed that the pH in
leaching solutions should be maintained at about 9.5 in order
to inhibit the decomposition of thiosulfate by iron(III) com-
pounds. For mildly refractory ores such as R1 in Table 9, Yen
et al. (1998) conducted bottle-roll thiosulfate leach tests,
which showed no indication of cupric ion and ammonia
consumption. Thus, replenishing thiosulfate could allow recy-
cling of the thiosulfate lixiviant. The gold extraction was 95%
to 97% under the optimum leaching conditions described in
Table 10 for R1, compared to the extraction of 80% to 90% of
gold in 24 hr with 0.5–1.0 g/L NaCN. However, the reagent
cost was 35% higher than that for cyanidation.
Zipperian et al. (1988) found that the leaching of fine-
grained gold particles disseminated in a rhyolite ore (Rh in
Table 9) was quite sensitive to thiosulfate and ammonia con-
centrations. Although copper(II) ions seemed to play a cata-
lytic role, only 70% of gold was extracted at 50°C when a very
high thiosulfate concentration of about 3 M was used. The
authors highlighted the importance of maintaining EH and pH
to prevent precipitation of Cu2S. Molleman and Dreisinger
(2002) tested the leaching of a copper-gold concentrate and
achieved a maximum of 84% gold extraction in 24 hr.
Pyrrhotite-containing gold ores need a pre-aeration stage
prior to cyanidation while the cyanide dosage and dissolved
oxygen plays an important role on the extent of gold leaching
in batch tests and plant trials (Ellis and Senanayake, 2004).
Xia and Yen (2005) conducted leaching experiments with
pure silicate gold ores and noted that the presence of pyrite
and pyrrhotite minerals led to lower gold recoveries and
extraction rates, and largely increased the consumption of
thiosulfate. A gold extraction of 93% was achieved in 3 hr,
under the optimum leaching condition: 0.2 M thiosulfate, 0.9
M ammonia, 1.4 mM copper(II), and 0.3 mg/L dissolved
oxygen. Xu et al. (2015) tested thiosulfate leaching of refrac-
tory gold concentrate calcine with high iron, high sulfur, and
arsenic; they concluded that the best leaching conditions
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 395

without additive were 0.3 M thiosulfate, 0.03 M copper(II), 1
M NH3 at pH 10 and 4 hr with 72.7% gold extraction.
4.5. Pure gold
As described in previous publications (Senanayake, 2004a,
2004b, 2004c, 2005a, 2005b, 2005c, 2005d, 2005e, 2005f, 2007,
2008, 2012), many research groups have made valuable con-
tributions to the understanding of the comparative kinetics of
gold oxidation in cyanide and Cu(II)-NH3-S2O32– systems
using massive gold in the form of foils, plates, or rotating
discs/electrodes, which assisted the studies on the effect of
various additives and host minerals. Recently, such studies
have been extended to non-ammoniacal thiosulfate leaching
of gold (Sitando et al., 2015). Table 11 lists maximum gold
dissolution rates in ammoniacal thiosulfate solutions obtained
by previous researchers. Feng and van Deventer (2002b) stu-
died the dissolution behavior of gold in ammoniacal thiosulfate
systems, using gold foil of thickness 0.2 mm and surface area
0.2 cm2. The results showed a gold dissolution of about 6 mg/
cm2, 10 mg/cm2, and 20 mg/cm2 in 3 hr, 5 hr, and 10 hr
respectively, at an average rate of 2.8 × 10–5 mol m–2 s–1.
However, much lower rates of 6 × 10–7 mol m–2 s–1 have been
reported in solutions of low concentrations (Table 11; Feng and
van Deventer, 2007c).
Tozawa et al. (1981) used gold plates of dimension 14 ×
15 mm and 1 mm thickness, and measured a gold dissolution
rate three times higher than that reported by Feng and van
Deventer (2002b) (Table 11). This indicated the beneficial
effect of high temperature, oxygen pressure, and copper con-
centration on gold dissolution. Bagdasaryan et al. (1983) used
a rotating disc and conducted experiments in the temperature
range 45–85°C. The activation energy from their work (17.6
kJ/mol) was characteristic of a diffusion controlled reaction.
They found deposits of sulfur and sulfides on the gold surface,
and the rate-determining step in gold dissolution was believed
to be the diffusion of ions through the sulfide layer.
Jeffrey et al. (2001a, 2001b) compared the leaching of gold
in cyanide and thiosulfate using a rotating electrochemical
quartz crystal microbalance (REQCM) and reported leach
rates in the range 2.1 × 10–5 mol m–2 s–1 to 5.6 × 10–5 mol
m–2 s–1 in thiosulfate solutions, comparable with leach rates of
cyanidation (4.1 × 10–5 mol m–2 s–1). Breuer and Jeffrey
(2000b) also measured gold dissolution rates of the order 5.6
× 10–5 mol m–2 s–1. Zhang et al. (2004b) studied the kinetics
of dissolution of gold colloid in ammoniacal copper(II) thio-
sulfate solutions; they reported gold dissolution rates in the
range 2.2 × 10–5 mol m–2 s–1 to 8.4 × 10–5 mol m–2 s–1, which
are much lower than a calculated copper(II) diffusion limited
rate of 24.6 × 10–5 mol m–2 s–1. Ha et al. (2014) tested the
leaching of gold from printed circuit boards (PCBs) of dis-
carded mobile phones, and reported the initial rate of gold
leaching was 2.4 × 10–5 mol m–2 s–1. These results led to the
conclusion that the leaching rate of gold was chemically con-
trolled, which was supported by the reaction activation energy
of 60 ± 10 kJ/mol (Breuer and Jeffrey, 2000b), 40 kJ/mol
(Zhang et al., 2004b), and 78.6 kJ/mol (Ha et al., 2014).
5. Factors affecting the thiosulfate leaching of gold
5.1. Effect of thiosulfate concentration
The results obtained with gold plates, gold foils, or gold discs
and gold colloids listed in Table 12 show the beneficial effects
of increasing thiosulfate concentration on the rate of gold
oxidation. Breuer and Jeffrey (2000b) and Jeffrey (2001) pro-
posed that at low concentrations of copper(II) and thiosulfate,
the leaching reaction was chemically controlled. At high con-
centrations of thiosulfate the reaction was controlled by the
diffusion of copper(II). Feng and van Deventer (2002b)
showed similar results for the dissolution of gold foil
(Table 12), where anodic and cathodic half reactions were
enhanced by increasing thiosulfate concentrations. Results
from experiments using gold plates at low oxygen pressures
(Tozawa et al., 1981) showed that the gold dissolution rate
increased with increasing thiosulfate concentration up to 0.44
M. At higher concentrations there was no appreciable effect
on the dissolution rate. Selected literature data on the effect of
increasing thiosulfate concentration on gold extraction from
different types of ores are listed in Table 13. Ha et al. (2010)
studied thiosulfate (0.06 M to 0.2 M) leaching of gold from
PCBs of waste mobile phones and found that the gold leach-
ing increased with increasing thiosulfate concentration reach-
ing maximum leaching, then decreased with a further increase
in thiosulfate concentration. The gold leaching behavior
showed a complex dependence with the variation of the con-
centration of thiosulfate, copper, and ammonia in solution.

Table 11. Dissolution rates of gold under optimum conditions.

Gold type/Reference T (°C) Oxygen NH3 (M) Cu(II) (mM) Na2S2O3 (M) 105 x rate (mol m–2 s–1)
Gold disc/Breuer and Jeffrey (2000b) 30 0.4 5 0.1 4.2
Gold foil/Feng and van Deventer (2002b) Ambient Open to air 2 12 0.5 2.89
Gold foil/Feng and van Deventer (2007c) 25 N2 or 0.5 0.8 0.165a 0.058b 0.064c
O2
Gold plates/Tozawa et al. (1981) 65 PO2 = 1.0 80 0.48 9.6
2 kg/m2
Gold–silver alloy (5%Ag)/Jeffrey et al. (2001b). 40 0.4 10 0.3 5.6
Gold/Jiang et al. (1993a) 50 Open to air 4.4 310 1.0 90d
Gold colloids/Zhang et al. (2004b) 25 N2 0.24 2 0.05 2.3
Gold colloids/Zhang (2008) 25 0.31 mM 0.24 2 0.05 1.7
Printed circuit boards of waste mobile phones/Ha et al. (2014) 20 N2 0.27 10 0.0727 2.395
a
Ammonium thiosulfate, pH 10.
b
At nitrogen flow rate of 10 mL/min.
c
At oxygen flow rate of 10 mL/min.
d
Percentage dissolution.
396 X. M. ZHANG AND G. SENANAYAKE

