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School of Engineering and Computing

Department of Civil Engineering

Gold Leaching in Thiosulfate Solutions and Its

Environmental Effects Compared With Cyanide

Elsayed A. Oraby

This thesis is presented for the Degree of

Doctor of Philosophy

Curtin University of Technology

November 2009
Declaration

To the best of my knowledge and belief this thesis contains no material previously
published by any other person except where due acknowledgment has been made.

This thesis contains no material which has been accepted for the award of any other
degree or diploma in any university.

Signature:……………………………………..

ii
 List of Publications

Oraby, E.A., Browner, R.E. and Nikraz, H.R., 2007, “Environmental and
metallurgical advantages of thiosulfate leaching of gold and silver in a closed vessel
system” International conference of mining, petroleum and metallurgical
engineering, Assiut university, Egypt.

Oraby, E.A., Jeffrey, M.I., Browner, R.E. and Nikraz, H.R., 2009, “Mercury
leaching in different thiosulfate and cyanide solutions and its effects on gold
recovery. Chemica 2009, Perth, Australia.

Oraby, E.A., Jeffrey, M.I., Browner, R.E. and Nikraz, H.R., 2009 (accepted),
“Mercury deportment in thiosulfate leaching and resin in pulp recovery of gold.
International Journal of Chemical Engineering, Australia.

Oraby, E.A., Browner, R.E., Jeffrey, M.I. and Nikraz, H.R., 2009, “Kinetic and
electrochemical study of silver leaching in thiosulfate solutions”, Chemica 2009,
Perth, Australia.

Oraby, E.A., Jeffrey, M.I. Browner, R.E. and Nikraz, H.R., (under press), “the
deportment of Mercury in thiosulfate leaching and resin in pulp recovery of gold
ores, Special Gold issue of Minerals and Metallurgical Processing Journal (MMP),
Society of Mining, Metallurgy and Exploration, Inc.

Oraby, E.A. and Jeffrey, M.I, (accepted), “An electrochemical studies on pure gold
and gold-silver alloys leaching in thiosulfate solutions”, the electrochemical society,
Doyle, F. M; Woods, R.; Kelsall, G. H. editors, Vol 28, No. 6.

Oraby, E.A., Browner, R.E. and Nikraz, H.R., (Submitted), “Thiosulfate leaching of
pure gold, pure silver, and gold-silver alloys”, International Journal of Minerals
Processing and Extractive Metallurgy Review.

iii
Abstract

Nowadays, keeping mining and the environment sustainable is a major concern all
over the world. Using toxic chemicals such as cyanide and mercury in the gold
leaching process is one of the main factors that need to be considered in terms of the
environment. Finding alternative lixiviants is one solution that would decrease the
uses of these toxic chemicals. Thiosulfate is one of the most promising alternative
substitutes to cyanide kinetically and environmentally.
Gold leaching in thiosulfate solutions was evaluated environmentally and
kinetically in different ways: (1) applying a closed system to leach gold (2)
evaluating the environmental and metallurgical optimum thiosulfate leaching
characteristics for pure gold and pure silver and gold silver alloys (4, 8, 20 and 50 wt
% silver), (3) studying the electrochemical behavior of gold, silver, and gold/silver
alloys (4) optimizing the leaching conditions of gold ore samples supplied from
Centamin Egypt Limited Company, (5) finally, studying the ability of thiosulfate
solutions to dissolve mercury and evaluating gold, copper, and mercury recovery
from ion-exchange resins.
The study showed that the leaching rate of gold and silver in the closed vessel was
greater than that obtained in the open vessel by 30% and 45% respectively. To avoid
the losses of ammonia a closed leaching system is recommended. Gold and silver
leaching in thiosulfate solution is preferable kinetically and environmentally if
conducted in a closed vessel system.
The effect silver alloyed with gold was evaluated and the result showed that the
dissolution rate of pure gold is higher than that form 4 and 8 wt% Ag alloys. And the
dissolution rate of gold from 20 and 50% silver alloys is more than that obtained for
pure gold. The silver dissolution rate is sensitive to copper(II) concentration being
1.67 x 10-5 mol.m-2.s-1 at an initial copper(II) concentration of 1.25 mM and 6.6x10-5
mol.m-2.s-1 at an initial copper(II) concentration of 10 mM. Silver dissolution is more
sensitive to ammonia than gold.
From the electrochemical study on gold/silver alloys, it was found that an
increase in silver in the alloy results in an increase of the current density from both
gold and silver oxidation in thiosulfate solutions in the range of potentials 0.242-
0.542 V. Also, it was found that in thiosulfate solutions containing thiourea, the
oxidation current of gold/silver alloys decreased and the oxidation current from pure

iv
Abstract

gold after the standard potential for gold oxidation (150 mV) is higher than the total
oxidation current from gold-silver alloys.
Leaching of a selected gold ore using thiosulfate solutions for 24 hours suggested the
optimum conditions to leach the ore to be 0.2 – 0.4 M thiosulfate, 400 mM NH3, 10 -
20 mM Cu(II), 30 ºC, 300 rpm, no air supplied, solid/liquid ratio 20%, and mean
particle size of < -106 µm.
Finally, the study showed that mercury dissolves in thiosulfate solutions as it
dissolves in cyanide. Mercury dissolves in thiosulfate solutions in the order: HgS2
<Hg0<Hg2Cl2<HgCl2. The effect of mercury on gold and copper loading and
recovery from resins was evaluated and the results showed that mercury does not
influence gold and copper loading and recovery. Also, it was found that mercury
elution from the loaded resin is slower than the recovery of gold and copper.

v
 Table of Contents

Chapter 1 Introduction ........................................................................................... 1

1.1 Mining and the Environment .............................................................................. 1

1.2 Gold Overview .................................................................................................. 1
1.2.1 Gold Properties ............................................................................................... 2
1.2.2 Gold Minerals and Ores .................................................................................. 3
1.2.3 Uses of Gold................................................................................................... 4
1.3 Gold Mining and the Environment ..................................................................... 5
1.4 Alternatives to Cyanide ...................................................................................... 5
1.5 Objectives of the Study ...................................................................................... 7
1.6 Methodology of the Study .................................................................................. 9
1.7 Thesis Organization ......................................................................................... 10

Chapter 2 Environmental Impacts of Gold Mining: Literature Review ................. 11

2.1 Introduction ..................................................................................................... 11

2.2 Environmental Impacts of Mercury in Gold mining .......................................... 12
2.2.1 Introduction .................................................................................................. 12
2.2.2 Mercury Overview ........................................................................................ 12
2.2.3 History of Mercury ....................................................................................... 12
2.2.4 Occurrence ................................................................................................... 13
2.2.6 Mercury Uses ............................................................................................... 14
2.2.7 Mercury Toxicity and Standards .................................................................... 16
2.2.8 Mercury Effects on Human Health ................................................................ 16
2.2.9 Mercury Releases to the Environment............................................................ 17
2.2.10 The Principle of the Amalgamation Process ................................................. 19
2.2.11 Mercury and Gold mining ........................................................................... 19
2.2.11.1 Environmental Problems of using Mercury in Gold mining ....................... 20
2.3 Environmental Impacts of Cyanide ................................................................... 22
2.3.1 Introduction .................................................................................................. 22
2.3.2 Chemistry of Cyanide ................................................................................... 23
2.3.3 Production of Sodium Cyanide ...................................................................... 26
2.3.4 Uses and Sources of Cyanide ........................................................................ 27

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2.3.5 History of Cyanide in Gold mining ................................................................ 28

2.3.5 Cyanide Toxicity .......................................................................................... 29
2.3.5.1 Occupational Exposure to Cyanide ............................................................. 31
2.3.5.2 Recent Cyanide Accidents .......................................................................... 31
2.3.6 Treatment and Recovery of Cyanide .............................................................. 33
2.3.6.1 Activated Carbon Adsorption ..................................................................... 33
2.3.6.2 Alkaline Chlorination ................................................................................. 34
2.3.6.3 Biological Treatment .................................................................................. 34
2.3.6.4 Caro`s Acid ............................................................................................... 35
2.3.6.5 Hydrogen Peroxide .................................................................................... 36
2.3.7 Alternatives to Cyanide ................................................................................. 36
2.3.7.1 Thiourea .................................................................................................... 37
2.3.7.2 Thiocyanate ............................................................................................... 38
2.3.7.3 Halides ...................................................................................................... 39
2.3.7.4 Thiosulfate................................................................................................. 40
2.3.7.5 Ammonia ................................................................................................... 41
2.3.7.6 The Toxicity of Different Alternative Leaching Reagents ............................ 41
2.4 Summary......................................................................................................... 41

Chapter 3 Thiosulfate Leaching of Gold: Literature Review ................................ 43

3.1 Introduction ..................................................................................................... 43

3.2 History of Gold Production .............................................................................. 43
3.3 An overview of Thiosulfate .............................................................................. 44
3.3.1 Chemistry of Thiosulfate ............................................................................... 45
3.3.1.1 Production of Thiosulfate ........................................................................... 45
3.3.1.2 Uses of Thiosulfate .................................................................................... 46
3.3.1.3 The Stability of Thiosulfate ........................................................................ 47
3.4 Cyanide Leaching of Gold (Cyanidation).......................................................... 50
3.4.1 Chemistry of Cyanide ................................................................................... 50
3.4.2 Gold Dissolution in the Cyanide System ........................................................ 51
3.4.2.1 The Anodic Reaction.................................................................................. 51
3.4.2.2 The Cathodic Reaction ............................................................................... 51
3.4.2.3 Overall Dissolution Reaction of Gold ......................................................... 52
3.5 Thiosulfate Leaching of Gold ........................................................................... 52

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3.5.1 Reaction Mechanism ..................................................................................... 53

3.5.2 The Effect of Reagent Concentration and Reaction Conditions ....................... 55
3.5.2.1 Effect of Thiosulfate .................................................................................. 56
3.5.2.2 Effect of Ammonia .................................................................................... 57
3.5.2.3 Effect of Copper ........................................................................................ 59
3.5.2.4 Effect of pH ............................................................................................... 60
3.5.2.5 Effect of Agitation Speed ........................................................................... 61
3.5.2.6 Effect of Temperature ................................................................................ 62
3.5.2.7 Effect of Impurities .................................................................................... 64
3.5.2.8 Effect of Oxygen........................................................................................ 66
3.5.2.9 Effect of Pulp Density ................................................................................ 67
3.5.3 Optimum Leaching Conditions ...................................................................... 67
3.6 Electrochemical Reactions ............................................................................... 69
3.6.1 Measurement of Solution Potentials............................................................... 69
3.6.2 Electrochemical Reactions in Thiosulfate Solution ......................................... 70
3.6.2.1 The Anodic Reaction (Gold Oxidation) ....................................................... 70
3.6.2.2 The Catholic Reaction (Copper(II) Reduction) ............................................ 73

Chapter 4 Materials and Methods......................................................................... 75

4.1 Leaching Kinetic Experiments ......................................................................... 75

4.1.1 Gold and Silver Sources ................................................................................ 75
4.1.1.1 Gold and Silver Discs................................................................................. 75
4.1.1.2 Gold Ore Samples ...................................................................................... 76
4.1.2 Rotating Disc Experimental Method .............................................................. 79
4.1.2.1 The Experimental Setup ............................................................................. 79
4.1.2.2 Disc Polishing ............................................................................................ 80
4.1.2.3 Disc Leaching Procedure ............................................................................ 80
4.1.2.4 Ore Leaching Procedure ............................................................................. 81
4.1.2.5 Gold and Silver Analysis ............................................................................ 82
4.1.2.6 Thiosulfate Analysis .................................................................................. 82
4.1.2.7 Copper(II) Analysis.................................................................................... 84
4.1.2.8 Ammonia Analysis..................................................................................... 86
4.2 Electrochemical Rotating Disc Experiments ..................................................... 88
4.2.1 Linear Sweep Voltammetry ........................................................................... 89

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4.2.1.1 Solution and Disc Preparations ................................................................... 89

4.2.1.2 Experimental Setup .................................................................................... 89
4.2.2 Coulometric Experiments .............................................................................. 89
4.2.2.1 Solution and Disc Preparation .................................................................... 89
4.2.2.2 Experimental Setup .................................................................................... 90
4.3 Mercury Dissolution ........................................................................................ 91
4.3.1 Mercury Dissolution Experiments ................................................................. 91
4.4 Gold, Copper and Mercury Recovery ............................................................... 91
4.4.1 Loading-Stripping Experiments ..................................................................... 92
4.4.2 Solution Speciation ....................................................................................... 92
4.4.3 Loading-Elution Experiments ........................................................................ 93

Chapter 5 Thiosulfate Leaching in Open and Closed Vessels ............................... 94

5.1 Introduction ..................................................................................................... 94

5.2 Thiosulfate Leaching in Open and Closed Vessels ............................................ 95
5.2.1 Gold and Silver Leaching in Open and Closed Vessels (1 hour run)................ 95
5.2.1.1 Thiosulfate Depletion in Open and Closed Vessels ...................................... 96
5.2.1.2 Ammonia Analysis in Open and Closed Vessels ......................................... 97
5.2.1.3 Copper(II) Analysis in Open and Closed Vessels ........................................ 98
5.2.1.4 Gold and Silver Leaching Rates in Open and Closed Vessels (one hour) ...... 99
5.3 Effect of Reagent Concentrations and Leaching Parameters (8 hours run) ........ 100
5.3.1 Effect of Temperature ................................................................................. 100
5.3.1.1 Effect of Temperature on Gold and Silver Dissolution............................... 101
5.3.1.2 Effect of Temperature on the Volatilization of Ammonia .......................... 104
5.3.1.3 Effect of Temperature on Cu(II) Reduction ............................................... 105
5.3.1.4 Effect of Temperature on the Decomposition of Thiosulfate ...................... 106
5.3.2 Effect of Initial Ammonia Concentration ..................................................... 107
5.3.2.1 Effect of Initial Ammonia Concentration on Gold and Silver Dissolution... 107
5.3.2.2 Effect of Initial Ammonia Concentration on Volatilization of Ammonia .... 109
5.3.2.3 Effect of Initial Ammonia Concentration on Cu(II) Reduction ................... 110
5.4 Dissolution Rates of Gold, Silver and Total Metal as a Function of Silver
Content. .............................................................................................................. 112
5.5 Dissolution Rate of Gold-Silver Alloys as a Function of Time......................... 113
5.6 Effect of the Leaching Conditions (8 hour run) ............................................... 113

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5.6.1 Effect of Time on the Gold and Total Metal Dissolution .............................. 114
5.6.2 Effect of Thiosulfate Concentration on Gold, Silver, and Total Metal
Dissolution.......................................................................................................... 115
5.6.3 Effect of Copper(II) Concentration on Gold, Silver and Total Metal
Dissolution.......................................................................................................... 117
5.6.4 Effect of Ammonia Concentration on Gold, Silver and Total Metal
Dissolution.. ........................................................................................................ 118
5.6.5 Effect of Temperature on Gold, Silver and Total Metal Dissolution .............. 120
5.6.6 Effect of Rotation Speed on Gold, Silver and Total Metal Dissolution .......... 121
5.6.7 Effect of pH (ammonium sulfate concentration) on Gold, Silver and Total
Metal Dissolution ................................................................................................ 123
5.7 Summary....................................................................................................... 124

Chapter 6 An electrochemical study of the leaching of gold, silver, and gold-silver

alloys in thiosulfate solutions.............................................................................. 126

6.1 Introduction ................................................................................................... 126

6.2 Linear Sweep Voltammetry............................................................................ 126
6.2.1 Effect of Ammonium Thiosulfate Concentration .......................................... 127
6.2.1.1 Pure Gold ................................................................................................ 127
6.2.1.2 Gold-Silver Alloys ................................................................................... 128
6.2.2 Effect of Sodium Thiosulfate Concentration ................................................ 129
6.2.2.1 Pure Gold ................................................................................................ 129
6.2.2.2 Gold-Silver .............................................................................................. 130
6.2.3 Effect of Ammonia Concentration ............................................................... 131
6.2.3.1 Effect of Ammonia Concentration on Pure Gold ....................................... 132
6.2.3.2 Effect of Ammonia Concentration on Gold-Silver Alloys .......................... 132
6.2.4 Effect of Thiourea Concentration................................................................. 134
6.2.4.1 Effect of Thiourea Concentration on Pure Gold ......................................... 134
6.2.4.2 Effect of Thiourea Concentrations on Gold-Silver Alloys .......................... 135
6.2.4.3 Effect of Silver Content in the Presence of Thiourea ................................. 136
6.2.4.4 Effect of Thiourea on Silver Oxidation ..................................................... 136
6.3 Coulometric Experiments at a Fixed Potential................................................. 137
6.3.1 Coulometric Experiments at 0.22 V ............................................................. 138
6.3.1.1 Ammonium Thiosulfate-Ammonia Solution ............................................. 138

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6.3.1.2 Sodium Thiosulfate-Ammonia Solution .................................................... 139

6.3.1.3 Thiosulfate-Ammonia-Copper Solution .................................................... 139
6.3.1.4 Thiosulfate-Thiourea Solution .................................................................. 141
6.3.1.5 Gold and Total Metal Dissolution Rates at 0.22 V Potential....................... 143
6.3.2 Coulometric Experiment at 0.256 V............................................................. 144
6.3.2.1 Thiosulfate-Ammonia Solution................................................................. 144
6.3.2.2 Thiosulfate-Ammonia-Copper Solution .................................................... 146
6.3.2.3 Thiosulfate-Thiourea Solution .................................................................. 148
6.3.2.4 Gold and total metal dissolution rates at 0.256 V potential ......................... 149
6.3.3 Coulometric Experiment at 0.292 V............................................................. 151
6.3.3.1 Thiosulfate Solutions ............................................................................... 151
6.3.3.2 Thiosulfate-Ammonia Solution................................................................. 155
6.3.3.3 Thiosulfate-Ammonia-Copper Solution .................................................... 156
6.3.3.4 Thiosulfate-Thiourea Solution .................................................................. 159
6.3.3.5 Gold and Total Metal Dissolution Rates at 0.292 V Potential ..................... 162
6.3.4 Coulometric Experiment at 0.35 V .............................................................. 164
6.3.4.1 Thiosulfate-Ammonia Solution................................................................. 164
6.3.4.2 Thiosulfate-Ammonia-Copper Solution .................................................... 164
6.3.4.3 Thiosulfate-Thiourea Solution .................................................................. 165
6.3.4.4 Gold and Total Metal Dissolution Rates at 0.35 V Potential....................... 166
6.3.5 Effect of Potential on Gold and Total Dissolution (gold and silver) Rate....... 168
6.4 Summary....................................................................................................... 169

Chapter 7 Thiosulfate leaching of gold ore in a closed vessel.............................. 171

7.1 Introduction ................................................................................................... 171

7.2 Quantitive XRD Analysis............................................................................... 173
7.3 Elemental Analysis ........................................................................................ 173
7.4 Ore Sample Leaching (standard conditions) .................................................... 176
7.4.1 Gold Extraction using Open and Closed Vessels .......................................... 176
7.4.2 Thiosulfate Consumption in Open and Closed Vessels ................................. 177
7.4.3 Gold Extraction from Screen Size Fractions ................................................. 178
7.5 Effect of Reagent Concentration and Leaching Parameters .............................. 179
7.5.1 Effects of Thiosulfate Concentration on Gold Extraction .............................. 179
7.5.2 Effect of Thiosulfate Concentration on Thiosulfate Consumption ................. 180

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7.5.3 Effect of Copper Concentration on Gold Extraction ..................................... 181

7.5.4 Effect of Copper Concentration on Thiosulfate Consumption ....................... 182
7.5.5 Effect of Ammonia Concentration on Gold Extraction ................................. 183
7.5.6 Effect of Ammonia Concentration on Thiosulfate Consumption ................... 184
7.5.7 Effect of Temperature on Gold Extraction ................................................... 185
7.5.8 Effect of Temperature on Thiosulfate Consumption ..................................... 186
7.5.9 Effect of Air Injection on Gold Extraction ................................................... 187
7.5.10 Effect of Air Injection on Thiosulfate Consumption ................................... 188
7.5.11 Effect of Pulp Density on Gold Extraction ................................................. 189
7.5.12 Effect of Agitation on Gold Extraction ...................................................... 190
7.5.13 Effect of Ore Weathering on Gold Extraction............................................. 191
7.5.14 Ore Leaching in Thiosulfate Compared to Cyanide Solutions ..................... 192
7.6 Summary....................................................................................................... 193

Chapter 8 Dissolution of mercury in thiosulfate and cyanide solutions: an

environmental problem ....................................................................................... 195

8.1 Introduction ................................................................................................... 195

8.2 Mercury Dissolution in Thiosulfate and Cyanide Solutions ............................. 195
8.2.1 Mercury Stability in the Collected Samples ................................................. 196
8.2.2 Effect of Tetrathionate on the Mercury Thiosulfate Complex Stability ......... 197
8.2.3 The Dissolution of Mercurous Chloride (Hg2Cl2) ......................................... 197
8.2.4 The Dissolution of Mercury Sulfide (HgS)................................................... 198
8.2.4.1 Effect of Ammonium Thiosulfate Concentration on the Dissolution of
Mercury Sulfide .................................................................................................. 199
8.2.5 The Dissolution of Mercury Metal (Hg0) ..................................................... 202
8.3 Effect of Mercury on Gold Loading and Recovery from Thiosulfate Solutions
Using Anion-Exchange Resins ............................................................................. 204
8.3.1 Introduction ................................................................................................ 204
8.3.2 Loading and Recovery of Gold .................................................................... 206
8.3.3 Loading and Recovery of Copper ................................................................ 207
8.3.4 Loading and Recovery of Mercury .............................................................. 208
8.3.5 Polythionate Speciation............................................................................... 210
8.3.6 Gold, Copper and Mercury Recovery Using an Elution Column ................... 211
8.3.6.1 Gold Recovery ......................................................................................... 211

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8.3.6.2 Copper Recovery ..................................................................................... 212

8.3.6.3 Mercury Recovery ................................................................................... 212
8.4 Summary....................................................................................................... 213

Chapter 9 Conclusions and Recommendations ................................................... 214

9.1 Conclusions ................................................................................................... 214

9.1.1 Gold leaching in open and closed vessels ..................................................... 214
9.1.2 Optimum thiosulfate leaching characteristics of pure gold, pure silver and
gold/silver alloys ................................................................................................. 215
9.1.3 Electrochemical studies of gold, silver, and gold/silver alloys in thiosulfate
solutions ............................................................................................................. 215
9.1.4 Thiosulfate leaching of gold ore samples ..................................................... 216
9.1.5 Mercury dissolutions in thiosulfate solutions and gold, copper, and mercury
recovery from ion-exchange resins ....................................................................... 217
9.2 Recommendations ......................................................................................... 218

Chapter 10 References........................................................................................ 219

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 List of Figures

Figure 1.1: The estimation gold mine production by country in 2003 (Gold Fields
Mineral Services Ltd, 2004). ................................................................... 2
Figure 1.2: The distribution of gold uses (Marsden & House, 2006). ........................ 5
Figure 1.3a: Flowchart of the goals and procedures of the project (part I). ................ 8
Figure 1.3b: Flowchart of the goals and procedures of the project (part
II)………………………………………………………………………….9
Figure 2.1: Atmospheric mercury pathways in areas of gold and silver mining ....... 18
Figure 2.2: The speciation of free cyanide and hydrogen cyanide in aqueous solution
as a function of pH. .............................................................................. 24
Figure 2.3: Eh-pH diagram for the CN- H2O system at 25 ºC (Smith, 1988). .......... 26
Figure 2.4: Industrial uses of hydrogen cyanide (Williams, 2001). ......................... 28
Figure 3.1: The chemical structure of the thiosulfate ion. ....................................... 45
Figure 3.2: The use distribution of ammonium thiosulfate (Bean, 1996). ................ 47
Figure 3.3: Schematic representation of the local corrosion cell at a gold surface in
contact with an oxygen containing cyanide solution (Marsden & House,
2006). .................................................................................................. 52
Figure 3.4: Eh - pH diagram for the Au - NH3 - S2O32- - H2O system at 25 ºC: 10-5 M
Au(I) , 0.1 M Na2S2O3, 1 M (NH3 + NH4+). ........................................... 54
Figure 3.5: Schematic dissolution mechanisms in ammonium thiosulfate solution on
gold surface (Aylmore & Muir, 2001a). ................................................ 55
Figure 3.6: Linear sweep voltammogram showing the oxidation of gold to gold
thiosulfate. Also shown is the mass change measured using the REQCM,
and thepartial current density (icalculated) derived from this (Breuer &
Jeffrey, 2002). ...................................................................................... 71
Figure 3.7: Linear sweep voltammograms showing the oxidation of a gold/silver
alloy containing 2% silver in 0.2 M ammonium thiosulfate (Chandra &
Jeffrey, 2004). ...................................................................................... 72
Figure 3.8: Linear sweep voltammograms showing the effect of thiourea (Tu) and
potassium ethyl xanthate (PEX) on the gold oxidation half reaction in 0.2
M ammonium thiosulfate (Chandra & Jeffrey, 2004). ............................ 73
Figure 3.9: Linear sweep voltammograms for the reduction of oxygen in ammonia-
thiosulfate solutions, and for the reduction of copper in ammonia and

xiv
List of Figures

ammonia-thiosulfate solutions. A platinum electrode was used in these experiments

(Breuer & Jeffrey, 2002). ...................................................................... 74
Figure 4.1: Pure gold, pure silver and gold-silver discs of different silver
composition: 4, 8, 20, and 50 wt.% silver. ............................................. 76
Figure 4.2: Enerpack hydraulic crusher (Enerpack model RR
308)…………………………………………………………………...…76
Figure 4.3: Bench top ring mill and its internal components.
………………………………………………………………...…………76
Figure 4.4: The experimental setup of the open and closed vessels. ........................ 80
Figure 4.5: The absorbance of copper(II) ammine in solutions containing 400 mM
ammonia and 100 mM sodium thiosulfate at 30 ºC using UV-Vis
spectrophotometer………………………………………………….…..…85
Figure 4.6: The calibration curve of copper(II) ammine. ........................................ 86
Figure 4.7: Wavelength scan of the absorbance of an ammonia standard solution
using UV-Vis spectrophotometry. ......................................................... 87
Figure 4.8: The calibration curve of different ammonia standards. ......................... 88
Figure 4.9: The electrochemical cell setup used to conduct the different
experiments.. ........................................................................................ 90
Figure 5.1: Chapter five goals and achievements. .................................................. 94
Figure 5.2: The amount of gold and silver dissolved in both open and closed vessels.
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, pH= 11.5 and 30 ºC. ............................................................... 96
Figure 5.3: Thiosulfate concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC. ................................ 97
Figure 5.4: Ammonia concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC. ................................ 98
Figure 5.5: Copper(II) concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC. ................................ 99
Figure 5.6: Gold and silver dissolution rates in open and closed vessels for 1 hour
experiments. Initial experiment conditions: 10 mM CuSO4, 0.4 M NH3,
0.2 M (S2O3)2-, 300 rpm, pH = 11.5 and 30 ºC. .................................... 100

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List of Figures

Figure 5.7: Effect of temperature on gold leaching in open and closed vessels. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, and pH= 11.5.............................................................................. 101
Figure 5.8: Effect of temperature on silver leaching in open and closed vessels.
Initial leaching conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, and pH= 11.5. ...................................................................... 102
Figure 5.9: Effect of temperature on ammonia volatilization in the open vessel.
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, ºC, and pH= 11.5. ................................................................ 104
Figure 5.10: Effect of temperature on Cu(II) concentration in open and closed
vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4
M NH3, 300 rpm, ºC, and pH= 11.5..................................................... 105
Figure 5.11: Effect of temperature on the decomposition of thiosulfate in open and
closed vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, ºC, and pH= 11.5................................... 106
Figure 5.12: Effect of ammonia concentration on gold dissolution in open and closed
vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
NH3, 300 rpm, 30 ºC, and pH= 11.5. ................................................... 107
Figure 5.13: Effect of ammonia concentration on silver leaching in open and closed
vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
NH3, 300 rpm, 30 ºC, and pH= 11.5. ................................................... 109
Figure 5.14: Effect of initial ammonia concentration on ammonia volatilization in
the open vessel. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5. ....................................... 110
Figure 5.15: Effect of initial concentration of ammonia on Cu(II) reduction in open
and closed vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5. ....................................... 111
Figure 5.16: The dissolution rate of gold, silver and gold-silver alloys after 1 hour.
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, 30 ºC, and pH= 11.5. ............................................................ 112
Figure 5.17: Gold dissolution rate for gold-silver alloys using a closed vessel. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, 30 ºC, and pH= 11.5. .................................................................. 113

xvi
List of Figures

Figure 5.18: Gold dissolution rate from gold and gold-silver alloys. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, 30 ºC, and pH= 11.5. .................................................................. 114
Figure 5.19: Total metal average dissolution rate for gold, silver and gold-silver
alloys. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4
M NH3, 300 rpm, 30 ºC, and pH= 11.5. ............................................... 115
Figure 5.20: Gold average dissolution rate from pure gold and gold-silver alloys at
different initial thiosulfate concentrations (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: (S2O3)2-, 10 mM CuSO4,
0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5. ......................................... 116
Figure 5.21: Total average metal dissolution rate from gold, silver and gold-silver
alloys at different initial thiosulfate concentrations (average rate of 3, 5,
and 8 hours leaching). Initial experiment conditions: (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5. ............................. 116
Figure 5.22: Gold average dissolution rate from gold and gold-silver alloys at
different initial copper sulfate concentrations (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, CuSO4, 0.4
M NH3, 300 rpm, 30 ºC, and pH= 11.5. ............................................... 117
Figure 5.23: Total average metal dissolution rate of pure gold, pure silver and gold-
silver alloys at different initial copper sulfate concentration (average rate
of 3, 5, and 8 hours leaching). Initial experiment conditions: 0.2 M
(S2O3)2-, CuSO4, 0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5. ............... 118
Figure 5.24: Gold dissolution rate from gold and gold-silver alloys at different initial
ammonia concentrations (average rate of 3, 5, and 8 hours leaching).
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, NH3, 300
rpm, 30 ºC, and pH= 11.5. .................................................................. 119
Figure 5.25: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different initial ammonia concentrations (average rate of 3, 5,
and 8 hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10
mM CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5................................. 119
Figure 5.26: Gold dissolution rates from gold and gold-silver alloys at different
temperatures (average rate of 3, 5, and 8 hours leaching). Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, ºC, and pH= 11.5 ........................................................................ 120

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List of Figures

Figure 5.27: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different temperatures (average rate of 3, 5, and 8 hours
leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
0.4 M NH3, 300 rpm, ºC, and pH= 11.5. .............................................. 121
Figure 5.28: Gold dissolution rate from gold and gold-silver alloys at different
rotation speeds (average rate of 3, 5, and 8 hours leaching). Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, rpm,
30 ºC, and pH= 11.5. .......................................................................... 122
Figure 5.29: The total average metal dissolution rate of pure gold, pure silver and
gold-silver alloys at different rotation speeds (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, rpm, 30 ºC, and pH= 11.5 .................................... 122
Figure 5.30: Gold dissolution rate from gold and gold-silver alloys at different pH
values (average rate of 3, 5, and 8 hours leaching). Initial experiment
conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300 rpm, 30 ºC
and pH (ammonium sulfate added). ..................................................... 123
Figure 5.31: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different pH values (average rate of 3, 5, and 8 hours leaching).
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, 30 ºC, and pH (ammonium sulfate added). ............................ 124
Figure 6.1: Linear sweep voltammograms showing the effect of ATS concentration
on the current density of the gold oxidation for pure gold. Experimental
conditions: 300 rpm, 30 ºC, and natural pH of the solution. .................. 127
Figure 6.2: Linear sweep voltammograms showing the effect of ammonium
thiosulfate concentration on the current density of both gold and silver
oxidation for 4, 8, 20, and 50% Ag alloys. Experimental conditions: 300
rpm, 30 ºC, and natural pH of the solution. .......................................... 128
Figure 6.3: Linear sweep voltammograms showing the effect of sodium thiosulfate
(STS) concentration on the current density of gold oxidation from a pure
gold disc. Experimental conditions: 300 rpm, 30 ºC, and natural pH of the
solution. ............................................................................................. 130
Figure 6.4: Linear sweep voltammograms showing the effect of sodium thiosulfate
(STS) concentration on the combined current density of gold and silver

xviii
List of Figures

oxidation in 4, 8, 20, and 50% Ag alloys. Experimental conditions: 300

rpm, 30 ºC, and natural pH of the solution. .......................................... 131
Figure 6.5: Linear sweep voltammograms showing the effect of ammonia
concentration on the current density of the gold oxidation for pure gold.
Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC, and natural pH of
the solution......................................................................................... 132
Figure 6.6: Linear sweep voltammograms showing the effect of ammonia
concentration on the current density of the gold oxidation from gold-
silver alloys. Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC, and
natural pH of the solution.................................................................... 133
Figure 6.7: Linear sweep voltammograms showing the effect of thiourea
concentration on the current density of gold oxidation from a pure gold
disc. Experimental conditions: 50 mM ATS or STS, 300 rpm, 30 ºC, and
natural pH of the solution.................................................................... 134
Figure 6.8: Linear sweep voltammograms showing the effect of thiourea
concentration on the current density of the combined gold and silver
oxidation from gold-silver alloys. Experimental conditions: 50 mM ATS
or STS, 300 rpm, 30 ºC, and natural pH of the solution. ....................... 135
Figure 6.9: Linear sweep voltammograms showing the effect of silver content on the
current density of the combined gold and silver oxidation from different
gold-silver combinations in the presence of thiourea. Experimental
conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30 ºC, and natural pH of the
solution. ............................................................................................. 136
Figure 6.10: Linear sweep voltammograms showing the effect of thiourea
concentration on the current density of the silver oxidation from pure
silver. Experimental conditions: 50 mM ATS or STS, 300 rpm, 30 ºC, and
natural pH of the solution.................................................................... 137
Figure 6.11: The anodic dissolution of gold and silver from a rotating disc of pure
gold and 4, 8, and 20% Ag alloys. Experimental conditions: 50 mM ATS,
400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the solution. ..... 138
Figure 6.12: The measured current of the leaching of pure gold and gold-silver
alloys in solutions containing thiosulfate-copper-ammonia at a fixed
potential of 0.22 V. Experimental conditions: 50 mM ATS, 10 mM

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List of Figures

CuSO4, 400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the

solution. ............................................................................................. 141
Figure 6.13: The anodic dissolution of gold and silver from pure gold, and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate and
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 142
Figure 6.14: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing sodium thiosulfate and
thiourea. Experimental conditions: 50 mM STS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 143
Figure 6.15: Dissolution rates of gold from a rotating disc of pure gold and 4, 8, 20,
and 50% Ag alloys in thiosulfate (50 mM ATS or STS) solutions. a) ATS,
400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu,
d) STS, 400 mM NH3, e) ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5
mM Tu. 300 rpm, 30 ºC. ..................................................................... 144
Figure 6.16: Total metal dissolution (gold and silver) rate from a rotating disc of
pure gold and 4, 8, 20, and 50% Ag in thiosulfate (50 mM ATS or STS)
solutions. a) ATS, 400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II),
c) ATS, 5 mM Tu, d) STS, 400 mM NH3, e)ATS, 400 mM NH3, 10 mM
Cu(II), f) ATS, 5 mM Tu. 300 rpm, 30 ºC. .......................................... 145
Figure 6.17: The anodic dissolution of gold and silver of a rotating disc of pure gold
and 4, 8, 20, and 50% Ag alloys at a potential of 0.256 V. Experimental
conditions: 50 mM ATS, 400 mM ammonia, 300 rpm, 30 ºC, and natural
pH of the solution. .............................................................................. 146
Figure 6.18: The measured current of pure gold and gold-silver alloys in solutions
containing thiosulfate-copper-ammonia at a fixed potential of 0.256 V.
Experimental conditions: 50 mM ATS, 10 mM CuSO4, 400 mM
ammonia, 300 rpm, 30 ºC, and natural pH of the solution..................... 147
Figure 6.19: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solution containing ammonium thiosulfate and
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 149
Figure 6.20: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing sodium thiosulfate and

xx
List of Figures

thiourea. Experimental conditions: 50 mM STS, 5 mM Tu, 300 rpm, 30

ºC, and natural pH of the solution........................................................ 149
Figure 6.21: Dissolution rates of gold from pure gold and 4, 8, 20, and 50% Ag
alloys in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS,
400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu.
300 rpm, 30 ºC. .................................................................................. 150
Figure 6.22: Total dissolution (gold and silver) rates from rotating discs of pure gold
and 4, 8, and 20% Ag in thiosulfate (50 mM ATS or STS) solutions. a)
ATS, 400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM
Tu, d) STS, 400 mM NH3, e)ATS, 400 mM NH3,10 mM Cu(II), f) ATS, 5
mM Tu. 300 rpm, 30 ºC. ..................................................................... 151
Figure 6.23: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate.
Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC, and natural pH of
the solution......................................................................................... 152
Figure 6.24: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate.
Experimental conditions: 100 mM ATS, 300 rpm, 30 ºC, and natural pH
of the solution. ................................................................................... 153
Figure 6.25: The anodic dissolution of gold and silver from a rotating disc of pure
gold and 4, 8, 20, and 50% Ag alloys in solutions containing ammonium
thiosulfate. Experimental conditions: 50 mM ATS, 400 mM NH3, 300
rpm, 30 ºC, and natural pH of the solution. .......................................... 156
Figure 6.26: The anodic current generated on pure gold and 4, 8, 20, and 50% Ag
alloys at a fixed potential of 0.292 V. Experimental conditions: 50 mM
ATS, 400 mM NH3, 10 mM Cu(II), 300 rpm, 30 ºC, and natural pH of the
solution. ............................................................................................. 157
Figure 6.27: The anodic current from pure gold and 4, 8, 20, and 50% Ag alloys at a
fixed potential of 0.292 V. Experimental conditions: 50 mM ATS, 100
mM NH3, 1 mM Cu(II), 300 rpm, 30 ºC, and natural pH of the solution.158
Figure 6.28: The total dissolution rate of gold and silver from pure gold and 4, 8, 20
and 50% Ag alloys at a fixed potential of 0.292 V in solutions containing
thiosulfate ammonia-copper(II). .......................................................... 159

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List of Figures

Figure 6.29: The anodic current from pure gold and 4, 8, 20, and 50% Ag discs at a
fixed potential of 0.292 V in solutions containing ammonium thiosulfate
and thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm,
30 ºC, and natural pH of the solution. .................................................. 160
Figure 6.30: The anodic current of from pure gold and 4, 8, 20, and 50% Ag alloys
at a fixed potential of 0.292 V in solutions containing ammonium
thiosulfate and thiourea. Experimental conditions: 50 mM ATS, 1 mM
Tu, 300 rpm, 30 ºC, and natural pH of the solution. ............................. 160
Figure 6.31: Gold dissolution rate form pure gold and 4, 8, 20, and 50% Ag alloys in
thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM NH3, b)
ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS, 400 mM
NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu. 300 rpm,
30 ºC. ................................................................................................. 163
Figure 6.32: Total metal dissolution rate from pure gold and 4, 8, 20, and 50% Ag
alloys in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS,
400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu.
300 rpm, 30 ºC. .................................................................................. 163
Figure 6.33: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in thiosulfate solution containing ammonia.
Experimental conditions: 50 mM ATS, 400 mM NH3, 300 rpm, 30 ºC,
and natural pH of the solution. ............................................................ 164
Figure 6.34: The anodic dissolution current of gold and silver from pure gold and 4,
8, 20, and 50% Ag alloys in solution containing thiosulfate-ammonia-
copper(II). Experimental conditions: 50 mM ATS, 400 mM NH3, 10 mM
Cu(II), 300 rpm, 30 ºC, and natural pH of the solution. ........................ 165
Figure 6.35: The anodic dissolution current of gold and silver from pure gold and 4,
8, 20, and 50% Ag discs in solutions containing thiosulfate and thiourea.
Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30 ºC, and
natural pH of the solution.................................................................... 166
Figure 6.36: Gold dissolution rate from pure gold and 4, 8, 20, and 50% Ag alloys in
thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM NH3, b)
ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS, 400 mM

xxii
List of Figures

NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu. 300 rpm,

30 ºC. ................................................................................................. 167
Figure 6.37: Total metal dissolution rate from pure gold and 4, 8, 20, and 50% Ag
discs in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS,
400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu.
300 rpm, 30 ºC. .................................................................................. 167
Figure 6.38: Gold dissolution rate measured after 30 min of leaching from pure gold
at 300 rpm and 30 ºC in thiosulfate solutions containing: a) 50 mM ATS,
400 NH3; b) 50 mM ATS, 400 mM NH3, 10 mM Cu(II); c) 50 mM ATS,
5 mM Tu. ........................................................................................... 168
Figure 6.39: Total metal dissolution rate of gold-silver alloys at 300 rpm 30 ºC
measured over 30 minutes in thiosulfate solutions containing: a) 50 mM
ATS, 400 NH3; b) 50 mM ATS, 400 mM NH3, 10 mM Cu(II); c) 50 mM
ATS, 5 mM Tu. .................................................................................. 169
Figure 7.1: The procedure used in gold ore leaching experiments. ........................ 172
Figure 7.2: Quantitative XRD analysis of mineralogy of different size fractions of
gold ore samples. ................................................................................ 174
Figure 7.3: Elemental analysis of different size fractions of gold ore samples. ...... 175
Figure 7.4: Gold extraction using open and closed vessels. Experimental initial
conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
20% S/L ratio. .................................................................................... 177
Figure 7.5: Thiosulfate consumption in closed and open vessels. Experimental initial
conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
20% S/L ratio. .................................................................................... 178
Figure 7.6: The effect of particle size fraction on gold extraction using a closed
vessel. Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10
mM Cu(II), 30 ºC, 300 rpm, 20% S/L ratio. ......................................... 179
Figure 7.7: The effect of thiosulfate concentration on gold extraction. Experimental
initial conditions: 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm, 20% S/L
ratio. .................................................................................................. 180
Figure 7.8: The effect of initial sodium thiosulfate concentration on its consumption.
Experimental initial conditions: 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300
rpm, 20% S/L ratio. ............................................................................ 181

xxiii
List of Figures

Figure 7.9: The effect of initial copper(II) concentration on gold extraction.

Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 30 ºC, 300
rpm, 20% S/L ratio. ............................................................................ 182
Figure 7.10: The effect of initial copper(II) concentration on thiosulfate
consumption. Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M
NH3, 30 ºC, 300 rpm, 20% S/L ratio. ................................................... 183
Figure 7.11: The effect of initial ammonia concentration on gold extraction.
Experimental initial conditions: 0.2 M (S2O3)2-, 10 mM Cu(II), 30 ºC, 300
rpm, 20% S/L ratio. ............................................................................ 184
Figure 7.12: The effect of initial ammonia concentration on thiosulfate consumption.
Experimental initial conditions: 0.2 M (S2O3)2-, 10 mM Cu(II), 30 ºC, 300
rpm, 20% S/L ratio. ............................................................................ 185
Figure 7.13: The effect of temperature on gold extraction from -106 µm weathered
gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3,
10 mM Cu(II), 300 rpm, 20% S/L ratio. .............................................. 186
Figure 7.14: The effect of temperature on thiosulfate consumption while leaching -
106 µm weathered gold ore. Experimental initial conditions: 0.2 M
(S2O3)2-, 400 mM NH3, 10 mM Cu(II), 300 rpm, 20% S/L ratio. .......... 187
Figure 7.15: The effect of airflow on gold extraction using -106 µm weathered gold
ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3, 10
mM Cu(II), 300 rpm, 20% S/L ratio. ................................................... 188
Figure 7.16: The effect of airflow on thiosulfate consumption using -106 µm
weathered gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400
mM NH3, 10 mM Cu(II), 30 ºC, 300 rpm, 20% S/L ratio. .................... 189
Figure 7.17: The effect of pulp density on gold extraction using -106 µm weathered
gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3,
10 mM Cu(II), 30 ºC, 300 rpm. ........................................................... 190
Figure 7.18: The effect of rotation speed (RPM) on gold extraction using -106 µm
weathered gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400
mM NH3, 10 mM Cu(II), 30 ºC, 20% S/L ratio. ................................... 191
Figure 7.19: The effect of weathering on gold extraction. Experimental initial
conditions: 0.2 M (S2O3)2-, 400 mM NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
20% S/L ratio. .................................................................................... 192

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List of Figures

Figure 7.20: Gold extraction from thiosulfate and cyanide solutions using -106 µm
weathered gold ore. Experimental initial conditions for the thiosulfate
solution: 0.2 M (S2O3)2-, 400 mM NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
closed vessel, 20% S/L ratio, and natural pH of the solution and for the
cyanide solution : 1.5 g NaCN/L, 20% S/L ratio, open vessel, pH
=11)…………………………………………………………………….193
Figure 8.1: The dissolution of mercurous chloride (Hg2Cl2) in thiosulfate and
cyanide solutions. Leaching conditions: Solution A, 50 mM ATS, 1 mM
Cu2+, pH 10; Solution B, 50 mM ATS, 400 mM NH3, 10 mM Cu2+, pH
11.4; Solution C, 2.5 g/L NaCN solution, no air, pH 12; Solution D, 50
mM ATS, 10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5, and
Solution E, 50 mM ATS, 10 mM Tu, 5 mM FeEDTA, pH 7. ............... 198
Figure 8.2: The effects of thiosulfate concentration on mercury dissolution in
solution A: (ATS, 1 mM Cu2+, pH 10)................................................. 200
Figure 8.3: The effect of thiosulfate concentration on mercury leaching in solution
B: (ATS, 400 mM NH3, 10 mM Cu2+, pH 11.4). .................................. 200
Figure 8.4: The effect of thiosulfate concentration on mercury leaching in solution D
(ATS, 10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5)................... 201
Figure 8.5: The effects of thiosulfate concentration on mercury dissolution in
solution E (ATS, 10 mM Tu, 5 mM FeEDTA, pH 7). .......................... 202
Figure 8.6: The dissolution of mercury metal (Hg0) in thiosulfate and cyanide
solutions. Experimental conditions: Solution A, 50 mM ATS, 1 mM Cu2+,
pH 10; Solution B, 50 mM ATS, 400 mM NH3, 10 mM Cu2+, pH 11.4;
Solution C, 2.5 g/L NaCN solution, pH 12; Solution D, 50 mM ATS,10
mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5, and Solution E, 50 mM
ATS, 10 mM Tu, 5 mM FeEDTA, pH 7. ............................................. 203
Figure 8.7: The amount of mercury loaded on resin and stripped from resin at
different initial mercury concentrations. .............................................. 209
Figure 8.8: Gold eluted and elution efficiency from 8 mL of the loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3. ............................................................................................. 211
Figure 8.9: Copper eluted and the elution efficiency from 8 mL of loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3. ............................................................................................. 212

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List of Figures

Figure 8.10: Mercury eluted and the elution efficiency from 8 mL of loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3. ............................................................................................. 213

xxvi
 List of Tables

Table 1.1: Some physical and mechanical properties of gold (Marsden & House, ..... 3
Table 1.2: Most of the alternatives to sodium cyanide (McNulty, 2001). .................. 6
Table 2.1: Maximum and minimum recorded global primary production of mercury
since 1981, metric tons/year (UNEP, 2003). .......................................... 13
Table 2.2: Summary of the physical properties of mercury (Robert, 1967). ............. 14
Table 2.3: Some examples of mercury uses in different industry applications
(UNEP, 2003). ..................................................................................... 15
Table 2.4: Properties of simple cyanide salts (Marsden & House, 2006). ................ 23
Table 2.5: Stability constants for some selected metal cyanide complexes (Tien,
1994). .................................................................................................. 25
Table 2.6: Toxicity of cyanide and cyanide derivatives (Lowehein & Moran,
1975).................................................................................................... 30
Table 2.7: Examples of cyanide spills and mine-related accidents and the
environmental impacts (Mudder & Botz, 2001; Moran, 1998). ............... 32
Table 2.8: Toxicity data for selected lixiviants (Gos & Rubo, 2000). ...................... 42
Table 3.1: Thiosulfate consumption during gold leaching as a function of ore type. 48
Table 3.2: Effect of ammonia concentration on the gold leaching rate in 0.4 M
thiosulfate and 25 mM copper(II) (Jeffrey, 2001)................................... 58
Table 3.3: List of various pH values used in thiosulfate solutions published in
different studies. ................................................................................... 60
Table 3.4: The effect of temperature on ammonia concentration after 2 hours of..... 63
Table 3.5: The optimum reagent concentrations and leaching parameters in ........... 68
Table 4.1: Quantitative XRD analysis (Wt.%) of the gold ore samples (weathered)
for size fractions: -38, -75+38, -106+75, and -125+106 µm.................... 77
Table 4.2: Quantitative XRD analysis (Wt.%) for weathered and unweathered gold
ore samples (size fraction -106 µm)....................................................... 78
Table 4.3: The elementary analysis (Wt.%) of the weathered gold ore for size
fractions: -38, -75 +38, -106+75, and -125+106 µm............................... 78
Table 4.4: The elementary analysis (Wt.%) for both weathered and unweathered
gold ore samples of size fraction (-106 µm). .......................................... 79
Table 5.1: Dissolution rates of gold after 1, 3, 5 and 8 hours at different temperatures
in open and closed reaction vessels. .................................................... 103

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List of tables

Table 5.2: The dissolution rates of silver after 1, 3, 5, and 8 hours at different
temperatures in the open and closed reaction vessels............................ 103
Table 5.3: The average volatilization rate of ammonia in the open vessel over the
eight hours of leaching at different temperatures. ................................. 105
Table 5.4: Dissolution rates of gold after 1, 3, 5 and 8 hours at different ammonia
concentrations in open and closed reaction vessels. .............................. 108
Table 5.5: The dissolution rate of silver after 1, 3, 5, and 8 hours at different
ammonia concentrations in open and closed reaction vessels. ............... 109
Table 6.1: Gold, silver, and total metal dissolution rate from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential of 0.22 V. Experimental
conditions: 50 mM ATS, 400 mM ammonia, 300 rpm, 30 ºC, and natural
pH of the solution. .............................................................................. 139
Table 6.2: Gold, silver, and total metal dissolution rates from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential 0.22 V. Experimental conditions:
50 mM STS, 400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the
solution. ............................................................................................. 140
Table 6.3: Gold, silver, and total dissolution rate from pure gold and 4, 8, 20, and
50% Ag alloys at fixed a potential 0.22 V. Experimental conditions: 50
mM ATS or STS, 400 mM ammonia, 10 mM CuSO4, 300 rpm, 30 ºC, and
natural pH of the solution.................................................................... 140
Table 6.4: Gold, silver, and total dissolution rate from pure gold and 4, 8, 20, and
50% Ag alloys at a fixed potential of 0.256 V. Experimental conditions:
50 mM ATS or STS , 400 mM ammonia, 300 rpm, 30 ºC, and natural pH
of the solution. ................................................................................... 146
Table 6.5: Gold, silver, and total metal dissolution rates from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential of 0.256 V. Experimental
conditions: 50 mM ATS or STS, 400 mM ammonia, 10 mM CuSO4, 300
rpm, 30 ºC, and natural pH of the solution. .......................................... 148
Table 6.6: The calculated rate from current and the total dissolution rate from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing ammonium
thiosulfate (ATS). Experimental conditions: 50 mM ATS, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 154
Table 6.7: The calculated rate from current and the total dissolution rate from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing ammonium

xxviii
List of tables

thiosulfate (ATS). Experimental conditions: 100 mM ATS, 300 rpm, 30

ºC, and natural pH of the solution........................................................ 154
Table 6.8: The calculated rate from current and ICP-OES analysis for pure gold and
4, 8, 20, and 50% Ag alloys in solution containing ammonium thiosulfate
(ATS). Experimental conditions: 50 mM ATS, 400 mM ammonia, 300
rpm, 30 ºC, and natural pH of the solution. .......................................... 156
Table 6.9: Calculated rate from current and the total dissolution rate from pure gold
and 4, 8, 20, and 50% Ag alloys in solution containing thiosulfate-
thiourea. Experimental conditions: 50 mM ATS, 1 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 161
Table 6.10: The calculated rate from current and the total dissolution rate, from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing thiosulfate-
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution. ....................................................... 162
Table 7.1: Reagent concentrations and parameters used in the gold ore leaching
experiments. ....................................................................................... 171
Table 8.1: The concentration of dissolved mercury in each solution stabilized with
tetra-sodium EDTA at room temperature after 48 hours. ...................... 196
Table 8.2: The dissolved mercury in thiosulfate solutions containing tetrathionate
after 0, 5, 24, and 48 hours. ................................................................. 197
Table 8.3: The percentage of mercury dissolved from mercury sulfide in thiosulfate
and cyanide solutions after 48 hours. ................................................... 199
Table 8.4: Typical physical and chemical characteristics of Purolite A500/2788
resin. .................................................................................................. 205
Table 8.5: The amount of gold loaded on resin and stripped from the resin as a
function of mercury concentration in a synthetic leach solution. ........... 207
Table 8.6: The amounts of copper loaded on resin and stripped from resin as a
function of mercury concentration in a synthetic leach solution. ........... 208
Table 8.7: The percentages of mercury loaded on resin and stripped from resin as a
function of initial mercury concentration. Possible loading is the loading
if all of the mercury was removed from solution and loaded on the
resin…. .............................................................................................. 209
Table 8.8: Thiosulfate and polythionate speciation of the barren loading solution
(Initial loading solution containing:100 mM ammonium thiosulfate

xxix
List of tables

(ATS), 4 mM trithionate (S3O62-), 1 mM CuSO4.5H2O, and 5 mM gold

(Au) as gold thiosulfate). .................................................................... 210
Table 8.9: Thiosulfate and polythionate speciation of the stripping solution (25 mL
of 0.5 M sodium perchlorate (NaClO4. H2O). ...................................... 210

xxx
 Acknowledgement

I am much indebted to Dr. Richard Browner, Associate Professor, Western Australia

School of Mines (WASM), Curtin University, for his discussions, encouragement,
generous advice, clarifying suggestion and support during each step of this work.

I would like to express my great thanks to Prof. Dr. Hamid Nikraz, Professor, Civil
Engineering Department, Curtin University for accepting me to be one of his PhD
students. I would also like to thank him for his continual help and support during my
research.

I also would like to express my deep and great thanks to Dr. Matthew Jeffrey,
CSIRO Minerals, Waterford, Western Australia, for accepting me to be one of Parker
Center students in CSIRO. I have to thank him for his guidance and collaboration in
conducting this research.

The financial support of the Egyptian government is gratefully acknowledged for

providing me the PhD scholarship, which enables me to commence and finalize this
PhD. I would also like to acknowledge support of Centamin Egypt Ltd for providing
me a top-up scholarship and the gold ore to complete an essential part of my PhD.

I must not forget to express my deepest thanks to my loving mother for her support.
Lastly, but not least, I would like to thank my lovely wife and two daughters for their
support, patience and love during my PhD study.

xxxi
Chapter 1 Introduction

1.1 Mining and the Environment

Mining by its nature always disturbs the natural air, earth and water systems
with the main challenge for the mining industry being to find, extract, and process
mineral and metal resources with the least possible disturbance to the environment.
The waste product of extracting valuable minerals or metals, known as tailings, may
contain hazardous chemicals and dissolved toxic metals. Tailings are produced from
the unit extraction processes commonly found in mineral processing (flotation,
gravity concentration, amalgamation, leaching, etc.). One of the main sources of
pollution from tailings into the air, earth and water is the chemical reagents that are
sometimes used extensively to beneficiate the minerals or to extract the metals from
the ore.
Chemicals are used extensively in extraction of gold and silver. Traditionally
mercury was used and is still used extensively with artisanal extraction while,
cyanide is the main chemical used for large scale extraction of these precious metals.
These two chemical reagents are classified as highly toxic to humans, and can cause
considerable harm to other living organisms and the environment.
This study concentrates on gold processing, which has had wide
environmental impacts that have been compounded by the use of mercury and
cyanide in the extraction process. The best way to secure the environment from the
negative effects of using mercury and cyanide in gold processing is using a less toxic
substitute. Alternatives regents to cyanide are considered with the focus of the
research on the most promising, thiosulfate.

1.2 Gold Overview

Gold is classified as a noble metal because it does not easily oxidise under
normal conditions. Its chemical symbol “Au” is derived from the Latin word for gold
“aurum”. The average concentration of gold in the earth’s crust is about 0.005 g/t,
which is lower than most of other metals such as silver (0.07 g/t) and copper (50 g/t)
(Marsden & House, 2006).

1
Chapter 1: Introduction

Gold ores may contain different amounts of silver, copper, nickel, arsenic,
antimony, mercury, thallium, sulfur, base metal sulfides, other precious metals, and
sulfosalts. The amount of these constituents depends on the nature of the deposit and
the amount of weathering that has occurred. Consequent alteration of the ore by
oxidation influences both gold recovery and dissolution of the other gangue minerals
(EPA, 1994).
Gold readily forms alloys with many other metals. Native gold contains
generally 8 to 10% silver, but can contain over 20% silver. Gold containing more
than 20% silver is known as electrum. As the silver percent in gold increased, the
gold colour turns whiter and its density gets lower (Cryssoulis & McMullen, 2005).
Many countries around the world produce gold. South Africa is the highest
gold producing country followed by Australia and the United States in third position
as shown in Figure 1.1.

16%

14%
Australia, 11%

Other, 15%
12%
South Africa, 15%

China, 8%

10%
Russia, 7%
United States, 11%

Indonesia, 6%
Peru, 7%

Papoua New Guinea, 3%

8%
Canada, 5%

Uzbekistan, 3%

6%
Ghana, 3%

Tansania, 2%

Brazil, 2%

4%
Mali, 2%

2%

0%

Figure 1.1: The estimated gold mine production by country in 2003 (Gold Fields
Mineral Services Ltd, 2004).

1.2.1 Gold Properties

The density of pure gold is around 19,300 kg/m3, though native gold typically
has a density of 15,000 kg/m3. Gold is very soft, ductile, and malleable (1 oz of gold
can be beaten into an area of 30 cm2) with Vickers and Mohs hardness numbers of 40

2
Chapter 1: Introduction

to 95 kg/mm2 and 2.5 to 3, respectively (Marsden & House, 2006). Pure gold is an
excellent electrical and thermal conductor. The melting and boiling points of gold are
1064 ºC and 2808 ºC, respectively. Some other properties of gold are listed in Table
1.1.

Table 1.1: Some physical and mechanical properties of gold (Marsden & House,
2006).
Property Value
Atomic weight 196.97
Melting point (ºC) 1064 ºC
Boiling point (ºC) 2808 ºC
Atomic radius, nm 0.1422
Density at 273 K (g/cm3) 19.32
Tensile strength (MPa) 123.6 – 137.3
Elongation (annealed at 573 K) (%) 34-45
Vapour pressure (Pa)
At 1000 (K) 5.5 x 10-8
At 2000 (K) 82 x 10-8
Thermal conductivity at 273 K (W/m.K) 311.4
Electrical resistivity at 273 K (Ω. cm) 2.05 x 10-5

1.2.2 Gold Minerals and Ores

There are many different gold minerals found in the Earth’s crust such as
native gold, electrum, gold tellurides, gold with bismuth (maldonite), and gold with
copper (auricupride and tetra-auricupride). The gold minerals are associated with
oxide and/or sulfide minerals (arsenopyrite, pyrite, tetrahedrite, and chalcopyrite)
forming gold ore. A comprehensive classification of gold ores with respect to the
ease of gold extraction using cyanide (cyanidation) was given by Marsden and House
(2006) as presented below:
1. Free milling ores: from which cyanidation can extract approximately 95% of the
gold when the ore is ground to a size of 80% <75 μm. The two main classes of free
milling ores are palaeoplacer and quartz vein gold.

3
Chapter 1: Introduction

2. Oxidised ores: the ore material has been oxidised or weathered in these ores.
Generally the degree of gold liberation is increased by oxidation. The most common
of these ores are the iron oxides such as hematite, magnetite, goethite, and limonite.
3. Iron sulfides: gold is principally unliberated in an iron sulfide matrix, or the
behaviour of the iron sulfide affects process selection or operation conditions. The
most common iron sulfide minerals are pyrite, marcasite, and pyrrhotite.
4. Arsenic sulfides: gold ores should be considered in this class if the gold is
associated with an arsenic sulfide or arsenide matrix. The most common arsenic
minerals are arsenopyrite, orpiment, and realgar.
5. Copper sulfides: ores containing gold associated with copper sulfide minerals
that affect process selection or operating conditions are considered in this class. It is
relatively uncommon for gold to be associated solely with copper minerals, and there
is usually some pyrite present. Chalcopyrite is the most abundant copper mineral.
Chalcosite and covellite also are important copper ore minerals.
6. Tellurides: are the only gold minerals other than metallic gold and gold-silver
alloys that are of economic significance. The most important tellurides encountered
in gold ores are calverite, petzite, hessite, krennerite, and maldonite. Gold telluride
ores usually contain some native gold, together with metal tellurides.
7. Carbonaceous ores: these gold ores contain carbonaceous components that
adsorb dissolved gold during cyanidation, thereby reducing gold extraction. These
gold ores sometimes require oxidative pre-treatment prior to cyanide leaching.

1.2.3 Uses of Gold

Most corrosive agents such as heat, moisture, and oxygen have very little
alteration effects on gold, making it as ideal metal to use in coins and jewellery. Gold
is also used in jewellery due to its beauty, properties, and rarity. Gold has a long
history of use as money or as a reserve backing for other forms of money, but that
role is shrinking as gold is gradually being demonetized in the industrial nations.
Gold also has special combinations of physical and chemical properties
(Table 1.1) that make it a very good material for use in a wide range of electronic
conductors and semi-conductors, and medical applications. Figure 1.2 shows the
different uses gold is put to around the world. It is clear from Figure 1.2 that
decoration and jewellery use is the major use (with 66% consumption) followed by
bar hoarding which consumes 19% of gold.

4
Chapter 1: Introduction

Electronics, 5%
Dentistry, 2%
Industrial, 2%
Medals, 1%
Coins, 5%

Bar Hoarding, 19%

Jewellry, 66%

Figure 1.2: The distribution of gold uses (Marsden & House, 2006).

1.3 Gold Mining and the Environment

Although gold mining is one of the main sources of income for many
countries, it can have a significant detrimental impact on the environment. Large
amounts of toxic chemicals such as mercury and cyanide are used to extract gold
from its ore. Based on recent knowledge of toxicity principles and updated
environmental standards, the activity of the mines that use mercury and cyanide
needs to be carefully regulated. Small-scale producers widely use the historic
amalgamation technique. This technique creates mercury vapour emissions as well as
liquid and solid wastes with toxic constituents (Müezzinolu, 2003).
Cyanidation is the most widely used method to extract gold from its ore,
because of its relatively low cost and selective efficiency gold dissolution. The main
disadvantage of using cyanide is its detrimental environmental impacts on soil,
surface and underground water (tailing and drainage water), and air (hydrogen
cyanide emission). The following section notes, in brief, some of the alternative
reagents to cyanide.

1.4 Alternatives to Cyanide

For more than 100 years, cyanide has been the leaching reagent of choice in
gold mining due to its high efficiency in gold recovery, stability, simplicity of use,

5
Chapter 1: Introduction

and relatively low cost. On the other hand, cyanide can have wide detrimental
environmental impacts. Thus, several other chemical reagents had been considered
for gold extraction from ores, not only to lessen the environmental impacts and
overcome the restrictions to the use of cyanide, but also for other reasons including:
1) potential of having faster gold leaching kinetics than cyanide, 2) possibility of
their use in acidic media, which is suitable in the treatment of refractory ores, and 3)
a greater degree of selectivity than cyanide for gold over other metals (Navarro et al.,
2007).
Unfortunately, most cyanide alternatives have not progressed past the
laboratory or pilot plant scale. To select a gold lixiviant for gold leaching,
economics, efficiency, and environmental concerns should all be considered (Gos &
Rubo, 2000). In recent years, many scientists aimed to identify and develop less toxic
leaching reagents. Only a few ligands form gold complexes of sufficient stability and
at a suitable rate for their use in gold leaching operations. Alternatives to sodium
cyanide are summarised by McNulty (2001) in Table 1.2.

Table 1.2: Most of the alternatives to sodium cyanide (McNulty, 2001).

Reagent type
Reagent type
1. Ammonia 14. Bisulfate/sulphur dioxide
2. Ammonia/cyanide 15. Bacteria
3. Ammonium thiosulfate 16. Natural organic acids
4. Slurry CN-electrolysis 17. DMSO, DMF
5. Sodium sulphide 18. Bromine/bromide
6. Alpha-hydroxynitriles 19. Thiourea
7. Malononitrile 20. Thiocyanate
8. Alkali cyanoform 21. Aqua regia
9. Calcium cyanide 22. Acid ferric chloride
10. Alkaline polysulphides 23. Ethylene thiourea
11. Hypochlorite/chloride 24. Haber process
12. Bromocyanide 25. High temperature chlorination
13. Iodine

6
Chapter 1: Introduction

1.5 Objectives of the Study

The main challenge in producing a suitable substitute for cyanide in gold
processing, lies in developing an equally effective and degradable leach reagent,
which at the same time, has less environmental impacts. One of the alternative
systems to cyanide that may achieve the environmental and gold leaching rate
objectives is the thiosulfate system. The optimum conditions for leaching gold using
the thiosulfate system are not clearly defined as there are a wide range of variables
that impact on the thiosulfate leaching system for gold. One of the variables that
limited research is the effect of silver on gold leaching rates in thiosulfate solutions.
Therefore the objectives of this project are to:
(1) optimise gold and silver using thiosulfate solutions in both closed and open
vessels;
(2) evaluate the metallurgical optimum thiosulfate leaching characteristics for pure
gold, pure silver and gold-silver alloys (4, 8, 20 and 50 wt% silver) in both closed
and open vessels;
(3) study the electrochemical nature of thiosulfate leaching using gold, silver, and
gold-silver alloys with linear sweep voltammetry and coulometric electrochemical
techniques at fixed potential values;
(4) optimise the thiosulfate leaching of gold ore samples supplied from the Centamin
Egypt Limited Company; and
(5) study the possibility of mercury dissolution in different thiosulfate and cyanide
solutions and the recovery of gold from ion-exchange resins in the presence of
mercury.
A flowchart of the goals and procedures of this project is presented in Figures 1.3a
and 1.3b.

7
Chapter 1: Introduction

Gold source

Gold discs Gold ore

Thiosulfate Leaching Optimise ore

leaching
parameters
Leaching comparison
between

Open Closed
Vesse Vessel

Which one is:

• Less efficient • More efficient

• Bad to the • Better to the
environment environment
• Ammonia loss & more • Less reagents consumed

Yes
No

Optimise leaching
parameters (short
run,1hr)

The optimised
parameters
Long run
leaching (8 hrs
and 24 hrs)

Figure 1.3a: Flowchart of the goals and procedures of the project (part I).

8
Chapter 1: Introduction

Electrochemical
studies on gold-
silver alloys

Understanding of gold and silver leaching

in different thiosulfate systems.

Kinetically Environmentally

Leaching of gold- Leaching of different

silver alloys in mercury forms in
thiosulfate systems. thiosulfate systems.

Best Best
system system

Figure 1.3b: Flowchart of the goals and procedures of the project (part II).

1.6 Methodology of the Study

The methodology used in this study was:
• review previous published work on the environmental impacts of mercury and
cyanide in the gold mining industry;
• review previous work related to the application of the thiosulfate leaching system
to gold leaching;
• apply the thiosulfate leaching system to pure gold and pure silver discs and gold-
silver alloy discs (4, 8, 20, 50 wt% silver) in open and closed vessels;
• evaluate the variables that affect thiosulfate leaching by testing the dissolution of
pure gold and pure silver discs and a range of gold and silver alloy discs (4, 8, 20, 50
wt.% silver) in open and closed vessels;
• study through electrochemical methods the effects of the different reagents,
additives and electrolytes on the dissolution of the gold, silver and gold-silver alloys;
• evaluate the variables that affect thiosulfate leaching of gold ore samples using a
rotating disc electrode technique; and

9
Chapter 1: Introduction

• evaluate the dissolution of different mercury forms in different thiosulfate and

cyanide solutions.

1.7 Thesis Organization

This thesis consists of nine chapters as follows:

• Chapter 1 is an introduction which presents a general overview on gold, notes

some cyanide alternatives and summarises the objectives of this work;
• Chapter 2 is a literature review of the environmental impacts of using mercury
and cyanide in gold processing;
• Chapter 3 is a review of the use of thiosulfate for gold leaching and this provides
the present state of advancement and understanding of the thiosulfate leaching
system;
• Chapter 4 presents the methodology and materials that have been used in this
study;
• Chapter 5 presents and discusses the results of experiments that were conducted
on pure gold and gold-silver alloys to evaluate open and closed leach vessels;
• Chapter 6 is the results and discussion of electrochemical experiments applying
linear sweep voltammetry and columetry on pure gold and gold-silver alloys to
provide a better understanding of the thiosulfate leaching system;
• Chapter 7 applies the optimum leaching reagent concentrations that were
determined from Chapter 5 to the leaching of gold ores from Sukari Gold Mine;
• Chapter 8 looks at the dissolution of mercury in different thiosulfate systems
and the cyanide system;
• Chapter 9 is the conclusions and recommendations derived from this work; and
• Chapter 10 is the references for this work.

10
Chapter 2 Environmental Impacts of Gold Mining: Literature
Review

2.1 Introduction
Generally, the gold mining industry has a negative environmentally image due
to its historically high polluting rates in soil, water, and air. The major environmental
problems caused by gold mining include: 1) acid mine drainage, 2) noise, 3) dust,
and 4) air and water pollution from toxic chemicals such as arsenic, cyanide, and
mercury.
Gold mining forms a significant part of the economic system in many
countries but, on the other hand, it can have wide environmental impacts to many
sections of the ecosystem. Non toxic gas emissions alter the normal constitutions of
air, while many toxic gas emissions have highly hazardous effects on human health.
The Pan American Health Organization (PAHO) reported that the gold mining
industry is frankly responsible for the high levels of air and water pollution and
health problems in Latin America and the Caribbean (Gatti, 2004).
Gold mining begins by extracting the ore from the earth. Often to access the
ore large amounts of waste rock needs to be removed. The volume of waste rock and
ore mined continues to increase, especially as open cut mining methods expand.
The ore is generally processed by cyanidation to remove the gold. Recently,
there has been growing arguments in many countries on the extensive use of cyanide
for gold leaching (McNulty, 2001). Many attempts have been made to find a more
environmentally friendly alternative.
The tailings that remain after cyanidation are usually deposited in a tailings
storage facility. The tailings contain toxic chemicals used in the gold extraction
process and heavy metals coextracted from the ore with gold. Waste rock movement
and tailings management need to be under tight control in most gold mines (Mudd,
2007).
Two highly toxic chemical reagents that are used widely in gold processing
are mercury and cyanide. In the following sections the environmental impacts of
using mercury and cyanide in gold processing will be reviewed.

11
Chapter 2: Environmental impacts of gold mining: Literature review

2.2 Environmental Impacts of Mercury in Gold mining

2.2.1 Introduction
Mercury is widely considered to be one of the most serious environmental
pollutants. It is a hazardous metal that has represented in the last decades a serious
source of environmental contamination and human toxicity in numerous locations
around the world.
As mercury has the property to adhere with metallic gold and silver forming
amalgams, this characteristic of mercury has been utilised as an effective technique
to concentrate and extract gold and silver from ores. The amalgamation method was
used on a large scale until the beginning of the twentieth century when it declined
due to the exhaustion of silver reserves in Colonial South and Central America and
later due to the invention of cyanidation. Unfortunately, recently, due to economic
and social factors in most of the developing countries located in the tropics, a new
rush for gold by individual miners, for whom mercury amalgamation is a cheap, easy
and reliable extraction process (Valenzuela & Fytas, 2002) has began.

2.2.2 Mercury Overview

Mercury is a natural component of the earth, with significant local variations
and an average abundance of approximately 0.05 mg/kg in the Earth’s crust.
Elemental mercury also is known as Quicksilver (symbol Hg for hydrargyrum).
Mercury is considered as one of the most hazardous chemicals that impacts upon the
global environment. It is among the best known and most poisonous metals in the
environment which causes serious human health problems; even death due to
inhalation of vapour and ingestion of contaminated food has been reported.
Mercury occurs in different forms:
• elemental or metallic mercury;
• inorganic mercury compounds; and
• organic mercury compounds (Eisler, 2006).

2.2.3 History of Mercury

Mercury was known to the ancient Chinese and Hindus, and has been
discovered in Egyptian tombs that date from 1500 BC (Eisler, 2006). The use of

12
Chapter 2: Environmental impacts of gold mining: Literature review

mercury in the extraction of gold by the amalgamation technique has been used for
more than 4500 years (Malm, 1998).
The main source of mercury, cinnabar (mercuric sulfide), has been mined
since 415 BC. In the 1800s, mercury was used in medical and electrical instruments,
and since 1900, it has been used in pharmaceuticals, in agricultural fungicides and
the production of plastics. During the Spanish colonial period of South America
(mainly Mexico, Peru, and Bolivia), mercury was widely used for silver and gold
recovery (Clarkson & Marsh, 1982). Over 260,000 metric tons of mercury was
emitted into the environment in the period from 1550 to 1930. After this period, the
mercury amalgamation process was not efficient to treat the remaining low grade
ores. The amalgamation extraction process was replaced partially by the cyanidation
process (UNEP, 2003).
The world production of mercury decreased from 7100 to 1800 metric tons in
the period from 1980 to 2000. Table 2.1 shows the decline of mercury production
from the year 1981 to the year 2000.

Table 2.1: Maximum and minimum recorded global primary production of mercury
since 1981, metric tons/year (UNEP, 2003).

1981- 1986- 1990-

Period 1996 1997 1998 1999 2000
1985 1989 1995

annual,
mercury
5500- 4900- 3300- 2600- 2500- 2000- 2100-
production 1800
7100 6700 6100 2800 2900 2800 2200
(in metric
tons)

2.2.4 Occurrence
The main source of atmospheric mercury is natural from volcanic eruptions
and ocean emissions (USGS, 2000). In addition to natural sources, mercury is
released into the air and water by human activities such as small-scale gold mining
(using amalgamation), coal-fired power plants, cement kilns, medical incinerators,
and other industries. The most important primary mercury minerals are cinnabar
(HgS) and its polymorph metacinnabar (HgS) and livingstonite (HgSb4S7). Native

13
Chapter 2: Environmental impacts of gold mining: Literature review

mercury (Hg0) is, by comparison, relatively rare in primary deposits but is found
more commonly in oxidation zones of such deposits (Valenzuela & Fytas, 2002).

2.2.5 Mercury Properties

Mercury exist in a large number of physical and chemical forms with a wide
range of physical, chemical, and eco-toxicological properties (Ebinghaus et al.,
1999). Mercury is a silver-white metal that is liquid at room temperature and highly
volatile. It exists in three oxidation states: elementary mercury (Hg0), mercurous ion
(Hg22+), and mercuric ion (Hg2+). It can form both inorganic and organic compounds
(USEPA, 1980). The mercuric species are the most toxic inorganic chemical form,
but all three forms of inorganic mercury may have a common molecular mechanism
of damage in which Hg2+ is the toxic species (Clarkson & Marsh, 1982).
The physical properties of mercury are summarised in Table 2.2. Mercury
freezes at about –39 ºC and when heated, the metal expands uniformly; boiling at
357 ºC at 760 mmHg, and has a vopour pressure of 0.0018 mmHg at 25 ºC. Mercury
vapour is colourless.

Table 2.2: Summary of the physical properties of mercury (Robert, 1967).

Property Value
Melting point, °C 39
Boiling point, °C 357
Specific gravity 13.54 at 22 °C
Density, g/mL 13.55
Vapour pressure, mmHg 0.0018 at 25 °C
Relative vapour density (Air =1) 7.0
Heat of vaporization, J/g 295.6

2.2.6 Mercury Uses

Mercury is the only metal that is found in a liquid form at room temperature
and atmospheric pressure. The following unique characteristics of mercury make
mercury useful in a large number of applications and processes:
• being liquid at room temperature;
• a good electrical conductor;
• having very high density and high surface tension;

14
Chapter 2: Environmental impacts of gold mining: Literature review

• expanding/contracting uniformly over its entire liquid range in response to

changes in pressure and temperature; and
• being toxic to micro-organisms (including pathogenic organisms) and other
pests (UNEP, 2003).
The world usage of mercury in recent years is estimated at 10,000 to 15,000
metric tons annually; major producers of mercury now include the former Soviet
Union, Spain, the former Yugoslavia, and Italy (Eisler, 2006). As noted in section
2.2.3 the primary production of mercury was 1800 metric tones, hence a large
percentage of usage is through recycling. Table 2.3 shows the application of mercury
in different industries. Mercury is used widely in gold and silver processing as well
as in many medical and electrical applications.

Table 2.3: Some examples of mercury uses in different industry applications

(UNEP, 2003).

Examples of mercury uses

As a metal (among others):
• for extraction of gold and silver (for centuries)
• as a catalyst for chlor-alkali production
• in manometers for measuring and controlling pressure
• in thermometers
• in electrical and electronic switches
• in fluorescent lamps
• in dental amalgam fillings
As chemical compounds (among others):
• in batteries (as a dioxide)
• biocides in paper industry, paints and on seed grain
• as antiseptics in pharmaceuticals
• laboratory analyses reactants
• catalysts
• pigments and dyes
• detergents
• explosives

15
Chapter 2: Environmental impacts of gold mining: Literature review

2.2.7 Mercury Toxicity and Standards

Mercury and its compounds are very toxic and must be handled with care and
under controlled conditions. Persons working with mercury should be monitored
regularly (EPA, 2007). Toxicologically, there are three forms of mercury (Eisler,
2006): (1) elemental mercury; (2) inorganic mercury compounds; and (3)
organomercurials.
The TLV value for metallic mercury in Germany is 0.1 mg/m3 (0.01 ppm) and
for mercury vapour, the TLV value is 0.05 mg/m3. In 1994, the American
Conference of Governmental Industrial Hygienists (ACGIH) decreased the threshold
limit value (TLV) form 0.05 mg/m3 as a Time Weighed Average (TWA) for 10h/day
to 0.025 mg/m3 as an 8h/day exposure or 40h/week time weighed average (ACGIH,
1997) .
The odour threshold for mercury is 13 mg/m3. With metallic mercury,
inorganic mercury compounds, and organic non-alkyl mercury compounds, mercury
values in urine should not exceed 150 mg/L and blood levels should be less than 35
mg/L. With organic alkyl mercury compounds, the maximum allowable blood level
is 75 mg/L. Acute poisoning occurs when mercury ion concentrations reach 0.2 mg
per 100 mL of blood. Daily 5h exposure to inhaled mercury vapour concentrations of
0.1 mg/m3 leads to severe mercury poisoning (Simons et al., 1997).

2.2.8 Mercury Effects on Human Health

The World Health Organization (WHO, 1976) reported that acute exposure,
4-8 hours, to the calculated elemental mercury levels of 1.1 to 4.4 mg/m3 result in
chest pain, dyspnea, cough, hemoptysis, and impairment of pulmonary function.
Furthermore, WHO indicated that acute exposure to mercury vapour results in
profound central nervous system effects, including psychotic reactions characterized
by delirium, hallucinations, and suicidal tendency. Mercury poisoning is manifested
in various neuromuscular malfunctions ranging from numbing of the extremities to
the loss of eye sight, paralysis, and even death (Barkay, 1992; WHO, 1990 & 1976)
The first case of fatal inorganic mercury poisoning in humans was reported in
1865 with two men exposed in a European chemical laboratory, and the first
documented human poisoning from agricultural exposure to an organo-mercury
compound was reported in 1940 (Das et al., 1982).

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Chapter 2: Environmental impacts of gold mining: Literature review

Mercury species differ greatly in their properties, however they are all toxic.
Elemental mercury (Hg0) volatilizes readily, emitting mercury vapour, which is
readily absorbed in the lungs; however, elemental mercury is very poorly absorbed
through the skin or gastrointestinal (GI) tract. Inorganic mercurial salts (Hg+ and
Hg2+) have a wide range in solubility and absorptive properties. All mercury
compounds are toxic to humans and animals, but the organic forms, in particular
methylmercury and dimethylmercury, have the highest toxicity. Methylmercury is
the form found most widely in nature where it bio-accumulates in the food chain. It
is the form to which most human exposure occurs (Gochfeld, 2003).

2.2.9 Mercury Releases to the Environment

Mercury is a widely spread pollutant due to its unique characteristics such as
low melting and boiling points, conversion between chemical forms and participation
in biological cycles. The pre-industrial deposition rate of mercury from the
atmosphere was approximately 4 ng/L in the western USA. The atmospheric mercury
value can be increased by 4-6 times during volcanic eruptions (USGS, 2000). The
global atmospheric mercury emissions rate is now nearly three times higher than in
pre-industrial times and has increased by a factor of 2-10 in and around most
industrialised regions (Lamborg et al., 2002; Bergan et al., 1999; Meili, 1995).
A study by Horvat et al. (2002) found that for every gram of gold produced by
amalgamation around 1.2 to 1.5 grams of mercury are lost to the environment.
Nearly 20% of the mercury is lost to tailings, soils, stream sediments and water with
70.8% emitted into the atmosphere.
In 1995, approximately 1900 metric tons of mercury entered the atmosphere,
most of it (about 75%) from the combustion of fossil fuels (Pacyna & Pocyina,
2002). Mercury enters the environment as a pollutant from various industries (EPA,
2007) including:
• coal-fired power plants are the largest aggregate source (40% of USA
emissions in 1999);
• large gold mines - the three largest point sources for mercury emissions in the
US are the three largest gold mines;
• gas fired power plants fueled with gas from mercury prone reservoirs where
the mercury has not been removed;
• small-scale gold mining;

17
Chapter 2: Environmental impacts of gold mining: Literature review

• industrial processes;
• medical applications, including vaccinations; and
• laboratory work involving mercury compounds.

Before the cyanidation process replaced the amalgamation process, gold and
silver mines using mercury were one of the major sources of mercury emission to the
environment. In addition, mercury can be released to the environment during the
recovery of precious metals from deposits that contain mercury as a minor
component, including volcanogenic massive sulfide and sedimentary exhalative
deposits (Shaw et al., 2006; Lacerda & Marins, 1997; Lacerda, 1997; Nriagu, 1993).
Figure 2.1 shows the different pathway of mercury emissions into the atmosphere
from gold and silver mining.