Table 12. Effect of thiosulfate concentration on gold dissolution rates. 1997). This was increased at higher temperatures and oxygen
Gold type/ NH3 Cu(II) Na2S2O3 105 x rate (mol pressures, indicating the formation of Au(NH3)2+ in the
Reference T (°C) (M) (mM) (M) m–2 s–1) Note absence of thiosulfate (Han, 2001). A refractory copper-gold
Gold disc/Breuer 30 0.4 0.005 0.05 1.1 a sulfide concentrate underwent self-catalyzed leaching of gold
and Jeffrey 0.2 8
(2000b) due to the presence of copper(II) in ore (G4), but the recovery
Gold foil/Feng and Ambient 2 0.012 0.1b 2.8 c of gold increased from 6% to 80% when thiosulfate concen-
van Deventer 0.5 29
(2002b)
tration was increased from 0.24 M to 1.2 M (Jiang et al.,
Gold powder/ 65 1.0 0.04 0.1 0.55 d 1992). Yen et al. (1998) used ammonia-thiosulfate solution
Tozawa et al. 0.53 4.6 to extract gold from a mildly refractory ore, and found that a
(1981)
Gold colloid/ 25 0.24 1.5 0.010 0.94 a decrease in thiosulfate concentration can dramatically
Zhang et al., 0.095 2.1 decrease gold extraction efficiency, due to the higher ratio of
(2004b) [NH3]/[S2O32–]. Zhang et al. (2004b) reported that increase in
Gold colloid/ 25 0.24 2.0 0.020 3.0 c
Zhang (2008) 0.050 1.7 thiosulfate concentration from 10 mM to 95 mM can increase
a
Nitrogen or argon atmosphere. dissolution of gold colloid from 10.8% to 22.5% in 10 min, but
b
(NH4)2S2O3. decrease from 92% to 61% in 5 hr. However, ammonium
c
Air or oxygen atmosphere. thiosulfate concentrations higher than 0.5 M caused only a
d
SO2 atmosphere.
slight increase in gold extraction from a refractory ore
(Table 13).
In the case of oxide ores (Table 13), a higher thiosulfate
However, Lampinen et al. (2015) found that the increase in concentration was beneficial for gold extraction, but the pre-
initial thiosulfate concentration from 0.05 M to 0.2 M has sence of a high concentration of sodium chloride has detri-
only a small effect on the leaching rate of gold from an mental effects at high thiosulfate concentrations (Li and
oxidized sulfide ore. Kuang, 1998, in Table 13). A higher thiosulfate concentration
Gold extraction of 10% to 20% has been achieved in is also detrimental to gold extraction from sulfide ores (Block-
ammoniacal copper(II) solutions in the absence of thiosulfate Bolten et al., 1985, in Table 13), unless a high ammonia
(Zipperian et al., 1988; Ji and Yu, 1991; Cao et al., 1992; Chai, concentration (≥3 M) is maintained (Bhaduri, 1987; Cao

Table 13. Effect of thiosulfate concentration on gold leaching.

NH3 SO32– Cu(II) Na2S2O3 % Au
Ore type/Reference T (°C) (M) (mM) Retention time (h) (mM) (M) leached
Gold colloid/Zhang et al. (2004b) 25 0.24 – 5b 1.5 0.010 92
0.020 97
0.095 61
Gold colloid/Zhang (2008) 25 0.12 – 2d 2.0 0.020 35
0.030 60
0.050 92
Gold plates/Jiang et al. (1993a) 50 – 0.07 0.36 28
1.33 56
b
Oxidized ore/Langhans et al. (1992) Ambient 0.09 6.25 4 1 0.05 25
0.125 30
0.2 38
Oxidized ore/Ji and Yu (1991) 60 1.68 79 2 78 0.063 42
0.32 58
0.65 94
1 95
Oxidized ore/Li and Kuang (1998) 50 1.5 0* 3d – 0.5 84
0.8 96
1.0 84
Sulfide ore/Block-Bolten et al. (1985) 21 1 – 2 0.125 60
0.5 25
Sulfide ore/Block-Boltenet al. (1985) 63 1 – 2 0.125 63
0.5 38
Sulfide ore/Aylmore (2001) Ambient 4 – 48c 50 0.1 3
0.8 90
Sulfide ore/Aylmore (2001) Ambient 4 – 2c 50 0.1 12
0.8 42
d
Sulfide ore/Bhaduri (1987) 35 3.0 90 1 40 0.04 35
0.19 42
d
Sulfide concentration/Cao et al. (1992) 60 3 2 47 0.0h 20
0.1 80
0.2 97.7
Note: Unless stated otherwise, atmosphere was not specified for reactions.
b
Nitrogen or argon.
c
SO2.
d
Air or oxygen.
h
(NH4)2S2O3.
*Contained 1 M NaCl.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 397

Table 13. Effect of thiosulfate concentration on gold leaching (continued).

Ore type/Reference T (°C) NH3 (M) SO32– (mM) Re* (hr) Cu(II) (mM) Na2S2O3 (M) % Au leached
Carbonaceous ore/Hemmati (1987) 35 3.0 100 2d 50 0.088h 64
0.88 74
Carbonaceous ore/Ji et al. (2003) 60 0 – 2d 0 0.05 65
0.1 72
0.2 73
Refractory ore/Yen et al. (1998) Ambient 6 10 100 0.1h 27
0.5 86
1.0 89
Chalcopyrite ore/Navarro et al. (2002) Ambient 1 – 7 50 0.1h 66
0.3 90
0.7 90
Rhyolite ore/Zipperian et al. (1988) 50 4.1 – 2 234 0 10
0.06h 40
0.63 82
1.39 84
Silicate ore/Xia and Yen (2005) Ambient 0.9 3 4.7 0.067 78
0.27 89
2.7 78
Gold (bearing) ore/Chai (1997) 25 2 3b 1000 0 10
120 0.1h 46
0.29 72
0.57 68
Gold (bearing) ore/Abbruzzese et al. (1995) Ambient 4 3 0.1 0.125 15
2.0 80
Gold (bearing) ore/Jiang et al. (1992) Ambient 1.47 4 0.24 6
1.20 80
PCBs of waste mobile phones/Ha et al. (2010) 25 0.3 – 2 15 0.06 8
0.1 52
0.14 100
Sulfide gold concentrate/Lampinen et al. (2015) 30 0.2 – 6 3.9 0.05 84
0.1 84
0.2 84
Refractory ore/Xu et al. (2015) 25 1 – 4 30 0.1 35
0.3 72.7
0.4 69
Note: Unless stated otherwise, atmosphere was not specified.
b
Nitrogen or argon.
d
Air or oxygen.
h
(NH4)2S2O3.
*Re. Retention time.

et al., 1992; Aylmore, 2001, in Table 13). In most other cases
described in Table 13, a higher thiosulfate concentration was
beneficial for gold extraction in the presence or absence of
ammonia. However, the extraction efficiency will decrease or
become independent of thiosulfate at high concentrations. In
the case of carbonaceous ore, gold extraction efficiency
appeared less sensitive to thiosulfate concentration.
5.2. Effect of copper concentration
Jeffrey (2001) investigated the relationship between reaction
rate and copper(II) concentration (<5 mM) at 30°C when
thiosulfate and ammonia concentrations were maintained at
0.4 M and 0.84 M, respectively. The linear increase in extrac-
tion rate with increasing copper(II) concentration was related
to the diffusion of copper(II) ions to the gold surface. Above
5 mM copper(II), however, the rate became almost indepen-
dent of the concentration of copper(II). Jiang et al. (1993a)
studied the dissolution kinetics of gold by measuring the loss
of mass from a gold plate in ammoniacal thiosulfate solution.
Their results showed that the concentration of Cu(NH3)42+
had a dramatic effect on the dissolution rate of gold. Over the
concentration range of 1 mM to 100 mM, the increase in rate
was proportional to the concentration of Cu(NH3)42+ ion. The
gold extraction from gold plates also increased from 20% to
90% with an increase in copper(II) concentration from 0% to
2% (Jiang et al., 1993a, 1993b). Zhang et al. (2004b) conducted
experiments in copper(II)-ammonia-thiosulfate solutions
without oxygen and found gold colloid dissolution increased
from 60% to 98% as initial copper(II) increased from 0.5 mM
to 4.5 mM in 5 hr. In the presence of oxygen, gold colloid
dissolution in 1 hr increased from 40% to 85% as the initial
copper(II) increased from 1.0 mM to 3.0 mM (Zhang, 2008).
Results for PCBs of waste mobile phones (Ha et al., 2010)
show that gold leaching increased with the increase in copper
concentration up to 15 mM, then it became almost indepen-
dent of higher concentrations; ammonia concentration was
0.1–0.4 M, thiosulfate was 0.06–0.2 M, and pH 10–10.5. The
change in initial copper concentration from 0.1 g/L to 0.25 g/
L does not have a beneficial effect on the final leaching of gold
in the experiments carried out on an oxidized sulfide ore
(Lampinen et al., 2015).
In the absence of copper(II), the aerated thiosulfate leach-
ing of gold is very slow. The presence of copper(II) ion in
thiosulfate-ammonia solution can increase the rate of gold
dissolution by 18–20 fold (Aylmore and Muir, 2001a,
2001b). Table 14 summarizes the effect of copper(II) concen-
tration on the percentage of gold extracted from different
types of materials. Despite the reaction between copper(II)
and thiosulfate, the increase in copper(II) concentration has a
398 X. M. ZHANG AND G. SENANAYAKE

Table 14. Effect of copper concentration on gold leaching.