 Rural atmosphere
Emission
From  Hg0 (vapor) dominant (> 70%)
Amalgam  Medium range transport
Burning
 Atmospheric residence time dependent on oxidation
 Strong interaction with vegetation

 Urban atmosphere

Gold  Hg2+ and Hg particle dominated (> 70%)

Purification  Short residence time, season dependent
 Strong physical-chemical interaction with
atmospheric constituents

 Rural atmosphere
 Hg0 (vapor) dominant (> 70%)
Degassing
From  Long range transport
Tailings  Residence time dependent on oxidation
 Season dependent

Figure 2.1: Atmospheric mercury pathways in areas of gold and silver mining
(de Lacerda & Salomons, 1998).

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Chapter 2: Environmental impacts of gold mining: Literature review

2.2.10 The Principle of the Amalgamation Process

Amalgamation is the main gold extraction technique used in small scale gold
mines. In general, gold processing requires a method to separate gold from the
impurities in the ore. This can be achieved by mixing metallic mercury with the ore,
which has a high affinity for gold, forming a gold-mercury amalgam. The amalgam
is separated for barren ore residue and heated in a process called burning. This heats
up the amalgam driving off the mercury as vapour, leaving gold metal.
A variation on amalgamation of gold, as an alternative to the ancient
sheepskin collection and water shaking methods, was developed by the Roman. In
this method sands or ground ores containing gold were mixed with metallic mercury
to produce gold amalgam and the mixture was put into leather bags. Amalgam would
leak out of the bag and residual solids would be retained inside. By distillation of the
amalgam, mercury would be condensed for recycling and gold was recovered
(Müezzinolu, 2003).
Donoghue (1998) summarised the process of amalgamation for gravity gold
on a medium scale by the following sequence of steps:
1. the mining of placer gold is undertaken by hydraulic excavators which extract
river bed gravel;
2. the gold-bearing gravel is delivered to a processing plants where the fine gold
bearing material is separated by rotary screens and vibrating tables. It is then
examined closely so that free gold particles can be collected;
3. the remaining gold-bearing sands are mixed with metallic mercury in barrels to
extract the gold in the form of a mercury-gold amalgam;
4. after washing in water to remove any remaining sand, the amalgam is placed in a
sealed retort and heated until the mercury has been evaporated off, condensed, and
collected under water; and
5. the remaining gold along with free gold obtained at the tabling stage is then
placed in a crucible, smelted on a furnace and cast into ingots.

2.2.11 Mercury and Gold mining

Numerous small-scale miners all over the world use mercury to extract gold
and silver. The environmental impacts of mercury effect not only the mine and
workers, but also on the surrounding environment. Any mercury released into the

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 Chapter 2: Environmental impacts of gold mining: Literature review

environment circulates through the ecosystem where it can bio-accumulate and stay
active.
Starting from the 16th century, Hg amalgamation was the major technique
used for the mining of precious metals (de Lacerda & Salomons, 1998). Around one
million tons of metallic mercury has been extracted from cinnabar and other ores
during the past five centuries. About half of this amount has been used for mining of
gold and silver (Hylander & Meili, 2003). Many studies report that most of the
mercury released to the environment is generally associated with mercury mining
and precious metal mines that utilises amalgamation methods (da Costa et al., 2007;
Shaw et al., 2006; Valenzuela & Fytas, 2002; Malm, 1998; Salomons, 1998; Malm et
al., 1995; Salomons, 1995).
Telmer (2006) reported that about 15 million small-scale gold miners around
the world use mercury to trap fine particles of gold. The inefficient recovery of
mercury amalgam and excess free mercury and the release of fugitive mercury
vapours during burning release mercury into the environment.
About 1,000 tons of mercury are released into the environment each year,
affecting up to 100 million people. In 1995, China produced 105 tons of gold, about
one third of which was from small-scale mines (alluvial ore, rock ore, and coexisting
ore). The small gold mines usually extracted gold with mercury amalgamation (Lin
et al., 1997). Haygrath and Jones (1992) reported that burning of mercury amalgam
or purification of the extracted precious metal bullion may produce various mercury
species such as Hg vapour (Hg0), HgO, and Hg2+, and Hg adhered or condensed onto
solid particles. The areas near to gold mines may be contaminated with at least two
forms of mercury, inorganic mercury, and methylmercury (Me.Hg) (Horvat et al.,
2002).
For large scale operation using cyanidation, the loss of mercury from gold
mining tailings to the surrounding environment is thought (Shaw et al., 2006) to
occur through two main processes:
1. leaching of soluble Hg to the groundwater in the form of Hg-CN complexes; and
2. diffusion of Hg gas (Hg0) to the atmosphere.

2.2.11.1 Environmental Problems of using Mercury in Gold mining

Environmental problems caused by the utilization of mercury in gold and
silver mining have been reported since Roman times. Around 77 A.D, Roman

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Chapter 2: Environmental impacts of gold mining: Literature review

authorities were importing 5000 kg/year of mercury from Spain to be used in gold
amalgamation in Italy (de Lacerda & Salomons, 1998).
One of the main problems of using mercury is that it is continuously present
in the environment. A study conducted by Lacerda (1997) found that most of the
mercury released to the atmosphere through gold and silver mining during the last
500 years may still participate in the mercury cycle through re-mobilization from
abandoned tailings and other contaminated areas. Wong et al. (2002) studied the
toxicity of metals from abandoned gold mine tailings at Goldenville, Nova Scotia,
Canada where large quantities of mercury were used in the gold recovery process.
There are around 3 million tons of tailings left from the mining processing. The
results showed that these tailings may contain up to 6.8 tons of mercury and there is a
continuous emission of mercury and other metals from the tailing field which causes
contamination of the surrounding environment.
Ikingura et al. (1997) studied the environmental impacts of using mercury in
gold extraction in Tanzania and reported elevated mercury concentrations in
environmental samples from the mining areas and average mercury concentrations in
river sediments and soils of 4.19 µg/L and 3.39 µg/g respectively. Another study
carried out by García-Sánchez et al. (2006) showed that the soil, mud, and waste rock
samples from gold mining areas where mercury is used in El Callao (Venezuela),
have high concentrations of mercury (around 0.5-500 µg/g ). This concentration is
very high if compared with the normal mercury concentrations (<0.1 µg/g ). In the
areas around the Murray Brook gold deposit, located in northern New Brunswick,
Canada, high mercury levels have been detected in the ground water (11,500 µg/L)
and 32 µg/L in the surface water (Shaw et al., 2006). In Brazil, the major source of
mercury pollution is gold mining and average mercury emissions are 77.9 ton per
year. The mercury emissions are more concentrated in the Amazon region with an
approximate concentration of 16 g/km2 (Lacerda & Marins, 1997).
In the Philippines, the effect of mercury in areas around an abandoned gold
mine located southeast of Manila proved disastrous with around 1 million tons of
tailings dumped into Honda Bay where about 2000 inhabitants live (Maramba et al.,
2006). High concentrations of total mercury were detected at locations with
extensive small-scale gold mining activities. All water mercury concentrations from
the sampling sites were higher than the WHO limit of 0.001 mg/L for drinking water.

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Chapter 2: Environmental impacts of gold mining: Literature review

• Problems of Mercury in the Cyanidation Process

The cyanidation process (section 3.4) uses cyanide to dissolve gold and silver
from the ore. The soluble gold cyanide complex is adsorbed onto activated carbon to
remove it from the ore slurry. Elution with sodium hydroxide and sodium cyanide
strips the gold cyanide complex from the activated carbon allowing electrowinning to
recover crude gold metal. The crude gold is upgraded by smelting. The eluted
activated carbon is regenerated by heating to about 700°C and reused.
During the cyanidation process, cyanide also leaches mercury and some other
metals present in the mined ore, including Co, Fe, Ni and Zn ( Shaw et al., 2006;
Smith & Mudder, 1991). Mercury cyanide complexes are adsorbed on activated
carbon along with gold and silver and other metal complexes. Mercury is then
recovered at the same time with the gold and silver in the elution circuit and
consequently electrowinning. Mercury contained in the electrowinning sludge can
present both environmental and industrial problems (Washburn & Hilldoi, 2003)
when the sludge is heated during smelting. Mercury left on the activated carbon is
vapourised to the atmosphere during the carbon regeneration.
An alternative to the carbon adsorption process is to filter the ore from the
solution and precipitate gold by using zinc metal (Merrill-Crowe process). As
mercury is also precipitated with gold and silver it reports to the smelting furnace
and causes processing, occupational health and safety and environmental concerns.

2.3 Environmental Impacts of Cyanide

2.3.1 Introduction
Cyanide was first applied commercially in New Zealand over a century ago
in the extraction and recovery of gold and silver. Although cyanide has determinable
toxicological effects, it has a wide application in many different fields. There is much
public concern about the use and toxicity of cyanide around the world. Some
countries such as the Czech Republic, and Turkey, and some states in the USA, such
as Colorado, Wisconsin, and Montana have campaigned to ban cyanide in mineral
processing applications (Arima et al., 2004; Anonymous, 2000; De Voto & McNulty,
2000).
Most of the hydrogen cyanide emitted into the atmosphere stays in the lower
troposphere. Environmental monitoring of free cyanide (FCN), weak acid dissociable

22
Chapter 2: Environmental impacts of gold mining: Literature review

cyanide (WAD) and total cyanide levels in the environment is required in all the
mines that utilise cyanide (Cicerone & Zellner, 1983).
The environmental degradation of hydrogen cyanide from surface waters
usually occurs through volatilization, biodegradation, hydrolysis, and sorption.
Volatilization and sorption are the two main physical processes that remove cyanide
from surface waters. Volatilization rates of hydrogen cyanide are dependent upon pH
(at lower pH, HCN emission rate is higher) and aeration. The pH should be
controlled because if the pH of the solution is <9.2, most of the free cyanide in the
solution exists as hydrogen cyanide. The most common cyanide salts (sodium and
potassium cyanide) may be lost from surface water through volatilization; whereas,
the soluble metal cyanides (copper, nickel, zinc) are removed from water mostly by
sedimentation and biodegradation (USEPA, 1992).
Oxidation and decay compounds derived from cyanide such as cyanate,
cyanogen chloride and thiocyanate (Souren, 2000) may also exit in process waste
solutions. In addition, cyanide can dissolve in water forming metal cyanide ions
(Klenk et al., 1996).

2.3.2 Chemistry of Cyanide

Cyanide is a chemical ion that contains one atom of carbon (C) and one atom
of nitrogen (N) represented by the chemical formula CN-. It is a triple-bonded
molecule with a negative one charge, where the carbon is in the +2 oxidation state
and the nitrogen in the -3 oxidation state (Franson, 1992).
Simple cyanide salts, such as sodium, potassium, and calcium cyanide,
dissolve and ionize in water to form their respective metal cation and free cyanide
ions as described by Equation 2.1 for sodium cyanide.
NaCN ⇔ Na + + CN − (2.1)
The solubility and the relative cyanide content of the different cyanide salts
are shown in Table 2.4. Sodium and potassium cyanide are more soluble than
calcium cyanide.
Table 2.4: Properties of simple cyanide salts (Marsden & House, 2006).

Compound. Available cyanide % Solubility in water at 25 °C

NaCN 53.1 48
KCN 40.0 50
Ca(CN)2 56.5 Decomposes

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Chapter 2: Environmental impacts of gold mining: Literature review

Cyanide ions hydrolyse in water to form molecular hydrogen cyanide (HCN)

and hydroxide ions, with a corresponding increase in pH as described in Equation
2.2.
CN − + H 2O ⇔ HCN + OH −
(2.2)
Hydrogen cyanide is a weak acid, which incompletely decomposes in water
as shown in Equation 2.3.
HCN ⇔ H + + CN − (2.3)
Figure 2.2 shows the extent of this dissociation reaction at equilibrium as a
function of pH. At pH 6.0, 100% of the total cyanide exists as hydrogen cyanide and
at pH 12, all the total cyanide exists as free cyanide. From the same figure, at
approximately pH 9.3, half of the total cyanide exists as hydrogen cyanide and half
as free cyanide ions.

120

100
Cyanide in HCN or CN (%)

80
-

60
HCN
CN-

40

20

0
6 7 8 9 10 11 12 13
pH

Figure 2.2: The speciation of free cyanide and hydrogen cyanide in aqueous solution
as a function of pH.

Free cyanide forms complexes with many metal species, principally the
transition metals as described by Equation 2.4 (Marsden & House, 2006), which vary
in stability and solubility
( y − x )−
M x + + yCN − ⇔ M (CN ) y (2.4)

where K diss = [ M x + ].[CN − ] y / M (CN ) y ( y − x ) −

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Chapter 2: Environmental impacts of gold mining: Literature review

Metal cyanides can be represented by the formula M(CN)x, where M is a

metal and x is the number of cyano-groups, dependant on the valence number of the
metal ion. The stability constants of some of the more important metal cyanide
complexes are shown in Table 2.5.

Table 2.5: Stability constants for some selected metal cyanide complexes (Tien,
1994).
Chemical Formula Quantity
HCN LogK1 = 9.21
Fe(CN)64- Log β6 = 35.4
Fe(CN)63- Log β6 = 43.6
Ni(CN)42- Log β4 = 30.22
Cu(CN)32- Log β3 = 21.66
Zn(CN)42- Log β4 = 19.62
Ag(CN)32- Log β3 = 21.40
Au(CN)2- Log β2 = 39.3
Cd(CN)42- Log β4 = 17.92
Co(CN)64- Log β6 = 19.1

With respect to table 2.5 cyanide and cyanide complex may be divided into
three main categories, based on their stability (Morgan, 1991).

• free cyanide (HCN, CN-);

• weak acid dissociate (WAD) cyanide complexes (for which log K ≤
approximately 30); and
• strong cyanide complexes (for which log K > approximately 30).

The ability of cyanide to form strong complexes and stabilise gold and silver
allows it to be used in the cyanidation process. Besides stabilising gold and silver in
solution, cyanide forms complexes with other metals, such as mercury, zinc, copper,
iron and nickel that leads to:
• increases in the consumption of cyanide in gold extraction circuits;
• waste waters that may be difficult to treat; and
• complications in the analysis of cyanide solutions (Mudder et al., 2001).
Both hydrogen cyanide and cyanide ion can be oxidized to cyanate in the
presence of oxygen and under suitably oxidizing conditions as illustrated in the Eh-
pH diagram for the CN- H2O system in Figure 2.3.

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Chapter 2: Environmental impacts of gold mining: Literature review

The important reactions (Mudder et al., 2001) are:

4 HCN + 3O2 ⇔ 4CNO − + 2 H 2O (2.5)

2CN − + O2 + catalst ⇔ 2CNO − (2.6)

These reactions are undesirable during leaching, because they reduce the free
cyanide concentration, and the cyanate species formed does not dissolve gold.

Figure 2.3: Eh-pH diagram for the CN- H2O system at 25 ºC (Smith, 1988).

Hydrogen cyanide is miscible with water, giving a weak acid. The CN triple
bond is readily hydrolysed by strong alkali or acid giving formic acid and ammonia,
with higher temperature favouring these reactions.

2.3.3 Production of Sodium Cyanide

Most cyanide that is produced is in the form of hydrogen cyanide (HCN) or
one of the simple alkali metal cyanides such as sodium cyanide (NaCN), potassium
cyanide (KCN) or calcium cyanide (Ca(CN)2).
Sodium cyanide was first prepared in 1834 by heating sodium carbonate and
Prussian blue (a mixture of cyanogen compounds of iron) with sodium cyanide
extracted from the cooled mixture using alcohol. Today, almost all sodium cyanide is
produced by reacting hydrogen cyanide with sodium hydroxide solution (NaOH) and

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Chapter 2: Environmental impacts of gold mining: Literature review

evaporating off the water. This is often called the neutralisation-wet process as
described in Equation 2.7 (Williams, 2001).
HCN + NaOH → NaCN + H 2O (2.7)
The wet process typically uses 50% (by weight) NaOH and purified
anhydrous hydrogen cyanide (liquid or vapour) replacing the alkali metal of the
hydroxide to produce the corresponding alkaline metal cyanide. As an example if
KOH is used, KCN will be produced
In most commercial sodium cyanide plants, reaction between the hydrogen
cyanide and NaOH occurs followed by the evaporation of water and crystallisation of
NaCN (for solid NaCN). The control of this system is important to avoid the
formation of hydrogen cyanide polymer and sodium formate, and to maximise
crystal size. One estimation by Towill et al. (1978) stated that 84% of North
Americian hydrogen cyanide production is used to produce organic cyanide, also
called nitriles. Some of the remaining hydrogen cyanide is used to produce 130,000
tons of sodium cyanide per year of which about 90% is used in gold mining.

2.3.4 Uses and Sources of Cyanide

Although many attempts have been made to find chemical replacements for
cyanide, it remains the main lixiviant of choice in the precious metals industry
worldwide.
The superiority of cyanide to other chemicals in this industry is due its:
• availability;
• effectiveness;
• low cost; and
• the ability to use it with acceptable risk to people and the environment if it is
used under control (Mudder & Botz, 2001).
Sodium cyanide is the most widely used type of cyanide by the precious
metal mining industry, though Ca(CN)2 and KCN are used in select locations.
Mudder (2001) reported that up to 90% of gold is produced using cyanide. About 1.4
Mt of hydrogen cyanide are produced annually. About 13% of this amount is
converted into sodium cyanide and used in the extraction of gold and silver as shown
in Figure 2.4. The remaining 87% of the hydrogen cyanide is used in the production
of different products such as adhesives, computer electronics, fire retardants,

27
Chapter 2: Environmental impacts of gold mining: Literature review

cosmetics, dyes, nylon, paints, pharmaceuticals, Plexiglas, rocket propellant, and

road and table salts (Williams, 2001).

Figure 2.4: Industrial uses of hydrogen cyanide (Williams, 2001).

In fact, natural production of cyanide occurs throughout the world. Cyanide

and chemically related compounds are generated in nature by different species of
bacteria, algae, fungi, plants, and insects ( Fish & Wildlife Service, 1991; Knowles,
1976). Cyanide is naturally present in the biosphere in both simple and complex
forms. Interestingly, for many years’ cyanide and cyanide compounds have been
referred to as the first organic compounds on earth, from which the remaining
compounds of life were derived (Oparin, 1983; Lehninger, 1970).

2.3.5 History of Cyanide in Gold mining

A short chronology of the history of the use of cyanide in gold processing is
summarised as follows (Logsdon et al., 1999):
• in 1704, Dippel and Diesbach discovered “Prussian blue” (iron ferrocyanide);
• the earliest well-documented work on Scheele’s studies in Sweden in 1783 is on
the solubility of gold in cyanide solutions;
• by 1840, Elkington held a patent for the use of potassium cyanide solutions for
electroplating gold and silver;
• Elsner’s equation describing the extraction of gold from ores by cyanide was
known by 1846;

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Chapter 2: Environmental impacts of gold mining: Literature review

• in 1887 and 1888, McArthur and the Forrest brothers effectively established the
current gold extraction process, dissolution by cyanidation and precipitation using
zinc;
• the first commercial-scale cyanidation plant started operating at the Crown Mine
in New Zealand in 1889; and
• by 1904 cyanidation processes were also in place in South Africa, Australia, The
United States of America, Mexico and France and the use of cyanide to extract gold
from low-grade ores was a fully established metallurgical technology.
To date, cyanide is still the main lixiviant used in gold and silver processing,
and there is no proven alternative for cyanide in the industry.

2.3.5 Cyanide Toxicity

Cyanide is poisonous with its toxicity depending on the type of cyanide
complexes that are present. Despite cyanide ions in process waste solutions and
hydrogen cyanide as gas emissions from cyanidation being monitored and measured
regularly, the accurate determination of cyanide concentrations in the field is difficult
to achieve due to sampling, and analytical errors associated with loss and
interferences following collection (Donato et al., 2007).
The principal toxicological hazard of cyanide is acute exposures, such as
rapid ingestion of cyanide-containing forage or solutions. Cyanides are absorbed
through inhalation, ingestion, or skin contact and are readily distributed throughout
the body via blood. Inhalation of cyanide salts is highly hazardous because the
cyanide dissolves on contact with moist mucous membranes (Mudder & Botz, 2001).
Ingestion of cyanide salts may be deadly with as little as 200 mg. Also solutions of
cyanide salts can be absorbed through intact skin or through the conjunctiva of the
eye.The dosage required to kill 50% of a population of rats under standard test
conditions, LD50, is generally used as a measures of cyanide toxicity. Table 2.6
shows the LD50 values that represent the toxicity of cyanide and its derivatives.

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Chapter 2: Environmental impacts of gold mining: Literature review

Table 2.6: Toxicity of cyanide and cyanide derivatives (Lowehein & Moran, 1975).

Substance Boiling Expousre LD50 Cyanide

point, °C limit (ppm) (mg/Kg) releasing
Bromobenzylcyanide Solid 3500 +
3
Cyanamide Solid 2 mg/m 1000 0
Cyanide salts Solid 5 mg/m3 2 +
Cyanoacetic acid 108 - 2000 0
Cyanogen gas 10 13 +
Cyanogen chloride 61 0.3 13 +
Ferric-cyanide Solid - 1600 0
Ferroc-cyanide Solid - 1600 0
Hydrogen cyanide 26.5 10 0.5 +
Malonitrile Solid 3 6 +
Methylcyano-acrylate liqiud 2 - +
Methyliso-cyanate 39 0.02 2ppm -
Nitoprusside Solid - 10 +
O-Tolunitrile 204 - 600 0
Note: + release free cyanide 0 No free cyanide released - No specification

Environmental issues generally related with cyanide are due to its high
toxicity. Cyanide eliminates fish of the trout species at concentrations as low as 0.04
mg/L of cyanide ion in water. According to the National Institute of Occupational
Safety and Health (NIOSH) of the USA, for HCN gas for humans (Muyunda, 1996):
• 270 ppm is immediately fatal;
• 180 ppm is fatal after 10 minutes;
• 135 ppm is fatal after 30 minutes;
• 110 ppm can be fatal;
• 45-55 ppm can be tolerated for up to 60 minutes without immediate effects; and
• 18-36 ppm results in symptoms of poisoning several hours after exposure.
Low dissolved oxygen and low pH are the main factors that increase the
toxicity of free cyanide in aquatic ecosystems (Alabaster et al., 1983). The acute
toxicity of cyanide on fish in solutions containing only free cyanide decreases with
increasing pH. Figure 2.1 shows that as pH increase the proportion of total cyanide
present as hydrogen cyanide increases. Hence more hydrogen cyanide is present at
low pH values and Alabaster et al (1983) report that hydrogen cyanide (HCN) is
more toxic (nearly 2.3 times) than the anionic form (CN-).

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Chapter 2: Environmental impacts of gold mining: Literature review

2.3.5.1 Occupational Exposure to Cyanide

The occupational exposure standard or threshold limit value (TLV) for
cyanide dust is 5 mg/m3, and for hydrogen cyanide is 10 ppm (Mudder & Botz,
2001). Workers must use engineering and work practice controls to reduce exposure
to or below an 8-hour time-weighted average (TWA) of 10 ppm of hydrogen
cyanide. The exposure to cyanide in gold mining should be controlled with physical
elimination methods and chemical treatment and recovery of cyanide to maintain the
levels of WAD cyanide below 5 mg/L (Mudder & Botz, 2001).
Respirators must be provided and used during the time period necessary to
install or implement feasible engineering and work practice controls (Ballantyne,
1988). The US Environmental Protection Agency has proposed a limit of 0.2 mg/L
cyanide in drinking water. German and Swiss regulations have set limit of 0.01 mg/L
for cyanide for surface water and 0.5 mg/L in sewers (Desai et al., 1998).

2.3.5.2 Recent Cyanide Accidents

A series of recent environmental accidents at various gold mines around the
world has precipitated widespread concerns over the use of cyanide as a leach
reagent. The majority of these accidents occurred either by cyanide leakage through
holes or tears in protective heap leach liners, or by losses in tailings storage areas
(Korte & Coulston, 1998). The number of cyanide tailing dam failures around the
world has increased from 10 in the years between 1969–1979 to 21 in the years
between 1989–1999 (Stenson, 2006).
Some examples of cyanide spills and mine-related accidents in the world and
the resulting environmental impacts are presented in Table 2.7. In each of these
accidents many tonnes of cyanide were released into the environment. For example
in the disaster at the Omai gold mine in Guyana, 1995, about 2.9 million m3 of
cyanide tailings and wastewater was released by a collapse of the tailings dam,
polluting the Essquibo River. Another accident occurred, in Romania, 2000, where
about 100 ton of cyanide contaminated the Danube River (Hilson & Monhemius,
2006). Gold mining in the Portovelo-Zaruma district in southern Ecuador is causing
considerable environmental impact; the main environmental impact of this mine is
the discharge of cyanide, mercury and metal rich tailings into rivers of the Puyango
catchment area (Tarras-Wahlberg et al., 2001).

31
Chapter 2: Environmental impacts of gold mining: Literature review

Table 2.7: Examples of cyanide spills and mine-related accidents and the
environmental impacts (Mudder et al., 2001; Moran, 1998).

Year of
Mine/country Impact
occurrence

Galactic Resources Ltd.'s Colorado, Severe environmental problems along a 17-mile

Summitville Mine USA, 1992 stretch of the Alamosa River

Pegasus Corporation's Montana, Severe contamination of groundwater;

Zortman–Landusky Mine USA, 1997 substantial wildlife deaths

Echo Bay's McCoy/Cove Nevada, Eight cyanide leaks over a two-year period
Gold Mine USA, 1989 released almost 900 lbs of cyanide.
and 1990

Harmony mine, South February,

10 miners killed by cyanide-laced mud.
Africa 1994

August, All aquatic life forms in a creek that runs into

Omai gold mine, Guyana
1995 the Essquibo river were killed.

Truck transporting cyanide to Kumtor mine

May 20,
Kumtor mine, Kyrgyzstan plunged off a bridge, spilling 2 tons of sodium
1998
cyanide. Four people died.

Thousand of tons of fish died in the Tiza and

January, Danube Rivers. Rare Osprey, birds, river otters,
Baia Mare, Romania
2000 fox, and other mammals died from eating
cyanide contaminated fish.

Dome helicopter dropped a crate containing 1

Tolukuma mine, Papua
March, 2000 tonne of sodium cyanide pellets into the water
New Guinea
system in the rainforest.

Ghana
 Bogoso Goldfields 1994
 Teberebie Goldfields
1996 Communities were re-located, waters polluted,
 Ashanti Goldfields 1998 there were reported cases of avian mortality,
1994–2001
 Goldfields (S.A.) 2001 and crops were affected. There were serious
 2001 – second spill health impacts including skin rashes.
occurred in the same area
after 2 weeks

Placer Dome tailings Loss of aquatic life forms in Mogpog River and
1975–1991
disposal, The Philippines Calancan Bay.

The spill affected aquatic life forms in Ajkwa

Grasberg Mine, Indonesia 1996
River and surrounding communities.

32
Chapter 2: Environmental impacts of gold mining: Literature review

With the many incidences of cyanide release into the environment and the
subsequent environmental damage control measures have been increased. Four major
directions are being pursued:
1. reduction in cyanide use in cyanidation plants;
2. replacement of cyanide with less toxic reagents;
3. destruction of excess cyanide after cyanidation; and
4. recovery and reuse of excess cyanide after cyanidation.

The next section, 2.3.6 reviews the methods available for the destruction and
recovery of cyanide after cyanidation.

2.3.6 Treatment and Recovery of Cyanide

The increase in global mining activity coupled with greater environmental
awareness has generated renewed interest in developing processes for the treatment
of metallurgical solutions and other mine waters. To minimize the environmental
impact of cyanide and make cyanidation acceptable, a variety of verified and reliable
chemical, physical, and biological processes have been developed for the treatment
and recovery of cyanide and related compounds, which are present in mine waters.
Due to the widespread use of cyanide in mining operations, the recovery and
destruction of cyanide is important both from the environmental aspects of
wastewater and effluent treatment, and in some cases, from the economic aspects
associated with high reagent consumption by the process itself. The following
sections will present, in brief, some methods of cyanide treatment and destruction.

2.3.6.1 Activated Carbon Adsorption

The use of activated carbon adsorption for cyanide removal originated from
attempts to employ it as a catalyst in the oxidation of cyanide with oxygen. It was
noted that the cyanide was first adsorbed, and then catalytically oxidized. The
presence of metal ions, particularly copper, enhanced the removal of cyanide through
formation of the copper cyanide complex. The best application of granular activated
carbon is in a polishing step for the removal of low levels of WAD cyanide and
cyanide complexed metals (Mudder et al., 2001).
Reed (1971) investigated the removal of cyanide using granular activated
carbon without oxidation. The addition of copper or nickel was necessary for the

33
Chapter 2: Environmental impacts of gold mining: Literature review

removal of cyanide. The process involves the addition of metal ions, followed by a
complexation period where metal cyanide complexes are formed, followed by
adsorption of these complexes onto the granular activated carbon.

2.3.6.2 Alkaline Chlorination

Alkaline chlorination is a widely used process that generally is used to
oxidise free and WAD forms of cyanide. This process is the oldest of the cyanide
destruction processes, with the first industrial applications being in the treatment of
metal plating and finishing waste water. The use of alkaline chlorination in mine
water treatment resulted from the chemical similarity noted between metal plating
and mine waters.
The alkaline chlorination process is best applied as a method on clear
solutions when WAD cyanide, thiocyanate and/or ammonia are required to be
removed (Moran, 1998). In this process, firstly free and WAD forms of cyanide are
converted to cyanogen chloride (CNCl) using chlorine (Cl2) or hypochlorite (OCl-).
The first stage of the alkaline chlorination process is described by Equations 2.8 and
2.9 (Mudder et al., 2001):
Cl 2 + CN − → CNCl + Cl − (2.8)

OCl − + CN − → OCN − + Cl − (2.9)

In the first stage, the control of pH is important in order to eliminate the
volatilization of cyanogen chloride, which occurs if the pH is less than about 8.0;
therefore, this reaction step is ideally carried out at a pH in the range of 10.5 to 11.5.
In this pH range, cyanogen chloride hydrolyses to yields cyanate:
CNCl + H 2O → OCN − + Cl − + 2 H + (2.10)
The second stage of the oxidation includes the hydrolyses of the cyanate in
the presence of chlorine or hypochlorite to yield ammonia and carbonate according
to the reaction represented by the Equation 2.11:
OCN − + OH − + H 2 O → NH 3 + CO32− (2.11)

2.3.6.3 Biological Treatment

Biological processes have proven effective in the treatment of elevated
concentrations of cyanide. Although biological treatment of cyanide is a relatively

34
Chapter 2: Environmental impacts of gold mining: Literature review

new phenomenon in the gold mining industry, there are several references to it dating
from as early as the 1950s (Mudder & Botz, 2001).
In this method, chemical and/or physical processes may be included, but the primary
treatment occurs through biologically mediated reactions. Biological treatment
occurs under carefully controlled conditions using a large number of micro-
organisms selected to remove one or more constituents (Moran, 1998).
In the biological treatment, the cyanide is converted to thiocyanate then about
90% of the thiocyanate is decomposed into NH4+, CO2 and SO4. This decomposition
is not affected by the feed flow-rate and the pollutant concentrations (Dictor et al.,
1997). The biological method is better than other physical and chemical destruction
methods, (Akcil, 2003) as the bio-treatment of cyanide tailings can be less expensive
than chemical and physical methods, but much faster than natural oxidation. In
addition, Mosher and Figueroa (1996) reported that chemical treatments of cyanide
are expensive and can bring some additional environmental problems such as by-
products of the cyanide oxidation (i.e. CNO−) possibly generating ammonia, which
has an environmental impact the same as the cyanide. Finally, Nelson et al. (1998)
conclude that the biological treatment methods have a higher capital cost, but a
significantly lower operating cost.
One of the limitations of the biological treatment system for cyanide is that it
can not be used to destroy raw electroplating wastewater (EPWW) because of the
low organic matter concentration of 10 ± 3 mg-BOD50/L and toxicity of the high
cyanide concentration of 23.0 ± 2.2 mg-CN/L (Sirianuntapiboon et al., 2008 ).

2.3.6.4 Caro`s Acid

In the early 1990s, Caro’s acid was postulated as a reagent for possible use in
oxidizing cyanide in cyanidation solutions. Caro’s acid, also known as
peroxymonosulphuric acid (H2SO5), is a strong oxidizing agent and has been used for
many years in industrial chemical formulations and bleaching agents. It has recently
been applied at a few mining operations for tailings detoxification, particularly for
tailings slurry. The mechanism of treating the cyanide with Caro’s acid is that it
reacts with both free and WAD cyanides to produce cyanate and sulphuric acid
according to reaction 2.12.
H 2 SO5 + CN − → OCN − + SO4−2 + 2 H + (2.12)

35
Chapter 2: Environmental impacts of gold mining: Literature review

Caro’s acid is the product of the reaction between concentrated hydrogen peroxide
and sulphuric acid and the treatment of cyanide with Caro’s acid is rapid, and it is
complete within only a few minutes (Norcross, 1996).

2.3.6.5 Hydrogen Peroxide

Cyanide treatment by hydrogen pyroxide was investigated in the 1980s. The
first full application of a hydrogen peroxide treatment in the mining industry was
operated by Degussa at the Ok Tedi Mine in Papua New Guinea (Knorre & Griffiths,
1984).
The mechanism and the chemistry of the hydrogen peroxide cyanide
destruction process can be explained by Equations 2.13 and 2.14 for the oxidation of
free and weakly complexed metal cyanides (i.e., M = cadmium, copper, nickel and
zinc):
CN − + H 2O2 → OCN − + H 2O (2.13)

M (CN ) 24− + 4 H 2 O2 + 2OH − → 4OCN − + 4 H 2 O + M (OH ) 2 ( solid ) (2.14)

Using copper as a catalyst in reactions 2.13 and 2.14 can increase the reaction
rate. The copper may be present naturally in the solution as a result of gold-silver
cyanidation or can be added as a reagent copper solution (Mudder et al., 2001).
There are many other methods used to treat and recover cyanide from the cyanide
tailings, such as natural attenuation, precipitation of cyanide, ion exchange, and
ozone oxidation.
The detrimental effects of cyanide can be alleviated by destroying excess
cyanide in tailings. An alternative is to eliminate cyanide from gold processing by
using another lixiviant. The alternative must be as efficient as cyanide at complexing
gold and silver and have less adverse environmental impacts. In the following
sections alternative lixiviants to cyanide are reviewed.

2.3.7 Alternatives to Cyanide

Many attempts have been made to find an efficient alternative to the cyanide
that can extract gold and silver with high recovery levels and less environmental
impacts. Some of the most promising alternatives including, thiourea, thiocyanate,
halides, thiosulfate, and ammonia (Gos & Rubo, 2000), will be discussed in this
section.

36
Chapter 2: Environmental impacts of gold mining: Literature review

2.3.7.1 Thiourea
The thiourea process has been chosen as one of the alternatives to cyanide to
be reviewed because thiourea is less detrimental to the environment, is less toxic to
humans and the dissolution of gold in thiourea solutions is much faster than in
cyanide solutions.
The use of thiourea (NH2CSNH2) as a gold extraction agent has shown
considerable promise. Thiourea leaching usually is applied in acidic conditions. It
dissolves gold to form a cationic complex; the reaction is rapid and gold extraction of
up to 99% can be achieved (Yannopoulos, 1991). The anodic reaction of this system
is described in Equation 2.15.
Au + 2 SC ( NH 2 ) 2 ⇔ Au[ SC ( NH 2 ) 2 ] 2+ + e − (2.15)
Groenewald (1976) used solutions containing 1.2 M thiourea to extract gold
from its ore within an hour; under these conditions the consumption of thiourea was
about 1.4 kg thiourea per ton of ore treated. The thiourea consumption could be
reduced to 0.4 kg/ton if 0.1 M thiourea was used; complete extraction of the gold
then occurred within eight hours.
Li and Miller (2007) studied the reaction kinetics for gold dissolution in acid
thiourea solutions using ferric sulfate as an oxidant. They concluded that the
thiourea-ferric sulfate system has rapid kinetics for gold dissolution. No passivation
of the gold surface or retardation of the leaching rate was observed during this study.
The use of thiourea to extract gold and silver from ore in an acidic medium was
studied by Chen et al. (1980). In this study, the leaching solution contained 1.0%
thiourea, 0.5% sulfuric acid, and 0.1% ferric ions, and the rate of gold and silver
dissolution was over 10 times faster than in a solution containing 0.5% sodium
cyanide and 0.05% calcium oxide.
After the optimisation of experimental conditions (Ubaldini et al., 1998)
obtained about 80% gold recovery using thiourea with low reagent consumption (5
g/kg of thiourea, 5 g/kg of sulfuric acid and 0.5 g/kg of ferric sulfate). Presad (1991)
reports the optimum parameters for thiourea leaching are: pH: 1.4 adjusted
accordingly with H2SO4; redox potential: max 250 mV, min 150 mV; thiourea
concentration: 1%; thiourea consumption: 2 kg/t; and leach time: 10–15 hours. Other
recent work conducted to evaluate and optimise thiourea gold leaching include
studies by Li and Miller (2007), Zheng et al. (2006) and Tanriverdi et al. (2005).

37
Chapter 2: Environmental impacts of gold mining: Literature review

Acidic thiourea as a leaching reagent for gold has a number of problems such
as high consumption of thiourea compared with cyanide, serious corrosion of
equipment in acidic solutions compared with steel passivation in alkaline cyanide
solutions, no selectivity for gold over gangue minerals compared with excellent
selectivity for cyanide, and complicated regeneration and purify procedures of the
thiourea lixiviant (Zheng et al., 2006). Due to these problems, thiourea has not been
applied on an industrial scale to date.

2.3.7.2 Thiocyanate
Thiocyanate (SCN-) is produced as a product of the reaction between cyanide
and sulfur species during cyanide leaching. In 1905, a study demonstrated that
thiocyanate dissolved gold effectively in the presence of a suitable oxidising agent
(White, 1905). The leaching of gold with thiocyanate, if performed between pH 1
and 2, enables the use of iron (III) as an oxidising agent. The chemistry and
thermodynamics of thiocyanate were described by (Barbosa-Filho & Monhemius,
1994). The authors concluded that thiocyanate is an effective lixiviant for gold in
acidic conditions, yielding dissolution rates that are comparable to those obtained
with thiourea whilst offering the advantage of much greater stability against
oxidative decomposition. Also Kholmogorov et al. (2002) found that more than 95%
of gold was dissolved in weak acidic solutions (pH=2–5) at a KSCN concentration of
0.4 mol/L.
Thiocyanate solutions have a lower toxicity than sodium and potassium
cyanide and better stability in various media. Moreover, it can be regenerated and
obtained as a by-product in technological processes.
Kholmogorov et al. (2002) compared the rate of gold leaching for the
different complex-forming reactants: thiocarbamide in H2SO4, Na2S2O3, KSCN, and
NaCN. It was found that the leaching rate in KSCN is slightly lower than that in
thiocarbamide solutions and is much greater than that in NaCN or Na2S2O3 solutions.
Broadhurst and du Perez (1993) studied the chemistry and thermodynamics
of the dissolution of gold in an acidic aqueous thiocyanate medium using iron (III)
sulfate as an oxidant. They found that thiocyanate is an effective reagent for
dissolving gold at fast rates. Gold thiocyanate can be adsorbed from solution onto ion
exchange resins. The recovery of gold from ion exchange resins can be achieved by
thiocarbamide solutions in H2SO4 at room temperature.

38
Chapter 2: Environmental impacts of gold mining: Literature review

2.3.7.3 Halides
The halides, C1, Br, and I have been used for many years to extract gold, in
fact the use of halide systems for gold dissolution predates cyanidation (La Brooy et
al., 1994).

• Chloride
Gold is leached rapidly by chlorine at low pH (Equation 2.17): The optimum
conditions for the chlorination process are low pH, high chloride and chlorine levels,
elevated temperatures, and high ore surface areas. Chlorine can be generated in
slurries and solutions via electrolysis of NaCl solution or by the addition of MnO2 to
hydrochloric acid as shown in Equation 2.16 (Yannopoulos, 1991).
MnO2 + 4 HCl → MnCl2 + 2 H 2O + Cl 2 (2.16)

2 Au + 3Cl2 + 2Cl − ⇔ 2 AuCl4− (2.17)

Although gold dissolution with chlorine is substantially faster than with
cyanide, low concentrations of sulfides or other reactive components in the ore can
make reagent consumption excessive and can reduce AuCl 4− back to metallic gold
(Hilson & Monhemius, 2006). Baghalha (2007) noted that calcium hypochlorite
produced sluggish gold leaching kinetics, requiring twice the time (46 h) to achieve
the maximum gold recovery of 58% compared to sodium hypochlorite. The amount
of HCl added and hence the initial pH has a major impact on gold leaching kinetics
and the maximum gold recovery. Very slow gold leaching kinetics are obtained
without the addition of acid.

• Iodide
Gold can dissolve in an iodine solution at moderate oxidizing potentials, but
insoluble gold iodine will be formed, which will hinder further reaction between gold
and the iodine solution.
Angelidis et al. (1993) concluded that the gold dissolution rate in the iodide
system depends upon the concentration of iodine and iodide as well as the ionic
strength. A fresh gold surface can be leached at a greater rate by iodine-iodide
solution than is possible by thiourea and by conventional cyanidation techniques.

39
Chapter 2: Environmental impacts of gold mining: Literature review

• Disadvantages of Halides
Because the reaction conditions for gold leaching with halogens require a
high redox potential, (Equations 2.18, 2.19, 2.20) and further extraction processes are
necessary to complete gold extraction, this method is not at present an alternative to
cyanidation (Anhong, 1997).
AuCl 2 + e − → Au + 2Cl − E = 1.15 V (2.18)
−
AuBr2 + e − → Au + 2 Br − E = 0.96 V (2.19)
−
AuI 2 + e − → Au + 2 I − E = 0.58 V (2.20)
The high oxidation potentials required in the halide systems for the leaching
of gold require bromine (Br2) or iodine (I2) as an oxidant, but these are toxic with a
time weighted exposure average limit of 0.1 mg/L (Lewis, 1997).

2.3.7.4 Thiosulfate
Thiosulfate (S2O3)2- is a less toxic alternative to cyanide. Up to 12 g of
thiosulfate can be taken daily by mouth with no ill effects (Lewis, 1997), hence
thiosulfate is usually classified as GRAS (generally recognized as safe). Thiosulfate
has a low toxicity with an LD50 (dose needed to kill 50% of a population) of 7.5
±0.752 g/kg (Grayson, 1983) for mice. It is commonly used as a fertilizer and an
indirect and direct human food ingredient (Langhans et al., 1992) .

In the thiosulfate leaching system for gold, thiosulfate is used as the principle
reagent but, both ammonia and cupric ions are required. Ammonia is required to
stabilize copper(II) as copper(II) tetraamine and also to adjust pH. Thiosulfate
leaching has emerged as one of the more attractive alternatives to cyanide (Molleman
& Dreisinger, 2002; Navarro et al., 2002; Aylmore & Muir, 2001a); because
thiosulfate is considered a non-toxic reagent and can leach gold faster than cyanide.
On the other hand, the main disadvantage of the thiosulfate leaching system is high
reagent consumption and the lack of a suitable gold recovery method. The oxidation
of gold to the aurous Au+ ion in ammoniacal thiosulfate in the presence of Cu(II) can
be represented by Equation 2.21 (Muir & Aylmore, 2004).

2− 2+ 3− 5−
Au + 5S 2O3 + Cu ( NH 3 ) 4 ⇔ Au ( S 2O3 ) 2 + 4 NH 3 + Cu ( S 2O3 ) 3 (2.21)

The thiosulfate leaching system will be reviewed in detail in Chapter 3.

40
Chapter 2: Environmental impacts of gold mining: Literature review

2.3.7.5 Ammonia
Ammonia is more commonly known as an additional reagent used to reduce
cyanide consumption in the cyanidation of copper containing gold ores. The
advantages of using ammonia as a leaching reagent are its availability, price and the
simplicity of recycling ammonia. The gold oxidation reaction with ammonia is
shown in Equation 2.22.
Au + 2 NH 3 → Au ( NH 3 ) 2+ + e − (2.22)
Ammonia has a threshold limit value (TLV) of 14 mg/m3 and in this context
is very similarly to HCN (Gos & Rubo, 2000). In addition, ammonia is classified as a
water contaminant. Hence, ammonia and other reagents containing ammonia can not
be considered as having a more favourable profile than cyanide with regard to
toxicity and exposure aspects. Despite the possibility of gold dissolution at ambient
temperature according to the reaction in Equation 2.22, the gold dissolution and
leaching kinetics may be slow and small (McNulty, 2001).

2.3.7.6 The Toxicity of Different Alternative Leaching Reagents

Table 2.8 summarises toxicity data for some selected alternatives to cyanide.
The TLV of an air contaminant is that concentration to which it is believed that most
workers can be exposed daily without adverse effects (effectively, the threshold
between safe and dangerous concentrations). Bromine is the most toxic alternative to
cyanide; its threshold limit value (TLV) is 0.6 mg/m3. Thiosulfate is the most
promising alternative to cyanide according to handling, toxicity, and water
contamination shown in Table 2.8.

2.4 Summary
Studying the environmental and kinetic problems resulting form using
cyanide and most of its alternative lixiviants has shown that, of the alternative
reagents, thiosulfate seems to be the most promising alternative to cyanide.
Thiosulfate is less-toxic, cheaper than cyanide and it has the potential to be utilised
for a number of applications in which cyanidation is not efficient such as the
treatment of carbonaceous (preg-robbing) ores or when it is not possible to use
cyanide due to political or environmental factors. Because of that, thiosulfate was
selected to be used for gold leaching in this study.

41
 Chapter 2: Environmental impacts of gold mining: Literature review

Table 2.8: Toxicity data for selected lixiviants (Gos & Rubo, 2000).

Toxicity/Handling Exotoxicity/transport spillages

Water
Reagent Emission contam- LC50/EC50
LD50/LC50 TLV
inant Lethal concent.
(WGK)

Thiourea NH3, H2S LD50 1750 none LC50>100mg/L

2
mg/kg
Thiosulfate H2S LD50 4000 LC50>10000mg/L
0
(sodium) mg/kg
Thiosulfate NH3, H2S LD50 2890 Consider
(ammonium mg/kg 1 ammonia/ammonium
)
Thiocyanate 764 mg/kg EC50> 100mg/L
1
(sodium)
Thiocyanate LD50 15 g Consider
(ammnoium ammonia/ammonium
1
) 280- 300 ppm/1h
killed sunfish.
Ammonia LD50 350 14 LC50 0.53 mg/L
2
mg/kg mg/m3
Chlorine LD50 293 1.45 LC50 0.05 mg/L
ppm/1h mg/m3 2

Bromine LD50 14 0.6 LC50 10 mg/L/10h

3
mg/kg mg/m3
Iodine LD50 14000 1.1 LC50 0.083 mg/L
1
mg/kg mg/m3
Cyanide LD50 6.4 5 mg/m3 LC50 0.16 mg/L/96h
3
(sodium) mg/kg
Cyanide LD50 3.7 5 mg/m3 LC50 2.29 mg/L/96h
3
(hydrogen mg/kg

Where:
LD50 = Lethal Dosage
LC50 = Lethal concentration
EC50 = Exotoxicity concentration
WGK is an indicator letters of water contaminant
WGK = 0 is not water contaminant
WGK = 1 is slight water contaminant
WGK = 2 is water contaminant
WGK = 3 is strong water contaminant

42
Chapter 3 Thiosulfate Leaching of Gold: Literature Review

3.1 Introduction
In this chapter, a review of the published literature relating to gold and silver
leaching in thiosulfate solutions is presented. Also for comparison, in brief, a review
of the cyanidation process is presented.
The first use of thiosulfate leaching of gold and silver was in the late
nineteenth century in the Von Patera process. Recently, the thiosulfate leaching
system was proposed for use on refractory ores and concentrates, such as ores that
contain large amounts of: cyanide-consuming copper, carbonaceous preg-robbing
materials, refractory sulfides, and the products of partial oxidative pre-treatment of
refractory sulfides that contain cyanide-consuming sulfur species (Marsden and
House, 2006).
Most of the published work related to thiosulfate leaching has used copper(II)
as an oxidant and ammonia as an oxidant ligand. However, other studies suggest
using nickel(III) (Arima et al., 2004) or iron(III) as an oxidant and oxalate or EDTA
as a ligand (Chandra & Jeffrey, 2005). Despite thiosulfate leaching showing promise
with high gold leaching rates, the application of the thiosulfate system on an
industrial scale may still be a long way off, due to high reagent consumption and the
difficulties of gold and silver recovery from the leach solution. However, recently,
extensive worldwide research has been conducted to optimise and model the
thiosulfate leaching system to advance it to an industry process.

3.2 History of Gold Production

Gold was first extracted from streambed gravels, where the gold occurred as
free native metallic gold. Gold recovery methods have ranged from the historic
gravity panning, sieving, and sheepskin collection techniques to amalgamation,
chlorination, and the presently practiced cyanidation methods. Despite the advances
in gravity concentration and amalgamation, they are unsuitable for the recovery of
fine gold and gold associated with sulfide minerals, hence cyanidation has developed
as the predominate gold recovery process.
Native metallic gold was found and used by prehistoric man as a tool. The
recovery of native gold by gravity concentration dates back at least 6000 years

43
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

(Puddephatt, 1978). The art of working gold and silver into jewellery/coins seems to
have arisen in Sumer, Egypt, and Crete at roughly the same time, probably around
3000 B.C. (Butterman & Amey, 2005).
Chlorination was first used commercially to treat Deetken ore in California in
1858 (Schnabel, 1921). By the mid 1860s various chlorination processes were used
in the United States, South Africa, and Australia.
In the first half of the 19th century, Russia was the main source of gold,
supplying 60% of the world’s production. The main mining activity was gravity
concentration by panning, although steam and water power driven trammels and
strakes were also used (Marsden & House, 2006). The environmental implications of
hand picking and mechanical hand sieving were low as there were no chemical
lixiviants and production was on a small scale (Müezzinolu, 2003).
The dissolution of gold in aerated cyanide solutions and the role of oxygen in
the mechanism were investigated by Elsner in 1846 (Elsner, 1846). The cyanidation
process, as it is now known, was patented between 1887 and 1888 by MacArthur and
the Forrest brothers and the first commercial application of the cyanide process was
in New Zealand in 1889 (McNulty, 1989).
Due to the environmental considerations of using cyanide, research is being
undertaken to fine suitable alternatives. The most promising reagent from both a
metallurgical and environmental standpoint is thiosulfate. The first proposed use of
thiosulfate to recover precious metals was in the early 1900s (White, 1905). In a
process known as the Von Patera process, gold and silver ores were first subjected to
a chloridising roast and then leached with thiosulfate. Thiosulfate was first used in
the silver mining industry for the recovery of silver from very high grade ores
(Gowland, 1930).

3.3 An overview of Thiosulfate

Sodium and ammonium thiosulfate are the two main commercial sources of
thiosulfate and the most common thiosulfate salt forms used in research on
thiosulfate leaching of gold and silver. The common thiosulfate salts (Na+, K+, Ca2+
and NH4+) are biodegradable and are regarded as non-hazardous by Worksafe
Australia (NOHSC, 1999). These thiosulfate salts are ‘Generally Recognised As

44
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Safe’ (GRAS) in the US, and are not considered to be dangerous substances by
European standards (Grosse et al., 2003; EEC/FDA, 2001).

3.3.1 Chemistry of Thiosulfate

Thiosulfate salts have been used in industry for more than two and a half
centuries (Schmidt, 1962). The chemical symbol for the thiosulfate anion is S2O32-.
The thiosulfate anion, shown in Figure 3.1, is tetrahedral in shape and is notionally
derived by replacing one of the oxygen atoms by a sulfur atom in a sulfate anion. The
sulfur to sulfur (S-S) distance indicates a single bond, implying that the sulfur bears a
significant negative charge and the S-O interactions have more double bond
character.

Figure 3.1: The chemical structure of the thiosulfate ion.

The thiosulfate anion is metastable and is a natural sulfur donor,

disproportionating to form sulfite and sulfur or an active sulfur species. Although
this tendency is medically useful, it can contribute to the corrosion of metals and
other materials. Thiosulfate is also subject to attack by microorganisms.

3.3.1.1 Production of Thiosulfate

Thiosulfate can be produced from elemental sulfur and sulfite at an elevated
temperature as shown by Equation 3.1.
2− 2−
SO3 + S → S 2O3 (3.1)

Under alkaline conditions, thiosulfate can be produced as a product of the

reaction between sulfur or sulfide and hydroxide as described by Equations 3.2 and
3.3 (Shieh et al., 1965).

S 8 + 8 NaOH → 2 Na 2 S 2 O3 + 4 NaHS + 2 H 2 O (3.2)

2( NH 4 ) 2 S 5 + 6 NH 4OH + 6O2 → 5( NH 4 ) 2 S 2O3 + 3H 2O (3.3)

45
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Thiosulfate is sometimes regenerated from tri, tetra, or penta thionates in an

alkaline aqueous ammonia solution as shown in Equations 3.4 to 3.8 (Zhang &
Dreisinger, 2002; Aylmore & Muir, 2001a; Naito et al., 1970).

2− 2− 2−
4 S 4O6 + 6OH − → 2 S 3O6 + 5S 2O3 + 3H 2 O (3.4)
2− 2− 2−
2 S 4O6 → S 3O6 + S 5O6 (3.5)
2− 2−
2 S 5O6 + 6OH − → 5S 2O3 + 3H 2 O (3.6)
2− 2− 2−
S 3O6 + 2OH − → SO4 + S 2O3 + H 2O (3.7)
2− − 2−
S 3O6 + NH 3 + OH − → SO3 NH 2 + S 2O3 + H 2O (3.8)

Sodium sulfide, or sodium hydrosulfide, is oxidised to form sodium

polysulfide and sodium hydroxide, which may be further oxidized to sodium
thiosulfate and sodium hydroxide. The oxidant is air, oxygen or oxygen in
combination with other gases; the reductant is aqueous sodium sulfide or sodium
hydrosulfide; and the reaction is carried out with both reactants in non-flooded
contact with a solid catalyst material, of which a typical example is a particulate
carbon treated with polytetrafluoroethylene (PTFE) (Smith & Sanders, 1979).

3.3.1.2 Uses of Thiosulfate

The use distribution (Bean, 1996) of ammonium thiosulfate is shown in
Figure 3.2. The greatest proportion of ammonium thiosulfate use is in the agriculture
industry as a fertilizer, where the sulfur and ammonium content are both important
plant nutrients. Photochemical grade ammonium thiosulfate is primarily used in the
development of photographic film by the dissolution of silver halides from the
negatives and prints.
Other uses of sodium thiosulfate include:
• an alternative solvent to cyanide for extraction of gold;
• in pH testing of bleach substances;
• the tanning of leather;
• removal of excess chlorine in paper and textile bleaching;
• preparation of matches;
• flue gas desulfurisation; and
• as a chemical reagent.

46
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Others
2%

Photography
48%
Agricultural
50%

Figure 3.2: The use distribution of ammonium thiosulfate (Bean, 1996).

3.3.1.3 The Stability of Thiosulfate

One of the major problems that hinders the application of thiosulfate in the
gold production industry is the high consumption of thiosulfate during the leaching
of gold ores, consequently increasing operating costs. Unlike cyanide, thiosulfate is
metastable and tends to undergo chemical decomposition. In short, with regard to
gold leaching, many factors influence the stability of thiosulfate solutions (Dhawale,
1993):
• the purity of the water used as the solvent;
• the concentration and pH of the solution;
• the presence of certain metals or alloys;
• the presence of certain metals and sulfur bacteria; and
• the exposure to ultraviolet light
It has been reported that thiosulfate decomposition increases in thiosulfate
solutions with increasing copper concentration. Also, it was found that oxygen has a
major negative effect on the stability of thiosulfate and oxygen use should be
controlled in thiosulfate solutions (Jeffrey et al., 2003). From the data shown in
Table 3.1, the consumption of thiosulfate in the process of gold leaching is very high
and depends on the type of ore minerals associated with the gold.

47
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Table 3.1: Thiosulfate consumption during gold leaching as a function of ore type.

Author Thiosulfate Ore type

consumption
Yen et al. (1996) 30 kg/t Copper bearing gold ore
Wan and Brierley (1997) 8.9 kg/t Carbonaceous gold ore
Zipperian et al. (1988) 50% consumed Rhyolite ore
Langhans et al. (1992) 0.4 kg/t Low grade gold ore
Aylmore (2001) 36-70 kg/t Gold – copper sulfide
Arima (2003) 23 kg/t Gold silicate ore ( 16g/t)
Xia et al. (2003) 30 kg/t Copper bearing gold ore

• Effect of pH
Thiosulfate is gradually decomposed to tetrathionate in the pH range from
neutral to alkaline. In acidic conditions, thiosulfate forms dihydrogen thiosulfate
which gradually decomposes to hydrogen sulfide and sulfite as shown in Equation
3.9 (Aylmore & Muir, 2001b).
H 2 S 2O3 → H 2 S + SO3 (3.9)
The chemical speciation of thisosulfate decomposition products were
determined by Jeffrey and Brunt (2007). They showed that tetrathionate and
pentathionate are the main reaction products from thiosulfate oxidation at pH 8.5 and
9, while trithionate and sulfate are generated at pH 10.4. The study concluded that
thiosulfate decomposition is greater at pH 9.0 than pH 10.4.

• Effect of Copper
The presence of the cupric ion in a thiosulfate solution increases the
thiosulfate oxidation rate according to Equation 3.10 (Byerley et al., 1975; Byerley et
al., 1973b; Naito et al., 1970).
2− 2−
2Cu 2+ + 2 S 2O3 → 2Cu + + S 4O6 (3.10)
During gold leaching the presence of copper greatly lowers the stability of
ammonium thiosulfate in solution due to copper-catalyzed thiosulfate oxidation and
the formation of copper sulfides or hydroxides, depending on the leaching conditions
(Zhang & Dreisinger, 2002). A decrease in the copper concentration in gold leach

48
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

solutions by a factor of 5 only decreased the rate of thiosulfate oxidation by a factor

of 2 (Breuer & Jeffrey, 2003b).

• Effect of Oxygen
Another more significant factor that affects thiosulfate stability and
consumption is the amount of oxygen or air in thiosulfate solutions. Breuer and
Jeffrey (2003b) measured thiosulfate concentration as a function of time for a 0.1 M
thiosulfate gold leach solution sparged with air or maintained under argon. The
results showed that the rate of thiosulfate consumption is very high in the presence of
oxygen or air, with all of the thiosulfate being oxidised in one hour. In comparison,
less than 5% of the thiosulfate was oxidised under argon for the same time period.
Another study carried out by Molleman and Dreisinger (2002) concluded that
using air or oxygen in a thiosulfate leach solution has a significant positive effect on
gold extraction but it decreases thiosulfate stability. Chu et al. (2003) indicate that, in
order to reduce the rate of thiosulfate oxidation, low partial pressure and flowrate of
oxygen is required. At these conditions, the rate of polythionate formation will also
be low; hence, the gold oxidation rate is considerably higher.

• Effect of Impurities
The effect of pyrite on the decomposition rate of thiosulfate (S2O32−) and the
formation rates of its decomposition products, sulfite (SO32−), sulfate (SO42−), and
tetrathionate (S4O62−), were investigated in aqueous solutions of pH 2.9–8.6 at 20°C
by Xu and Schoonen (1995). They concluded that the pyrite surface catalyzed
oxidation of S2O32− to S4O62− by dissolved oxygen is the dominant S 2O32−
decomposition mechanism. Feng and Deventer (2007a) studied the effect of hematite
on thiosulfate decomposition and unlike pyrite found that hematite catalysed the
oxidative decomposition of thiosulfate to polythionates in the presence of oxygen.
Senanayake (2004) summarised some of the published data (Muir &
Aylmore, 2004; West-Sells et al., 2003; Nicol & O'Malley, 2002; Abbruzzese et al.,
1995; Zipperian et al., 1988) of the effect of thiosulfate decomposition on the
leaching of gold with thiosulfate as:
(i) high reagent cost;
(ii) decrease in rate of gold dissolution caused by the decrease in concentration of
copper(II) and thiosulfate;

49
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

(iii) formation of insoluble products especially in thiosulfate and/or ammonia

deficient solutions; and
(iv) interference of polythionates with gold separation and recovery stages
subsequent to the leaching stage.

3.4 Cyanide Leaching of Gold (Cyanidation)

Cyanide has been used in the gold mining industry since its value as a leach
reagent for gold ores was recognised by John Stewart MacArthur in the 1880s. About
1.4 Mt of hydrogen cyanide is produced each year worldwide, 13% of which is
converted into sodium cyanide and used in gold and silver extraction from their ores
(Mudder et al., 2001). The major factors affecting the dissolution rate of gold in
cyanide solutions are the cyanide and oxygen concentrations, temperature, pH,
surface area of gold exposed, agitation speed, gold impurity, and the presence of
other ions in the solution.
During the application of cyanide to treat precious metals, waste has to be
disposed of or treated properly to achieve the environmental requirements. In spite of
procedures to decrease the hazardous effects of using cyanide, sometimes the
concentration of cyanide in waste processes reaches up 2000 mg/L total cyanide
(Barriga-Ordonez et al., 2006).
In this section, gold leaching in cyanide solution is briefly reviewed, as it is
the standard that any other leaching agent must be compared against.

3.4.1 Chemistry of Cyanide

Simple cyanide salts, such as sodium, potassium, and calcium cyanide,
dissolve and ionise in water to form their representive metal cation and free cyanide
ions, as shown by Equations 3.11a, 3.11b, and 3.11c.

NaCN ⇔ Na + + CN − (3.11a)
KCN ⇔ K + + CN − (3.11b)

Ca (CN ) 2 ⇔ Ca 2+ + 2CN − (3.11c)

Both hydrogen cyanide and free cyanide can be oxidized to cyanate in the
presence of oxygen under suitably oxidizing conditions. The oxidation of hydrogen
cyanide and free cyanide is represented by Equations 3.12 and 3.13:

50
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

2 HCN + O2 ⇔ 2 HOCN (3.12)

2CN − + O2 ⇔ 2OCN − (3.13)

3.4.2 Gold Dissolution in the Cyanide System

The dissolution of gold in cyanide solutions includes an anodic reaction (gold
oxidation) and a cathodic reaction (oxygen reduction). Both reactions are discussed
in this section.

3.4.2.1 The Anodic Reaction

In aqueous, alkaline cyanide solutions, gold is oxidised and dissolved to form
the Au(I) cyanide complex, Au (CN ) −2 . For dissolution the oxidation of gold will be
the anodic reaction in this system, the opposite of the standard reduction reaction
shown in Equation 3.14 (Marsden & House, 2006):
Au (CN ) −2 + e − ⇔ Au + 2CN − (3.14)
The gold anodic reaction can be affected negatively or positively by the
presence of impurities in the leaching solution. Heavy metals such as lead and
mercury can have a positive effect on gold oxidation by reducing passivation of the
gold surface (Jeffrey & Ritchie, 2000b; Hughes et al., 1984; Nicol, 1980). On the
other hand, the presence of sulfur forms a passive layer on the gold surface which
reduces gold oxidation and leaching rate (Wang & Forssberg, 1990).

3.4.2.2 The Cathodic Reaction

The mechanism of the cyanidation process includes several parallel and series
cathodic reactions. The cathodic dissolution reaction in cyanide solutions containing
oxygen is represented by Equations 3.15 to 3.17 (Habashi, 1966).
O 2 + 2 H + + 2e − ⇔ H 2 O 2 (3.15)
The hydrogen peroxide formed is a strong oxidizing agent, which may take
part in further oxidation reactions:
−
H 2 O2 + 2e − ⇔ 2OH (3.16)
Finally oxygen may be directly reduced to hydroxide ions, as described in
Equation 3.17.

O2 + 2 H 2 O + 4e − ⇔ 4OH − (3.17)

51
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

3.4.2.3 Overall Dissolution Reaction of Gold

The overall dissolution reaction of gold in alkaline cyanide solutions in the
presence of oxygen or air, considering both the anodic and the cathodic half-reaction,
is most accurately described by Equation 3.18.
4 Au + 8CN − + O2 + 2 H 2O ⇔ 4 Au (CN ) −2 + 4OH − (3.18)
The component reactions of gold dissolution in the cyanide system are
illustrated schematically in Figure 3.3.

Solid Solution
Anodic area CN-
2 Au + 4CN − → 2 Au (CN ) 2− + 2e − Au(CN)2-

Bulk solution
Flow of electrons

e-
O2

H2O2
Cathodic area
2OH-
O2 + 2 H 2 O + 2e − → H 2 O2 + 2OH − δn

Figure 3.3: Schematic representation of the local corrosion cell at a gold surface in
contact with an oxygen containing cyanide solution (Marsden & House,
2006).

3.5 Thiosulfate Leaching of Gold

Cyanide, a very toxic chemical is presently used in the gold leaching process.
Thiosulfate is one of the most promising alternatives and substitutes to cyanide,
kinetically and environmentally. In comparison with conventional cyanide
processing, the thiosulfate process shows promise of greater efficiency, less expense,
and lower environmental impacts compared with cyanide.
Langhans et al. (1992) indicated that thiosulfate leaching may be competitive
with conventional cyanidation for application to heap, dump, or in situ leaching
where longer leach times are normally utilized. Newmont mining was the first
mining company to undertake a pilot scale thiosulfate heap leaching as a means of
recovering gold from carbonaceous pre-robbing ores (Wan, 1997).

52
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Navarro et al. (2002) observed that by using ammonium thiosulfate leaching,

the initial rate of extraction is enhanced, allowing about 90% gold dissolution from a
concentrate after 10 hours. The same percentage dissolution was reached by
cyanidation, but after about 46 hours.
Thiosulfate leaching has significant potential as an effective leaching agent
and metal can be recovered from the thiosulfate solution using a variety of
procedures (i.e. adsorption onto ion exchange resins), (Navarro et al., 2007). The
following sections (3.5.1 and 3.5.2) review the literature on the mechanism and
variables that influence thiosulfate leaching of gold and silver.

3.5.1 Reaction Mechanism

Gold forms a stable complex with thiosulfate (S2O3)2- in an aqueous solution,
as shown in the half Equation, 3.19:
2− 3−
Au + 2 S 2 O3 ⇔ Au ( S 2 O3 ) 2 + e− E0= + 0.153 (V) (3.19)

In alkaline thiosulfate solutions, in the presence of oxygen as an oxidant, the

complete redox reaction is shown in Equation 3.20:
2−
4 Au + 8S 2 O3 + O2 + 2 H 2 O ⇔ 4 Au ( S 2 O3 ) 32− + 4OH − (3.20)

The thiosulfate leaching of gold in the presence of oxygen according to

Equation 3.20 is very slow in the absence of a suitable catalyst. Copper(II) is a very
efficient catalyst for this reaction, which is used with ammonia that stabilises the
copper(II) in solution as the Cu(II) tetraamine complex (Cu ( NH 3 ) 24+ ) as shown in
Equation 3.21 (Breuer & Jeffrey, 2003a).
Cu 2+ + 4 NH 3 ⇔ Cu ( NH 3 ) 24+ (3.21)
Gold forms stable complexes (β= 3x1019) in ammonia solutions (Skibsted &
Bjerrum, 1997). Therefore, in an ammoniacal thiosulfate solution, both thiosulfate
and ammonia (Equation 3.22) have the ability to form complexes with gold.
Au ( S 2O3 ) 32− + 2 NH 3 ⇔ Au ( NH 3 ) 2+ + 2S 2O32− (3.22)

53
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

The Eh-pH diagram that best represents the equilibrium species in the Au,
NH3, S2O32-, H2O system is shown in Figure 3.4 (Senanayake et al., 2003).

Figure 3.4: Eh - pH diagram for the Au - NH3 - S2O32- - H2O system at 25 ºC: 10-5 M
Au(I) , 0.1 M Na2S2O3, 1 M (NH3 + NH4+).

The chemistry of the ammoniacal copper-thiosulfate system is complex due

to the side reactions that may occur in the system, such as the reduction of copper(II)
to copper(I) and the decomposition of thiosulfate to the different species of
polythionates due to reaction between copper(II) and thiosulfate. The exact
mechanism of gold dissolution and the catalytic action of Cu(II) is still not
completely understood (Breuer & Jeffrey, 2003b; Lam & Dreisinger, 2003;
Senanayake et al., 2003; Chen et al., 1993). As the Cu ( S 2 O3 ) 53− complex is more

stable than Cu (NH 3 ) +2 under the conditions applied for effective gold dissolution the
major reduction reaction is given by Equation 3.23:
Cu ( NH 3 ) 24+ + 5S 2 O32− ⇔ Cu ( S 2 O3 ) 53− + 4 NH 3 + S 4 O62− + e − (3.23)
The reduction of Cu(II) tetramine is accompanied by oxidation of thiosulfate
to tetrathionate. The oxidant species, Cu(II), is then regenerated by oxidation of
Cu ( S 2 O3 ) 53− by oxygen:

4Cu ( S 2O3 ) 53− + 16 NH 3 + O2 + 2 H 2O ⇔ 4Cu ( NH 3 ) 24+ + 8S 2O32− + 4OH − (3.24)

54
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

From Equations 3.23 and 3.24, the overall dissolution reaction for gold in
ammoniacal copper-thiosulfate solutions has been proposed (Hiskey & Atluri, 1988)
as:
Au + 5S 2O32− + Cu ( NH 3 ) 24+ ⇔ Au ( S 2O3 ) 32− + 4 NH 3 + Cu ( S 2O3 ) 53− (3.25)
The presence of ammonia is critical to stabilize Cu(II) in the solution as the
Cu(II) tetraamine ion, to prevent the formation of Cu(OH)2 and to prevent
passivation of the gold surface by preferential adsorption (i.e., avoiding coating with
sulfur species).The mechanism of gold dissolution in the ammoniacal copper-
thiosulfate system is illustrated schematically in Figure 3.5.

Figure 3.5: Schematic dissolution mechanisms in ammonium thiosulfate solution on

gold surface (Aylmore & Muir, 2001a).

3.5.2 The Effect of Reagent Concentration and Reaction Conditions

Many published studies (Aylmore & Muir, 2001a; Abbruzzese et al., 1995;
Anhong, 1997; Breuer, 2002; Briones & Lapidus, 1998; Jeffrey, 2001; Jeffrey et al.,
2001) have reported the effects of the reagent concentration and reaction conditions
on the gold dissolution rate and the oxidation of thiosulfate. The most studied
variables are thiosulfate, copper(II), ammonia and oxygen concentration and,
agitation speed, temperature pH of solution, and the effect of impurities. Most of the

55
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

published results from these studies showed that gold and silver dissolution rate is
dependent on the thiosulfate and Cu(II) concentration, up to a certain concentration
(Jeffrey, 2001).

3.5.2.1 Effect of Thiosulfate

It has been reported that increasing thiosulfate concentration increases the
gold leaching rate (Arima, 2003; Navarro et al., 2002; Jeffrey, 2001; Briones &
Lapidus, 1998; Muyunda, 1996; Abbruzzese et al., 1995; Langhans et al., 1992).
Thiosulfate concentration is an important variable, particularly given the
small driving force for the leaching reaction shown in Equation 3.25 (Jeffrey, 2001).
Thiosulfate concentrations ranging from 0.05 to 2.0 M have been investigated to
determine their affect on gold and silver leaching. Both sodium and ammonium
thiosulfate have been used as the primary reagent for the thiosulfate leaching system.
A number of studies have examined the effects of thiosulfate concentration on gold
dissolution; one of these studies was carried out by Chai (1997). The results showed
that the amount of gold extracted was only 10% in the absence of thiosulfate but in
the presence of ammonia and copper sulfate. The amount of gold extracted increased
with increasing initial thiosulfate concentration up to 0.287 M, but decreased at
higher initial thiosulfate concentrations.
The rate of gold leaching is reduced at lower thiosulfate concentrations due to
both the oxidation of thiosulfate, and the reduction of copper(II) amine to copper(I)
thiosulfate (Breuer & Jeffrey, 2000). In oxygenated thiosulfate solutions, the
thiosulfate concentration needs to be optimised to increase the dissolution of gold
and to decrease the effect of thiosulfate on copper(II) reduction and hence, the
[Cu(II)]:[Cu(I)] ratio (Breuer & Jeffrey (2003b).
The following results summarise the effect of thiosulfate on gold and silver
leaching from some of the published studies:
• increasing thiosulfate concentration from 0.1 M into 0.2 M, gold recovery
increased from 76% into 90%, but thiosulfate consumption increased from 18 kg/t-
ore to 32 kg/t-ore (Arima, 2003);
• Langhans et al. (1992) concluded that high gold extractions (90%) were obtained
at higher thiosulfate concentrations;
• gold and silver extraction increases with an increase in thiosulfate concentration
(Zipperian et al., 1988);

56
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

• gold extraction is enhanced by the increase in thiosulfate concentration up to 0.3

M but a negligible effect on gold dissolution is obtained at higher thiosulfate
concentrations (Navarro et al., 2002); and
• leaching at high thiosulfate concentrations, the rate of gold extraction is high: a
recovery of about 60% after the first hour of attack is achieved (Abbruzzese et al.,
1995).
To conclude, gold dissolution is very low in the absence of thiosulfate
however, it is enhanced by increasing the thiosulfate concentration up to an optimum
value according to the type of gold ore. On the other hand, an increase in the
thiosulfate concentration increases the reduction of copper(II) to copper(I).

3.5.2.2 Effect of Ammonia

Ammonia is one of the important reagents in the thiosulfate leaching system
of gold as it initially dissolves gold and complexes the copper as the copper
tetraamine complex. The two dominant functions of ammonia in thiosulfate solutions
are explained by Chai (1997) as follows:
1. ammonia reacts with gold first to form Au (NH 3 ) +2 , which then reacts with
2−
S 2 O3 to form Au ( S 2 O3 ) 32− in the anodic reaction; and

2. ammonia stabilises the cupric ion by reacting with it to form the cupric amine
complex, which is a strong oxidizing agent.
The gold ammonia complex is substituted by thiosulfate ions and releases
ammonia according to Equation 3.26 (Chen et al., 1996).
+ 2− 3−
Au ( NH 3 ) 2 + 2S 2 O3 = Au ( S 2 O3 ) 2 + 2 NH 3 (3.26)

The effect of ammonia concentration was studied by Jeffrey (2001) who

found that the gold leaching rate varies with ammonia concentration as shown in
Table 3.2. For example, at low ammonia concentrations (0.2 and 0.4 M), the gold
leach rate is higher than that obtained at higher ammonia concentrations (0.84 and
1.68 M).
Chai (1997) reported a gold recovery of only 9% with thiosulfate in the
absence of ammonia. However, after adding 0.5 M ammonia to the solution, the
extracted gold was found to increase significantly with the optimum concentration of
ammonia was determined to be 2 M. In another study (Arslan et al., 2008), an
increase in ammonia concentration up to 1 M, increased the gold and silver leaching

57
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

rates, but ammonia concentrations higher than 1M were found to decrease the gold
leaching rate. Briones and Lapidus (1998) found that the silver dissolution rate also
decreased at higher ammonia concentrations. Silver extraction is more sensitive to
changes in ammonia concentration than gold (Zipperian et al., 1988).

Table 3.2: Effect of ammonia concentration on the gold leaching rate in 0.4 M
thiosulfate and 25 mM copper(II) (Jeffrey, 2001).

NH3 (M) 105 x Rate (mol m-2 s-1)

0.2 10.2
0.4 11.9
0.84 9.9
1.68 6.3

Increasing ammonia concentration has no noticeable effects on the thiosulfate

oxidation rate, however, an increase in the sustainable copper(II) concentration is
noticed (Arima, 2003; Breuer & Jeffrey, 2003a,b; Wan & LeVier, 2003; Aylmore,
2001; Muyunda, 1996).
Ammonia prevents gold passivation by being preferentially adsorbed on gold
surfaces over thiosulfate (Jiang et al., 1993). Furthermore, the presence of ammonia
prevents the dissolution of iron oxides, silica, silicates and carbonates, the most
common gangue minerals found in gold bearing ores (Abbruzzese et al., 1995).
In conclusion, it is important to optimise the ammonia concentration to ensure the
stability of copper(II) in solution as the copper(II) amine complex and to decrease the
reaction between free copper(II) ions and thiosulfate in the solution.

• Environmental Impacts of Ammonia

Although ammonia is an important reagent of the gold thiosulfate leaching
system, it poses environmental and toxicity problems both as a gas and dissolved in
solutions. The US National Institute for Occupational Safety and Health (NIOSH)
recommend an airborne exposure limit of 25 ppm (18 mg/m3) averaged over a 10-
hour work-shift, with a limit of 35 ppm (27 mg/m3), not to be exceeded during any
15 minute work period (NIOSH, 2000). Ammonia is relatively stable, but it may
eventually metabolize to nitrate, which has the potential to promote algal growth and

58
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

to pollute ground water; hence precautions have be considered to control ammonia

emissions, usually from tanks or heaps, and to prevent its release into the
environment (Muir & Aylmore, 2004).

3.5.2.3 Effect of Copper

Copper(II) has an important role in the thiosulfate leaching system as an
oxidant for the gold, hence, (Breuer and Jeffrey, 2003b) the gold leaching rate in
thiosulfate solutions without copper is extremely poor. The copper concentration has
a significant effect on the observed sustainable copper(II) concentration and the
[Cu(II)]:[Cu(I)] ratio. As copper concentration decreases, the [Cu(II)]:[Cu(I)] ratio
and hence the cathodic potential for gold leaching also decreases significantly
(Breuer & Jeffrey, 2003b).
Gold recovery increased from 75% to 90% with an increase of copper(II)
concentration from 5 mM to 10 mM, however, an increase of copper concentration
up to 50 mM was reported to have no effect on gold recovery (Arima, 2003). In the
absence of cupric ion, Chai (1997) reported gold extraction could only reach 34%
however, when cupric ion was added 76% extraction was achieved. The gold
extracted increased with the increase of cupric ion until the concentration of copper
sulfate became 0.12 M. The reason for the disparity in the recovery (Wan & LeVier,
2003; Langhans et al., 1992) is that the optimum concentration of copper in the leach
solution depended on the ore characteristics and the concentration of thiosulfate
used.
Silver extraction like gold has been found to increase as the copper
concentration increases (0.15% to 1.5%) (Zipperian et al., 1988). Silver is quite
sensitive to the variation in the concentration of copper (Langhans et al., 1992).
The best gold leach rate is achieved when the copper sulfate concentration is 0.01 M
and the rate of gold leaching sharply decreased at higher concentration (Arima,
2003). Muyunda (1996) stated that gold dissolution rates increased by increasing the
copper concentration up to 0.025 M.
Generally (Arima, 2003; Breuer & Jeffrey, 2003a,b; Wan & LeVier, 2003;
Aylmore, 2001; Breuer & Jeffrey, 2002; Briones & Lapidus, 1998; Abbruzzese et al.,
1995 Langhans et al., 1992; Zipperian et al., 1988), it is reported that increasing
copper(II) concentration enhances gold and silver dissolution rates, but has the side
effect of increasing the thiosulfate oxidation rate.

59
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

In conclusion, although copper(II) can affect gold and silver leaching rates
positively, it also has a negative effect on the thiosulfate oxidation. Gold leaching
recoveries decrease significantly after a certain value of copper(II) concentration.
The main reason for this may be that an increase in Cu2+ ion concentration reduces
the stability region of the Cu (NH 3 ) 24+ complex while widening the stability region of
the solid copper compounds such as CuO, Cu2O, CuS, and Cu2S (Arslan et al.,
2008).

3.5.2.4 Effect of pH
The correct pH of thiosulfate solutions is essential to ensure the presence and
the stability of the required reagents and concentrations in the system. Many
published studies have studied the effect of the pH of thiosulfate solutions containing
copper and ammonia. Table 3.3 shows a list of the various pH values published
within the literature related to gold leaching using thiosulfate solutions.

Table 3.3: List of various pH values used in thiosulfate solutions published in

different studies.

pH Author

8.5-9.5 Wan and LeVier (2003)

9-11 Breuer and Jeffrey (2003b); Senanayake et
al. (2003)
10.5-12 Muyunda (1996)
10 Arima, (2003); Jiang et al. (1993c);
Zipperian et al. (1988)
10.2 Aylmore (2001)
11 Yen et al. (1996); Langhans et al. (1992)
9-10 Navarro et al. (2002)
9 Wan (1997); Dasgupta et al. (1997)
8.5-10.5 Abbruzzese et al. (1995)

Using ammonium thiosulfate instead of sodium thiosulfate in thiosulfate

leach solutions changes the solution pH according the equilibrium shown in Equation

60
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

(3.27). The pKa for ammonia is 9.25 (Equation 3.27) hence, the pH of thiosulfate
solutions containing ammonia should be greater than 9.25 in order to maintain
ammonia in the system which is essential to stabilise copper (II) as the copper (II)
ammonia complex (Breuer & Jeffrey, 2003b).
NH 3 + H 2O ⇔ NH 4+ + OH − (3.27)
According to the studies shown in Table 3.4 some conclusions can be
summarized as follows:
• pH of thiosulfate solution should be between 8.5 and 9.5 depending on the ore
characteristics (especially sulfide content) and acidity/alkalinity levels prior to
thiosulfate leaching (Wan & LeVier, 2003);
• Muyunda (1996) studied and noted the effects of pH on gold leaching rates in
thiosulfate solutions as follows:
o the dissolution of gold is extremely poor at a pH lower than 9.2;
o at low pH values, thiosulfate decomposes into sulfur and polythionate
components and sulfur may then coat the surface of gold and stop the process of gold
dissolution;
o at high pH values, above 12.0 with or without ammonia, gold dissolution rates
are very poor; and
o a pH of 11- 12 is required for better dissolution rates in thiosulfate solutions
than those of cyanide;
• gold dissolution was found to increase with the increase in the solution pH up to
a value of about 9.2. However, a further increase was reported to have no effect on
the rate of gold dissolution (Dasgupta et al., 1997);
• a pH value of 10.0 is the optimum value for high gold extraction and lesser
thiosulfate consumption. Increasing pH up to 10.7 decreases the gold recovery and
increases thiosulfate consumption (Arima, 2003); and
• Senanayake et al. (2003) stated that, typically, leaching is carried out between
pH 9 and 11. Below pH 9, however, the Cu(I) triamine Cu (NH 3 ) 3+ complex becomes
prevalent, making the copper species less effective as a catalyst.