NH3 Na2SO3 Retention Na2S2O3 Cu(II) % Au
Ore type/Reference T (°C) (M) (mM) time (hr) (M) (mM) leached
Gold colloid/Zhang et al. (2004b) 25 0.24 – 5b 0.05 0.5 60
4.5 98
Gold colloid/Zhang (2008) 25 0.12 – 1d 0.05 1.0 40
3.0 85
Gold disc/Jeffrey et al. (2001b) 30 0.84 – 0.4h 0 0
1 1.6k
5 6.2k
25 10k
Gold powder/Jiang et al. (1993a) 50 7.5% – 1.0 0 20
62.5 56
312 90
Refractory ore/Ji and Yu (1991) 60 1.7 79 2 0.63 2 38
20 94
40 95
Refractory Ambient 4 24c 0.8 12.5 20
Sulfide ore/Aylmore (2001) 50 90
62.5 70
Refractory Au-Cu ore/Yen et al. (1998) Ambient 6 10 0.5h 30 70
200 87
Rhyolite ore/Zipperian et al. (1988) 50 4.1 1 1.4h 23 83
940 88
Carbonaceous Ambient 0.2 24d 0.1 5 64
Ore/West-Sells and Hackl (2005) 50 75
100 78
Silicate ore/Xia and Yen (2005) Ambient 0.9 3 0.2 4.7 84
15.7 92
47 92
Gold ore/Abbruzzese et al. (1995) 25 4 2 2 30 30
100 80
Gold concentrate/Navarro et al. (2002) Ambient 0.5 7 0.3h 10 80
50 90
100 82
PCBs of waste mobile phones/Ha et al. (2010) 25 0.3 2 0.14 5 15
15 100
30 80
Sulfide concentrate/Lampinen et al. (2015) 30 0.2 0.5–1.5 0.2 0.1 g/L 78
0.25 g/L 84
0.5 g/L 84
Refractory ore/Xu et al. (2015) 25 1 – 4 0.3 20 67
30 72.7
40 66
k
Rate x 105 (mol m–2 s–1).
b
Nitrogen or argon.
c
SO2.
d
Air or oxygen.
h
(NH4)2S2O3.

positive effect on gold extraction. As noted in Table 10, the according to Eq. 53 at higher concentration, reduced the
optimum copper(II) concentration depends on the type of ore reduction potential of the cathodic half-cell reaction:
and concentrations of other reagents. These observations also 
suggest the possible participation of copper(II) during the CuðNH3 Þ4 2þ þ 3ðS2 O3 Þ2 þ e
chemical breakdown of host minerals. ¼ CuðS2 O3 Þ3 5 þ 4NH3 (53)

5.3. Effect of ammonia concentration

Tozawa et al. (1981) conducted autoclaved leaching experi-
ments (Table 15) and reported that the maximum dissolution
rate of gold plates was observed in 0.5 M ammonia. The
decrease in dissolution rate, at ammonia concentrations
higher than 0.5 M, was related to an increase in OH– ions,
which suppress the dissolution of gold. Breuer and Jeffrey
(2000a, 2000b) found that the reaction rate decreased in the
ratio of 3:2:1, with increasing ammonia concentrations (mol/
L) in the ratio 0.2:0.4:0.6 (Table 15). The decrease in dissolu-
tion rate was related to the fact that the mixed potential
became more negative with the increase in ammonia concen-
tration. For example, the enhanced stability of copper(II),
Tozawa et al. (1981) believe that there is an optimum ammonia
concentration at which a maximum leaching rate is observed. If
the concentration of ammonia is lower than this value, excess
copper(II) reacts with thiosulfate to reduce the concentration of
Cu(NH3)42+ available for the oxidation of gold. If the concentra-
tion of ammonia is greater than the optimum value, it will decrease
the reduction potential of the copper(II)/copper(I) couple, thereby
decreasing the oxidizing ability of copper(II). The optimum
ammonia concentration is dependent on thiosulfate and copper
concentrations. Feng and van Deventer (2002a, 2002b) also
observed the negative effect of concentrated ammonia in a set of
electrochemical experiments that used 0.1 M Na2S2O3 and 0.5–2.0
M NH3 (Table 15). Experiments conducted on PCBs of waste
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 399

mobile phones proved the same trends (Ha et al., 2010); if copper
concentration was ≥ 15 mM, the increase in ammonia concentra-
tion from 0.1 M to 0.3 M increased gold leaching, but leaching of
gold decreased if ammonia concentration was higher than 0.3 M.
When copper concentration was 5 mM and 10 mM, leaching of
gold decreased even at ammonia concentrations higher than 0.1
M. In the case of ammoniacal thiosulfate leaching of pressure
oxidized sulfide gold concentrate, the gold dissolution rate and
final gold extraction increased with increasing initial ammonia
concentration from 0.1 M to 0.2 M. However, further increase in
initial ammonia concentration from 0.2 M to 0.3 M did not
increase gold dissolution rate and final gold conversion
(Lampinen et al., 2015).
Without ammonia, thiosulfate can leach only up to 4% gold
from a sulfide ore (Cao et al., 1992) and 32% gold from a gold
concentrate containing copper (Jiang et al., 1992); although the
main role of ammonia is to stabilize cupric ions by forming
copper(II)-ammine complexes, it also prevents the formation of
elemental sulfur on the surface of gold (Chen et al., 1996). Most
of the published data (Table 15) show that an increase in
ammonia concentration has a positive effect on gold extraction
up to a point, but very high ammonia concentration has little
benefit or may exert a negative effect on gold extraction (Gong
et al., 1993; Chai, 1997; Yen et al., 1998).
Aylmore (2001) reported results for a refractory gold-copper
sulfide concentrate (Table 15) where the gold extraction
increased from 80% to 95% as the ammonia concentration was
increased from 1.5 M to 4 M. In contrast, Chai (1997) reported
that at a range of ammonia concentrations of 0 M to 6 M, the
highest gold extraction of 90% was achieved in a solution of 2 M
ammonia, 0.12 M copper(II), and 0.287 M thiosulfate at 60°C in
3 hr. Yen et al. (1998) obtained results similar to those of
Aylmore (2001) from a mildly refractory gold-copper ore from
Canada. Gold extraction increased from 60% to 85% as ammo-
nia concentration was increased from 1 M to 6 M. However, a
further increase in ammonia to 9 M reduced the gold extraction
to 5%. Their explanation for these observations was based on the
equilibrium between the two gold(I) complexes:

Table 15. Effect of ammonia concentration on gold leaching.