3.5.2.5 Effect of Agitation Speed

The interaction between the reacting material in a heterogeneous reaction (a
solid and liquid reaction) may proceed via different steps (Habashi, 1970):

61
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

• diffusion of reacting molecules to the interface;

• absorption at the interface;
• reaction at the interface;
• desorption of the products; and
• diffusion of the products from the interface.
When the diffusion of the reactants and/or products is the slow step, the
reaction is said to be diffusion controlled. If the reaction is diffusion controlled, the
rate will depend on (i) the thickness of the diffusion layer, (ii) the concentration
gradient across the diffusion layer, (iii) the diffusion rate across the diffusion layer,
and, (iv) the surface area of the solid reactant.
In diffusion controlled reactions, the rate should be inversely proportional to
the thickness of the diffusion layer and directly proportional to the stirring speed.
Chai (1997) found that the amount of gold extracted using a mechanical stirrer was
14% more than without agitation. This result is likely due to the increase in the
surface area of the ore sample exposed to the solution by the agitation suspending
and separating the ore particles.
A Levich plot was constructed for the gold leaching system in a study done
by Jeffrey (2001). The Levich plot was not linear indicating that the dissolution of
gold in thiosulfate solutions containing copper and ammonia is not a diffusion
controlled reaction. The same study showed that the gold leaching rate slightly
increased with increasing agitation speed.
Muyunda (1996) studied the effects of agitation speed on gold dissolution in
the thiosulfate system containing copper and ammonia. The results showed that when
the rotation speed increased, there was no change in the gold dissolution rate. This
result confirms that the gold leaching reaction is not a diffusion controlled reaction.
On the other hand, the leaching of silver in thiosulfate solutions is a diffusion
controlled reaction and hence, the leaching of silver depends on the agitation speed
(Jeffrey, 2001).

3.5.2.6 Effect of Temperature

Temperature has a significant effect on the rate of a leaching process if the
reaction is chemically controlled but, little effect on diffusion controlled reactions.
As will be described in this section temperature is an important variable during gold

62
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

extraction with thiosulfate because of its positive effects on the gold extraction rate;
and its negative effects on the decomposition of thiosulfate and the evaporation of
ammonia.
A chemically controlled reaction will be affected by a temperature change
according to the proportion of the reactant species with sufficient energy to
overcome the chemical activation energy. The activation energy can be calculated
from the reaction rate constant according to Equation 3.28.
k = Ae − Ea / RT (3.28)
where
k is the reaction rate constant,
R is the gas constant (8.31 J/K/mole),
T is the temperature, K,
A is the frequency factor, and
Ea is the activation energy.
Zipperian et al. (1988) found that the initial rate of extraction for both gold
and silver is enhanced as the leach temperature increases, but the rate falls off
dramatically after approximately one hour of leaching. Nearly 90% of gold is leached
at higher temperatures in less than one hour.
Muyunda (1996) studied the effect of temperature on the gold leach rate. The
results showed that by increasing the temperature from 25 °C to 35 °C, the gold leach
rate was doubled but, at high temperatures (55 °C), almost 95% of the gold leach rate
was obtained after an hour of leaching. By increasing the temperature, the ammonia
loss from an open leach vessel is increased as shown by Manunda (1996) whose
results are tabulated in Table 3.4.

Table 3.4: The effect of temperature on ammonia concentration after 2 hours of

leaching (Muyunda, 1996).

Temperature, Ammonia remaining after 2 hours

°C (% of original)
25 98.4
35 96.8
45 45.1
55 22.6

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Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Chai (1997) found that gold extraction was preferably carried out at a
temperature of 60 °C, because when the temperature is below 40 °C, the rate of the
reaction will be adversely affected; and at a temperature more than 60 °C, the
volatilization of ammonia will be fast.
Breuer and Jeffrey (2000) concluded that the rate of gold leaching increases
with increasing temperature. Temperature has a significant effect on the gold
leaching reaction rate (which is expected for chemically controlled reactions). Also
the authors found that the activation energy of the leaching reaction was 60±10 kJ
mol-1. This result confirms that the reaction is chemically controlled. The rate of
copper(II) reduction also increases with increasing temperature. Arslan et al. (2008)
stated that increasing the temperature has positive influences on the gold leaching
efficiency but only up to a certain point. After 60°C gold leaching recoveries rapidly
decreased.
Conversely, Abbruzzese et al. (1995) observed that the temperature does not
have any positive effects on gold dissolution and an increase of temperature from 25
to 60°C produces a decrease in gold recoveries. The authors explained that by using
high temperature the speed of cupric sulfide film formation becomes very fast,
hindering gold dissolution. In addition, increasing the temperature to 60°C enhances
the thiosulfate decomposition into sulphur compounds. Zipperian et al. (1988)
concluded that the increase in temperature above 40 °C accelerated the loss of
ammonia and the reduction of copper(II). Temperatures of 25-40°C may, therefore,
be regarded as ideal, reducing volatilisation and maintaining ammonia levels. Also it
was found that the extraction of silver is more temperature sensitive than that of gold.
Based on several published studies, it can be concluded that a controlled
temperature at 30-40 °C in the thiosulfate system is indeed required to achieve the
best results of gold dissolution and minimizes the amount of ammonia losses and
copper(II) reduction.

3.5.2.7 Effect of Impurities

Gold in ore is associated with other various minerals which act as impurities
in thiosulfate leaching solutions. Some of them can enhance the gold dissolution rate
but most of them reduce the gold dissolution rate and increase thiosulfate oxidation.

64
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Hematite: Feng and Deventer (2007a) studied the effect of hematite on gold
recovery. The results clearly showed that hematite significantly reduced the
dissolution of gold and this negative effect became more obvious with increasing
hematite concentration. This may be due to hematite formed coatings on gold
surfaces, which would prevent the leach solution from diffusing to the gold surface.
Feng and Deventer (2007a) also showed that hematite catalysed the oxidative
decomposition of thiosulfate to polythionates in the presence of oxygen.

Sulfite: Arslan et al. (2008) found that almost 100% gold and silver recoveries were
observed with the addition of sodium sulfite during leaching. Increasing the sulfite
concentration reduced thiosulfate consumption from 95.6 to 22.2 kg/t over a 4-hour
leaching period. Kerley (1983) also reported that the presence of sulfite inhibits the
decomposition of thiosulfate. Free sulfite ions regenerate thiosulfate according to
Equation 3.29.
2− 2−
SO3 + S o ⇔ S 2 O3 (3.29)

Manganese: The addition of a small amount of manganese dioxide in the thiosulfate

leaching of sulfide bearing gold ores improved both the kinetics and the overall gold
extraction without much impact on thiosulfate consumption (Feng & van Deventer,
2007b).

Sulfur: The presence of the sulphur species, tetrathionate, trithionate and sulfur ions
has a significant effect on the thiosulfate leaching of gold in both pure gold and ore
leaching systems. Gold dissolution increased with the addition of the sulfur species at
low levels, while the amount of dissolved gold decreased at high levels. The presence
of these sulfur species significantly reduced thiosulfate decomposition, and this
beneficial effect became more prominent at high levels of the sulfur species (Feng &
van Deventer, 2007b).

Lead and Zinc: Feng and Van Deventer (2002) found that the presence of lead(II)
and zinc(II) ions affects thiosulfate degradation as well as gold oxidation by
ammoniacal copper(II) solutions. The effect of lead(II) and zinc(II) ions on
thiosulfate consumption is negligible, but the presence of lead(II) and zinc(II) shows
beneficial effects on gold dissolution. On the other hand, Navarro et al. (2002) stated
that by using a concentration of 4.5 g/L zinc in the thiosulfate solution, recovery

65
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

from a gold concentrate after 10 hours decreased from 92% gold without zinc
addition to 86%.

Pyrite: The presence of pyrite significantly reduced gold dissolution in ammoniacal

thiosulfate solutions and this detrimental effect became more prominent with higher
pyrite content. Pyrite has a catalytic effect on the decomposition of thiosulfate (Feng
& van Deventer, 2006).

3.5.2.8 Effect of Oxygen

Oxygen is required to convert copper(I) to copper(II) for further gold
leaching, but, oxygen concentration should be controlled in thiosulfate solutions in
order to reduce the degree of thiosulfate decomposition and hence, the gold
dissolution rate. The decrease in the gold dissolution rate in the thiosulfate system
upon the addition of oxygen could be attributed to: (a) the decrease in mixed
potential, (b) the decrease in thiosulfate concentration (Chu et al., 2003).
Breuer and Jeffrey (2003b) found that the rate of thiosulfate oxidation is very
rapid when the solution is injected with pure oxygen; all the thiosulfate is
decomposed in less than 25 min, compared to 1 hour for air. However, when the
solution is sparged using a gas composed of 1.9% oxygen in nitrogen, the thiosulfate
oxidation rate is significantly reduced, and after 2 hours only 10% of the thiosulfate
has been destroyed. Chu et al. (2003) also found that the gold-thiosulfate leaching
reaction is hindered when oxygen is present in the solution and although the decrease
in thiosulfate concentration due to its oxidation by oxygen does affect the leaching
process, this alone could not account for the slow leaching kinetics observed in the
presence of oxygen.
Some other studies reported that the presence of oxygen in the thiosulfate
leaching system has an adverse effect on both gold recovery and thiosulfate
oxidation. In addition, the presence of oxygen should be controlled in order to get an
optimum balance between the gold extraction and thiosulfate consumption (Feng &
van Deventer, 2007c; Zhang et al., 2004; Jeffrey et al., 2003; Muyunda, 1996;
Byerley et al., 1975 & 1973a,b)
On the other hand, Wan and LeVier (2003) noted that oxygen availability in
the system is of vital importance, as in the absence of oxygen, Cu(I) ions can not
return to the Cu(II) state which causes copper sulfide precipitation from the solution.

66
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Jeffrey et al. (2003) noted that without oxygen added to the leach solution, gold
leaching was very slow. Only small amounts of oxygen are required to enhance the
gold dissolution rate. Jenkins also found that gold leaching decreased when oxygen
was added in excess amounts due to the decomposition of thiosulfate.
From the discussion provided in this section, it is important to control the use
of oxygen or air in thiosulfate solutions in order to achieve high rates of gold
leaching and low rates of thiosulfate decompositions. The optimum level of oxygen
or air required in thiosulfate solutions is a function of the ore characteristics used.

3.5.2.9 Effect of Pulp Density

Pulp density is defined as the ratio between the weight of ore in kilograms
and the volume of solution in litres. Navarro et al. (2002) concluded that using 10%
pulp density increased the percentage of gold extracted compared to 25 and 40%.
Arslan et al. (2008) stated that an increase in the solid-liquid ratio decreased gold and
silver leach recoveries with the optimum solid-liquid ratio as 10%.
Xia et al. (2003) studied the effects of pulp density on both thiosulfate
consumption and the amount of gold extracted. As the pulp density increased from
28.6% to 61.5%, the thiosulfate consumption for 24 hours was reduced from 77.9 to
17.4 kg/t. At the lower pulp density, the gold extraction increased but the difference
was very small; around 1.9% difference between the pulp density of 28.6% and
61.5%.

3.5.3 Optimum Leaching Conditions

From the previous discussion on the effects of different reagent
concentrations and experimental conditions on gold leaching rate, it is possible to
tabulate the optimum leach conditions for gold ore, concentrate and pure gold (as
disc or foil) as shown in Table 3.5.
From the data shown in Table 3.5, it can be concluded that the reported
optimum reagent concentrations and leaching parameters have a wide range and the
optimum leaching conditions were affected by the type of the gold source used.

67
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Table 3.5: The optimum reagent concentrations and leaching parameters in

thiosulfate solutions reported by various authors.

Author Optimum conditions Type of gold

Arslan et al. (2008) 0.5 M S2O32-, 1 M NH3, 10 mM Cu(II), S/L Gold ore (6.4 g/t Au
ratio 10 %, 20 ºC and 10.4 g/t Ag)
Arima (2003) 0.4 M S2O32-, 3 M NH3, 30 mM Cu(II), room Gold ore (16g/t)
temperature.

Xia et al. (2003) 0.3 MS2O32-, 3 M NH3, 30 mM Cu(II), pH Copper-bearing ore

10.2
Aylmore (2001) 0.8 M S2O32-, 4 M NH3, 50 mM Cu(II), Au-Cu sulfide

Jeffrey (2001) Heap leaching: 0.2 M S2O32-, 0.4 NH3, 5 mM Gold/Silver disc
Cu(II);
Standard gold leaching circuits: 0.4 M S2O32-,
0.6 M NH3, 10 mM Cu(II)

Breuer and Jeffrey 0.2 M S2O32-, 0.09 M NH3, 1 mM Cu(II), Gold disc
(2000) 6.25mM SO32-

Chai (1997) 0.287 M S2O32-, 2 M NH3, 0.12 M Cu(II), 60 Gold ore

ºC, aeration
Muyunda (1996) 0.4 M S2O32-, 0.84M NH3, 25 mM Cu(II), pH Pure gold disc
10.5, 35 ºC

Abbruzzese et al. 2 M S2O32-, 4 M NH3, 0.1 M Cu(II), 25 ºC Ore (51.6 g/t Au)
(1995)
Langhans et al. 0.1 M S2O32-, 0.4 M NH3, 10 mM Cu(II), 30 Low-grade Ore
(1992) ºC, pH > 11.4

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Chapter 3: Thiosulfate Leaching of Gold: Literature Review

3.6 Electrochemical Reactions

Electrochemical reactions are caused by, and can result in, an electron
transfer. The electrochemical driving force is a potential (voltage difference) which
results in a flow of electrons (an electrical current). Any electrochemical process
must have two half reactions; one is the oxidation (anodic reaction) and the other is
the reduction reaction (cathodic reaction).

3.6.1 Measurement of Solution Potentials

Actual electrode potentials in aqueous solutions can be measured using
suitable indicator and reference electrodes. There are many different types of
reference electrodes. Care should be taken to ensure that the potential measurements
are compared against similar reference electrodes, or appropriate adjustments are
made to measurements. The most commonly used reference electrodes are as follows
(Marsden & House, 2006):
• platinum/calomel with saturated potassium chloride (HgCl2), E0 = 0.242 V vs.
SHE (standard hydrogen electrode);
• platinum/mercury sulfate, 0.618 V vs. SHE; and
• silver/silver chloride, 0.222 V vs. SHE.
The most suitable electrodes for measuring potentials are those that are un-
reactive in the conditions used.
Potential sweep voltammetry methods are among the most powerful methods
of investigating electrochemical reaction rates. The most important and easiest to use
is a linear potential sweep. Among the electrochemical methods, voltammetry is one
of the most popular methods for investigation of the overall electrochemical reaction,
since it combines the advantages of short time scales and large potential variations. It
consists in applying to the electrode under study a linear potential sweep between
two potential limits, Ea and Ec, and recording the current flowing through the
electrode as a function of the applied potential (Bockris et al., 1992). The output of
this method is a relation between the applied potential and the measured current.
From this method, the potential at which the reactions take place can be
compared to the thermodynamics to identify the reactions that may occur. Solid or
solution reaction products can be determined from the effects of the sweep rate, and
the formation of solid surface species that may cause passivation can be determined.

69
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

3.6.2 Electrochemical Reactions in Thiosulfate Solution

The leaching of gold occurs as a result of the oxidation of gold (anodic
reaction) and the reduction of the oxidant (cathodic reaction).
In the thiosulfate leaching system, the fundamental electrochemistry of the
anodic oxidation of gold and of the cathodic reduction of oxygen and redox
mediators such as the copper(II)/copper(I) couple have not been studied extensively
(Zhang & Nicol, 2005).
The overall stoichiometric reaction for the dissolution of gold in aqueous
alkaline thiosulfate solutions in the presence of oxygen is described in Equation 3.20.
This consists of two reaction equations, the oxidation of gold, and the reduction of
oxygen as shown in Equations 3.30 and 3.31.
Au + 2 S 2 O32− → Au ( S 2 O3 ) 32− + e − (3.30)

O2 + 2 H 2O + 4e − → 4OH − (3.31)
However, this reaction has been found to be very slow in the absence of
ammonia due to the formation of a sulfur-like film as a result of decomposition of
thiosulfate on the gold surface ( Zhang & Nicol, 2005 & 2003; White, 1905).
In the presence of copper(II) and ammonia in the thiosulfate solution, however, there
is another reaction. Copper(II) is reduced by thiosulfate to copper(I). This reduction
reaction is represented by Equation 3.32.
Cu ( NH 3 ) 24+ + 3S 2O32− + e − → Cu ( S 2O3 ) 53− + 4 NH 3 (3.32)
In the electrochemistry of gold in thiosulfate solutions containing copper and
ammonia, the cathodic half reaction, the reduction of copper(II), occurs readily in the
potential region where gold should be oxidised to gold thiosulfate. However, the gold
oxidation half reaction in thiosulfate solutions without ammonia is hindered; the
presence of ammonia is required for the reaction to occur at an appreciable rate
(Breuer and Jeffrey, 2002).
To investigate an electrochemical process, each half reaction should be
studied independently. Sections 3.6.2.1 and 3.6.2.2 will present the electrochemical
mechanism of gold dissolution in thiosulfate solutions.

3.6.2.1 The Anodic Reaction (Gold Oxidation)

The oxidation of gold in thiosulfate has been studied using traditional
electrochemical techniques (Zhang & Nicol, 2005; Chandra & Jeffrey, 2004; Chai &

70
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Wang, 2003; Zhang & Nicol, 2003; Jiang et al., 1997 & 1993a; Zhu et al., 1994).
Polarisation curves were recorded by Breuer and Jeffrey (2002) for a gold
electrode in a solution containing 0.1 M thiosulfate and 0.4 M ammonia. The data
has been plotted in Figure 3.6, which shows that at the potential region 150–300 mV,
there is an oxidation reaction occurring, although at a low rate. At potentials more
positive than 300 mV, the current density increases rapidly.

Figure 3.6: Linear sweep voltammogram showing the oxidation of gold to gold
thiosulfate. Also shown is the mass change measured using the
REQCM, and thepartial current density (icalculated) derived from this
(Breuer & Jeffrey, 2002).

Voltammetry and electrochemical impedance spectra (EIS) experiments were

conducted by Zhu et al. (1994). The results indicated that the anodic voltammetric
curves of the gold electrode in thiosulfate solution did not indicate the features of
gold dissolution, but passivation of the gold occurred. With the addition of ammonia
into the system, however, the passivation of gold is completely eliminated, and gold
dissolution increased. On the other hand, Dasgupta et al. (1997) concluded that the
rate of dissolution of gold was not affected by the total ammonia (NH3 + NH4)
concentration of the solution.
The effect of copper on the anodic dissolution of gold was studied
electrochemically by Zhang and Nicol (2005) and they concluded that copper has a
positive effect on the anodic dissolution of gold, with increasing concentrations of
copper resulting in higher dissolution rates of gold at a potential of 0.3V.

71
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

The oxidation of gold in ammoniacal solutions at 75 ºC was evaluated using

electrochemical techniques by Dasgupta et al. (1997). The results showed that the
dissolution current increased with the increase of the overpotential before gold
became oxidised at 0.46 V vs. SCE in ammoniacal solutions. A current density peak
during anodic polarization at 0.46 V vs. SCE is believed to be due to the formation
of Au(OH)3.
Electrochemical experiments were carried out by Chandra and Jeffrey (2004)
using solid gold/silver alloy containing 2% silver. The linear sweep voltammograms
for pure gold and the gold/silver alloy (Figure 3.7) show that when silver is present
as an alloying element, the current density for gold/silver oxidation in thiosulfate
solutions at all potentials is higher than that of pure gold.

Figure 3.7: Linear sweep voltammograms showing the oxidation of a gold/silver

alloy containing 2% silver in 0.2 M ammonium thiosulfate (Chandra &
Jeffrey, 2004).

Chandra and Jeffrey (2004) also studied the effects of additives on the gold
oxidation half reaction. In ammonium thiosulfate solutions containing 5 mM of
either xanthate or thiourea, the addition of thiourea was found to be beneficial to the
oxidation of gold, with the current density rapidly increasing as the potential is
increased above 125 mV (Figure 3.8).

72
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

Figure 3.8: Linear sweep voltammograms showing the effect of thiourea (Tu) and
potassium ethyl xanthate (PEX) on the gold oxidation half reaction in
0.2 M ammonium thiosulfate (Chandra & Jeffrey, 2004).

3.6.2.2 The Catholic Reaction (Copper(II) Reduction)

The main reduction reaction in thiosulfate solutions is the reduction of
copper(II) into copper(I) as shown in Equation 3.31. Breuer and Jeffrey (2002) from
an electrochemical study on thiosulfate solutions found that the cathodic half
reaction, the reduction of copper(II), occurs readily in the potential region where
gold should be oxidised to gold thiosulfate.
Although there are limited published work on the cathodic reaction in
thiosulfate solutions, Breuer and Jeffrey (2002) studied the cathodic reaction by
replacing the gold electrode with an inert platinum electrode. Figure 3.9 shows the
linear sweep voltammograms for three systems, these systems are:

Ammonia-thiosulfate: In air-saturated solutions containing ammonia and thiosulfate

there are two possible reactions: the reduction of dissolved oxygen and the reduction
of thiosulfate. It can be seen that both oxygen and thiosulfate reduction occurs at
potentials more negative than 50 mV.

Copper-ammonia: For the solution containing cupric tetraamine without thiosulfate,

there is the possibility of reducing copper(II) to copper(I), as the copper(I)–amine

73
Chapter 3: Thiosulfate Leaching of Gold: Literature Review

complex is also stable in alkaline solutions. It can be seen that this reaction occurs at
potentials more negative than 150 mV.

Figure 3.9: Linear sweep voltammograms for the reduction of oxygen in ammonia-
thiosulfate solutions, and for the reduction of copper in ammonia and
ammonia-thiosulfate solutions. A platinum electrode was used in these
experiments (Breuer & Jeffrey, 2002).

Copper-ammonia-thiosulfate: In the presence of thiosulfate, there is the possibility

of forming both thiosulfate and ammonia complexes of copper(I) (Breuer & Jeffrey,
2002). The voltammogram for this system is not just a combination of the other two
systems. The most obvious change is the difference in the copper(II) reduction
potential in the presence and absence of thiosulfate. The more positive value for
solutions containing thiosulfate indicates that the copper(II) ion is more readily
reduced in a solution containing thiosulfate. Other studies (Michel & Frenay, 1996;
Jiang et al., 1993a) have also found that increasing the concentrations of copper(II)
and ammonia has a positive effect on the polarisation curve potentials of copper(II)
reduction to copper(I).

74
Chapter 4 Materials and Methods
This section describes the materials and methods used in this research.
Section 4.1 is the leaching kinetic experiments. These experiments were conducted
on gold, silver and gold-silver alloys and a sample of gold ore from the Sukari Gold
Mine. Section 4.2 describes the experimental procedure for electrochemical
experiments performed on the gold, silver and gold-silver alloy discs. Section 4.3 is
the dissolution of mercury, a common element found in gold ores and section 4.4 the
recovery of gold, copper and mercury onto ion exchange resins.

4.1 Leaching Kinetic Experiments

The kinetic aspects of gold and silver leaching in thiosulfate solutions using
pure gold, pure silver, and four different compositions of gold-silver alloys were
studied using the rotating disc technique in open and closed 1 L vessels. Then, gold
ore samples were used to optimise the process of gold leaching in thiosulfate and
cyanide solutions.

4.1.1 Gold and Silver Sources

In this study, the sources of gold and silver were as follows:
1) Discs: Pure gold (99.99), pure silver (99.99), and gold-silver alloys of 4, 8, 20, and
50% silver; and
2) Ore samples: Gold ore samples were provided from the Sukari Gold Mine, Eastern
Desert, Egypt, by the Centamin Egypt Limited Company.

4.1.1.1 Gold and Silver Discs

The gold and silver discs were made from 99.99% pure gold and silver (Perth
Mint). A 17 mm diameter by 2 mm thick disc (with a surface area of 2.27 cm2) was
formed in a stainless steel mould and embedded in a black phenolic (PremoldsTM)
resin. The resin specimen mount was polished away to reveal one disc face. A hole
was then drilled and tapped into the opposite side of the mount to attach a stainless
steel shaft, which in turn could be attached to an agitator.
Pure gold, pure silver and gold-silver discs of silver compositions 4, 8, 20,
and 50 wt.% silver were constructed (Figure 4.1).

75
Chapter 4: Materials and Methods

100% Au 4% Ag 8% Ag 20% Ag 50% Ag 100% Ag

Figure 4.1: Pure gold, pure silver and gold-silver discs of different silver
composition: 4, 8, 20, and 50 wt.% silver.

4.1.1.2 Gold Ore Samples

Gold ore samples were supplied from the Sukari Gold Mine, Eastern Desert,
Egypt, by Centamin Egypt Limited. The ore consisted of about 50 kg of drill core
pieces around 10 to 15 cm in length and 5 cm in diameter. The ore samples were
separated according to weathered (near surface drill core) and unweathered (deep
core) samples. Both the weathered and unweathered samples were crushed, firstly by
a hydraulic Enerpack crusher (Enerpack model RR 308) shown in Figure 4.2. The
crushed ore samples were sieved at a sieve size of 707 µm (25 mesh). The minus 707
µm fraction was collected for grinding and the plus 707 µm fraction was recycled
back to the crusher. The crushed samples were ground by a bench top ring mill,
which is shown in Figure 4.3.

Figure 4.2: Enerpack hydraulic Figure 4.3: Bench top ring mill and its
crusher (Enerpack internal components.

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Chapter 4: Materials and Methods

The ground weathered sample was mixed well by a rotary splitter and a subsample of
the weathered ore and all the unweathered ore sieved at a size of -106 µm. The
sieved ore samples (-106 µm) were passed through the splitter two times to
homogenise them and then 250 g samples were split and packed into sample bags for
use in the leaching experiments.
In order to study the gold leaching rate of different ore size fractions, about
one kilogram of the weathered ground ore sample was screened into different size
fractions by using sieves of 38, 75, 106, and 125 µm. Four size fractions, -38, -
75+38, -106+75, and -125+106 µm, were collected. Finally, each size fraction was
mixed well using the splitter and then 100 g samples were packed for the leaching
experiments.
Quantitative X-Ray Diffraction (XRD) was used to determine the mineralogy
of each size fraction for the weathered samples (Table 4.1) and the minus 106 µm
material of the weathered and unweathered samples (Table 4.2). The XRD analysis
was carried out in the X-Ray Analytical Science Laboratory, Faculty of Science,
Curtin University of Technology.

Table 4.1: Quantitative XRD analysis (Wt.%) of the gold ore samples (weathered)
for size fractions: -38, -75+38, -106+75, and -125+106 µm.

Sample
Phase
-38µm -75+38µm -106+75µm -125+106µm
Quartz 25.0 30.9 31.3 30.4
Albite 49.5 46.4 46.1 48.2
Muscovite 13.3 10.5 8.3 10.5
Calcite 2.6 0.6 1.7 1.9
Microcline 8.6 9.4 9.5 6.9
Niningerite - 0.9 1.0 0.3
Gupeiite 0.3 0.6 0.5 0.5
Pyrite 0.7 0.7 1.6 1.3

An element analysis for each size fraction was performed by Ultratrace

Laboratories, Perth, Western Australia, tabulated in Tables 4.3 and 4.4. The analysis
was performed by acid digestion of the ore, followed by ICP–OES determination.

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Chapter 4: Materials and Methods

Table 4.2: Quantitative XRD analysis (Wt.%) for weathered and unweathered gold
ore samples (size fraction -106 µm).

Samples

Phase Weathered Unweathered

(-106µm) (-106µm)

Quartz 29.6 24.7

Albite 50.3 63.4
Muscovite 9.3 3.5
Calcite 1.9 -
Microcline 7.2 4.8
Niningerite 0.5 -
Gupeiite 0.6 0.2
Pyrite 0.6 1.1
Ankerite - 2.3

Table 4.3: The elementary analysis (Wt.%) of the weathered gold ore for size
fractions: -38, -75 +38, -106+75, and -125+106 µm.

Element -38µm -75+38µm -106+75µm -125+106µm

Au, ppm 4.12 4.23 5.39 3.22
Si, % 66 68 70.5 67.6
Al, % 15.1 14.6 13.6 14.6
Ca, % 2.08 1.6 1.28 1.6
Fe, % 4.5 4.19 3.68 4.22
K, % 2.14 2.15 1.95 2.17
Mg,% 0.44 0.47 0.4 0.48
Na, % 5.37 5.15 4.95 5.09
P, % 0.04 0.04 0.035 0.04
S, % 0.29 0.38 0.4 0.42
Ti, % 0.34 0.33 0.3 0.34
Mn,% 0.08 0.08 0.07 0.08

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Chapter 4: Materials and Methods

Table 4.4: The elementary analysis (Wt.%) for both weathered and unweathered
gold ore samples of size fraction (-106 µm).

Weathered Unweathered
Element
(-106µm) (-106µm)
Au, ppm 3.71 4.59
Si, % 68.9 68.4
Al, % 14.3 13.4
Ca, % 1.61 1.37
Fe, % 3.97 4.2
K, % 1.95 1.05
Mg,% 0.35 0.59
Na, % 5.35 6.55
P, % 0.036 0.07
S, % 0.26 3.22
Ti, % 0.31 0.37
Mn,% 0.07 0.09

4.1.2 Rotating Disc Experimental Method

The following sections present the experimental setup and method for gold,
silver and gold-silver disc leaching.

4.1.2.1 The Experimental Setup

• Setup Using Discs
The leaching of gold, silver, and gold-silver discs in the thiosulfate solutions
was conducted using a rotating disc technique. The experiment setup for this
consisted of:
• a mechanical agitator;
• a stainless steel rod;
• 1 L glass reactor, water bath with a thermostat;
• a five-necked glass cover (for closed vessel experiments);
• gold, silver and gold-silver alloy discs; and
• Teflon seals.

• Setup Using Ore Samples

The leaching of gold ore samples was conducted using a mechanical stirrer.
The experiment setup consisted of the same components of the leaching disc setup
except using a plastic agitation stirrer instead of the disc.

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Chapter 4: Materials and Methods

For both disc and ore leaching, a closed vessel system was used. In this
system, a 1 L glass vessel was sealed by a five-necked glass cover and a mechanism
that permits the stirrer rod to rotate in a Teflon seal in the middle neck of the cover.
The same setup was used for the open vessel experiments, but the reactor vessel was
left open to the ambient atmosphere. Figure 4.4 shows the experimental setup of the
open and closed vessel systems.

Open Vessel Closed Vessel

Figure 4.2: The experimental setup of the open and closed vessels.

4.1.2.2 Disc Polishing

Before each experiment, the surface of the gold or silver or gold-silver disc
was polished to obtain a clean and shiny surface to ensure that the surface in direct
contact with the solution was free of passivaion layers. The disc polishing was
conducted with a waterproof silicon carbide paper (FEPA # 2400) and 3 micron
aluminium oxide powder. Finally, the disc was washed with distilled water and
allowed to dry for 5 minutes.

4.1.2.3 Disc Leaching Procedure

In this study, gold and silver leaching from pure gold, pure silver and 4, 8, 20,
and 50% of silver gold-silver discs were used to evaluate the effect of silver on the
gold leaching rate in thiosulfate solutions. In the leaching experiment for each alloy
in thiosulfate- copper- ammonia solutions, a solution volume of 500 mL was used in
both the open and closed 1 L vessel experiments, maintained at a constant
temperature to ±0.1 ºC. Unless specified, the standard conditions used in the open
and closed vessel experiments for the short run (1 hour) and the long run (8 hours

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Chapter 4: Materials and Methods

and 24 hours) were 0.2 M sodium thiosulfate, 10 mM copper(II) sulfate, 0.4 M

ammonia, 30 ºC and 300 rpm. All the experiments were conducted at a fixed pH of
11.5 and without air or oxygen injection.

4.1.2.4 Ore Leaching Procedure

During ore samples leaching, all experiments were carried out using solutions
prepared from analytical reagents and de-ionized water. The main size fraction of the
gold samples for most of the leaching experiments was -106 µm. One hundred grams
of the ground ore was put into a 1L glass vessel as described in the experimental
setup (section 4.1.2.1). A solution volume of 400 mL containing 0.2 M sodium
thiosulfate, 10 mM Cu(II) sulfate, and 0.4 M ammonia was added to the ore sample
to achieve a solid/liquid ratio of 20% weight to volume. The temperature was
adjusted at 30 ºC, and the rotation speed to 300 rpm. The leaching experiments were
run for 24 hours.
Gold analysis was carried out using atomic absorption spectrophotometry
(AAS) on filtered samples taken after 3, 8, 12, and 24 hours of leaching. At the end
of each experiment, the solution was filtered and collected for assay. The residue was
then washed by 50 mL of de-ionized water 3 times to ensure that all dissolved gold
was washed from the residue. The gold concentration was measured using AAS. The
solid residue was dried in an oven for 24 hours at 60 ºC.
The dried solid residue was analysed for gold by firing a 40 gram (approx)
portion of the sample (fire assay analysis), and the gold in the dore bead determined
by the Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES). The
percentage of extracted gold was calculated from the gold in the leached residue, the
main solution and the wash solution as follows:

{( Au) main.sol . + ( Au) wash. sol. }

Gold Extraction (%) = X 100
{( Au) main.sol. + ( Au) wash sol. . + ( Au) residue }

where:
(Au)main.sol. : total amount of gold in the main solution (mg);
(Au)wash.sol : total amount of gold in the wash solution (mg); and
(Au)residue : total amount of gold in the residue solution (mg).

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Chapter 4: Materials and Methods

4.1.2.5 Gold and Silver Analysis

The analysis of the dissolved gold and silver from each disc during the open
and closed vessel experiments was measured by atomic adsorption spectro-
photometry.

4.1.2.6 Thiosulfate Analysis

The concentration of thiosulfate in the leach solution for both gold-silver disc
and ore experiments was determined by the idometric titration method (Lenahan &
Murray-Smith, 1986) during, and at the end of each test. The principle and procedure
of this method are as follows.

• Principle
The principle behind thiosulfate analysis depends on the determination of
thiosulfate, sulfite, and sulfide in the solution. In an acidic solution, sulfite, sulfide
and thiosulfate are oxidized by iodine to sulfate, sulfur and tetrathionate respectively
according to Equations 4.1, 4.2, and 4.3.
SO32− + I 2 → SO4 + 2 I − (4.1)

S 2− + I 2 → S + 2 I − (4.2)

2 S 2 O32− + I 2 → S 4 O62− + 2 I − (4.3)

Titration, based on these reactions, provides an accurate method for the
determination of all three species. The sample to be analysed is divided into three
portions. One portion is titrated with a standard iodine solution: the result obtained is
the combined concentration of the three ions. A second portion of the sample is
treated with formaldehyde with which the sulfite reacts (Equation 4.4).
Na 2 SO3 + HCHO + H 2 O → CH 2 .OH .SO3 Na + NaOH (4.4)
The hydrosulfonate thus formed does not react with iodine. By iodiometric
titration, the combined concentration of sulfide and thiosulfate is therefore obtained.
A third portion of the sample is treated with zinc acetate to precipitate zinc sulfide
(Equation 4.5).
Na 2 S + Zn(CH 3 COO ) 2 → ZnS + 2CH 3 COONa (4.5)
Iodiometric titration then determines the combined sulfite and thiosulfate.
Subtraction of this value, from the value obtained from the first titration, provides the

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Chapter 4: Materials and Methods

sulfide content. By deduction of the combined concentration of sulfite and sulfide

from the total value, the thiosulfate concentration is derived.
Exposure of the sample to air should be minimised to prevent oxidation.
Certain metal ions, such as Cu2+, may catalyse the oxidation of sulfite to sulfate on
exposure of the sample to air. As a general precaution against auto-oxidation,
solutions should be analysed no later than six hours after the time of sampling.

• Solutions
The solutions and their concentrations used in the thiosulfate determination were:
(a) Standard iodine solution: 0.05 M I2;
(b) Starch solution: 5 g/L;
(c) Acetic acid: glacial;
(d) Formaldehyde solution: 370 g HCHO/L;
(e) Sodium hydroxide solution: 6 M NaOH (Stored in a plastic bottle); and
(f) Zinc acetate solution: 1 M Zn(CH3COO)2.

• Procedure
Into each of three 250 cm3 Erlenmeyer flasks, the appropriate volume of the
sample to be analysed was pipetted.
(a) Determination of the sum of sulfite, sulfide and thiosulfate concentrations.
To the sample in the first flask, 5 cm3 of acetic acid was added. One cm3 of starch
solution was then added and mixed. The solution was swirled and titrated with
standard iodine to the first permanent blue color. The volume of iodine solution used
was recorded: titre a (cm3).
(b) Determination of the sum of sulfide and thiosulfate concentrations.
To the sample in the second flask, 35 cm3 of formaldehyde solution was added. The
pH was adjusted to 8.2 by the addition of sodium hydroxide solution. Twenty five
cm3 of water and 5 cm3 of acetic acid were added. The solution was swirled and
titrated with standard iodine to the first permanent blue color. The volume of iodine
solution used was recorded: titre b (cm3).
(c) Determination of the sum of sulfite and thiosulfate concentrations.
To the third aliquot, 5 cm3 of zinc acetate solution was added. The pH was adjusted
to 12 by the addition of sodium hydroxide solution. The solution was mixed well and

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Chapter 4: Materials and Methods

left to allow the precipitate of zinc sulfide to settle. The solution was filtered through
a paper of medium porosity. To the filtrate, 5 cm3 of acetic acid and 1 cm3 of starch
solution were added. The solution was swirled and titrated with standard iodine to
the first permanent blue color. The volume of iodine solution used was recorded: titre
c (cm3).
From the iodiometric titrations, the thiosulfate concentration was calculated by
Equation (4.6)
(b + c − a ) × M × 224 × 1000
Concentration of thiosulfate, (mg/L) = (4.6)
V
where:
a is the titre (cm3) of the sum of sufite, sulfide and thiosulfate;
b is the titre (cm3) of the sum of sulfide and thiosulfate;
c is the titre (cm3) of the sum of sulfite and thiosulfate;
M is the concentration of the iodine solution (0.05M); and
V is the volume of sample (cm3).
At the end of each ore leaching experiment, the final concentration of
thiosulfate obtained from Equation (4.6) was subtracted from the initial thiosulfate
concentration and the thiosulfate consumption during leaching calculated using
Equation (4.7).
V × ( S 2 O32− ) consumed
Sodium thiosulfate consumption, (kg/t-ore) = (4.7)
W
where:
V is the volume of thiosulfate solution used in the leaching experiment, L;
( S 2 O32− ) consumed is the amount of thiosulfate consumed in the experiment, mg/L; and
W is the weight of the ore sample used in the experiment, g.

4.1.2.7 Copper(II) Analysis

Copper(II) is the main oxidant in the thiosulfate leaching system and its
concentration has a significant influence on the gold leach rate. Copper(II)
concentrations were measured by using UV-Vis spectrophotometry in order to
monitor the concentration of the copper(II) ammine complex. The maximum
absorbance of this component (copper(II) ammine) was found at a wavelength of 605
nm in concordance with Breuer (2002). Figure 4.5 shows the absorbance of
copper(II) ammine as a function of wavelength at different concentrations of Cu(II).

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Chapter 4: Materials and Methods

0.7

0.6 10 mM Cu(II)
5 mM Cu(II)
0.5 2.5 mM Cu(II)
1.25 mM Cu(II)
Absorbance

0.4

0.3

0.2

0.1

0
400 450 500 550 600 650 700 750 800 850 900
Wavelength, nm

Figure 4.3: The absorbance of copper(II) ammine in solutions containing 400 mM

ammonia and 100 mM sodium thiosulfate at 30 ºC using UV-Vis
spectrophotometer.

• Procedure
The procedure to determine copper(II) concentration is given in the following steps:
1. A blank solution containing only 0.4 M ammonia and 0.2 M sodium thiosulfate
was prepared;
2. A stock solution of 100 mM Cu(II) as copper ammine complex was prepared. To
decrease the contact reaction time between thiosulfate and copper(II), another stock
solution of 1 M sodium thiosulfate was prepared separately. These solutions were
stored in sealed volumetric flasks (500 mL) maintained at a constant temperature 30
± 0.1 ºC;
3. The appropriate volumes of copper(II) ammine complex and thiosulfate stock
solutions were mixed in 50 mL volumetric flasks to form Cu(II) standards of 1.25,
2.5, 5, 10, and 20 mM Cu(II). A sample was taken from each standard solution, as
well as the blank, and these were sealed within UV cells which were placed in a
covered cell holder of a SHIMADZU (UV mini1240) UV-Vis spectrophotometer;
4. Firstly, the absorbance of the blank sample was read and the instrument was
adjusted to read zero absorbance. This step removes the effects of ammonia and
thiosulfate on the absorbance at the wavelength 605 nm;
5. The absorbance at 605 nm was measured for each copper(II) standard;

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Chapter 4: Materials and Methods

6. From the previous step, a calibration curve was constructed, as shown in Figure
4.6; and
7. Finally, the absorbance of the samples from each experiment at different times
were recorded, and the absorbance readings were converted into copper(II)
concentrations using the calibration curve (Figure 4.6).

1.2

0.8
Absorbance

0.6

0.4

0.2

0
0 0.005 0.01 0.015 0.02

Cu (II) concentration, M

Figure 4.4: The calibration curve of copper(II) ammine.

4.1.2.8 Ammonia Analysis

For all gold leaching experiments conducted in the open and closed vessels,
the ammonia analysis was carried out by the phenate method as described by
Greenberg et al. (1992).

• Principle
In an alkaline solution (pH 10.4-11.5), ammonia reacts with hypochlorite and
phenol catalyzed by a manganous salt to form the blue coloured indophenol. The
concentration of ammonia is then determined spectrophotometrically using a UV
mini 1240 UV-Vis spectrophotometer. To ensure the peak value of indophenol was
at a wavelength of 630 nm, a wavelength scan of a 3.05 mg/L ammonia standard was
conducted, as shown in Figure 4.7.

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Chapter 4: Materials and Methods

0.9
0.8
0.7
0.6
Absorbance

0.5
0.4
0.3
0.2
0.1
0
300 400 500 600 700 800 900
Wavelength, nM

Figure 4.5: Wavelength scan of the absorbance of an ammonia standard solution

using UV-Vis spectrophotometry.

• Solutions
The solutions and their concentrations used in the determination of ammonia
were:
• Phenol (C6H5OH): Dissolve 2.5 g NaOH and 10g phenol in 100 mL water;
• Sodium hypochlorite solution: To 40 mL water, 10 mL (5-6% NaOCL solution)
was added and the pH adjusted to 6.5 to 7 with HCl (Prepared Weekly);
• Manganese sulfate ( 0.05 mL MnSO4); and
• Stock ammonia solution: 0.3819 g of the dried salt (ammonium chloride ,NH4Cl)
was dissolved in water in a 1000 mL volumetric flask and diluted to the mark with
water. The solution is stable for six months when stored in a refrigerator.

• Procedure
The procedure for ammonia determination by this method was:
1. Preparation of the standards: a calibration curve in the range from 0 to 12 mg/L
was prepared;
2. 5.0 mL of each of these standard solutions and 5.0 mL of water were transferred
to a 30 mL test tube;
3. One drop (0.05 mL MnSO4) solution was added;
4. 0.5 mL sodium hypochlorite was added and mixed well;

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Chapter 4: Materials and Methods

5. 0.6 mL phenol was added and mixed well until a blue colour is formed;
6. The sample was then transferred to a 10 mm UV cell and the absorbance was
measured at 630 nm;
7. A calibration curve, plotting the absorbance of each of the standard solutions
against its concentration of ammonium, was prepared; and
8. In order to check for ammonium in the reagents, a photometric reading of a
reagent blank (0.00 mg NH 3+ /L) against water was taken. The absorbance should not
exceed 0.020.
To analyse the samples, firstly, they were diluted to suit the calibration curve
values, and then 5.0 mL of the sample and 5.0 mL of water were transferred to a 30
mL test tube. The procedure followed the instructions, as in points 3, 4 and 5. The
spectrophotometric readings of the sample were converted to mg NH 3+ /L by means

of the calibration curve shown in Figure 4.8.

If the pH-value of the sample was lower than 3, the sample was neutralized.
If the sample was turbid, both the sample and the blank was filtered through a white
band filter.

3.5

2.5
Absorbance

1.5

0.5

0
0 2 4 6 8 10 12 14
Ammonaia concentration, mg\L

Figure 4.6: The calibration curve of different ammonia standards.

4.2 Electrochemical Rotating Disc Experiments

Electrochemical rotating disc experiments were carried out using pure gold,
pure silver and 4, 8, 20, and 50% silver gold-silver discs using two different

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Chapter 4: Materials and Methods

electrochemical techniques: (1) linear sweep voltammetry, and (2) coulometry at a

fixed potential value.

4.2.1 Linear Sweep Voltammetry

4.2.1.1 Solution and Disc Preparations
All experiments were carried out using 50 mL of solutions prepared from
analytical reagents and Millipore water.
The solutions used in these experiments were:
• Ammonium thiosulfate (ATS) or sodium thiosulfate (STS) only;
• Ammonium thiosulfate (ATS) or sodium thiosulfate (STS) and ammonia;
• Ammonium thiosulfate (ATS) or sodium thiosulfate (STS) and ammonia and
copper sulfate; and
• Ammonium thiosulfate (ATS) or sodium thiosulfate (STS) and thiourea.
All solutions were deaerated using nitrogen gas for 20 minutes and performed
at 30 ºC, with a rotation rate of 300 rpm, and at the natural pH of the solution, which
was typically pH 11-11.5. Before each experiment, the surface of the gold or silver or
gold-silver disc was polished as described in section 4.1.2.2.

4.2.1.2 Experimental Setup

Linear sweep voltammetry was carried out using a Radiometer PGP201
-1
potentiostat. All experiments were performed at a scan rate of 1 mV s . All
potentials were measured relative to the saturated calomel electrode (+0.242 V vs.
SHE), but are reported relative to the standard hydrogen electrode (SHE). The
current was measured at a range of potentials between -22 mV and 300 mV.

4.2.2 Coulometric Experiments

The electrochemical coulometric experiments were carried out to study the
effects of ammonium thiosulfate (ATS), sodium thiosulfate (STS), ammonia,
copper(II), and thiourea concentrations on the total leach rate (gold and silver) from
pure gold and t gold-silver alloys.
4.2.2.1 Solution and Disc Preparation
All experiments were carried out using in 50 mL of solution prepared from
analytical reagents and Millipore water.

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Chapter 4: Materials and Methods

The solutions used were:

• Ammonium thiosulfate (ATS) only;
• Ammonium thiosulfate (ATS) and ammonia;
• Ammonium thiosulfate (ATS), ammonia and copper(II); and
• Ammonium thiosulfate (ATS) and thiourea.
Before each experiment, the surface of the gold or silver or gold-silver disc
was polished as described in section 4.1.2.2.

4.2.2.2 Experimental Setup

Coulometric experiments were conducted at fixed potentials on pure gold and
gold-silver alloys in an electrochemical cell containing thiosulfate solutions for 30
minutes. All experiments, unless specified, were performed at a rotation speed of 300
rpm and at a temperature of 30 ºC for 30 minutes at different fixed potential values.
All the solutions were deaerated using nitrogen for 20 minutes.
The produced current in the electrochemical cell was measured and the
electric charge density (mC.cm-2) was obtained by the integration of the current-time
plot. After each experiment, a sample was collected and analysed for gold and silver
by ICP-OES. The setup of the electrochemical cell that was used in the
electrochemical experiments is shown in Figure 4.9.

Figure 4.7: The electrochemical cell setup used to conduct the different experiments.

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Chapter 4: Materials and Methods

4.3 Mercury Dissolution

In this project, the ability of thiosulfate and cyanide solutions to dissolve
different mercury compounds was evaluated. All the mercury compounds used were
analytical reagents grade. In this section, the dissolution of each mercury form in
thiosulfate and cyanide solutions was studied.

4.3.1 Mercury Dissolution Experiments

The dissolution of the different mercury compounds in thiosulfate and
cyanide solutions was studied. The different mercury compounds used were:
elementary mercury (Hg0), mercuric chloride (HgCl2), mercurous chloride (Hg2Cl2),
and mercury sulfide (HgS). All the mercury leaching experiments were conducted
using the bottle roll technique. One hundred millilitres of solution was used in 250
mL plastic bottles.
The thiosulfate and cyanide solutions used were:
• 2.5 g/L NaCN solution;
• 50 mM ammonium thiosulfate (ATS), 400 mM NH3, 10 mM Cu2+;
• 50 ATS, 1 mM Cu2+;
• 50 ATS, 10 mM thiourea (Tu), 12.5 mM ferric oxalate, 5 mM FeCl3; and
• 50 ATS, 10 mM Tu, 5 mM FeEDTA.
The initial pH of the solution was: 12 for the cyanide system solution; 11.4
for the ATS, copper, ammonia solution; 10 for the ATS, 1 mM Cu2+ solution; 5.5 for
the solution containing Ferric Oxalate; and, 7 for the solution containing FeEDTA.
Following the addition of the mercury compount, the solutions were rolled on an
electric roller for 48 hours at ambient temperature and at a rotation speed of 60 rpm.
For mercury analysis, 12 mL samples were taken after 5, 24, and 48 hours leaching,
and filtered immediately with a 0.5 mm micro filter. Ten mL from each filtered
sample was treated with 1 mL of 0.1 M tetra-sodium EDTA to stabilise the mercury.
All the samples were analysed for mercury by the ICP-OES.

4.4 Gold, Copper and Mercury Recovery

The recovery of gold, copper and mercury from pregnant ammonium
thiosulfate (ATS) solutions using a strong anion-exchange resin was evaluated.
Commercially available anion-exchange resin, Purolite A500/2788, was obtained in

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Chapter 4: Materials and Methods

its wet form. The physical and chemical properties of the resin will be shown in
Chapter 8 (Table 8.4). The metal loading and recovery was conducted using two
different experiments: (1) loading-stripping and (2) loading-elution.

4.4.1 Loading-Stripping Experiments

The anion-exchange resin experiments were carried out using plastic bottles
(500 mL) that were sealed and placed on an electric roller at 60 rpm at room
temperature (24 - 25 ºC). Loading was accomplished by contacting 0.667 g of the
resin with 250 mL of solution for 5 hours. The stock loading solution consisted of
100 mM ammonium thiosulfate (ATS), 4 mM trithionate (S3O62-), 1 mM
CuSO4.5H2O, and 5 mM gold (Au) as gold thiosulfate [Au(S2O3)2]3-. Different
mercury concentrations of 0, 2, 3, 5, 7, 10, 15, and 20 mg/L Hg as HgCl2 were added
to the stock loading solution. At the start of each experiment, two samples of 10 mL
were taken for analysis, one for gold and copper and the second for mercury. After 5
hours of loading, the experiment was stopped and two more samples were taken from
the solution to measure the amount of gold, copper, and mercury left unloaded in
each solution.
The loaded resin was stripped two times for 30 minute each using 25 mL of
0.5 M sodium perchlorate (NaClO4. H2O). The concentration of gold, copper, and
mercury were analysed before loading (t= 0 hour), after loading (t= 5 hours), and
after each stripping batch using ICP-OES. Solution speciation for thisoulfate and
polythionates was carried out using HPLC after loading (t= 5 hours) and for each
stripping batch.

4.4.2 Solution Speciation

Solution speciation for thiosulfate and polythionate components after 5 hours
loading and for each stripping batch was carried out using a high performance liquid
chromatography (HPLC) system. The HPLC system comprised a Dionex AS16
strong base anion exchange column (4 × 250 mm) with AG16 guard, coupled with a
Waters 2695 separation module. Detection of UV active components was
accomplished using a Waters 2996 UV Photodiode Array (PDA) detector (λ = 190–
400 nm). An isocratic elution with perchlorate at 1 mL/min flow rate was used to
separate the anionic sample components. Waters Empower software was used for

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Chapter 4: Materials and Methods

analysis of component peak areas, and the concentration determined were based on
comparisons with calibration standards ( Jeffrey & Brunt, 2007).

4.4.3 Loading-Elution Experiments

Six grams of wet resin were loaded overnight in 1.5 L of solution containing
2-
100 mM ammonium thiosulfate (ATS), 4 mM trithionate (S3O6 ), 1 mM
CuSO4.5H2O, 5 mM gold (Au) as gold thiosulfate [Au(S2O3)2]3-, and 5 mg/L Hg as
HgCl2. The solution and the resin were put in a 2 L volumetric flask and stirred
overnight at a speed of 150 rpm. The loaded resin was washed with de-ionised water,
and then 8 mL of the loaded resin was measured by a volumetric cylinder and
transferred into the elution column. The loaded resin was eluted using 100 mL of an
eluant solution containing 2 M NaCl and 0.2 M Na2SO3. The solution was pumped
into a column at a flow rate of 14.8 mL/h. An automatic fraction collector was
adjusted to collect 8 mL fractions. Each fraction was analysed for gold, copper, and
mercury using ICP-OES. Finally, the rest of the loaded resin was stripped two times
in series for 30 minutes using a solution of 0.5 M perchlorate (NaClO4. H2O). After
each batch was stripped, samples were collected for gold, copper, and mercury
analysis.

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Chapter 5: Thiosulfate leaching in open and closed vessels

Chapter 5 Thiosulfate Leaching in Open and Closed Vessels

5.1 Introduction
One of the main advantages of using thiosulfate is that it has less adverse
environmental impact than cyanide. However, of environmental concern when using
thiosulfate is that ammonia is required to stabilise the copper(II) ions in solution as
the copper(II) tetraamine complex. In this chapter, the main objective is to compare
both the leaching kinetics and associated environmental issues of using open and
closed leaching tanks with thiosulfate leaching in the presence of ammonia. After
determining whether an open or closed tank gave the best leaching kinetics and
which was more environmentally acceptable, an optimisation of different leaching
reagent concentrations was conducted in the chosen system for short run (1 hour) and
long run (8 hours) leaching experiments. Figure 5.1 shows the procedure adopted to
achieve the objectives of this section of the project.

Thiosulfate
leaching

Comparison
Open Closed
Vessel Vessel
Which system is?

• More efficient
• Better for the environment
• Less reagents consumed

Optimisation of
leaching parameters
in the chosen system
(1hr and 8 hrs runs)

Figure 5.1: Procedure to achieve the goals and achievements.

94
Chapter 5: Thiosulfate leaching in open and closed vessels

5.2 Thiosulfate Leaching in Open and Closed Vessels

The kinetic aspects of sodium thiosulfate leaching of gold and silver were
studied using a rotating disc technique in open and closed vessels to compare which
one of them is more efficient for gold and silver leaching, has less environmental
impact and lower reagents consumption. The setup of the experiment for leaching in
open and closed vessels has been shown in Figure 4.4 (Chapter 4). Both the open and
closed vessel experiments were conducted with 500mL of leaching solutions in a 1L
vessel thermostatted to ±0.1 ºC. For the open vessel experiments, the vessel was left
open to the atmosphere providing a 100mm diameter interface between the solution
and the atmosphere. For the closed vessel experiments, the vessel was sealed with a
glass cover, which provided a head space above the solution of approximately
500mL (Figure 4.4).

5.2.1 Gold and Silver Leaching in Open and Closed Vessels (1 hour run)
The standard leaching conditions used to compare the gold and silver
leaching in open and closed vessels were selected from the previous published
studies: 0.2 M sodium thiosulfate, 10 mM copper(II) sulfate, 0.4 M ammonia, 30 ºC,
and 300 rpm. The pH was fixed at a value of 11.5. Leaching began when the gold or
silver disc was inserted into the leaching solution. The leaching experiment lasted an
hour with samples being extracted after 15, 30, 45 and 60 minutes. Figure 5.2 shows
the amount of gold and silver dissolved from both open and closed vessel runs in
solutions containing the selected standard leaching conditions.
The data in Figure 5.2 shows that the amount of gold and silver dissolved in
thiosulfate solutions using the closed vessel for the 1 hour run is slightly higher than
that for the open vessel. It can be seen that silver dissolution in the thiosulfate
solution is higher than that of gold. This observation has also been observed in
cyanide solutions by Jeffrey, (2001). Jeffrey noted that gold dissolves nearly seven
times slower than silver with the dissolution rate of silver and gold about 26.6 x 10-5
mol m-2 s-1 and 3.9 x 10-5 mol m-2 s-1 respectively. According to Lide (1990), the
chemical bond strength of Au-Au (53.8 ± 0.5 kcal/mol at 25 ºC) is higher than that of
Ag-Ag (39 ± 2.0 kcal/mol) indicating that the dissolution rate of silver is higher than
that of gold.

95
Chapter 5: Thiosulfate leaching in open and closed vessels

20
Gold (closed)
18
Gold (open)
16
Silver (closed)
Gold/silver dissolution, mg/L 14 Silver (open)
12

10

0
0 15 30 45 60
Time, minute

Figure 5.2: The amount of gold and silver dissolved in both open and closed vessels.
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M
NH3, 300 rpm, pH= 11.5 and 30 ºC.

In order to determine the reason for the difference in gold and silver leaching
between the open and closed vessels, the concentrations of thiosulfate, ammonia, and
copper(II) were analysed after 30 and 60 minutes of gold leaching using pure metal.
The results are shown and discussed in sections (5.2.1.1, 5.2.1.2, & 5.2.1.3).

5.2.1.1 Thiosulfate Depletion in Open and Closed Vessels

Sodium thiosulfate concentrations were assayed in the open and closed
vessels by idometric titration (Lenahan and Murray-Smith, 1986). Figure 5.3 shows
the thiosulfate concentration as a function of time in solutions initially containing 0.2
M thiosulfate, 10 mM copper sulfate, 0.4 M ammonia without any air or oxygen
injection. The results show that there is a slight decrease in the thiosulfate
concentration (around 3.5% loss) after 60 minutes leaching in both open and closed
vessels. The greater decrease in thiosulfate in the open vessel may be due to the
reaction of thiosulfate with the oxygen from the ambient atmospheric air. This result
is similar to that of Breuer and Jeffrey (2003), where it was found that only 5% of
thiosulfate was decomposed after 1 hour of leaching without air or oxygen injections.

96
Chapter 5: Thiosulfate leaching in open and closed vessels

202
Open vessel
200 Clossed vessel

Thiosulfate concentration, mM
198

196

194

192
0 10 20 30 40 50 60 70
Time, minute

Figure 5.3: Thiosulfate concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC.

5.2.1.2 Ammonia Analysis in Open and Closed Vessels

The concentration of ammonia was analysed after 30 and 60 minutes
leaching. Figure 5.4 shows the concentration of ammonia as a function of time. The
analysis of ammonia in the open and closed vessels was carried out by the phenate
method (Greenberg, et al., 1992). It was found that loss of ammonia from the open
vessel was higher than that from the closed one and hence, the stability of Cu(II)
tetraammine complex may have been compromised allowing greater reduction of
Cu(II) by thiosulfate. Keeping ammonia in the leaching solution is necessary to
stabilise the copper(II) in the system. Ammonia loss from the open vessel might have
a secondary detrimental effect causing environmental problems. Therefore, it would
be preferable, kinetically and environmentally, to run the thiosulfate leaching of gold
or silver in the presence of ammonia in a closed vessel.

97
Chapter 5: Thiosulfate leaching in open and closed vessels

0.45
0.4

Ammonia concentration, M
0.35
0.3
0.25
Closed vessel
0.2
0.15 Open vessel

0.1
0.05
0
0 10 20 30 40 50 60 70
Time, minute

Figure 5.4: Ammonia concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC.

5.2.1.3 Copper(II) Analysis in Open and Closed Vessels

In order to understand all the effects of the open vessel compare to the closed,
copper(II) concentration was analysed by UV-Vis spectrophotometry. The
absorbance of copper(II) tetraammine was measured at a wavelength of 605 nm.
Figure 5.5 shows a comparison between the concentrations of copper(II) for open
and closed vessels. It can be observed that the concentration of copper(II) remains
slightly higher in the closed vessel experiments compared with the open vessel
experiments. The higher copper(II) concentrations in the closed vessel may be due to
the high percentage of ammonia retained in the closed vessel hence, the stability of
the copper(II) tetraamine complex is increased in the closed vessel leaching.

98
Chapter 5: Thiosulfate leaching in open and closed vessels

12
Closed vessel
10
Open vessel

Copper II concentration, mM
8

0
0 10 20 30 40 50 60 70
Time, minute

Figure 5.5: Copper(II) concentrations in open and closed vessels after 30 and 60
minutes leaching. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, pH= 11.5 and 30 ºC.

5.2.1.4 Gold and Silver Leaching Rates in Open and Closed Vessels (one hour)
The kinetic aspects of gold and silver dissolution from pure gold and silver in
thiosulfate solutions containing copper and ammonia for a short run experiments
(one hour leaching) in both open and closed vessels were studied using rotating discs
at the standard leaching conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, pH= 11.5 and 30 ºC. The amount of gold and silver dissolved were determined
after 15, 30, 45, and 60 minutes of leaching from which the gold and silver leaching
rates were calculated and the results are shown in Figure 5.6. It can be seen that
silver dissolved in the thiosulfate solution at a faster rate than gold. Both gold and
silver leached faster in the closed vessel than in the open vessel. The leach rate
decreased slightly over the leach period which, can be attributed to the decrease in
the reagent concentrations, thiosulfate, ammonia, and copper(II) as demonstrated in
sections 5.2.1.1, 5.2.1.2, and 5.2.1.3.

99
Chapter 5: Thiosulfate leaching in open and closed vessels

25 25

-2 -1
-2 -1

5 x 10 x Gold dissolution rate, mol.m.s

10 x Silver dissolution rate, mol.m.s
20 20

15 15

10 Silver (Clossed vessel) 10

Gold (Clossed vessel)
5 Gold (Open vessel) 5

5
Silver (Open vessel
5

0 0
0 10 20 30 40 50 60 70
Time, minute

Figure 5.6: Gold and silver dissolution rates in open and closed vessels for 1 hour
experiments. Initial experiment conditions: 10 mM CuSO4, 0.4 M NH3,
0.2 M (S2O3)2-, 300 rpm, pH = 11.5 and 30 ºC.

It is obvious that the dissolution rate of gold and silver in the closed vessel
are greater than that in the open vessel for the 1 hour leaching experiments. To
ensure and understand these differences in gold and silver leaching rates in both open
and closed vessels, the leaching run time was increased to 8 hours.

5.3 Effect of Reagent Concentrations and Leaching Parameters (8

hours run)
The gold and silver dissolution rates for thiosulfate solutions (Figure 5.6) are
comparable to those for cyanide solutions. This indicates the leaching residence time
for ores on plants using thiosulfate solutions would be longer than the one hour time
frame used so far in these experiments. Another series of experiments were
conducted to determine the effect of thiosulfate, ammonia and copper concentrations,
temperature, pH and rotation speed over an extended time period of 8 hours. Both
open and closed vessels were evaluated.

5.3.1 Effect of Temperature

In this section, the effect of temperature on gold and silver dissolution rates,
the volatilization of ammonia, the reduction of copper(II) to copper(I), and the

100
Chapter 5: Thiosulfate leaching in open and closed vessels

oxidisation of thiosulfate in both open and closed vessels are presented and
discussed.

5.3.1.1 Effect of Temperature on Gold and Silver Dissolution

The volatilization of ammonia and hence, the stability of the copper-
ammonia- thiosulfate leach system depends on the temperature of the solution. The
effect of temperature on the dissolution of gold and silver was determined under
standard leaching conditions of 0.2 M sodium thiosulfate, 10 mM Cu(II) sulfate, 0.4
M ammonia, 30 ºC, and 300 rpm. All experiments were carried out at a fixed pH of
11.5.
Figure 5.7 shows the effect of temperature on gold dissolution from pure gold
in open and closed vessels. Gold dissolution increased with increasing temperature in
both open and closed vessels, but the dissolution was higher in the closed vessel.
From the decrease in the slope of the lines in Figure 5.7, the gold dissolution rate
decreased with time. The decrease in dissolution rate is particularly evident for the
50 ºC leach in the open vessel which became the slowest towards the end of the eight
hour leach.

20

Temperature
Gold dissolustion, mg/L

16
25 ºC Closed
12 25 ºC Open
30 ºC Closed
8 30 ºC Open
40 ºC Closed
4 40 ºC Open
50 ºC Closed
50 ºC Open
0
0 2 4 6 8 10
Time, hour

Figure 5.7: Effect of temperature on gold leaching in open and closed vessels. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, and pH= 11.5.

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Chapter 5: Thiosulfate leaching in open and closed vessels

Fig. 5.8 shows the effect of temperature on silver dissolution from pure silver
in the open and closed vessels. The dissolution of silver is sensitive to the
temperature with the greatest dissolution, after 8 hours of leaching occurring at 30
ºC.

60 Temperature

50 25 ºC Closed
Silver dissolustion, mg/L

25 ºC Open
40
30 ºC Closed
30 ºC Open
30
40 ºC Closed
20 40 ºC Open
50 ºC Closed
10
50 ºC Open

0
0 2 4 6 8 10
Time, hour

Figure 5.8: Effect of temperature on silver leaching in open and closed vessels.
Initial leaching conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, and pH= 11.5.

Table 5.1 shows the dissolution rate of gold, from pure gold, after 1, 3, 5 and
8 hours of leaching at different temperatures in the open and closed reaction vessels.
The initial rate of gold extraction is enhanced by an increase in the leach temperature
but the rate falls off sharply after a leach time of approximately one hour for both
open and closed vessels. The average dissolution rate of gold over the 8 hour
leaching period is around 18% more in the closed than in the open vessel at 25 ºC,
while this percentage increased up to about 35% at 50 ºC.
Table 5.2 shows the dissolution rate of silver, from pure metal, after 1, 3, 5
and 8 hours of leaching at different temperatures in open and closed vessels. The
dissolution rates of silver after 8 hours in the open vessel at any temperature were
lower than the closed vessel. The silver dissolution rates after one hour of leaching
increased with increasing temperature but the rates decreased over time being about
25% of the initial rate after 8 hours of leaching. As a percentage there is a slight
difference in silver dissolution rates in the open and closed vessels after 1 hour of

102
Chapter 5: Thiosulfate leaching in open and closed vessels

leaching, but the difference increases to more than 43% at a temperature of 50 ºC

after 8 hours of leaching.

Table 5.1: Dissolution rates of gold after 1, 3, 5 and 8 hours at different temperatures
in open and closed reaction vessels.

Gold dissolution rate, 105 x mol.m-2.s-1

Temp., ºC Open vessel Closed vessel

1hr 3 hrs 5 hrs 8 hrs 1hr 3 hrs 5 hrs 8 hrs
25 2.16 1.52 1.17 0.88 2.18 1.74 1.41 1.08
30 2.52 1.74 1.27 0.89 2.79 2.06 1.65 1.27
40 3.99 2.14 1.50 1.02 4.44 2.52 1.81 1.31
50 2.55 1.51 1.04 0.71 4.65 2.26 1.56 1.10

Table 5.2: The dissolution rates of silver after 1, 3, 5, and 8 hours at different
temperatures in the open and closed reaction vessels.

Silver dissolution rate, 105 x mol.m-2.s-1

Temp., ºC Open vessel Closed vessel

1hr 3 hrs 5 hrs 8 hrs 1hr 3 hrs 5 hrs 8 hrs
25 13.32 7.57 5.07 3.41 17.22 10.84 8.01 5.71
30 16.79 8.85 5.77 3.88 19.23 11.87 9.21 6.90
40 18.88 9.11 5.92 3.99 21.19 12.54 9.36 6.55
50 17.53 7.60 5.27 3.43 22.84 10.81 6.90 4.49

A comparison between Tables 5.1 and 5.2 indicates that the dissolution rate
of silver is more than 6.5 times greater than the dissolution rate of gold. In addition,
the differences in the average gold and silver dissolution rates over the eight hour of
leaching at 50 ºC in open and closed vessels were 35% and 43% respectively. The
decrease in dissolution over time for both gold and silver and the greater decrease
observed in the open vessel may be attributed to:
• the volatilization of ammonia and hence a decrease of the Cu(II) tetraammine
complex stability;

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Chapter 5: Thiosulfate leaching in open and closed vessels

• an increase in the reduction rate of Cu(II) to Cu(I); and

• the decomposition of thiosulfate and the passivation of the gold surface by the
products of thiosulfate decomposition.

5.3.1.2 Effect of Temperature on the Volatilization of Ammonia

The open vessel experiments allowed free volatilization of ammonia from the
solution surface; therefore, volatilization was followed in the open vessel
experiments to determine the amount of ammonia loss. Figure 5.9 shows the
ammonia concentration decrease during the leaching experiments for the open vessel,
indicating that ammonia loss increased rapidly with increasing temperature.

Temperature
0.5
Ammonia concentration, M

25 ºC Open
0.4
30 ºC Open
0.3
40 ºC Open

0.2 50 ºC Open

0.1

0
0 2 4 6 8 10
Time, hour

Figure 5.9: Effect of temperature on ammonia volatilization in the open vessel.

Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3,
300 rpm, ºC, and pH= 11.5.

From the amount of ammonia remaining in the open vessel solution, the
average volatilization rates of ammonia (g/m2.s) over the eight hour experiment was
calculated by using the diameter of the open vessel of 10 cm. The results are
tabulated in Table 5.3. The volatilization of ammonia increased as the temperature
increased and doubled when the temperature was increased from 25 to 50 ºC.

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Chapter 5: Thiosulfate leaching in open and closed vessels

Table 5.3: The average volatilization rate of ammonia in the open vessel over the
eight hours of leaching at different temperatures.

Temperature, ºC 25 30 40 50
Volatilization rate of ammonia, g/m2.s x 102 1.053 1.278 1.729 2.256

The volatilization of ammonia is of metallurgical and environmental concern

especially during heap leaching where a closed system can not be used. Temperature
should be minimized in the thiosulfate leaching system in order to avoid the loss of
ammonia from the solution, but this must be balanced against the lower dissolution
rates at lower temperatures.

5.3.1.3 Effect of Temperature on Cu(II) Reduction

The volatility of ammonia and temperature are confounding variables on the
stability of the copper(II) tetraammine complex in the ammoniacal thiosulfate
leaching system. The concentration of Cu(II) was measured in open and closed
vessels after 1 and 8 hours of leaching at different temperatures (Figure 5.10). The
rate of Cu(II) reduction increased with increasing temperature. At temperatures
greater than 40 ºC, the concentration of Cu(II) in the open vessel was virtually zero
after 2 hours of leaching.

12 Temperature
25 ºC Closed
10
Cu(II) Concentration, mM

25 ºC Open
8 30 ºC Closed
30 ºC Open
6 40 ºC Closed
40 ºC Open
4 50 ºC Closed
50 ºC Open
2

0
0 2 4 6 8 10
Time, hour

Figure 5.10: Effect of temperature on Cu(II) concentration in open and closed

vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
0.4 M NH3, 300 rpm, ºC, and pH= 11.5.

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Chapter 5: Thiosulfate leaching in open and closed vessels

The results of Figure 5.10 show, also, that reduction of Cu(II) in the open
vessel was greater than for the closed vessel. Moreover, loss of ammonia from the
open vessel was high and hence, the stability of Cu(II) tetraamine complex in the
solution may have been reduced allowing greater reduction of Cu(II) to Cu(I) by
thiosulfate.

5.3.1.4 Effect of Temperature on the Decomposition of Thiosulfate

It has been found that temperature has positive influences on gold leaching
efficiency. However, raising temperature increases copper(II) reduction and
thiosulfate decomposition rates (Arslan et al., 2008; Breuer and Jeffrey, 2000;
Abbruzzese et al., 1995). Because of this, the effect of temperature on the
decomposition of thiosulfate in the open and closed vessels was studied and the
results are shown in Figure 5.11. There exists a general decrease in thiosulfate
concentration with increasing temperature, however, the concentration of thiosulfate
remains slightly higher in the closed vessel experiments compared with the open
vessel experiments. Comparison of the copper reduction and the thiosulfate
decomposition experiments indicate that thiosulfate continues to decompose even
when the copper(II) ions in solution are exhausted.

0.21
Temperature
Thiosulfate concentrations, M

25 ºC Closed
0.2
25 ºC Open
30 ºC Closed
0.19
30 ºC Open
40 ºC Closed
0.18 40 ºC Open
50 ºC Closed
0.17 50 ºC Open

0.16
0 2 4 6 8 10
Time, hour

Figure 5.11: Effect of temperature on the decomposition of thiosulfate in open and

closed vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, ºC, and pH= 11.5.

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Chapter 5: Thiosulfate leaching in open and closed vessels

5.3.2 Effect of Initial Ammonia Concentration

In the following sections, the effect of ammonia concentration ranging from
0.2 to 0.8 M on gold and silver dissolution rates, ammonia volatilization, and
copper(II) reduction in open and closed vessels are reported and discussed.

5.3.2.1 Effect of Initial Ammonia Concentration on Gold and Silver Dissolution

In this section the effect of initial ammonia concentration on the dissolution
rate of pure gold and pure silver in both open and closed vessels were studied. The
results in Figure 5.12 show that for all initial ammonia concentrations, the
dissolution rate of gold in the closed vessel was greater than the open vessel, which
can be attributed to the loss of ammonia from the open vessel and hence, the reduced
stability of the Cu(II) tetraammine complex.
The results indicate that the dissolution of gold increased with increasing
initial ammonia concentration up to 0.6 M then decreased at 0.8 M, but the rate of
gold dissolution, as shown in Table 5.4, decreased over time for all ammonia
concentrations.

25 Ammonia
0.2 M Closed
Gold dissolustion, mg/L

20
0.2 M Open
0.4 M Closed
15 0.4 M Open
0.6 M Closed
10 0.6 M Open
0.8 M Closed
5 0.8 M Open

0
0 2 4 6 8 10
Time, hour

Figure 5.12: Effect of ammonia concentration on gold dissolution in open and closed
vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
NH3, 300 rpm, 30 ºC, and pH= 11.5.

107
Chapter 5: Thiosulfate leaching in open and closed vessels

Table 5.4: Dissolution rates of gold after 1, 3, 5 and 8 hours at different ammonia
concentrations in open and closed reaction vessels.

Ammonia Gold dissolution rate, 105 x mol m-2s-1

Conc.,
M Open vessel Closed vessel

1hr 3 hrs 5 hrs 8 hrs 1hr 3 hrs 5 hrs 8 hrs

0.2 1.93 0.91 0.64 0.45 2.24 1.18 0.89 0.70
0.4 2.52 1.74 1.27 0.89 2.79 2.06 1.65 1.27
0.6 2.97 1.90 1.47 1.09 3.44 2.47 2.02 1.63
0.8 2.55 1.51 1.04 0.71 4.65 2.26 1.56 1.10

As the gold dissolution rate (Table 5.4) for the 0.8 M initial ammonia
experiment was below that obtained for the 0.6 M initial ammonia experiment when
the ammonia concentration decreased to 0.6 M through volatilization, the decrease in
rate must be attributed to a reduction in the copper (II) tetraammine concentration.
Figure 5.13 shows the dissolution of silver at different initial ammonia
concentrations in open and closed vessels. The dissolution of silver is very low at 0.2
M ammonia and increases rapidly with increasing ammonia concentration. Silver
dissolution is more sensitive to ammonia concentration than gold as reported by
Zipperian et al. (1988).
The dissolution rate of silver was calculated after 1, 3, 5, and 8 hours of
leaching in open and closed vessels (Table 5.5). Again the dissolution rates are
greater in the closed compared to the open vessel. Unlike gold, the dissolution rate of
silver continues to increase up to an initial ammonia concentration of 0.8M. If the
sole function of ammonia was to stabilize the Cu(II) ion in the system, the same
optimum copper to ammonia ratio as observed for gold dissolution would have been
expected.

108
Chapter 5: Thiosulfate leaching in open and closed vessels

120
Ammonia

Silver dissolustion, mg/L

100 0.2 M Closed
80 0.2 M Open
0.4 M Closed
60 0.4 M Open
0.6 M Closed
40
0.6 M Open
20 0.8 M Closed
0.8 M Open
0
0 2 4 6 8 10
Time, hour

Figure 5.13: Effect of ammonia concentration on silver leaching in open and closed
vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
NH3, 300 rpm, 30 ºC, and pH= 11.5.

Table 5.5: The dissolution rate of silver after 1, 3, 5, and 8 hours at different
ammonia concentrations in open and closed reaction vessels.

Ammonia Silver dissolution rate, 105 x mol m-2 s-1

Conc.,
M Open vessel Closed vessel

1hr 3 hrs 5 hrs 8 hrs 1hr 3 hrs 5 hrs 8 hrs

0.2 3.70 1.76 1.16 0.77 5.97 2.66 1.73 1.11
0.4 16.79 8.85 5.77 3.88 19.23 11.87 9.21 6.90
0.6 16.94 9.90 7.52 5.71 21.67 16.67 13.69 10.54
0.8 19.34 11.69 9.70 7.68 23.94 20.19 17.05 14.26

5.3.2.2 Effect of Initial Ammonia Concentration on Volatilization of Ammonia

The remaining ammonia concentration for different initial ammonia
concentrations, in the thiosulfate system at 30 ºC, in open vessels after 1 and 8 hours
of leaching were analysed and the results are shown in Figure 5.14.

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Chapter 5: Thiosulfate leaching in open and closed vessels

0.9

0.8 Ammonia
Ammonia concentration, M 0.7
0.2 M Open
0.6
0.4 M Open
0.5
0.6 M Open
0.4
0.8 M Open
0.3
0.2

0.1

0
0 2 4 6 8 10
Time, hour

Figure 5.14: Effect of initial ammonia concentration on ammonia volatilization in

the open vessel. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5.

Referring to Figure 5.14, it is evident that the amount of ammonia loss

increased when the initial concentration of ammonia was increased. The maximum
loss was about 37% at an initial concentration of 0.8 M ammonia.

5.3.2.3 Effect of Initial Ammonia Concentration on Cu(II) Reduction

The effect of the initial ammonia concentration on Cu(II) reduction at 30°C
are presented in Figure 5.15. All the copper(II) measurements in the closed vessel
were higher than in the open vessel. Increasing the initial concentration of ammonia,
stabilized the Cu(II) tetraammine in the solution for a longer period, hence, using the
closed vessel had a positive effect on the Cu(II) concentration.

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Chapter 5: Thiosulfate leaching in open and closed vessels

12
Ammonia
10
Cu(II) concentration, mM 0.2 M Closed
8 0.2 M Open
0.4 M Closed
6
0.4 M Open

4 0.6 M Closed
0.6 M Open
2 0.8 M Closed
0.8 M Open
0
0 2 4 6 8 10
Time, hour

Figure 5.15: Effect of initial concentration of ammonia on Cu(II) reduction in open

and closed vessels. Initial experiment conditions: 0.2 M (S2O3)2-, 10
mM CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5.

From the previous sections that compared the leaching of gold and silver in
open and closed vessels, some noticable observations are summerized as follows:
• the leaching of gold and silver in solutions containing Cu(II), ammonia and
thiosulfate in a closed vessel maintains the optimum leaching conditions and
enhances the leaching kinetics compared with an open vessel;
• the leaching rate of gold and silver in the closed vessel was greater than that
obtained in the open vessel by approximately 35% and 43% respectively;
• higher temperatures increased the volatilization rate of ammonia during leaching
in the open vessel, which raises environmental concern about using ammonia; and
• Cu(II) reduction increased in the open vessel with higher temperatures due to the
loss of ammonia and hence the amount of free Cu(II) that reacts with thiosulfate.
• Temperature should be minimized in the thiosulfate system to avoid ammonia
losses and the consumption of thiosulfate.
From the pervious observations, it can be suggested that leaching in a closed
vessel is preferred to leaching in an open vessel due to its kinetic and environmental
advantages. Therefore, the closed vessel (tanks) for the leaching of gold or silver in
thiosulfate solutions containig copper and ammonia was selected. In the following

111
Chapter 5: Thiosulfate leaching in open and closed vessels

sections, the leaching of pure gold, pure silver and gold-silver alloys in the selected
closed vessel are presented and discussed.

5.4 Dissolution Rates of Gold, Silver and Total Metal as a Function

of Silver Content
The dissolution rate of gold, silver, and total metal (gold-silver) as a function
of silver content from pure gold and silver and gold-silver alloys is shown in Figure
5.16. It can be seen that the gold dissolution rate for pure gold is higher than that for
4 and 8% Ag alloys. Further increase in silver content up to 50% increased the gold
dissolution rate to values higher than that for pure gold. The results also demonstrate
that the silver dissolution rate from the pure metal is 6.89 times that of pure gold.
The findings are consistent with those observed by Jeffrey (2001). Moreover, the
silver and total metal dissolution rates increased with increasing the silver content.
Not surprisingly, the silver dissolution rate is very slow at low percentages of silver,
but increased significantly when the silver content was more than 20%.

Ag, wt.%
0 4 8 20 50 100

25 25
10 5 x Gold/silver dissolution rate, mole.m-2 .s-1

Gold

20 20
Silver

15 T otal 15

10 10

5 5

0 0
0 10 20 30 40 50 60 70 80 90 100
Ag, mole %

Figure 5.16: The dissolution rate of gold, silver and gold-silver alloys after 1 hour.
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M
NH3, 300 rpm, 30 ºC, and pH= 11.5.

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Chapter 5: Thiosulfate leaching in open and closed vessels

5.5 Dissolution Rate of Gold-Silver Alloys as a Function of Time

The leaching of gold-silver alloy discs of different silver composition, 4, 8,
20, and 50% was carried out in a closed vessel. Figure 5.17 shows gold dissolution
rates for each alloy after 15, 30, 45, 60 minutes using the selected initial standard
concentrations of 0.2 M sodium thiosulfate, 10 mM copper sulfate, 0.4 M ammonia,
30 ºC, and 300 rpm. The results of Figure 5.17 show that the gold dissolution rate
under the standard conditions varied significantly with the amount of silver in the
alloy. Increasing gold dissolution rate with the presence of silver was also reported in
cyanide solutions by Wadsworth and Zhu (2003), Jeffrey and Ritchie, (2000), and
Wadsworth et al. (2000).