Cu(II) NH3 % Au
Ore type/Reference T (°C) (mM) Na2S2O3 (M) (M) Retention time (hr) leached
Gold colloid/Zhang et al. (2004b) 25 1.5 0.02 0.05 5b 74
0.58 96
Gold disc/Jeffrey et al. (2001a, 2001b) 30 0.025 0.4h 0.4 12k
1.68 6.3
Gold disc/Breuer and Jeffrey (2000b) 30 0.01 0.1 0.2 –b 6.0k
0.6 2.0
Gold powder/Tozawa et al. (1981) 65 0.04 0.25 0 3d 0 g/m2
0.5 150 g/m2
3.0 50 g/m2
Gold foil/Feng and van Deventer (2002a, 2002b) Ambient 0.012 0.1h 0.5 24d 90
2.0 50
Oxidized ore/Ji and Yu (1991) 60 78 0.63 0.82 2 80
1.71 94
5.2 95
Oxidized 50 – 0.8 0.1 2d 74
ore/Li and Kuang (1998) 0.5 96
1 94
Sulfide ore/Aylmore (2001) Ambient 50 0.8 1.5 24c 60
3 75
4 75
Refractory ore/Yen et al. (1998) Ambient 100 0.5h 1 24 80
6 96
9 90
Rhyolite ore/Zipperian et al. (1988) 50 230 1.4h 0.41 1 83
8.2 86
Silicate ore/Xia and Yen (2005) Ambient 4.7 3 0.2 0.2 78
2.7 94
Gold concentrate/Jiang et al. (1992) Ambient 1.3 0 3–4 32
7.35 94
Gold ore/Jiang et al. (1992) 25 0.1 2 1–4 3 50–78
4–8 78–2
PCBs of waste mobile phones/Ha et al. (2010) 25 15 0.10 0.1–0.2 2 100–100
15 0.14 0.3–0.4 2 100–54
Sulfide gold concentrate/Lampinen et al. (2015) 30 0.25 g/L 0.1 0.1 6 73
0.2 84
0.3 78
Refractory ore/Xu et al. (2015) 25 30 0.3 0.5 4 60
1 73
2 66
Note: Unless stated otherwise, atmosphere was not specified.
b
Nitrogen or argon.
c
SO2.
d
Air or oxygen.
k
Rate x 105 (mol m–2 s–1).
h
(NH4)2S2O3.
i
Contained 1% Na2SO3.
400 X. M. ZHANG AND G. SENANAYAKE

 n o
AuðNH3 Þ2 þ þ 2S2 O3 2 ¼ AuðS2 O3 Þ2 3 þ 2NH3 (54) ½NH3  ¼ ½NH3 þ NH4 þ  = 10ðpKapHÞ þ 1 (56)
A high concentration of ammonia makes the equilibrium
Most laboratory (batch) leaching tests reported in the litera-
favorable to the left, therefore reducing the gold extraction
ture have been conducted in the pH range of 9.5–10.5. This is
(Yen et al., 1998).
due to the fact that at pH values lower than 9, gold extraction is
Abbruzzese et al. (1995) noted that the rate of gold dis-
retarded due to the low concentration of free ammonia and the
solution from a gold-bearing ore was rapid during the first
precipitation of CuO. At pH values higher than 10.5, the pre-
hour. Gold recovery increased from 50% to 78% and then
cipitation of Cu2S, CuO, or Cu2O as indicated by EH-pH dia-
decreased to 2% as the concentration of ammonia was chan-
gram (Aylmore and Muir, 2001a, 2001b) retards gold extraction.
ged from 1 M to 4 M and then to 8 M (Table 15). They
Thus, maximum recovery of gold can be obtained in the pH
concluded that the increase in ammonia concentration
range 9.5–10.5, as shown in Table 16.
reduced the thermodynamic stability of Cu(NH3)42+ and Cu
At low pH values and low total ammonia, the rate of gold
(S2O3)35–, widening the regions of thermodynamic stability of
dissolution increased with increasing pH values, due to the
CuO and Cu2O. They noted that the precipitation of CuO
increase in the stability of copper(II) caused by high ammonia
reduced the activity of the Cu(NH3)42+ complex and hindered
concentration. When pH values were changed from 9.8 to
the thiosulfate attack by covering the mineral surface. It can
11.4, the rate decreased from 6 × 10–5 mol m–2 s–1 to 4 × 10–5
be seen from the EH-pH diagram published by Aylmore and
mol m–2 s–1 (Breuer and Jeffrey, 2000a, 2000b). Similar results
Muir (2001a, 2001b) that the rise in pH caused by an increase
were obtained from experiments using gold plates (Jiang et al.,
in ammonia concentration enlarges the stability area of CuO
1993a), where a change in pH value from 8 to 10 increased
and Cu2O. In general, an increase in ammonia concentration
gold dissolution from 30% to 55%, but a further increase in
increases gold extraction. The most effective ammonia con-
pH value to 11 decreased gold dissolution to 50% (Table 16).
centration is in the range 0.5 M to 6 M, while the most
Studies with colloidal gold (Zhang et al., 2004b) did not see
appropriate ratio of [NH3]/[Na2S2O3] is 0.3 to 6 depending
the negative effect at higher pH; however, pH 9.6–10.0 deliv-
on the type of ore. Experimental results with gold colloid
ered the fastest initial rate. The decrease in rate at high pH
(Zhang et al., 2004b) show that the most appropriate ratio
values is similar to the effect of high concentration of ammo-
of free [NH3]/[Na2S2O3] is 3 to 4.5.
nia observed in Table 15.

5.4. Effect of pH
At a given temperature, the total concentration of NH3 +
NH4+, pH, and pKa (= –log Ka) govern the concentration
of NH3:
NH4 þ ¼ NH3 þ H þ ðKa ¼ equilibrium constantÞ
5.5. Effect of temperature
It is notable that the results from experiments that used pure
gold (Table 17) showed a positive effect with an increase in
temperature from 25°C to 40°C (Breuer and Jeffrey, 2000a,
(55) 2000b). Experiments with gold plates (Tozawa et al., 1981)

Table 16. Effect of pH on gold leaching.

Ore type/References T (°C) NH3 (M) Retention time (h) Cu(II) (mM) S2O32– (M) pH % Au leached
Gold colloid/Zhang et al. (2004b) 25 0.24 2.5b 2 40 8.9 65
11 94
Gold disc/Breuer and Jeffrey (2000b) 30 0.4 –b 0.005 0.1 9.8 6k
10.8 4.8k
11.4 4k
Gold plates/Jiang et al. (1993a) 50 – 0.0625 1.0 8 30
10 55
11 50
Carbonaceousn/Hemmati (1987) 55 Up to 4.5 2d 60 1.19h 9 8
10.5 60
Carbonaceous/West-Sells and Hackl (2005) Ambient 0.2 24d 0.79 0.1 8 70
9 75
9.5 73
10 64
Refractory/Yen et al. (1998) Ambient 6 10 100 0.5h 8.5 10
10 85
11.5 50
Chalcopyrite/Navarro et al. (2002) Ambient 15 50 0.7h 9 10
10 92
Gold bearingp/Chai (1997) 60 0.29–2.3 2.5b 120 0.287h 8.5 72
10.5 89
11 87.5
Note: Unless stated otherwise, atmosphere was not specified for reactions.
b
Nitrogen or argon.
d
Air or oxygen.
k
Rate x 105 mol m–2 s–1.
h
(NH4)2S2O3.
n
220 mM SO32–.
p
0.8 M SO42–.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 401

Table 17. Effect of temperature on gold leaching.

Gold/Ore type/Reference NH3 (M) Retention time (h) Cu(II) (mM) Na2S2O3 (M) T(°C) Au leached % or g/m2
b
Gold colloids/Zhang et al. (2004b) 0.24 1 2.0 0.05 22 55
48 97
Gold colloids/Zhang et al. (2004a) 0.12 5d 0 0.02 25 23
48 38
Gold disc/Breuer and Jeffrey (2000b) 0.4 – b
0.01 0.1 25 Reaction rate increases
30
40 significantly
Gold plates/Tozawa et al. (1981) 0.5 3d 0.04 0.25 20 (20)
60 (120)
100 (20)
140 (140)
180 (60)
Oxide ore/Li and Kuang (1998) 1.5m 2d – 1 30 70
50 95
60 95
Sulfide gold
concentrate/Cao et al. (1992) 3 2d 47 0.2h 30 52
50 94
60 97
Refractory ore/Ji and Yu (1991) 1.7n 2 78 0.63 30 66
50 88
60 89
Rhyolite/Zipperian et al. (1988) 4.1 3 230 1.4h 25 70
50 90
60 90
Gold ore/Abbruzzese et al. (1995) 4 3 100 2 25 79
40 75
60 56
Gold-bearing ore/Chai (1997) 2 3b 120 0.287h 20 80
60 90
80 75
Sulfide gold concentrate/Lampinen et al. (2015) 0.2 1.5 0.1 g/L 0.2 20 60
30 78
40 80
Discarded mobile phone/Ha et al. (2014) 0.26 1 or 5 min 10 0.06 20 10/48
30 28/95
40 82/97
50 88/88
Note: Unless stated otherwise, atmosphere was not specified for reactions; values in parentheses show dissolution per unit area in (g/m2).
b
Nitrogen or argon.
d
Air or oxygen.
h
(NH4)2S2O3.
m
1 M NaCl.
n
79 mM Na2SO3.