5
4% Ag
4.5 8% Ag
20% Ag
-2 -1
10 x Gold dissolution rate, mol.m.s

4 50% Ag

3.5

2.5

2
5

1.5

1
0 15 30 45 60
Time, minute

Figure 5.17: Gold dissolution rate for gold-silver alloys using a closed vessel. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, 30 ºC, and pH= 11.5.

5.6 Effect of the Leaching Conditions (8 hour run)

To get a better understanding of gold, silver, and gold/silver leaching in
thiosulfate solutions, the effects of different leaching conditions used in the system
were investigated. Different concentrations of thiosulfate, ammonia, and copper(II)
were used in this part of the project. Furthermore, the effects of temperature, pH, and
agitation speed are evaluated in the closed vessel for a leaching time of 8 hours. The
calculated dissolution rates throughout this investigation except the ones for the

113
Chapter 5: Thiosulfate leaching in open and closed vessels

effect of time are the average rate over 3, 5, and 8 hours of leaching. The results of
these experiments are reported and discussed in this section.

5.6.1 Effect of Time on the Gold and Total Metal Dissolution

Figures 5.18 and 5.19 show gold and total metal dissolution rate from pure
gold, pure silver and gold-silver alloys over 1, 3, 5, and 8 hours of leaching. The
amount of gold dissolved from 20 and 50% silver alloys is higher than that from pure
gold, and the 4, and 8% silver alloys for all the time periods (Figure 5.18).

4
Pure gold
3.5
4% Ag
-2 -1
10 x Gold dissolution rate, mol.m.s

3 8% Ag
20% Ag
2.5 50% Ag

1.5

1
5

0.5

0
0 2 4 6 8 10
Time, hour

Figure 5.18: Gold dissolution rate from gold and gold-silver alloys. Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, 30 ºC, and pH= 11.5.

The gold and total metal dissolution rates decreased over time due to the
conditions changing with the consumption of reagents and the reduction of copper(II)
to copper(I). Passivation of gold and alloy surfaces by the products of thiosulfate
decomposition may also contribute to the decrease in the dissolution rate. The
average dissolution rate of pure silver decreased the most, 64% compared with 55%
for pure gold, when the average dissolution rate for eight hours is compared with that
for 1 hour (Figure 5.19).

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Chapter 5: Thiosulfate leaching in open and closed vessels

20

18 Pure gold
4% Ag

-2 -1
16 8% Ag
10 x total dissolution rate, mol.m .s 14 20% Ag
50% Ag
12 Pure silver

10

6
5

0
0 2 4 6 8 10
Time, hour

Figure 5.19: Total metal average dissolution rate for gold, silver and gold-silver
alloys. Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4
M NH3, 300 rpm, 30 ºC, and pH= 11.5.

5.6.2 Effect of Thiosulfate Concentration on Gold, Silver, and Total Metal

Dissolution
The effect of initial sodium thiosulfate concentration on gold and total metal
average dissolution rate over an eight hour period is presented in Figures 5.20 and
5.21. When the initial thiosulfate concentration was increased from 0.1 M to 0.2 M to
0.4 M, the gold and total dissolution rate increased for pure gold, pure silver and the
gold–silver alloys. The increased dissolution rate is due to an increase in gold and
silver oxidation caused by the increase in thiosulfate concentration. However, using
higher concentrations of thiosulfate leads to an increase in the reduction rate of
Cu(II) to Cu(I) and thus, increases decomposition of thiosulfate. The results are
consistent with those of Muyunda (1996) and Jeffrey (2001). The total dissolution
rate (Figure 5.21) increased sharply after the silver content exceeded 20% indicating
that the silver dissolution starts to increase significantly after this percentage of silver
as has also been shown in section 5.5.

115
Chapter 5: Thiosulfate leaching in open and closed vessels

thiosulfate
0.1 M
2.5
10 5 x Gold dissolution rate, mol.m-2 .s-1
0.2 M
0.4 M
2

1.5

0.5

0
0 5 10 15 20 25 30 35 40 45 50
Ag, Wt.%

Figure 5.20: Gold average dissolution rate from pure gold and gold-silver alloys at
different initial thiosulfate concentrations (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: (S2O3)2-, 10 mM CuSO4,
0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5.

12
thiosulfate
0.1 M
10 0.2 M
105 x Total dissolution rate, mol.m -2.s-1

0.4 M

0
0 10 20 30 40 50 60 70 80 90 100
Ag, Wt.%

Figure 5.21: Total average metal dissolution rate from gold, silver and gold-silver
alloys at different initial thiosulfate concentrations (average rate of 3, 5,
and 8 hours leaching). Initial experiment conditions: (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5.

116
Chapter 5: Thiosulfate leaching in open and closed vessels

5.6.3 Effect of Copper(II) Concentration on Gold, Silver and Total Metal

Dissolution
The effects of changing the initial Cu(II) concentration in thiosulfate leaching
solutions on average gold and total metal dissolution rates are shown in Figures 5.22
and 5.23 respectively. By increasing the initial concentration of Cu(II), the amount of
gold dissolved from all the gold-silver alloys increased. In addition, the gold
dissolution rate from pure gold was higher than that obtained from 4 and 8% Ag
alloys and less than that from the 20 and 50% Ag alloys.

2.5
copper(II)
1.25 mM
-2 -1
10 x Gold dissolution rate, mol.m.s

2
2.5 mM
5 mM
10 mM
1.5

1
5

0.5

0
0 5 10 15 20 25 30 35 40 45 50
Ag, Wt.%

Figure 5.22: Gold average dissolution rate from gold and gold-silver alloys at
different initial copper sulfate concentrations (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, CuSO4,
0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5.

Results presented in Figure 5.23 show that changing the initial Cu(II)
concentration has a significant influence on the metal dissolution rate, being, 1.67
x10-5 mol.m-2.s-1 at 1.25 mM Cu(II) and increasing to 6.6 x10-5 mol.m-2.s-1 at 10 mM
Cu(II) for pure silver.

117
Chapter 5: Thiosulfate leaching in open and closed vessels

10
copper(II)
9
1.25 mM
-2 -1
8
10 x total dissolution rate, mol.m .s 2.5 mM
7
5 mM
6 10 mM

3
5

0
0 10 20 30 40 50 60 70 80 90 100
Ag, Wt.%

Figure 5.23: Total average metal dissolution rate of pure gold, pure silver and gold-
silver alloys at different initial copper sulfate concentration (average
rate of 3, 5, and 8 hours leaching). Initial experiment conditions: 0.2 M
(S2O3)2-, CuSO4, 0.4 M NH3, 300 rpm, 30 ºC, and pH= 11.5.

5.6.4 Effect of Ammonia Concentration on Gold, Silver and Total Metal

Dissolution
The effect of ammonia on the average gold and total dissolution rate was
conducted with ammonia concentration ranging from 0.2 to 0.8 M and the results are
presented in Figures 5.24 and 5.25. It can be seen from Figure 5.24 that the amount
of gold dissolved from each disc increased by increasing the concentration of
ammonia up to 0.6 M but increasing the concentration up to 0.8 M decreased the
amount of gold dissolved.
Alloys that contain higher concentrations of silver were more sensitive to
ammonia concentration. The pure silver dissolution rate at 0.2 M ammonia was very
low while the maximum dissolution rate of silver was 15.29 x10-5 mol.m-2.s-1 at an
initial concentration of 0.8 M ammonia. For pure gold, the maximum dissolution rate
was 1.63 x10-5 mol.m-2.s-1 at an initial ammonia concentration of 0.6 M and 1.25 x10-
5
mol.m-2.s-1 at an initial concentration of 0.8 M ammonia. It has been observed that
ammonia improves the anodic dissolution of the gold, reduces passivation of the gold
surface (Jiang et al., 1993), produces Cu(II) tetra-ammine in the system, and is
important to the Cu(II) ions function as an oxidant (Aylmore, 2001).

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Chapter 5: Thiosulfate leaching in open and closed vessels

3.5

ammonia
3 0.2 M
0.4 M
-2 -1
10 x gold dissolution rate, mol.m .s 2.5 0.6 M
0.8 M
2

1.5

1
5

0.5

0
0 10 20 30 40 50
Ag, Wt.%

Figure 5.24: Gold dissolution rate from gold and gold-silver alloys at different initial
ammonia concentrations (average rate of 3, 5, and 8 hours leaching).
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, NH3, 300
rpm, 30 ºC, and pH= 11.5.

Referring to Figure 5.25, it is evident that silver dissolution rate is enhanced

by increasing the initial concentration of ammonia. The results indicate that the
optimum ammonia concentration to achieve the maximum gold and silver dissolution
rates were 0.6 M for gold and 0.8 M for silver.
20

18
ammonia
16 0.2 M
-2 -1
10 x Total dissolution rate, mol.m .s

14 0.4 M

0.6 M
12
0.8 M
10

6
5

0
0 10 20 30 40 50 60 70 80 90 100
Ag. Wt.%

Figure 5.25: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different initial ammonia concentrations (average rate of 3, 5,
and 8 hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10
mM CuSO4, NH3, 300 rpm, 30 ºC, and pH= 11.5.

119
Chapter 5: Thiosulfate leaching in open and closed vessels

5.6.5 Effect of Temperature on Gold, Silver and Total Metal Dissolution

The dissolution of gold and total metal as a function of silver contents at
different temperatures was studied under the leaching conditions of 0.2 M sodium
thiosulfate, 10 mM Cu(II) sulfate, 0.4 M ammonia, and 300 rpm. All experiments
were performed at a fixed pH of 11.5. Figure 5.26 shows the effects of temperature
on the average gold dissolution rate using different percentages of silver. The results
presented in Figure 5.26 indicate that gold dissolution rate varied with temperature.
An increase in temperature would be expected to enhance the activity of the
solution and thus, increase the rate of gold dissolution. However, when temperature
was increased from 30 ºC to 50 ºC, the average gold dissolution rate from all discs
was significantly decreased. As can also be seen from Figure 6.27, the total metal
average dissolution rate also varied with temperature. In addition, there is an increase
in the average total metal dissolution rate from 25 to 30 ºC, but a decrease as the
temperature is increased from 30 to 50 ºC. This is because at high temperatures, the
rates of ammonia losses, Cu(II) reduction into Cu(I) and the decomposition of
thiosulfate increase.

2.5

2.3

2.1
-2 -1
10 x gold dissolution rate, mol.m .s

1.9

1.7

1.5
25 °C
1.3
30 °C

1.1 40 °C
5

50 °C
0.9

0.7

0.5
0 5 10 15 20 25 30 35 40 45 50
Ag, Wt.%

Figure 5.26: Gold dissolution rates from gold and gold-silver alloys at different
temperatures (average rate of 3, 5, and 8 hours leaching). Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300
rpm, ºC, and pH= 11.5

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Chapter 5: Thiosulfate leaching in open and closed vessels

It is evident from the results shown in Figures 5.26 and 5.27 that there exists
an optimum temperature at which maximum rates of gold and total metal dissolution
will result. The results indicate that the optimum temperature for gold and silver
dissolution was 30 ºC.
10

8
-2 -1
10 x total dissolution rate, mol.m .s

6 25 °C

5 30 °C

4 40 °C

50 °C
3
5

0
0 10 20 30 40 50 60 70 80 90 100
Ag, Wt.%

Figure 5.27: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different temperatures (average rate of 3, 5, and 8 hours
leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4,
0.4 M NH3, 300 rpm, ºC, and pH= 11.5.

5.6.6 Effect of Rotation Speed on Gold, Silver and Total Metal Dissolution
The effects of rotation speed on the gold and total metal dissolution rate from
pure gold, pure silver and gold-silver alloys was investigated at rotation speeds
ranging from 300 rpm to 600 rpm. The results of these experiments are shown in
Figures 5.28 and 5.29. The results show that both gold and total metal dissolution
rate increased with rotation speed. However, the silver dissolution rate from the pure
silver disc was more sensitive to change in rotation speed than gold from the pure
gold disc. The sensitivity to rotation speed indicates that the dissolution of silver in
thiosulfate solutions is a diffusion controlled reaction in which the rotation speed
enhances the dissolution rate. This result is consistent with those observed by Jeffrey
(2001).

121
Chapter 5: Thiosulfate leaching in open and closed vessels

300 RPM
2.5 400 RPM
-2 -1
10 x Gold leaching rate, mol.m.s 500 RPM
600 RPM
2

1.5
5

0.5
0 5 10 15 20 25 30 35 40 45 50
Ag, Wt.%

Figure 5.28: Gold dissolution rate from gold and gold-silver alloys at different
rotation speeds (average rate of 3, 5, and 8 hours leaching). Initial
experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, rpm,
30 ºC, and pH= 11.5.

14

12 300 RPM
400 RPM
-2 -1
10 x total leaching rate, mol.m.s

10 500 RPM
600 RPM
8

4
5

0
0 10 20 30 40 50 60 70 80 90 100
Ag, Wt.%

Figure 5.29: The total average metal dissolution rate of pure gold, pure silver and
gold-silver alloys at different rotation speeds (average rate of 3, 5, and 8
hours leaching). Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM
CuSO4, 0.4 M NH3, rpm, 30 ºC, and pH= 11.5

122
Chapter 5: Thiosulfate leaching in open and closed vessels

5.6.7 Effect of pH (ammonium sulfate concentration) on Gold, Silver and

Total Metal Dissolution
The effect of ammonium sulfate concentration and hence pH on the total metal
dissolution rate form pure gold, pure silver and gold-silver alloys was investigated
and the results are shown in Figures 5.30 and 5.31. The experiments were conducted
using 0, 0.01, 0.1, and 0.4 M ammonium sulfate giving solution pH values of 11.50,
10.97, 9.96, and 9.60 respectively. The average gold dissolution rate from the pure
gold disc increased slightly when the pH was increased from 9.60 to 9.96. However,
the total metal dissolution rates using different percentages of silver were
significantly increased by increasing the pH up to 11.50. The dissolution rate of
silver from pure metal decreased with increasing ammonium sulfate concentration
(hence decreasing the value of pH) with the highest rate when no ammonium sulfate
was present. It has to be pointed out that the optimum pH value to maximize the gold
and silver dissolution rates is 11.50.

2.5
-2 -1
10 x gold dissolution rate, mol.m .s

pH 11.50
1.5
pH 10.97

pH 9.96

pH 9.60
1
5

0.5
0 10 20 30 40 50
Ag, Wt.%

Figure 5.30: Gold dissolution rate from gold and gold-silver alloys at different pH
values (average rate of 3, 5, and 8 hours leaching). Initial experiment
conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M NH3, 300 rpm, 30 ºC
and pH (ammonium sulfate added).

123
Chapter 5: Thiosulfate leaching in open and closed vessels

10

9
pH 11.50
8 pH 10.97
-2 -1
10 x total dissolution rate, mol.m .s
pH 9.96
7
pH 9.60
6

3
5

0
0 10 20 30 40 50 60 70 80 90 100
Ag, Wt.%

Figure 5.31: Total average metal dissolution rate of gold, silver and gold-silver
alloys at different pH values (average rate of 3, 5, and 8 hours leaching).
Initial experiment conditions: 0.2 M (S2O3)2-, 10 mM CuSO4, 0.4 M
NH3, 300 rpm, 30 ºC, and pH (ammonium sulfate added).

5.7 Summary
In this chapter, a comparison between using open and closed vessels in the
thiosulfate leaching system was carried out. The experiments were conducted using
pure gold, pure silver and gold-silver alloys. It was found that using a closed vessel
to dissolve gold and silver in thiosulfate solutions containing Cu(II) and ammonia
maintains the optimum reagents concentrations for a longer time and enhances the
leaching kinetics compared with an open vessel. The leaching rate of gold and silver
in the closed vessel was greater than that obtained in the open vessel by 35% and
43% respectively. Silver leaching rates were found to be more sensitive to
temperature and ammonia concentration than gold. Higher temperatures increased
the volatilization rate of ammonia during the leaching in the open vessel which will
be of metallurgical and environmental concern. In addition, the study has shown that
in thiosulfate solutions containing Cu(II) and ammonia, the gold dissolution rate was
enhanced with the presence of silver.

124
Chapter 5: Thiosulfate leaching in open and closed vessels

The optimisation of leaching conditions was carried out using the closed
vessel. Gold and silver dissolution rates were increased with increasing thiosulfate,
copper(II), and ammonia concentrations. It was determined that the optimum
leaching conditions for gold and silver were: 10 mM Cu(II), 0.6 M NH3 for gold and
0.8 M for silver, 0.2 M (S2O3)2-, 30 ºC, 300 rpm, and pH =11.5.

125
Chapter 6 An electrochemical study of the leaching of gold, silver,
and gold-silver alloys in thiosulfate solutions

6.1 Introduction
The leaching of gold in thiosulfate solutions is an electrochemical reaction
and like other electrochemical reactions, it combines of the oxidation of gold (anodic
reaction) and the reduction of the oxidant copper(II) (cathodic reaction). In the
present chapter, electrochemical techniques are used to study the oxidation of gold
from pure gold and gold-silver discs to the gold thiosulfate complex. The anodic half
reaction of gold is shown in Equation 6.1 which has a standard potential of 0.15 V
(Nicol et al., 1987).
2−
Au + 2 S 2 O3 → Au ( S 2 O3 ) 32− + e − (6.1)
As silver often is present as an alloying element with native gold, in this
chapter, the effect of silver contents on the gold oxidation half reaction is studied.
Gold-silver alloys discs of 4, 8, 20, and 50 wt.% silver were used.
The experimental work was carried out in two ways: linear sweep
voltammetry and coulometric electrochemical experiments at a fixed potential value.
The experiments were performed at a rotation rate of 300 rpm and at a temperature of
30 ºC for 30 minutes. The solutions were kept at the natural pH. After 30 minutes,
samples were collected and analysed for gold and silver by ICP-OES.

6.2 Linear Sweep Voltammetry

Linear sweep voltammetry was carried out using a Radiometer PGZ 301
potentiostat. All experiments were performed at 30 ºC, with a rotation rate of 300
rpm and a scan rate of 1 mV s-1. Potentials were measured relative to the saturated
calomel electrode (+0.242 V vs. SHE). Solutions were de-aerated using nitrogen for
20 minutes. The current was measured at a range of potential between -22 mV and
300 mV (relative to SCE). In the following sections, the effect of different reagent
and additive concentrations on the gold oxidation half reaction are presented and
discussed.

126
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.2.1 Effect of Ammonium Thiosulfate Concentration
Thiosulfate is the main reagent in the thiosulfate system and has the most
noticeable effect on the rate of gold leaching. Thus, the effect of different ammonium
thiosulfate (ATS) was investigated using the liner sweep voltammetry technique on
pure gold, pure silver and gold-silver discs of 17 mm diameter (surface area 2.27
cm2).

6.2.1.1 Pure Gold

Figure 6.1 shows the effect of ammonium thiosulfate (ATS) concentration on
the current density resulting form gold oxidation. It can be seen from Figure 6.1 that
an increase in ammonium thiosulfate concentration results in an increase in the
produced current due to the oxidation of gold. This result is consistent with those of
Breuer and Jeffrey (2002) and Jeffrey (2001). Also this confirms the result that has
been shown in the kinetics studies (Chapter 5) of this project.

Pure Gold
7

6 25 mM ATS
50 mM ATS
5 100 mM ATS
-2
Current, A m

200 mM ATS
4
300 mM ATS
3

0
0 50 100 150 200 250 300
Potential, mV

Figure 6.1: Linear sweep voltammograms showing the effect of ATS concentration
on the current density of the gold oxidation for pure gold. Experimental
conditions: 300 rpm, 30 ºC, and natural pH of the solution.

127
 Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.2.1.2 Gold-Silver Alloys
The effect of ammonium thiosulfate (ATS) concentration on the current
density of both gold and silver oxidation from gold-silver alloys in thiosulfate
solutions is shown in Figure 6.2.

4% Ag 8% Ag
8 12
25 mM ATS 25 mM ATS
7
50 mM ATS 10 50 mM ATS
6 100 mM ATS 100 mM ATS
200 mM ATS 8 200 mM ATS
-2

-2
5
Current, A m

Current, A m
300 mM ATS 300 mM ATS
4 6

3
4
2
2
1

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

20% Ag 50% Ag
16 20
25 mM ATS 25 mM ATS
14 18
50 mM ATS 50 mM ATS
16 100 mM ATS
12 100 mM ATS
14 200 mM ATS
200 mM ATS
-2

Current, A m -2

10
Current, A m

12 300 mM ATS
300 mM ATS
8 10

6 8
6
4
4
2
2
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

Figure 6.2: Linear sweep voltammograms showing the effect of ammonium

thiosulfate concentration on the current density of both gold and silver
oxidation for 4, 8, 20, and 50% Ag alloys. Experimental conditions: 300
rpm, 30 ºC, and natural pH of the solution.

Figure 6.2 shows that an increase of silver percent in the alloy results in an
increase of the current density for combined gold and silver oxidation in the
thiosulfate solutions over the whole range of applied potentials. This result is
consistent with the total leaching rate of gold and silver from these alloys obtained
from the kinetics study in this project (Chapter 5). For all gold silver alloys the

128
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
current density increased with increasing concentration of ammonium thiosulfate
(ATS). This result also is consistent with those observed by Chandra and Jeffrey
(2004) for the oxidation of pure gold and 2% Ag.

6.2.2 Effect of Sodium Thiosulfate Concentration

To compare the effect of the two main commercial thiosulfate salts, the effect
of using sodium thiosulfate (STS) concentration on the votammograms of pure gold
and gold-silver alloys was investigated.

6.2.2.1 Pure Gold

The effect of sodium thiosulfate (STS) concentration on the current density of
the gold oxidation form a gold thiosulfate complex is shown in Figure 6.3. Results in
Figure 6.3 show that the same trend was obtained using ammonium thiosulfate
compared with STS on leaching of pure gold (Figure 6.1). A comparison between
Figure 6.1 and 6.3 shows that gold oxidation is faster in ammonium thiosulfate
solution than sodium thiosulfate solution. It has been shown by Chandra and Jeffrey
(2004) that gold oxidation using ATS is faster than that of STS. The increase in the
gold oxidation in the presence of ammonium thiosulfate can be attributed to the
increased pH value with the presence of ammonium ions from the ATS.

129
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

Pure Gold
2
25 m M STS
1.8
50 m M STS
1.6
100 m M STS
1.4
200 m M STS
-2
Current, A m
1.2
300 m M STS
1
0.8
0.6
0.4
0.2
0
0 50 100 150 200 250 300
Potential, mV

Figure 6.3: Linear sweep voltammograms showing the effect of sodium thiosulfate
(STS) concentration on the current density of gold oxidation from a
pure gold disc. Experimental conditions: 300 rpm, 30 ºC, and natural
pH of the solution.

6.2.2.2 Gold-Silver
The effect of sodium thiosulfate (STS) concentration on the current density
resulting from gold-silver oxidation from gold-silver alloys in thiosulfate solution is
shown in Figure 6.4. From a comparison between the data in Figures 6.3 and 6.4, the
current density resulting from the gold oxidation of pure gold is slightly higher than
the total metal oxidation obtained from 4, and 8% Ag alloys, however, for 20 and
50% Ag alloys the current density was much higher than for pure gold.

130
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

4% Ag 8% Ag
1.4 2
25 m M STS 25 m M STS
1.8
1.2 50 m M STS 50 m M STS
1.6
100 m M STS 100 m M STS
1 1.4
200 m M STS 200 m M STS
-2

-2
Current, A m

Current, A m
0.8 300 m M STS 1.2 300 m M STS
1
0.6
0.8

0.4 0.6
0.4
0.2
0.2
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

20% Ag 50% Ag
4.5 20
25 m M STS 25 m M STS
4 18
50 m M STS 50 m M STS
3.5 16
100 m M STS 100 m M STS
14 200 m M STS
3 200 m M STS
-2

-2
Current, A m

Current, A m

12 300 m M STS
2.5 300 m M STS
10
2
8
1.5
6
1 4
0.5 2
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

Figure 6.4: Linear sweep voltammograms showing the effect of sodium thiosulfate
(STS) concentration on the combined current density of gold and silver
oxidation in 4, 8, 20, and 50% Ag alloys. Experimental conditions: 300
rpm, 30 ºC, and natural pH of the solution.

6.2.3 Effect of Ammonia Concentration

Ammonia is required in thiosulfate solutions in order to stabilise the copper in
the copper(II) oxidation state. In this section, the effect of ammonia concentration on
the gold oxidation process from pure gold and gold-silver alloys was studied using
the linear sweep voltametry technique. It has been noted by Zhu et al. (1994) that the
oxidation of gold in the presence of ammonia occurs in two steps, the formation of a
gold-ammonia complex (Equation 6.2) and then the thiosulfate ion substitutes for the
ammonia ion to form a gold-thiosulfate complex as shown in Equation 6.3.

131
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Au + + 2 NH 3 → Au ( NH 3 ) +2 (6.2)

Au ( NH 3 ) 2+ + 2 S 2O32− → Au ( S 2O3 ) 32− + 2 NH 3 (6.3)

6.2.3.1 Effect of Ammonia Concentration on Pure Gold

Figure 6.5 shows the measured current density of gold oxidation as a function
of potential at different ammonia concentrations. In the absence of ammonia, the
process of gold oxidation is very slow over all the potentials. However, in solutions
containing high ammonia concentrations, gold oxidation occurs rapidly. This result is
consistent with those of Chandra and Jeffrey (2004) and Jiang et al. (1993a).

Pure Gold
16
Ammonia
14
0 mM
12 50 mM
100 mM
-2

10
Current, A m

200 mM
8 400 mM

0
0 50 100 150 200 250 300
Potential, mV

Figure 6.5: Linear sweep voltammograms showing the effect of ammonia

concentration on the current density of the gold oxidation for pure
gold. Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC, and
natural pH of the solution.

6.2.3.2 Effect of Ammonia Concentration on Gold-Silver Alloys

The effect of ammonia concentration on combined gold and silver oxidation
in thiosulfate solutions containing 50 mM ATS was investigated. Figure 6.6 shows
the measured current density of total metal oxidation from the gold-silver alloys at
different ammonia concentrations.

132
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

4% Ag 8% Ag
16 25
Ammonia Ammonia
14
0 mM
20 0 mM
12 50 mM
50 mM
100 mM

-2
-2

Current, A m
10 100 mM
Current, A m

15
200 mM
200 mM
8 400 mM
400 mM
10
6

4
5
2

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

20% Ag 50% Ag
35 50
Ammonia 45 Ammonia
30 0 mM 0 mM
40
50 mM 50 mM
25 35
100 mM 100 mM

-2
-2

Current, A m
Current, A m

30
20 200 mM 200 mM
400 mM 25 400 mM
15 20

10 15
10
5
5

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

Figure 6.6: Linear sweep voltammograms showing the effect of ammonia

concentration on the current density of the gold oxidation from gold-
silver alloys. Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC,
and natural pH of the solution.

It can be seen from Figure 6.6 that ammonia is an important reagent in the
thiosulfate system. Moreover, the combined oxidation current of gold and silver from
each alloy in the absence of ammonia is very low compared with the oxidation
current in the presence of ammonia. As the percent of silver increases, the oxidation
current for both gold and silver increased indicating that the leaching rate for total
metal (gold and silver ) increases with increasing the silver content.

133
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.2.4 Effect of Thiourea Concentration
From the previous electrochemical studies, it has been shown that the oxidation
of gold in solution just containing thiosulfate is very slow. Therefore, high (5 mM)
and low (1 mM) concentrations of thiourea were tested to evaluate its affect on the
oxidation rate of gold from pure gold and gold-silver alloys. Also, the effect of
thiourea on the oxidation of gold and gold-silver alloys was determined for both
ammonium and sodium (50 mM) thiosulfate solutions.

6.2.4.1 Effect of Thiourea Concentration on Pure Gold

Figure 6.7 shows the effect of thiourea on the anodic dissolution of gold from
a pure gold disc. There was an increase in oxidation current in the presence of
thiourea which increased with increasing concentration of thiourea from 1 mM to 5
mM.

Pure Gold
35

30 50 mM ATS + 0 mM Tu

25 50 mM ATS +1mM Tu
-2
Current, A m

20 50 mM STS +1 mM Tu

50 mM ATS + 5 mM Tu
15
50 mM STS + 5 mM Tu
10

0
0 50 100 150 200 250 300
Potential, mV

Figure 6.7: Linear sweep voltammograms showing the effect of thiourea

concentration on the current density of gold oxidation from a pure
gold disc. Experimental conditions: 50 mM ATS or STS, 300 rpm, 30
ºC, and natural pH of the solution.

In the absence of thiourea, gold oxidation in the thiosulfate system is very

slow, but in the presence of up to 5 mM thiourea the oxidation current is greatly
increased. For all potentials the gold oxidation in solutions containing ammonium
thiosulfate was higher than that containing sodium thiosulfate.

134
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.2.4.2 Effect of Thiourea Concentrations on Gold-Silver Alloys
The effect of thiourea concentration on gold-silver oxidation from different
gold-silver alloys was investigated with the results shown in Figure 6.8. It is obvious
that an increase in thiourea concentration results in an increase in the metal (gold and
silver) oxidation current for both ammonium and sodium thiosulfate solutions.

4% Ag 8% Ag
30 30

25 50 mM ATS + 0 mM Tu 50 mM ATS + 0 mM Tu
25
50 mM ATS +1mM Tu 50 mM ATS +1 Tu
20 20
-2

-2
Current, A m

Current, A m
50 mM STS +1 mM Tu 50 mM STS +1 Tu
15 15
50 mM ATS + 5 mM Tu 50 mM ATS + 5 Tu

10 50 mM STS + 5 mM Tu 10 50 mM STS + 5 Tu

5 5

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

20% Ag 50% Ag
25 35

50 mM ATS + 0 mM Tu
50 mM ATS + 0 mM Tu 30
20
50 mM ATS +1 Tu
50 mM ATS +1 Tu 25
-2

-2

50 mM ATS +1 Tu
Current, A m

Current, A m

15 50 mM STS +1 Tu 20
50 mM ATS + 5 Tu
50 mM ATS + 5 Tu
15
10 50 mM STS + 5 Tu
50 mM STS + 5 Tu
10
5
5

0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Potential, mV Potential, mV

Figure 6.8: Linear sweep voltammograms showing the effect of thiourea

concentration on the current density of the combined gold and silver
oxidation from gold-silver alloys. Experimental conditions: 50 mM
ATS or STS, 300 rpm, 30 ºC, and natural pH of the solution.

Also from Figure 6.8, it can be noted, that when silver is present with gold,
the oxidation current density for total metal dissolution (gold and silver) decreases.
At high percentage of silver (50%), the oxidation current of gold and silver in the
absence of thiourea significantly increased, compared with alloys of low silver
percentages.

135
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.2.4.3 Effect of Silver Content in the Presence of Thiourea
To focus on the effect of silver, the polarisation curves for pure gold, 4, 8,
and 20% Ag are plotted together in Figure 6.9 for a thiosulfate solution containing 50
mM ATS. In the presence of silver, the combined oxidation current of gold and silver
decreased. In addition, the oxidation current from pure gold at larger potentials than
the standard potential for gold oxidation of 150 mV, is higher than the total metal
(gold and silver) oxidation current for all the gold-silver alloys. This phenomenon
was also observed by Chandra and Jeffrey (2004). The authors observed that with the
presence of 2% silver, the oxidation current is less than that of the pure gold in the
presence of thiourea in the solution.

35

30 Pure gold

25 4% Ag
-2

8% Ag
Current, A m

20
20% Ag
15

10

0
0 50 100 150 200 250 300
Potential, mV

Figure 6.9: Linear sweep voltammograms showing the effect of silver content on the
current density of the combined gold and silver oxidation from different
gold-silver combinations in the presence of thiourea. Experimental
conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30 ºC, and natural pH of
the solution.

6.2.4.4 Effect of Thiourea on Silver Oxidation

To determine the effect of thiourea on silver oxidation, the oxidation current
of silver in the absence and the presence of thiourea in solution containing 50 mM of
either ammonium or sodium thiosulfate was investigated. Figure 6.10 shows the
effect of thiourea concentration on the oxidation current of silver resulting from a

136
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
pure silver (99.99%) disc. From the data shown in Figure 6.10, the addition of
thiourea to the thiosulfate solution retards the oxidation of silver and the lowest silver
oxidation occurs at the highest thiourea concentration.

90
50 mM ATS + 0 Tu
80
50 mM STS + 0 Tu
70 50 mM ATS +1 Tu
50 mM STS +1 Tu
60 50 mM ATS + 5 Tu
Current, A m -2

50 mM STS + 5 Tu
50

40

30

20

10

0
0 50 100 150 200 250 300
Potential, mV

Figure 6.10: Linear sweep voltammograms showing the effect of thiourea

concentration on the current density of the silver oxidation from
pure silver. Experimental conditions: 50 mM ATS or STS, 300 rpm,
30 ºC, and natural pH of the solution.

6.3 Coulometric Experiments at a Fixed Potential

In order to investigate the occurrence of gold and silver dissolution in
different thiosulfate concentrations, coulometric experiments were carried out by
applying a constant potential to pure gold and gold-silver rotating discs in the
electrochemical cell. In this system, the oxidation current for gold or/and silver was
measured as a function of time.
These sets of experiments were performed at a rotation rate of 300 rpm and at a
temperature of 30 ºC for 30 minutes. All the solutions were de-aerated using nitrogen
gas for 20 minutes. The experiments were carried out at the natural pH of the
solution. After 30 minutes, the solutions were analysed for gold and silver by ICP-
OES. Various concentrations of reagents were added to thiosulfate solutions and the
current density measured at selected potentials of 0.22, 0.256, 0.292, and 0.35V
(potential values are reported relative to the standard hydrogen electrode (SHE).

137
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Three thiosulfate solutions were used to achieve the goals of this section: (1)
thiosulfate-ammonia solution; (2) thiosulfate-ammonia-copper solution; and (3)
thiosulfate-thiourea solution.

6.3.1 Coulometric Experiments at 0.22 V

The effect of thiosulfate and other reagents were studied to determine the
oxidation behaviour of pure gold and gold-silver alloys in solution at a fixed
potential of 0.22 V. The results are shown and discussed in the following sections.

6.3.1.1 Ammonium Thiosulfate-Ammonia Solution

Figure 6.11 shows the measured current that flowed through the
electrochemical cell as a function of time for 30 minutes at a fixed potential 0.22 V
in solution containing 50 mM ATS and 400 mM ammonia. These conditions were
applied to pure gold and gold-silver alloys. It is clear from the data shown in Figure
6.11 that the dissolution of gold and/or silver from pure gold and 4, and 8% Ag
alloys is very low at this potential. The current density increased with increasing
percentage of silver up to 20%, which indicates that the alloy dissolves more easily
than gold at this potential.

0.25

0.2
Pure gold
4% Ag
Current, Am -2

0.15
8% Ag
20% Ag
0.1

0.05

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000

Time, second

Figure 6.11: The anodic dissolution of gold and silver from a rotating disc of pure
gold and 4, 8, and 20% Ag alloys. Experimental conditions: 50 mM
ATS, 400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the
solution.

138
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Table 6.1 shows the leaching rate of gold and silver from each disc at 0.22 V
potential calculated from the ICP-OES determination of gold and silver metal
dissolved in solution in 30 minutes. The data from Table 6.1 verifies the data shown
in Figure 6.11 that as the percent silver increases, the total metal dissolution
increases.

Table 6.1: Gold, silver, and total metal dissolution rate from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential of 0.22 V. Experimental
conditions: 50 mM ATS, 400 mM ammonia, 300 rpm, 30 ºC, and natural
pH of the solution.

Dissolution rate, 105 x mol.m-2.s-1

Disc type
Gold Silver Total rate
Pure Gold 0.015 - 0.015
4% Ag 0.032 0.003 0.035
8% Ag 0.069 0.013 0.082
20% Ag 0.210 0.094 0.304
50% Ag 1.105 1.921 3.026

6.3.1.2 Sodium Thiosulfate-Ammonia Solution

The current that flowed through the electrochemical cell as a function of time
for 30 minutes at a fixed potential of 0.22 V in solutions containing 50 mM STS and
400 mM ammonia were measured. From the amount of gold and silver dissolved, the
dissolution rate of gold, silver, and total metal were calculated (Table 6.2). The data
shows the same trend obtained for ammonium thiosulfate; that by increasing the
percentage of silver, the gold dissolution rate, as well as the total metal dissolution
rate, increased.

6.3.1.3 Thiosulfate-Ammonia-Copper Solution

The current that flowed through the electrochemical cell as a function of time
for 30 minutes at a fixed potential 0.22 V in solutions containing 50 mM ATS or 50
mM STS, 400 mM ammonia, and 10 mM Cu(II) were measured. The calculated
leaching rate for both gold and silver, tabulated in Table 6.3, show that gold
dissolution from pure gold is faster than from 4, 8 and 20% Ag alloys. The total

139
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
metal dissolution rate decreases for alloys of 4 and 8% Ag compared with pure gold
but increases for 20 and 50% Ag alloys.

Table 6.2: Gold, silver, and total metal dissolution rates from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential 0.22 V. Experimental conditions:
50 mM STS, 400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the
solution.

Dissolution rate, 105 x mol.m-2.s-1

Disc type
Gold Silver Total rate
Pure Gold 0.012 - 0.012
4% Ag 0.017 0.004 0.021
8% Ag 0.022 0.005 0.027
20% Ag 0.217 0.102 0.319
50% Ag 0.990 1.756 2.746

Table 6.3: Gold, silver, and total dissolution rate from pure gold and 4, 8, 20, and
50% Ag alloys at fixed a potential 0.22 V. Experimental conditions: 50
mM ATS or STS, 400 mM ammonia, 10 mM CuSO4, 300 rpm, 30 ºC, and
natural pH of the solution.

Dissolution rate, 105 x mol m-2 s-1

Disc type Ammonium thiosulfate (ATS) Sodium thiosulfate (STS)

Gold Silver Total rate Gold Silver Total rate

Pure Gold 1.13 - 1.13 0.95 - 0.95
4% Ag 0.83 0.07 0.90 0.68 0.05 0.73
8% Ag 0.82 0.13 0.95 0.69 0.12 0.80
20% Ag 0.90 0.40 1.30 0.87 0.39 1.26
50% Ag 1.15 2.12 3.27 1.06 1.98 3.04

Figure 6.12 shows the measured current that flowed through the
electrochemical cell over time for 30 minutes at a fixed potential 0.22 V in solutions
containing 50 mM ATS, 400 mM ammonia, and 10 mM Cu(II) as a function of silver
content. Comparison of figure 6.11 to 6.12 for the 20% Ag alloy shows that the

140
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
current density has decreased yet the total metal dissolution rate increased. In the
presence of copper(II), thiosulfate, and ammonia, the measured current does not
include only the oxidation of metal to metal thiosulfate complex, but also the
reduction of copper(II) to copper(I) as shown in Equation 6.4 (Breuer and Jeffrey,
2002). The standard potential for this reaction according to Jeffrey (2001) is 0.22 V
and it is the sum of metal oxidation and copper reduction reactions that the
coulometric experiment is measuring.
Cu ( NH 3 ) 24+ + 3S 2O32− + e − → Cu ( S 2O3 ) 53− + 4 NH 3 (6.4)

2.5

2
Current, Am -2

1.5
pure gold
4% Ag
1 8% Ag
20% Ag
50% Ag
0.5

0
0 200 400 600 800 1000 1200 1400

Time, second

Figure 6.12: The measured current of the leaching of pure gold and gold-silver
alloys in solutions containing thiosulfate-copper-ammonia at a fixed
potential of 0.22 V. Experimental conditions: 50 mM ATS, 10 mM
CuSO4, 400 mM ammonia, 300 rpm, 30 ºC, and natural pH of the
solution.

6.3.1.4 Thiosulfate-Thiourea Solution

The effect of thiourea addition on pure gold and gold-silver alloy dissolution
in thiosulfate solutions was investigated by coulometric experiments at a fixed
potential of 0.22 V. The measured anodic current versus the time is plotted in Figure
6.13. The results show that the measured current increases rapidly at the start of the
experiment for all alloys reaching a maximum current that depends on the percentage
of silver.

141
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Minor passivation is observed for pure gold and for the 50% silver alloy but
after about a 500 second induction time although the reason is unclear. As can also
be seen form Figure 6.13, the addition of thiourea was accompanied by increasing in
gold and gold/silver oxidation.

1.4
pure gold
4 % Ag
1.2
8 % Ag
1 20 % Ag
Current, Am -2

50 % Ag
0.8

0.6

0.4

0.2

0
0 500 1000 1500 2000
Time, second

Figure 6.13: The anodic dissolution of gold and silver from pure gold, and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate and
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution.

These experiments were repeated using sodium thiosulfate, the results of

which are shown in Figure 6.14. It can be noticed that similar results were obtained
but the anodic current is slightly higher for ammonium thiosulfate for all alloys
except 4% Ag.

142
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

1.4
pure gold
1.2 4% Ag
8% Ag
Current, Am -2 1 20% Ag

0.8 50% Ag

0.6

0.4

0.2

0
0 500 1000 1500 2000
Time, second

Figure 6.14: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing sodium thiosulfate and
thiourea. Experimental conditions: 50 mM STS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution.