under an oxygen pressure in the range of 0.2 kg/cm2 to 10 kg/
cm2 showed a positive effect in the temperature ranges 18–60°C
and 100–140°C. In contrast, a negative effect was shown in the
temperature range 60–100°C and 140–180°C (Table 17). The
decrease in rate of gold dissolution from 65°C to 100°C has
been related to the formation of cupric sulfide on the gold sur-
face. However, at temperatures below 140°C, the rate showed a
remarkable increase as a result of thiosulfate ions being regen-
erated on the surface of gold by the oxidation of cupric sulfide
(Tozawa et al., 1981). The increase in temperature from 140°C to
180°C caused a decrease in dissolution rates of gold due to the
enhanced oxidation of thiosulfate ions. The leaching of colloidal
gold (Zhang et al., 2004b) also shows a positive effect caused by
increasing the temperature from 22°C to 48°C.
Table 17 also summarizes the effect of increase in tempera-
ture in the range 25–80°C on gold extraction from different
types of gold ores and pure gold. Most of the previous studies
indicate that the increase in temperature from 25°C to 50°C or
60°C has a positive effect, which in turn could lead to a
10–50% increase in gold extraction (Zhang and Li, 1987;
Zipperian et al., 1988; Ji and Yu, 1991; Cao et al., 1992;
Chai, 1997; Li and Kuang, 1998). Some other important
aspects are as follows:
(i) Results from an oxide gold ore showed that gold
extraction increased from 74% to 100% as the tem-
perature was increased from 30°C to 50°C, and
decreased to 95% with a further increase in tempera-
ture to 60°C in 3 hr (Li and Kuang, 1998).
(ii) Results from a Rhyolite ore (Zipperian et al., 1988)
showed that almost 90% of gold was leached in an
hour at 60°C, compared to only 25% of gold leached
at 25°C.
(iii) Results from a refractory gold ore in the temperature
range 30–55°C (Ji and Yu, 1991) showed that the gold
recovery increased from 6% at 30°C to 89% at 55°C,
but a further increase in the leaching temperature to
65°C had little effect on gold recovery.
(iv) Similar results were obtained from a sulfide copper-
gold concentrate (Cao et al., 1992) in which gold was
found to be predominantly associated with pyrite,
chalcopyrite, and bornite. The gold extraction
increased from 52% (30°C) to 89% (40°C) and to
97.7% (60°C); no further increase in extraction was
observed beyond 60°C.
(v) Chai (1997) reported that the change in temperature
from 25°C to 80°C only slightly affected the
402 X. M. ZHANG AND G. SENANAYAKE
Table 18. Effect of sulfur-oxy species on gold dissolution rates.
S4O62– SO42– S3O62– S2O52–
No (25 (25 (25 (25
Sulfur-oxy species addition mM) mM) mM) mM)
105 Rate/(mol m–2 s–1) 3.25 2.75 2.85 2.9 0.25
5
10 Rate/(mol m –2 –1
s ) 1.1 0.94 – 0.94 – Zhang
extraction of gold, which led to the conclusion that
diffusion and transport processes are likely to be the
rate-limiting steps.
(vi) Abbruzzese et al. (1995) reported a negative effect of
high temperature on gold extraction, where a decrease
from 79% to 56% was observed when the temperature
was increased from 25°C to 60°C. They also related
this behavior to the passivating effect of cupric sulfide
formed and the decomposition of thiosulfate to sulfur
compounds according to Eqs. 33, 34, and 36:
CuðII Þ þ S2 O3 2 þ 2OH  ! CuS þ SO4 2 þ H2 O
2
2S2 O3 þ H2 O þ 0:5O2 ¼ S4 O6 þ 2OH 2
 dent on the ratio of [S2O32–]/[SO32–]. They added
3S2 O3 2 þ 3H2 O ¼ 4SO3 2 þ 2S2 þ 6H þ
Thus, the effect of temperature on gold extraction is largely
dependent on the composition (mineralogy) of gold ore,
which may lead to the precipitation of various solids on the
gold surface, especially at high temperatures. The general
trend within a low temperature range of 25°C to 60°C is a
positive effect with increasing temperature.
The leaching rate and final conversion of gold from a pres-
sure oxidized sulfide gold concentrate increased when tem-
perature was increased from 20°C (60%) to 30°C (78%) at
pH10 (Lampinen et al., 2015). However, further increase in
temperature from 30°C to 40°C and a decrease in pH to 9.5
showed only a small beneficial effect as the increase in tem-
perature together with continuous aeration caused greater
vaporization of ammonia. Ha et al. (2014) conducted experi-
ments on gold leaching from printed circuit boards of dis-
carded mobile phone at varying temperature (20°C–50°C),
using solution containing 10 mM CuSO4, 60 mM Na2S2O3,
0.2 M NH4Cl, and 0.26 M NH3; the gold leaching was signifi-
cantly affected by increasing temperature from 20°C to 30°C,
40°C, and 50°C. The gold leaching was 10%, 28%, 82%, and
88%, respectively, after 1 min of leaching; and changed to 48%,
95%, 97%, and 88% after 5 min of leaching.
5.6. Effect of sulfur containing anions
Chu et al. (2003) studied the impact of thiosulfate oxidation
products on the oxidation of gold in ammoniacal thiosul-
fate solutions. They found that the addition of sulfur-oxy
species, which could be produced by the oxidation of thio-
sulfate, could decrease the oxidation rate of gold as shown
in Table 18. Experiments were carried out at a constant
potential of 250 mV and oxygen-sparging rate of 200 mL/
min. The disulfite ion (S2O52–) gave the largest negative
impact on the oxidation of gold. Thus, it was postulated
that disulfite, which is an intermediate product of thiosul-
fate oxidation by copper(II) in the presence of oxygen
(Byerley et al., 1975), was responsible for the slow leaching
Reference kinetics. The gold dissolution from a sulfide ore increased
Chu et al. with the addition of sulfur species such as tetrathionate,
(2003)
trithionate, and sulfide at low levels, but decreased at high
(2008) levels (Feng and van Deventer, 2007a). Experiments with
colloidal gold (Zhang, 2008) showed that the addition of
S4O62- or S3O62– caused a negative effect on gold dissolu-
tion (Table 18).
Addition of sulfite can inhibit the precipitation of sulfur
and copper sulfide as noted previously (Eqs. 39–40, Table 7).
Some researchers have reported that sulfite and sulfate ions
can stabilize thiosulfate in solutions and thus be beneficial in
gold leaching (Zhang and Li, 1987). However, the addition of
sulfite would decrease EH, so this effect could be positive,
negative, or negligible. Some examples of the different obser-
vations on the effects of sulfite and sulfate addition are as
listed below:
(33) (i) Zhang and Li (1987) found that the effect of sulfite

(34) on gold extraction from a concentrate was depen-
(36)
sulfite to ammoniacal thiosulfate solution to stabi-
lize thiosulfate and found that a ratio of [S2O32–]/
[SO32–] = 4 gave the highest extraction of gold
(95%) and silver from gold concentrates.
(ii) Bagdasaryan et al. (1983) studied the dissolution
rate of gold and silver using a rotating disc. They
found that the addition of sodium sulfite to thiosul-
fate solution prevented the deposition of sulfur and
sulfides on the surface of the gold and silver disc.
The optimum molar ratio of sodium sulfite to
sodium thiosulfate for this effect was 1:1.
(iii) Electrochemical studies by Sullivan and Kohl (1997)
have showed that the reduction peak of gold thio-
sulfate shifted in the negative direction with increas-
ing sulfite concentration. This may have been due to
the formation of a mixed Au(I) complex of thiosul-
fate and sulfite, or sulfite adsorbed onto the gold
substrate. Studies by Perera et al. (2005) have con-
firmed the formation of mixed Au(I)-S2O32–-SO32–
complexes.
(iv) Gold extraction increased from 30% to 42% in
leaching experiments on a refractory ore in the
presence of sulfite up to 0.09 M (Bhaduri, 1987).
(v) Sulfite concentration up to 0.4 M at 55°C gave a
positive effect in experiments conducted with car-
bonaceous ore, but the addition of up to 0.4 M
sulfite at a lower temperature of 35°C showed no
effect (Hemmati, 1987).
(vi) The leaching of a flotation concentrate gave similar
results (Navarro et al., 2002), where the addition of
0.07 M sulfite slightly increased the gold dissolution
from 71% to 74%.
(vii) Sulfate addition has also shown a positive effect with
up to 9% increase in gold extraction (Chai, 1997).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 403

Table 19. Effect of retention time on gold leaching.

Ore type/Reference T (°C) NH3 (M) Cu(II) (mM) Na2S2O3 (M) Retention time (h) Au leached (% or g/m2)
Pure gold/Jiang et al. (1993a) 50 0.063 0.95 1 50
4 52
Gold foil/Feng and van Deventer (2002b) Ambient 2 0.012 0.5h 5d 100 g/m2
24 500 g/m2
Oxide ore/Langhans et al. (1992) Ambient 0.09m 1 0.125 4b 32
48 82
Oxide ore/Li and Kuang (1998) 30 1.5 n
– 1 0.5d 51
3 74
s
Carbonaceous/Hemmati (1987) 55 3.0 150 0.71h 1d 70
4 72
Carbonaceous/Wan and Brierley (1997) Ambient 0.1 0.5 0.1 60 days 62
Chalcopyrite/Navarro et al. (2002) Ambient 1 50 0.3h 1 40
10 90
Rhyolite/Zipperian et al. (1988) 50 4 230 0.63h 1 80
3 85
Refractory/Bhaduri (1987) 60 3.0p 64 1.35h 0.5d 68
2.5 75
Refractory/Yen et al. (1998) Ambient 6 100 0.25h 10 50
24 80
Sulfide/Block-Bolten et al. (1985) 21 1 – 0.125 1 60
3 61
Sulfide ore/Gong and Hu (1990) 50 2 160 1 1d 92
2 94.5
q
Sulfide concentrate/Cao et al. (1992) 60 3 47 0.2h 1d 97.4
3 93.5
Sulfide ore/Aylmore (2001) Ambient 3r 50 0.8 2c 40
24 75
Gold-bearing ore/Chai (1997) 25 2q 120 0.287h 1b 55
3 70
Gold ore/Abbruzzes et al. (1995) 25 4 100 2 1 68
3 80
Gold concentrate/Ji et al. (2003) Ambient 50 0.3h 0.5 32
7 90
Note: Unless stated otherwise, atmosphere was not specified.
b
Nitrogen or argon.
c
SO2.
d
Air or oxygen.
h
(NH4)2S2O3.
m
6.3 mM Na2SO3.
n
1 M NaCl.
p
110 mM Na2SO3.
q
0.8 M Na2SO4.
r
SO2 gas.
s
100 mM Na2SO3.

(viii) Xia et al. (2002) showed that the addition of sulfite,
sulfide, and sulfate had beneficial effects on gold
extraction.
(ix) The addition of 6.25 mM sulfite showed a negative
effect on gold leaching from an oxide ore (Langhans
et al., 1992), while the addition of 12.5 mM sulfite
showed a negligible effect on gold extraction from a
sulfide concentrate (Navarro et al., 2002).
(x) Wan (1997) investigated gold leaching from a car-
bonaceous-sulfide ore, but did not find a beneficial
effect caused by the addition of sulfite in a heap
leach operation system. He suggested that an excess
of sulfite may significantly change the redox poten-
tial of the system and affect gold extraction.
(xi) Ji and Yu (1991) claimed that the addition of sodium
sulfite did not reduce the consumption of thiosulfate
during the leaching of refractory gold ore using
thiosulfate.
(xii) The leaching results of sulfide ore in a copper(II)-
ammonia-thiosulfate system (Feng and van Deventer,
2002a, 2002b) showed that the presence of sulfides in
the leaching system enhanced the decomposition of
thiosulfate.
In summary, there is no clear understanding on the role of
sulfur containing anions in the leaching and recovery of gold
using the Cu(II)-NH3-S2O32– system, warranting further studies.
5.7. Effect of retention time
The effect of retention time on gold extraction is dependent
on leaching conditions, where increased leach time is more
beneficial at low thiosulfate concentration than at high thio-
sulfate concentration. These effects are summarized in
Table 19. In general, the increase in retention time increases
gold dissolution, but longer retention times are not necessarily
effective in some cases. It is clear from Table 19 that in the
case of carbonaceous or sulfide ores at temperature 50–60°C
and thiosulfate concentration in the range 0.6–1 M, gold
extraction in the first hour can be as high as 70–90% due to
the faster leaching rate. However, a further increase in leach-
ing time showed no significant influence on gold extraction.
404 X. M. ZHANG AND G. SENANAYAKE
In other cases, low temperature or low reagent concentrations
caused low leaching rates, and longer residence time benefited
gold extraction. For example, in the case of an oxidized ore
noted in Table 19, increase in residence time from 4 hr to 48
hr improved gold leaching from 32% to 82% at ambient
conditions (Langhans et al., 1992). For the second oxidized
ore in Table 19, gold leaching increased from 51% to 74% as
the residence time was increased from 0.5 hr to 3 hr at 30°C
(Li and Kuang, 1998). A chalcopyrite-gold concentrate and a
refractory gold ore showed similar trends (Table 19).
5.8. Effect of foreign ions
Feng and van Deventer (2002b) studied how heavy metal ions
would affect gold dissolution kinetics. They used gold foils
(99.99% Au) and found that the presence of lead(II) at a low
concentration (50 mg/L) increased gold dissolution, but a
high concentration inhibited it. Metalions of cadmium, nickel,
cobalt, and chromium inhibited gold dissolution at all reagent
concentrations, but zinc had a slightly positive effect at very
low concentrations (10 mg/L). At zinc(II) concentrations
higher than 10 mg/L, the rate of gold dissolution and the
free thiosulfate concentration decreased. This was related to
the decomposition of thiosulfate or the formation of thiosul-
fate complexes with foreign metal ions. Zhang (2008) found
that the presence of lead(II) at 2 mg/L slightly inhibited gold
dissolution. Alonso-Gomez and Lapidus (2009) considered
that lead is co-extracted in ammoniacal thiosulfate solutions
during the leaching of gold and silver; it can largely consume
thiosulfate causing a decrease in the leaching capacity for gold
and silver. They demonstrated that the addition of 0.1M
(NH4)2HPO4 diminished the soluble lead concentration by
40–50% in a sulfide concentration and another mineral; so it
significantly increased gold leaching.
Results based on a sulfide concentrate (Navarro et al.,
2002) showed that the addition of 4.5 g/L zinc(II) to thiosul-
fate solutions reduced gold extraction from 92% to 86% after
10 hr. Chai (1997) showed that the addition of zinc(II)
reduced thiosulfate concentration by forming complex species
such as Zn(S2O3)n+2(1–n). Webster (1986) found that the pre-
sence of silver-thiosulfate complexes or alloyed silver
increased the rate of gold dissolution in oxygenated 0.1 M
thiosulfate solution. Zhang et al. (2008) reported silver dis-
solves faster than gold in ammoniacal copper(II) thiosulfate
solutions. The addition of silver colloids or silver(I) nitrate
has a beneficial effect on gold dissolution. The diffusion con-
trolled dissolution of silver is faster than the chemical con-
trolled dissolution of gold by copper(II).
Li and Kuang (1998) reported that NaCl could increase
gold extraction from an oxide ore. For example, the addition
of 1 M NaCl enhanced gold extraction from 39% to 84% in
ammonium thiosulfate solution. They noted that chloride
increased gold dissolution according to the reaction:
2Au þ 4Cl þ 0:5O2 þ H2 O ¼ 2AuCl2  þ 2OH  (57)
where the intermediate AuCl2–(β2
≈ 10 ) is subsequently con-
9
verted to the more stable thiosulfate complex: Au(S2O3)23-
(β2 ≈ 1026, Table 3).

AuCl2  þ 2ðS2 O3 Þ2 ¼ AuðS2 O3 Þ2 3 þ 2Cl (58)
The formation of AuCl2– reduces the reaction activation
energy, which in turn increases the reaction rate (Li and
Kuang, 1998). However, the half reaction for gold oxidation
in Eq. 57 seems unlikely as Eh required for the oxidation of
Au to AuCl2– is too high compared to that of Cu(II)/Cu(I)-
ammonia-thiosulfate system.
Zhang et al. (2008) noted that the presence of NaCl can
increase gold dissolution in both oxygen-ammonia-thiosulfate
solution and copper(II)-ammonia-thiosulfate solution,
although the presence of sodium chloride does not signifi-
cantly affect the residual copper(II) concentration in the pre-
sence or absence of thiosulfate. However, the increase in
sodium chloride concentration increases the initial rate in
both cases. This indicates the involvement of chloride ion as
a catalyst in the surface reaction of gold with copper(II); this
may be due to effect of chloride ions on surface film and/or
affecting copper(II) activity, both via the formation of mixed
complexes, and warrants further studies.
Feng and van Deventer (2011a, 2011b) conducted experi-
ments in ammoniacal thiosulfate leaching of pure gold and a
sulfide gold ore in the presence of orthophosphate and poly-
phosphate. In pure gold leaching, the kinetics and overall gold
dissolution increased (from 21% up to 35%) with increasing
orthophosphate and hexametaphosphate concentration. In
contrast, there was an optimal hexametaphosphate concentra-
tion of about 0.8 g/L for the sulfide ore leaching, and the gold
leaching was significantly retarded at a hexametaphosphate
concentrations higher than 1.6 g/L.
Senanayake and Zhang (2012) investigated the effect of addi-
tives on the dissolution of gold colloids by copper(II) in ammo-
niacal thiosulfate media by measuring the residual gold and
copper(II) concentration. Results show the beneficial effect of
additives, which follows the descending order: AgNO3> NaCl >
Na2SO4> no additives ~ Na2CO3> NaNO3> Pb(NO3)2>
Na2S4O6 ~ Na2S3O6> Na2SO3. The two reagents AgNO3 and
NaCl do not affect the residual copper(II) concentration, solu-
tion potential (EH), or mixed potential (Emix) but enhance gold
dissolution due to the involvement of Ag(I) and Cl– in the anodic
reaction of gold. Both Na2SO4 and Na2CO3 have beneficial
effects on residual Cu(II), which enhance EH and retard the
reaction with thiosulfate due to ion-association and stabilization
of Cu(NH4)x2+. Thus, the gold dissolution is slow and steady
with Na2CO3 (95% in 5 hr).
Feng and van Deventer (2010e) studied the effect of ethy-
lenediaminetetraacetic acid (EDTA) on leaching of pure gold
Table 20. Effect of oxidants on gold leaching.
Cu(II)/
Air Open open to Cu(II)/air
Oxidant bubbling to air Cu(II)/N2 air bubbling Reference
Au leached 28 32 52 76 90 Chai
% after 3 (1997)
hr
Au leached 27a 18 77 76 63b Zhang
% after et al.
2.5 hr (2004a)
a
oxygen bubbling.
b
Cu(II)/oxygen bubbling.

by thiosulfate. A low concentration of EDTA can increase
gold dissolution, but excessive EDTA decreased gold dissolu-
tion. They found that EDTA can stabilize thiosulfate, and
decrease the formation of the passivation layers of elemental
sulfur and copper sulfide at the gold surface. In the leaching
of a sulfide ore, the leaching kinetics and overall extraction of
gold were enhanced substantially, and this beneficial effect
became more obvious at a higher EDTA concentration; mean-
while, the consumption of ammonium thiosulfate was
reduced. Feng and van Deventer (2010c) also studied the
effect of iron contaminants on thiosulfate leaching of gold;
metallic iron and ferric ions were added to wet grinding with
sulfide ore in a ceramic ball mill to investigate the effect of
iron species on the ammoniacal thiosulfate leaching of gold.
Metallic iron and ferric ions reduced kinetics of gold leaching
and overall extraction, and higher concentrations gave more
negative effect on both kinetics of gold leaching and overall
extraction. The thiosulfate decomposition was also high.
Further studies by Feng and van Deventer (2011a) showed
that carboxymethyl cellulose (CMC) can increase the dissolu-
tion of pure gold in thiosulfate solution and reduce the
decomposition of thiosulfate. In the case of sulfide ores, the
presence of CMC can also improve the rate of gold leaching.
Feng and van Deventer (2010d) investigated the role of amino
acids in the thiosulfate leaching of gold from pyrite concen-
trate. They found that the addition of amino acids largely
improved the overall gold extraction (lower initial kinetics),
and also reduced thiosulfate consumption. This is because the
amino acids can form more stable complexes with cupric ions
than does ammonia, then reduce interaction between thiosul-
fate and the copper complexes.
Xu et al. (2015) improved thiosulfate leaching of a refrac-
tory gold concentrate (calcine) with additives, which reduced
thiosulfate consumption and simultaneously increased gold
leaching. The additives included sodium chloride, sodium
carboxymethyl cellulose (CMC), sodium carboxymethyl
starch (CMS), and sodium humate. They found that sodium
humate showed the best performance with 84.1% gold extrac-
tion, compared to 72.7% without any additives; it was also
higher than gold extraction by cyanidation (78.2%). Other
additives can increase gold extraction to 78.4% (CMC) and
78.5% (CMS). Meanwhile, CMC, CMS, and sodium humate
reduce thiosulfate consumption from 42.4% to 17.7%, 17.5%,
and 13.2%, respectively (Senanayake 2012).
5.9. Effect of oxidants
Gold dissolution in the ammonia-thiosulfate system is
caused by copper(II) acting as the oxidant. The direct oxida-
tion of gold by oxygen in thiosulfate media is very slow as
revealed by the results reported by Chai (1997) from a gold-
bearing ore using oxygen or copper(II), or both of them as
oxidants (Table 20). The conditions used were 2 M NH3,
0.287 M to 0.8 M (NH4)2SO4, temperature: 25–60°C (Chai,
1997). Air as an oxidant can only oxidize 28–32% of gold to
gold(I) after 3 hr, whereas Cu(II) /N2 can oxidize 52% and
copper(II)/air (bubbling) can oxidize 90% of gold (Table 20).
This has been attributed to the low solubility and hence low
diffusion rate of oxygen, compared to Cu(NH3)42+. Although
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 405
oxygen is a slower oxidant compared to copper(II), it can
oxidize copper(I) to copper(II) and thus facilitate the leach-
ing process so that copper ions act as a redox mediator
(Ritchie et al., 2001): Au + Cu(II) = Au(I) + Cu(I); 2Cu(I)
+ 0.5O2 + H2O = 2Cu(II) + 2OH–.
Han (2001) conducted electrochemical leaching experi-
ments with various oxidants: 0.157 M Cu(NH3)42+, 0.047 M
Co(NH3)63+, 1200 kPa O2, and 0.32 M NaOCl. He found that
the descending order of oxidation ability was: Cu(II)/NaOCl >
Cu(II)/O2> Cu(II) > Co(III) > O2> NaOCl. Breuer and Jeffrey
(2002) obtained similar results in their electrochemical study
of gold oxidation in thiosulfate solutions. For the three oxi-
dants: copper(II), cobalt(III), and O2 in 0.1 M (NH4)2S2O3
and 0.2 M NH3 at the same mixed potential of 175 mV, the
oxidation ability decreased in the order Cu(II) > Co(III) > O2.
Zhang et al. (2004a) showed that the relative rates and the
extent of gold colloid dissolution at 25°C in different lixiviant
systems in a given time interval are in the order: oxygen-cyanide
> copper(II)-ammonia-thiosulfate ≈ oxygen-copper(II)-ammo-
nia-thiosulfate > oxygen-ammonia-thiosulfate ≥ oxygen-ammo-
nia > copper(II)-ammonia. In general, without copper(II)
oxygen bubbling has a positive effect on gold dissolution, but
in the presence of copper(II), oxygen bubbling has a negative
effect on gold dissolution from colloidal gold as shows in
Table 20. A systematic study of speciation, reaction rates, and
mechanisms is essential to understand the relative effects of
oxidants and ligands on gold extraction.
6. The mechanism of gold dissolution
The complexity of the leaching chemistry and reaction mechan-
ism for the oxidation of gold by copper(II) is largely due to a
number of competing reactions within the system, such as the
reduction of Cu(II) to Cu(I) by S2O32– producing polythionates,
and the subsequent oxidation of Cu(I) to Cu(II) by oxygen. Few
attempts have been made to compare the results from funda-
mental studies with leaching results and interpretation of results
using kinetic models. Some interpretations presented by pre-
vious researchers are described below:
(i) Zhang and Li (1987) identified that the leaching pro-
cess from a sulfide gold concentrate involved a diffu-
sion (shrinking core) controlled reaction. The
apparent activation energy for gold dissolution from
ores was about 12 kJ/mol. Cathodic reaction of copper
(II) to copper(I) and the oxidation of copper(I) to
copper(II) were described by Eqs. 59 and 60:
CuðNH3 Þ4 2þ þ e ¼ CuðNH3 Þ3 þ þ NH3 (59)
2CuðNH3 Þ3 þ þ 0:5O2 þ H2 O þ 2NH3
¼ 2CuðNH3 Þ4 2þ þ 2OH  (60)
(ii) Gong et al. (1993) claimed that the corrosion reac-
tion of pyrite controls the kinetics of gold leaching
in thiosulfate solution. This process consists of two
stages. The initial stage (in the first 5 min) involves
the dissolution of gold and this includes free gold
and gold exposed on the surface of granules of
chalcopyrite. The second stage of the reaction is
406 X. M. ZHANG AND G. SENANAYAKE
controlled by diffusion of reagents through solid
reaction products. Copper(II) ions catalyze the
initial dissolution of gold. These complex issues led
to more fundamental work on the reaction mechan-
ism of gold oxidation.
(iii) Jiang et al. (1993b) proposed the following mechan-
ism of gold leaching with ammoniacal copper(II) in
thiosulfate media:
Au ¼ Auþ þ e ðAnodic processÞ (61)
Auþ þ 2NH3 ¼ AuðNH3 Þ2 þ (62)
AuðNH3 Þ2 þ þ 2S2 O3 2 ¼ AuðS2 O3 Þ2 3 þ 2NH3 (63)
CuðNH3 Þ4 2þ þ e ¼ CuðNH3 Þ2 þ
þ 2NH3 ðCathodic processÞ (64)
þ the appropriate potential region even in the absence
CuðNH3 Þ2 þ 0:25O2 þ 0:5H2 O þ 2NH3
¼ CuðNH3 Þ4 2þ þ OH  (65)
On the anodic gold surface, Au+ ions react with ammo-
nia to form the complex Au(NH3)2+. After entering the
solution, Au(NH3)2+ reacts with S2O32- to form the more
stable complex Au(S2O3)23–. On the cathodic surface, Cu
(NH3)42+ is reduced to Cu(NH3)2+. After entering the solu-
tion, oxygen oxidizes Cu(NH3)2+ back to Cu(NH3)42+.
Wensveen and Nicol (2005) showed that the oxidation of
Cu(NH3)2+ by oxygen (Eq. 65) is much faster than the
oxidation of Cu(S2O3)23–.
(iv) Zhu et al. (1994b) conducted an electrochemical
study on the mechanism of gold dissolution in thio-
sulfate solutions. They reported that in the absence
of ammonia, the anodic process of the gold elec-
trode consists of an active dissolution reaction
described by Eqs. 61 and 66.
Au ¼ Auþ þ e (61)
þ
Au þ 2S2 O3 2 ¼ AuðS2 O3 Þ2 3 (66)
Simultaneous passivation of gold occurs with the adsorp-
tion of elemental sulfur on the surface of the electrode (Eqs.
67 and 68):
S2 O3 2 þ 2Au ¼ Au2 S þ SO3 2 (67)
 In summary, there has been significant progress on
S2 þ 2Au ¼ Au2 S þ 2e (68)
(v) The addition of ammonia into the thiosulfate system
can eliminate the passivation of the electrode as
described in Eqs. 61–63, proposed by Jiang et al.
(1993b).
(vi) Aylmore and Muir (2001a) proposed an electrochemi-
cal-catalytic mechanism in which gold ions react with
thiosulfate ions to form Au(S2O3)23– after entering solu-
tion (Eq. 63). On the cathodic surface, Cu(NH3)42+ is
reduced to Cu(NH3)2+. After entering solution, oxygen
oxidizes Cu(NH3)2+ back to Cu(NH3)42+ as described
by Jiang et al. (1993b). Simultaneously, Cu(NH3)2+
is converted to Cu(S2O3)35– ions and oxidized to
Cu(NH3)42+ with oxygen (Wan, 1997). The predomi-
nant cathodic reaction depends upon the relative con-
centrations of the species in solution (Eqs. 64, 65,
and 69).
CuðNH3 Þ2 þ þ 3S2 O3 2 ¼ CuðS2 O3 Þ3 5 þ 2NH3 (69)
(vii) In addition, the Cu(NH3)42+ ions gain electrons
from both S2O32– and Au, as described by Eq. 32
(in Table 6) and Eq. 70, leading to the oxidation of
S2O32–.
2CuðNH3 Þ4 2þ þ 8S2 O3 2 ¼ 2CuðS2 O3 Þ3 5
þ S4 O6 2 þ 8NH3 (32)
2þ þ þ
CuðNH3 Þ4 þ Au ¼ CuðNH3 Þ2 þ AuðNH3 Þ2 (70)
(viii) Breuer and Jeffrey (2002) noted that, if Eqs. 61 and
62, proposed by Jiang et al. (1993b), were rate con-
trolling, the reactions would still occur without thio-
sulfate. This would result in a measurable current in
of thiosulfate, a feature that was not observed in
practice. They claimed that ammonia could form a
mixed gold-ammonia-thiosulfate complex, such as
Au(S2O3)(NH3)– proposed by Wang (1992), or that
ammonia affects the surface of the gold electrode in
some other way.
(ix) Zhang and Nicol (2003, 2005) carried out an electro-
chemical study of the dissolution of gold in thiosulfate
solutions and noted that:
a. in the absence of thiosulfate, the anodic current
for gold oxidation was negligible in an aqueous
ammonia solution;
b. the addition of ammonia to the thiosulfate solu-
tion resulted in an increase in gold dissolution as
well as elimination of the passivating (sulfur) film;
c. in the absence of ammonia, copper ions enhance
the rate of gold dissolution, increasing copper
ion concentration resulting in higher dissolution
rates of gold at a potential of 0.3 V; and
d. the role of copper ions in enhancing the dissolu-
tion rate of gold is possibly associated with the
formation of a copper-thiosulfate-oxygen inter-
mediate, which is more reactive than dissolved
oxygen in terms of cathodic reduction.
defining the reaction mechanism for the dissolution of
gold in a Cu(II)-NH3-S2O32–-O2 system, despite the com-
plexity, largely due to the lack of knowledge of exact species
involved on the gold surface and in solution. Work by
Senanayake et al. (2003) and Perera and Senanayake
(2004) have confirmed the stability order of the gold(I)
complexes: Au(S2O3)23–> Au(S2O3)(NH3)–> Au(NH3)2+.
Senanayake (2004c) showed the importance of considering
the involvement of Cu(NH3)p(S2O3)n–2(n-1) (p = 2,3; n =
1,2) in the oxidation of both thiosulfate and gold by ammo-
niacal copper(II) solutions. Wensveen and Nicol (2005)
confirmed the formation of an intermediate copper(II)-
ammonia-thiosulfate complex that is responsible for the
oxidation of thiosulfate by copper(II). Black (2006) con-
firmed the formation of mixed copper(I)-ammonia-thiosul-
fate complexes. Reinterpretation of literature data for the
Cu(II)-NH3-S2O32– system on the basis of adsorption and

mixed potential theory points out that the dissolution reac-
tion take place via the adsorption of copper(II)-ammonia-
thiosulfate onto the gold surface, forming the adsorbed
species Au(S2O3)nCu(NH3)p–(2n-2) Senanayake (2005a).
Ammonia facilitates gold dissolution via oxidation of the
surface adsorbed species Au(S2O3)(NH3)2– in copper-free
thiosulfate solution (Senanayake, 2005b). In ammoniacal
copper(II) thiosulfate solutions (Senanayake, 2005e), che-
mical oxidation of gold by copper(II) takes place via the
adsorbed species Au(S2O3)nCu(NH3)p(S2O3)°. The con-
trolled aeration/oxygenation enhances the concentration
of Cu(NH3)p(S2O3)° and thus benefits gold oxidation.
Summary
For over 100 years, the cyanidation process has been the most
important process in the extraction of gold due to its effective,
low cost, and efficient and convenient recovery of gold from
leach liquors using carbon in leach/pulp technology. However,
cyanide cannot effectively extract gold from some sulfide ores,
complex copper manganese arsenic ores, or carbonaceous ores;
and environmental problems arise occasionally due to the high
toxicity of cyanide. Therefore, researchers have been testing for
alternative lixiviants for leaching gold. Despite the research
interest in non-cyanide gold lixiviants, alternative non-cyanide
gold processes are still being tested or developed. This is due to
the low stability of the lixiviant due to side reactions. The Au
(CN)2– complex is the most stable complex (β2 ≈ 1038), but the
reasonably high stability constants of Au(S2O3)23– (β2 ≈1024)
offers a relative less toxic ligand suitable for leaching gold.
This review has compared the advantages and disadvan-
tages of ammoniacal thiosulfate leaching of gold, and outlined
the history and recent progress on gold extraction using
thiosulfate; thiosulfate production, oxidation, and stabilization
in relation to side reactions. Previous studies on deferent
types of gold ores, concentrates, and pure gold, have been
summarized along with the optimum leaching conditions.
The update is useful in further research for developing thio-
sulfate or other lixiviant systems for gold ores as well as
concentrates and recycling gold from secondary resources.
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