6.3.1.5 Gold and Total Metal Dissolution Rates at 0.22 V Potential

The gold and total metal dissolution rate from pure gold and gold-silver
alloys in thiosulfate solutions were calculated from ICP-OES measurements of
dissolved gold and silver after 30 minutes for a fixed potential of 0.22 V. Figures
6.15 and 6.16 show the calculated gold and total metal (gold and silver) dissolution
rate respectively versus the percent of silver. From the plots of gold dissolution rate
after 30 minutes at a fixed potential of 0.22 V versus the percent of silver in different
solutions (Figure 6.15), the trends are the same whether ammonium thiosulfate or
sodium thiosulfate was used, with ammonium thiosulfate giving a slightly higher
gold dissolution rate.
For either thiosulfate salt with ammonia, the gold dissolution rate increased
with an increase in silver content. In comparison, when copper was added to the
thiosulfate salt and ammonia solution, the dissolution rate was higher. Pure gold had
a high dissolution rate which decreased with 4% Ag and then increased slowly as the
silver content of the alloy was increased.
In the presence of thiourea the gold dissolution rate is higher than that
obtained from thiosulfate and ammonia up to about 25% silver.

143
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
1.4
a) ATS + ammonia
1.2

105 x Gold dissolution rate, mol.m -2.s-1

b ) ATS + ammonia + copper(II)

c) ATS + Tu
1.0
d) STS + ammonia
0.8 e) STS + ammonia + copper(II)

f) STS + Tu
0.6

0.4

0.2

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.15: Dissolution rates of gold from a rotating disc of pure gold and 4, 8, 20,
and 50% Ag alloys in thiosulfate (50 mM ATS or STS) solutions. a)
ATS, 400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5
mM Tu, d) STS, 400 mM NH3, e) ATS, 400 mM NH3, 10 mM Cu(II), f)
ATS, 5 mM Tu. 300 rpm, 30 ºC.

Figure 6.16, shows that solutions containing thiosulfate-copper-ammonia

dissolve gold from pure metal disc faster than the total metal dissolution obtained
from 4, and 8% Ag alloys. In solutions containing thiosulfate-thiourea and
thiosulfate-ammonia, the total metal dissolution rate increased with an increase in
silver content.

6.3.2 Coulometric Experiment at 0.256 V

Different thiosulfate solutions and reagent concentrations were studied to
determine the oxidation behaviour of pure gold and gold-silver alloys in solutions at
a fixed potential of 0.256 V. The results are shown and discussed in this section.

6.3.2.1 Thiosulfate-Ammonia Solution

Figure 6.17 shows the measured current that flowed through the
electrochemical cell as a function of time for 30 minutes at a fixed potential of 0.256
V in solution containing 50 mM ATS and 400 mM ammonia. It can be seen from
Figure 6.17 that the dissolution of gold and/or silver from pure gold and 4% Ag is
very low at a potential of 0.256 V and the current density is increased with increasing
percentage of silver in the alloy. Increasing oxidation current with increasing

144
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
percentage silver is due to the dissolution of silver besides gold as the percentage of
silver increases.
3.5
a) ATS + ammonia
105 x total dissolution rate, mol.m -2.s-1

3.0 b ) ATS + ammonia + copper(II)

c) ATS + Tu
2.5
d) STS + ammonia
2.0 e) STS + ammonia + copper(II)
f) STS + Tu
1.5

1.0

0.5

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.16: Total metal dissolution (gold and silver) rate from a rotating disc of
pure gold and 4, 8, 20, and 50% Ag in thiosulfate (50 mM ATS or STS)
solutions. a) ATS, 400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II),
c) ATS, 5 mM Tu, d) STS, 400 mM NH3, e)ATS, 400 mM NH3, 10 mM
Cu(II), f) ATS, 5 mM Tu. 300 rpm, 30 ºC.

The current passing through the cell at this potential increases rapidly at the
start of the experiment (Figure 6.17) until reaching a maximum value. The time laps,
before the maximum current value is obtained, decreases as the percentage of silver
increases. Increasing oxidation current with increasing percentage silver indicates
that the rate of alloy dissolution is dependent on the silver content.

Table 6.4 shows the calculated leaching rate of gold, silver, and total metal
from each disc. The data from Table 6.4 verifies the results shown in Figure 6.17 that
increasing the percentage silver leads to an increase in the total metal dissolution.
For all the percentages of silver except 4%, the gold, silver, and total metal
dissolution in solutions containing ammonium thiosulfate was higher than that
containing sodium thiosulfate. For example, in an alloy containing 50% Ag, gold
dissolution rate in solutions containing ammonium thiosulfate was higher than that
from solutions containing sodium thiosulfate by 13.7%.

145
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

6
Pure gold
5 4% Ag
8% Ag
4 20% Ag
Current, Am -2

50% Ag
3

0
0 500 1000 1500 2000
Time, second

Figure 6.17: The anodic dissolution of gold and silver of a rotating disc of pure gold
and 4, 8, 20, and 50% Ag alloys at a potential of 0.256 V. Experimental
conditions: 50 mM ATS, 400 mM ammonia, 300 rpm, 30 ºC, and
natural pH of the solution.

Table 6.4: Gold, silver, and total dissolution rate from pure gold and 4, 8, 20, and
50% Ag alloys at a fixed potential of 0.256 V. Experimental conditions:
50 mM ATS or STS , 400 mM ammonia, 300 rpm, 30 ºC, and natural pH
of the solution.

Dissolution rate, 105 x mol.m-2.s-1

Disc type Ammonium thiosulfate (ATS) Sodium thiosulfate (STS)

Gold Silver Total rate Gold Silver Total rate

Pure Gold 0.03 - 0.03 0.02 0.02
4% Ag 0.09 0.01 0.11 0.19 0.01 0.20
8% Ag 0.39 0.06 0.45 0.31 0.04 0.35
20% Ag 1.99 0.98 2.97 1.85 0.72 2.56
50% Ag 2.32 4.18 6.51 2.04 3.26 5.29

6.3.2.2 Thiosulfate-Ammonia-Copper Solution

The current that flowed through the electrochemical cell as a function of time
for 30 minutes at a fixed potential of 0.256 V in solutions containing 50 mM ATS or
STS, 400 mM ammonia, and 10 mM Cu(II) for pure gold and different gold-silver

146
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
alloys was measured. The measured current as a function of time (Figure 6.18) in the
presence of Cu(II) as an oxidant agent, is the total current of all the electrochemical
reactions occurring at the electrode-solution interface which include gold oxidation
and reduction of copper(II) tetraammine into a copper(I) thiosulfate complex. At a
potential of 0.256 V, there was an increase of oxidation current as the percentage of
silver increased.

8
Pure gold
7 4% Ag
6 8% Ag
20% Ag
Current, Am-2

5
50% Ag
4

0
0 500 1000 1500 2000
Time, second

Figure 6.18: The measured current of pure gold and gold-silver alloys in solutions
containing thiosulfate-copper-ammonia at a fixed potential of 0.256
V. Experimental conditions: 50 mM ATS, 10 mM CuSO4, 400 mM
ammonia, 300 rpm, 30 ºC, and natural pH of the solution.

The calculated leaching rate for both gold and silver tabulated in Table 6.5
show that gold dissolution for pure gold is still faster than that of 4 and 8% Ag alloys
as observed at a potential of 0.22 V. Furthermore, by increasing the percentage of
silver to 20 and 50%, both gold and silver dissolution rates increased.

147
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Table 6.5: Gold, silver, and total metal dissolution rates from pure gold and 4, 8, 20,
and 50% Ag alloys at a fixed potential of 0.256 V. Experimental
conditions: 50 mM ATS or STS, 400 mM ammonia, 10 mM CuSO4, 300
rpm, 30 ºC, and natural pH of the solution.

Dissolution rate, 105 x mol.m-2.s-1

Disc type Ammonium thiosulfate (ATS) Sodium thiosulfate (STS)

Gold Silver Total rate Gold Silver Total rate
Pure Gold 1.29 - 1.29 0.98 - 0.98
4% Ag 0.86 0.06 0.93 0.73 0.08 0.81
8% Ag 0.96 0.13 1.09 0.79 0.13 0.92
20% Ag 1.11 0.47 1.58 1.03 0.43 1.46
50% Ag 1.51 2.62 4.13 1.32 2.23 3.55

6.3.2.3 Thiosulfate-Thiourea Solution

The effect of thiourea addition to thiosulfate solutions was investigated by
coulometric experiments at a fixed potential of 0.256 V on pure gold and gold-silver
alloys. The anodic current was plotted versus time at a fixed potential of 0.256 V.
The results show that the trend is similar to that observed at a potential of 0.22 V but,
the measured anodic current increased by increasing the potential, which indicates
that the dissolution of gold and gold-silver alloys is faster at a potential of 0.256 V
than 0.22 V.

The anodic current was measured as a function of time at a fixed potential of

0.256 V in solutions containing sodium thiosulfate and thiourea and the results are
plotted in Figure 6.20. The trend is similar to what was obtained with ammonium
thiosulfate (Figure 6.19) but the measured current decreased indicating that both gold
and silver dissolved in sodium thiosulfate solutions slower than in ammonium
thiosulfate solutions.

148
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

6
Pure gold
4% Ag
5
8% Ag

4 20% Ag
Current, Am -2

50% Ag
3

0
0 500 1000 1500 2000
Time, second

Figure 6.19: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solution containing ammonium thiosulfate and
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm,
30 ºC, and natural pH of the solution.

2.5
Pure gold
4% Ag
2 8% Ag
20% Ag
Current, Am -2

1.5 50% Ag

0.5

0
0 500 1000 1500 2000
Time, second

Figure 6.20: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing sodium thiosulfate and
thiourea. Experimental conditions: 50 mM STS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution.

6.3.2.4 Gold and total metal dissolution rates at 0.256 V potential

The gold and total metal dissolution rates from pure gold and gold-silver
alloys in thiosulfate solutions were calculated from the metal dissolved after 30

149
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
minutes of at a fixed potential of 0.256 V. Figures 6.21 and 6.22 show the calculated
gold and total metal (gold and silver) dissolution rate as a function of the percent
silver in the disc. From the results in Figures 6.21 and 6.22, it is obvious that the
presence of silver enhances the gold dissolution rate in thiosulfate solutions.
Comparison of gold dissolution from pure gold and gold-silver alloys in different
thiosulfate solutions shows that:
• gold dissolution from pure metal is faster than that from 4 and 8% Ag but is
slower than that from 20 and 50% Ag alloys in thiosulfate-ammonia-copper
solutions;
• pure gold had a high dissolution rate which decreased with 4% Ag and then
increased as the silver content of the alloy increased in thiosulfate-thiourea solutions;
• gold dissolution from pure metal was very slow in thiosulfate-ammonia solutions,
however, the gold and total metal dissolution rate were the highest at 20 and 50%
silver.
It has to be determined that with low percentages of silver (up to 8%) the best
system in terms of faster gold dissolution is thiosulfate-copper-ammonia. However,
with high percentages of silver, thiosulfate-ammonia has the highest gold dissolution
rates.
2.5
a) ATS + ammonia
10 5 x gold dissolution rate, mol.m-2 .s-1

b ) ATS + ammonia + copper(II)

2.0
c) ATS + Tu
d) STS + ammonia
1.5
e) STS + ammonia + copper(II)
f) STS + Tu
1.0

0.5

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.21: Dissolution rates of gold from pure gold and 4, 8, 20, and 50% Ag
alloys in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d)
STS, 400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5
mM Tu. 300 rpm, 30 ºC.

150
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
7.0
a) ATS + ammonia

6.0 b ) ATS + ammonia + copper(II)

105 x total dissolution rate, mol.m -2.s-1

c) ATS + Tu
5.0 d) STS + ammonia
e) STS + ammonia + copper(II)
4.0
f) STS + Tu

3.0

2.0

1.0

0.0
0 10 20 30 40 50
Silver, Wt.%

Figure 6.22: Total dissolution (gold and silver) rates from rotating discs of pure gold
and 4, 8, and 20% Ag in thiosulfate (50 mM ATS or STS) solutions. a)
ATS, 400 mM NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5
mM Tu, d) STS, 400 mM NH3, e)ATS, 400 mM NH3,10 mM Cu(II), f)
ATS, 5 mM Tu. 300 rpm, 30 ºC.

6.3.3 Coulometric Experiment at 0.292 V

Different thiosulfate solutions and reagent concentrations were used to
determine the oxidation behaviour of pure gold and gold-silver alloys. The
experiments were conducted at a fixed potential of 0.292V and the results are shown
and discussed in this section.

6.3.3.1 Thiosulfate Solutions

The effects of ammonium thiosulfate concentration on gold and silver
dissolution rate from pure gold and gold-silver alloys was evaluated using the
electrochemical coulometric method at a fixed potential of 0.292 V. Figure 6.23
shows the measured current that flowed through the electrochemical cell as a
function of time for 30 minutes at 0.292 V in solutions containing 50 mM ATS. The
results demonstrate that increasing silver content results in a higher combined
oxidation current for both gold and silver. For pure gold and low percentage silver
alloys, the gold and combined gold-silver oxidation is very slow in the absence of
copper(II) and ammonia.

151
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Figure 6.24 shows the effect of increasing the ammonium thiosulfate
concentration (ATS) from 50 mM to 100 mM on the anodic current resulting from
the oxidation of gold and silver from pure gold and gold-silver alloys at a fixed
potential of 0.292 V. The results of Figure 6.24 demonstrate that an increase of
thiosulfate concentration results in an increase in the oxidation current. The
maximum oxidation current for the 50% Ag alloys is around 2.2 A.m-2 at 50 mM
ATS while this value increased to be about 6 A.m-2 at 100 mM ATS. The
enhancement of gold oxidation by increasing thiosulfate concentrations has also been
observed by Chandra and Jeffrey (2004), Zhang and Nicol (2003) and Breuer and
Jeffrey (2002).

2.5
Pure gold
4% Ag
2 8% Ag
20% Ag
Current, Am -2

1.5 50% Ag

0.5

0
0 500 1000 1500 2000
Time, second

Figure 6.23: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate.
Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC, and natural
pH of the solution.

152
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

7
Pure gold
6 4% Ag
8% Ag
Current, Am -2 5 20% Ag
50% Ag
4

0
0 500 1000 1500 2000
Time, second

Figure 6.24: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing ammonium thiosulfate.
Experimental conditions: 100 mM ATS, 300 rpm, 30 ºC, and natural pH
of the solution.

The gold and total metal dissolution rates was calculated from the amount of
gold and silver dissolved in the electrochemical cell after 30 minutes of leaching.
The rate of gold and total metal dissolution was also calculated from the measured
current according to Equation (6.5).
t =30
Q= ∫ Idt = NnF
t =0
(6.5)

Where: Q = the electric charge through the cell, Coulombs (Ampere.sec.);

N = number of moles of the analyte, mol;
I = current density, Am-2;
t = time, sec.;
n = number of moles of the electrons per mole of the analyte (mol.mol-1);
and
F = Faraday constant (96485 Coulombs.mol-1)

The current efficiency was calculated as a ratio between the total dissolution
rate (measured) and calculated rate from the charge. When the current efficiency is
100%, all the current can be attributed to gold/silver oxidation. Due to accuracy of
gold and silver analysis, the current efficiency sometimes slightly exceeds 100%.

153
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
The rates calculated from the current and the gold/silver dissolution and the
corresponding current efficiencies at 50 mM and 100 mM ATS are shown in Table
6.6 and 6.7 respectively.

Table 6.6: The calculated rate from current and the total dissolution rate from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing ammonium
thiosulfate (ATS). Experimental conditions: 50 mM ATS, 300 rpm, 30 ºC,
and natural pH of the solution.

Rate from
Dissolution rate, Current
Disc type current,
105 x mol.m-2.s-1 efficiency, %
10 x mol.m-2.s-1
5

Pure Gold 0.03 0.02 98

4% Ag 0.04 0.04 100
8% Ag 0.09 0.089 99
20% Ag 0.31 0.307 99
50% Ag 2.19 2.14 98

Table 6.7: The calculated rate from current and the total dissolution rate from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing ammonium
thiosulfate (ATS). Experimental conditions: 100 mM ATS, 300 rpm, 30
ºC, and natural pH of the solution.

Rate from
Dissolution rate, Current
Disc type current,
105 x mol m-2 s-1 efficiency, %
105 x mol m-2 s-1
Pure Gold 0.06 0.06 100

4% Ag 0.07 0.068 98

8% Ag 0.25 0.24 96

20% Ag 1.07 1.06 99

50% Ag 6.25 6.36 102

154
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
From the results shown in Tables 6.6 and 6.7, the following observations can be
made:
• in solutions containing only thiosulfate, the current efficiencies are close to 100%
for all the alloy compositions at different concentrations of thiosulfate. This result
indicates that all the measured current is due to the oxidation of gold and silver;
• by increasing thiosulfate concentration, gold and total metal dissolution rate
increased for all alloy compositions. The dissolution rate for the 50% silver alloy in
100 mM ATS reaches more than three times the value in 50 mM ATS; and
• as the percentage of silver alloyed with gold increased, gold and total metal
dissolution rates increased.

6.3.3.2 Thiosulfate-Ammonia Solution

The effect of ammonia addition to thiosulfate solutions on the oxidation of
gold and gold-silver alloys was studied electrochemically by adding 400 mM
ammonia to thiosulfate solutions containing 50 mM ATS. Figure 6.25 shows the gold
and gold/silver oxidation current from pure gold and gold-silver alloys at a fixed
potential of 0.292 V. Comparing the results of Figure 6.25 (in the presence of
ammonia) with those in Figure 6.23 (in the absence of ammonia), shows significant
enhancement of gold and gold-silver oxidation resulting from ammonia addition into
thiosulfate solutions. Because of the de-oxygenation of the solution using pure
nitrogen, the only electrochemical reaction that occurs is the oxidation of gold and
silver, so the measured current is a true indicator of the gold and silver dissolution
rates in solutions containing thiosulfate and ammonia.
Table 6.8 shows the total metal dissolution rate, calculated from the amount
of gold and silver dissolved in the electrochemical cell after 30 minutes of leaching
and the measured current, in solutions containing thiosulfate and ammonia.
By comparing the data shown in Table 6.8 (in the presence of ammonia and the data
in Table 6.6 (absence of ammonia), a significant effect of ammonia addition on gold
and total metal dissolution rate can be seen. The total metal dissolution rate increases
when a high percentage of silver is alloyed with gold. The increase of the dissolution
rate, for example, for the 50% Ag alloy in solutions containing 50 mM ATS and 400
mM ammonia is more than six times the value from solutions containing 50 mM
ATS.

155
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

14
Pure gold

12 4% Ag
8% Ag
Current, Am -2 10 20% Ag
50% Ag
8

0
0 500 1000 1500 2000
Time, second

Figure 6.25: The anodic dissolution of gold and silver from a rotating disc of pure
gold and 4, 8, 20, and 50% Ag alloys in solutions containing
ammonium thiosulfate. Experimental conditions: 50 mM ATS, 400
mM NH3, 300 rpm, 30 ºC, and natural pH of the solution.

Table 6.8: The calculated rate from current and ICP-OES analysis for pure gold and
4, 8, 20, and 50% Ag alloys in solution containing ammonium thiosulfate
(ATS). Experimental conditions: 50 mM ATS, 400 mM ammonia, 300
rpm, 30 ºC, and natural pH of the solution.

Rate from
Dissolution rate, Current
Disc type current,
Mol m-2 s-1 efficiency, %
Mol m-2 s-1
Pure Gold 0.06 0.05 95
4% Ag 0.43 0.45 104
8% Ag 0.79 0.82 103
20% Ag 4.61 4.48 97
50% Ag 13.16 12.61 96

6.3.3.3 Thiosulfate-Ammonia-Copper Solution

The current that flowed through the electrochemical cell as a function of time
for 30 minutes at a fixed potential of 0.292 V in solutions containing 50 mM ATS,
400 mM ammonia, and 10 mM Cu(II) was measured. These conditions were applied
to pure gold and gold-silver alloys with the experimental results shown in Figure

156
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.26. The measured current is the sum of metal oxidation and reduction of copper(II)
tetraammine to a copper(I) thiosulfate complex. The results show that the addition of
copper(II) leads to measured oxidation rates greater than those for thiosulfate
solution containing only ammonia (Figure 6.25) even though confounded by the
presence of copper(II). Figure 6.26 also shows that as a result of increasing the silver
content of the alloys, the measured current increases significantly.

14
Pure gold
12 4% Ag
8% Ag
10 20% Ag
Current, Am -2

50% Ag
8

0
0 500 1000 1500 2000
Time, second

Figure 6.26: The anodic current generated on pure gold and 4, 8, 20, and 50% Ag
alloys at a fixed potential of 0.292 V. Experimental conditions: 50
mM ATS, 400 mM NH3, 10 mM Cu(II), 300 rpm, 30 ºC, and natural
pH of the solution.

The effect of decreasing ammonia and copper(II) concentration was also

studied with the results shown in Figure 6.27. It can be seen that the trends are the
same as observed using high reagent concentrations, however, with decreased
oxidation currents at low ammonia and copper concentrations.

157
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

6
Pure gold
4% Ag
5
8% Ag
20% Ag
4
Current, Am -2

50% Ag

0
0 500 1000 1500 2000
Time, second

Figure 6.27: The anodic current from pure gold and 4, 8, 20, and 50% Ag alloys at a
fixed potential of 0.292 V. Experimental conditions: 50 mM ATS, 100
mM NH3, 1 mM Cu(II), 300 rpm, 30 ºC, and natural pH of the
solution.
Figure 6.28 shows the total metal dissolution rate from pure gold and 4, 8, 20,
and 50% Ag alloys in solutions containing high and low concentrations of ammonia
and copper(II). The solution concentrations used in this set of experiments were:
Solution A: 50 mM ATS thiosulfate, 400 mM ammonia, and 10 mM copper(II);
Solution B: 50 mM STS thiosulfate, 400 mM ammonia, and 10 mM copper(II);
Solution C: 50 mM ATS thiosulfate, 100 mM ammonia, and 1 mM copper(II); and
Solution D: 50 mM STS thiosulfate, 100 mM ammonia, and 1 mM copper(II).

From the data in Figure 6.28, it can be seen that increasing ammonia and
copper concentration leads to higher gold and silver leaching rates from the ICP-OES
analysis. Moreover, it is evident that total metal dissolution increased with increasing
silver percentages alloyed with gold.

158
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
9.0

8.0 Solution A

105 x total dissolution rate, mol.m -2.s-1

7.0
Solution B
6.0
Solution C
5.0
Solution D
4.0

3.0

2.0

1.0

0.0
0 10 20 30 40 50
Silver, Wt.%

Figure 6.28: The total dissolution rate of gold and silver from pure gold and 4, 8, 20
and 50% Ag alloys at a fixed potential of 0.292 V in solutions
containing thiosulfate ammonia-copper(II).

6.3.3.4 Thiosulfate-Thiourea Solution

The effect of thiourea addition to thiosulfate solutions was studied by using
coulometric experiments at a fixed potential of 0.292 V on pure gold and gold-silver
alloys in solutions containing 50 mM ATS and 5 mM thiourea. The measured anodic
current as a function of time is plotted in Figure 6.29. It can be seen that the
oxidation current increased with an increase in silver in the alloy. The results
demonstrate that after an initial induction period gold oxidation is faster than total
metal oxidation for 4, 8, and 20% Ag alloys. A further increase in the silver
percentage up to 50% increases the total metal oxidation to a higher value than that
of pure gold.
It was also found that in the presence of silver, total metal oxidation was
slower in thiosulfate-thiourea solutions than in solutions containing thiosulfate-
ammonia-copper(II).

The effect of decreasing thiourea concentration to 1 mM on the oxidation

current is shown in Figure 6. 30. As the percent of silver increased the oxidation
current also increased. From Figure 6.30 it is clear that the measured current
increases at the start of the experiment until it reaches a plateau value. It can also be
seen that when thiourea concentration was decreased to 1 mM, the gold oxidation

159
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
from pure metal was significantly decreased as compared with that at 5 mM thiourea
(Figure 6.29).

6 Pure gold
4% Ag
5 8% Ag
20% Ag
4 50% Ag
Current, Am -2

0
0 500 1000 1500 2000
Time, second

Figure 6.29: The anodic current from pure gold and 4, 8, 20, and 50% Ag discs at a
fixed potential of 0.292 V in solutions containing ammonium thiosulfate
and thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300
rpm, 30 ºC, and natural pH of the solution.

6
Pure gold
4% Ag
5
8% Ag

4 20% Ag
Current, Am -2

50% Ag
3

0
0 500 1000 1500 2000
Time, second

Figure 6.30: The anodic current of from pure gold and 4, 8, 20, and 50% Ag alloys
at a fixed potential of 0.292 V in solutions containing ammonium
thiosulfate and thiourea. Experimental conditions: 50 mM ATS, 1 mM
Tu, 300 rpm, 30 ºC, and natural pH of the solution.

160
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

The gold and total metal dissolution rate from pure gold and gold-silver
alloys in solutions containing high and low thiourea concentrations were calculated
from ICP-OES analyses of the solution after 30 minutes for a fixed potential of 0.292
V. The rates in the presence of 1 mM and 5 mM thiourea are shown in Tables 6.9
and 6.10 respectively, with the greater thiourea concentration having the higher gold
and total metal leaching rate. The gold dissolution rate from pure gold is higher than
that from 4 and 8% Ag alloys in solutions containing thiosulfate and a low thiourea
concentration. Increasing the thiourea concentration to 5 mM increases the gold
dissolution rate from pure gold with only the 50% Ag alloy having a higher rate.

Table 6.9: Calculated rate from current and the total dissolution rate from pure gold
and 4, 8, 20, and 50% Ag alloys in solution containing thiosulfate-
thiourea. Experimental conditions: 50 mM ATS, 1 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution.

Rate from
Dissolution rate, Current
Disc type current,
105 x mol.m-2.s-1 efficiency, %
105x mol.m-2.s-1
Pure Gold 1.43 1.41 102

4% Ag 0.59 0.61 97

8% Ag 0.92 0.94 97

20% Ag 1.54 1.58 98

50% Ag 3.87 3.79 102

161
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
Table 6.10: The calculated rate from current and the total dissolution rate, from pure
gold and 4, 8, 20, and 50% Ag alloys in solution containing thiosulfate-
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm, 30
ºC, and natural pH of the solution.

Rate from
Dissolution rate, Current
Disc type current,
mol.m-2.s-1 efficiency, %
mol.m-2.s-1
Pure Gold 2.80 3.06 92

4% Ag 1.25 1.18 106

8% Ag 1.55 1.57 98

20% Ag 2.40 2.54 94

50% Ag 5.23 5.75 91

6.3.3.5 Gold and Total Metal Dissolution Rates at 0.292 V Potential

The gold and total metal dissolution rate from pure gold and gold-silver
alloys in thiosulfate solutions was calculated after 30 minutes for a fixed potential of
0.292 V. Figures 6.31and 6.32 show the calculated gold and total metal (gold and
silver) dissolution rates from the ICP-OES analysis respectively as a function of
percent silver. From the data in Figure 6.31, the highest gold dissolution rate from
pure gold was in thiosulfate solutions containing thiourea. The gold dissolution rate
was the slowest in thiosulfate solutions containing only ammonia. The important two
points, here, are that (1) at a potential value of a 0.292 V in thiosulfate solutions
containing thiourea, the gold-silver alloys dissolve slower that pure gold; (2) gold
dissolution rates from gold-silver alloys containing high silver percentages are the
highest in thiosulfate solutions containing only ammonia.

162
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
5.0
a) ATS + ammonia
4.5
b ) ATS + ammonia + copper(II)

105 x gold dissolution rate, mol.m-2.s-1

4.0 c) ATS + Tu
3.5 d) STS + ammonia

3.0 e) STS + ammonia + copper(II)

f) STS + Tu
2.5

2.0

1.5

1.0

0.5

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.31: Gold dissolution rate form pure gold and 4, 8, 20, and 50% Ag alloys in
thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM NH3, b)
ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS, 400 mM
NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu. 300 rpm,
30 ºC.
14.0
a) ATS + ammonia

12.0 b ) ATS + ammonia + copper(II)

105 x total dissolution rate, mol.m -2.s-1

c) ATS + Tu
10.0 d) STS + ammonia
e) STS + ammonia + copper(II)
8.0
f) STS + Tu

6.0

4.0

2.0

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.32: Total metal dissolution rate from pure gold and 4, 8, 20, and 50% Ag
alloys in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d)
STS, 400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5
mM Tu. 300 rpm, 30 ºC.

163
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.3.4 Coulometric Experiment at 0.35 V
The effect of different thiosulfate solutions and reagent concentrations were
studied to determine the oxidation behaviour of pure gold and gold-silver in
thiosulfate solutions by coulometry. Coulometric experiments were conducted at a
fixed potential of 0.35 V. The results are shown and discussed in this section.

6.3.4.1 Thiosulfate-Ammonia Solution

The effect of ammonia addition to thiosulfate solution on the oxidation
current from pure gold and gold-silver alloys at a fixed potential of 0.35 V was
studied (Figure 6.33) electrochemically by adding 400 mM ammonia to thiosulfate
solution containing 50 mM ATS. The results demonstrate that the trends are the same
as those at potential values of 0.22, 0.256 and 0.292 V however, the oxidation current
is higher than those at lower potential values.

14
Pure gold
12 4% Ag
8% Ag
10 20% Ag
Current, Am -2

50% Ag
8

0
0 500 1000 1500 2000
Time, second

Figure 6.33: The anodic dissolution of gold and silver from pure gold and 4, 8, 20,
and 50% Ag alloys in thiosulfate solution containing ammonia.
Experimental conditions: 50 mM ATS, 400 mM NH3, 300 rpm, 30 ºC,
and natural pH of the solution.

6.3.4.2 Thiosulfate-Ammonia-Copper Solution

The current that flowed through the electrochemical cell for 30 minutes at a
fixed potential of 0.35 V in solutions containing 50 mM ATS, 400 mM ammonia,
and 10 mM Cu(II) for pure gold and gold-silver alloys was measured. Figure 6.34
shows the gold and gold/silver oxidation current as a function of time in solution

164
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
containing ammonium thiosulfate, ammonia and copper(II). At the beginning of the
experiment, for each alloy, the measured current increased quickly but after a short
induction period reached a nearly constant value. The oxidation current increased as
the percent silver in the alloys increased.

18
Pure gold
16
4% Ag
14 8% Ag
20% Ag
12
Current, Am -2

50% Ag
10

0
0 500 1000 1500 2000
Time, second

Figure 6.34: The anodic dissolution current of gold and silver from pure gold and 4,
8, 20, and 50% Ag alloys in solution containing thiosulfate-ammonia-
copper(II). Experimental conditions: 50 mM ATS, 400 mM NH3, 10
mM Cu(II), 300 rpm, 30 ºC, and natural pH of the solution.

6.3.4.3 Thiosulfate-Thiourea Solution

The effect of thiourea addition to thiosulfate solution on the oxidation current
from pure gold and gold-silver alloys was studied by coulometric experiments at a
fixed potential of 0.35V in thiosulfate solution containing 50 mM ATS and 5 mM
thiourea. Figure 6.35 shows the gold/silver oxidation current as a function of time.
The measured current for thiosulfate solution containing only thiourea is
representative of the gold/silver oxidation. The data shown in Figure 6.35
demonstrates that the gold oxidation rate from pure gold is higher than the total
oxidation rate of gold and silver from the alloys containing 4, 8 and 20% silver.

165
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions

9
Pure gold
8
4% Ag
7 8% Ag

6 20% Ag
Current, Am -2

50% Ag
5

0
0 500 1000 1500 2000
Time, second

Figure 6.35: The anodic dissolution current of gold and silver from pure gold and 4,
8, 20, and 50% Ag discs in solutions containing thiosulfate and
thiourea. Experimental conditions: 50 mM ATS, 5 mM Tu, 300 rpm,
30 ºC, and natural pH of the solution.

6.3.4.4 Gold and Total Metal Dissolution Rates at 0.35 V Potential

The gold and total metal dissolution rate from pure gold and gold-silver
alloys in thiosulfate solution were calculated from ICP-OES analysis after 30
minutes at a fixed potential 0.35 V. Figures 6.36 and 6.37 show the calculated gold
and total metal (gold and silver) dissolution rates respectively as a function of
percent silver. The results are consistent with those of the current-time graphs for
each solution: 1) in thiosulfate-ammonia solution, gold and total dissolution rate
increased as the silver content of the alloy increased :2) the same trend was observed
in the thiosulfate-ammonia-copper solution; 3) for solutions containing thiosulfate
and thiourea, it was observed that as the percent of silver increased, gold dissolution
rate decreased (Figure 6.36).
The gold dissolution rate from the pure gold disc is higher than the total metal
dissolution rate from gold-silver alloys up to 20% Ag but, for 50% Ag, the total
dissolution rate is higher than the dissolution rate from pure gold (Figure 6.37). This
result confirms the results shown in the current-time graph (Figure 6. 35).

166
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.0
a) ATS + ammonia
b ) ATS + ammonia + copper(II)

105 x gold dissolution rate, mol.m-2.s-1

5.0
c) ATS + Tu
d) STS + ammonia
4.0
e) STS + ammonia + copper(II)

3.0 f) STS + Tu

2.0

1.0

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.36: Gold dissolution rate from pure gold and 4, 8, 20, and 50% Ag alloys in
thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM NH3, b)
ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS, 400 mM
NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu. 300 rpm,
30 ºC.

14.0
a) ATS + ammonia
105 x total dissolution rate, mol.m -2.s-1

12.0 b ) ATS + ammonia + copper(II)

c) ATS + Tu
10.0
d) STS + ammonia

8.0 e) STS + ammonia + copper(II)

f) STS + Tu
6.0

4.0

2.0

0.0
0 10 20 30 40 50

Silver, Wt.%

Figure 6.37: Total metal dissolution rate from pure gold and 4, 8, 20, and 50% Ag
discs in thiosulfate (50 mM ATS or STS) solutions. a) ATS, 400 mM
NH3, b) ATS, 400 mM NH3, 10 mM Cu(II), c) ATS, 5 mM Tu, d) STS,
400 mM NH3, e)ATS, 400 mM NH3, 10 mM Cu(II), f) ATS, 5 mM Tu.
300 rpm, 30 ºC.

167
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
6.3.5 Effect of Potential on Gold and Total Dissolution (gold and silver)
Rate
The effect of potential in the range of 0.22-0.35 V on gold and total metal
dissolution rate is shown in this section by plotting the dissolution rate of gold and
gold silver alloys in different thiosulfate solutions as a function of potential.

• Pure Gold
Figure 6.38 shows the gold dissolution rate after 30 minutes of leaching pure
gold in different thiosulfate solutions as a function of potential ranging from 0.22-
0.35 V. An increase in the gold dissolution rate occurs when the potential is
increased. The dissolution rate is increased when copper is added to the thiosulfate-
ammonia solution. Moreover, it was found that the gold dissolution rate, when
thiourea is present, is slow at low potentials and increases significantly at high
potentials.
4.50

4.00 a) ATS + ammonia

b)ATS + ammonia + cop p er(II)

-2 -1

3.50
10 x gold dissolution rate, mol.m .s

c)ATS + Tu
3.00

2.50

2.00

1.50
5

1.00

0.50

0.00
0.2 0.25 0.3 0.35 0.4
Potentail, V

Figure 6.38: Gold dissolution rate measured after 30 min of leaching from pure gold
at 300 rpm and 30 ºC in thiosulfate solutions containing: a) 50 mM
ATS, 400 NH3; b) 50 mM ATS, 400 mM NH3, 10 mM Cu(II); c) 50
mM ATS, 5 mM Tu.

• Gold-Silver Alloys
Figure 6.39 shows the effect of different thiosulfate solutions on the total
metal dissolution rate form gold-silver alloys (4, 8, 20, and 50% silver) after 30
minutes of leaching as a function of potential ranging from 0.22-0.35 V. For all

168
 Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
solutions the total metal dissolution rate increased as the percent silver in the alloy
and the potential increased. A thiosulfate-ammonia-copper(II) solution was found to
dissolves gold/silver at a faster rate than either a thiosulfate-ammonia or a
thiosulfate-thiourea solution at a potential value of 0.22 V. However, at higher
potentials the solution that gives the greatest metal dissolution is dependant on the
silver concentration in the gold-silver alloy.

4% Ag 8% Ag
4.00 3.50
.s -1

.s -1
3.50
-2

3.00

-2
a) ATS + ammonia a) ATS + ammonia
10 5 x total metal dissol. rate, mol.m

10 5 x total metal dissol. rate, mol.m

3.00 b)ATS + ammonia + copper(II) b)ATS + ammonia + copper(II)
2.50
2.50 c)ATS + Tu c)ATS + Tu
2.00
2.00
1.50
1.50

1.00
1.00

0.50 0.50

0.00 0.00
0.2 0.25 0.3 0.35 0.4 0.2 0.25 0.3 0.35 0.4
Potentail, V Potentail, V

20% Ag 50% Ag
7.00 18.00
.s -1

.s -1

16.00
-2

6.00
-2

a) ATS + ammonia
10 5 x total metal dissoluti rate, mol.m

10 5 x total metal dissol. rate, mol.m

14.00
b)ATS + ammonia + copper(II)
5.00
c)ATS + Tu 12.00

4.00 10.00

8.00
3.00
6.00
2.00 a) ATS + ammonia
4.00
b)ATS + ammonia + copper(II)
1.00 2.00
c)ATS + Tu
0.00 0.00
0.2 0.25 0.3 0.35 0.4 0.2 0.25 0.3 0.35 0.4
Potentail, V Potentail, V

Figure 6.39: Total metal dissolution rate of gold-silver alloys at 300 rpm 30 ºC
measured over 30 minutes in thiosulfate solutions containing: a) 50
mM ATS, 400 NH3; b) 50 mM ATS, 400 mM NH3, 10 mM Cu(II); c)
50 mM ATS, 5 mM Tu.

6.4 Summary
In this chapter, a fundamental electrochemical study on the gold and
gold/silver oxidation half reaction in different thiosulfate solutions has been carried
out using linear sweep voltammetry and fixed potential coulometric experiments.
The electrochemical experiments were conducted using rotating disc electrodes of
pure gold (99.99%) and 4, 8, 20, and 50 wt% silver. The effect of potential in a range

169
Chapter 6: An electrochemical study of the leaching of gold, silver and gold-silver
alloys in thiosulfate solutions
of 0.22–0.35 V on the gold and gold/silver oxidation half reaction was also
investigated. It has also been shown that when silver is present as an alloying
element with gold, it enhances the gold oxidation half reaction for all gold-silver
alloy compositions investigated. This occurs only in thiosulfate-ammonia and
thiosulfate-copper-ammonia solutions. For solutions containing thiosulfate and
thiourea, it has been found that when up to 50% silver is present as an alloying
element the gold dissolution rate at high potentials is slower than that of pure gold.
In addition, it was found that the gold dissolution rate in a thiosulfate-
ammonia solution is higher than that in a thiosulfate-ammonia-copper and a
thiosulfate-thiourea solution at percentages of silver more than 20%. Linear sweep
voltammograms have shown that increasing thiosulfate, ammonia, and copper(II)
concentrations has positive effects on the gold/silver oxidation. Moreover, it was
observed that thiourea addition to thiosulfate solutions enhances the gold oxidation
rate and in the presence of thiourea gold oxidises from pure gold more rapidly than
gold-silver alloys.
Gold dissolution rates increased as the silver percentage increased in
thiosulfate-ammonia solutions at all potential values. At high potentials and silver
content it has been observed that the gold dissolution rate in thiosulfate solutions
containing only ammonia is higher than in solutions containing thiosulfate-copper-
ammonia and thiosulfate-thiourea.

170
Chapter 7 Thiosulfate leaching of gold ore in a closed vessel

7.1 Introduction
In this chapter, the application of sodium thiosulfate leaching on selected
gold ore samples in a closed vessel has been studied and evaluated. The samples used
in all the experiments were provided from the Sukari Gold Mine, Eastern Desert,
Egypt by the Centamin Egypt Limited Company.
The main aims of the chapter are: (1) to investigate the effects of various
reagent concentrations and parameter conditions on gold extraction and thiosulfate
consumption in a closed vessel on a laboratory scale; (2) to compare gold ore
leaching in a closed vessel to an open vessel; and in thiosulfate and cyanide solutions
using the resulting optimum parameters from the first aim.
The effects of sodium thiosulfate, ammonia, and copper(II) concentration,
temperature, solid-liquid ratio, and the particle size fraction of the ore sample on gold
extraction and thiosulfate consumption were investigated. Primarily, the leaching of
ore samples in open and closed vessels was conducted based on selected initial
standard conditions of 0.2 M sodium thiosulfate, 10 mM copper(II), 0.4 M ammonia,
30 ºC, 300 rpm, 20% solid-liquid (S/L) ratio; and minus 106 µm ore size. The gold
ore was classified into weathered and unweathered gold samples which were ground
to 100% minus 106 µm. A second portion of the weathered ore was sieved into
different size fractions. Table 7.1 shows the reagent concentrations and parameters
used in this section.

Table 7.1: Reagent concentrations and parameters used in the gold ore leaching
experiments.

Parameter The concentrations and values used

Sodium thiosulfate, M 0.1, 0.2, 0.3, and 0.4
Ammonia, M 0.2, 0.4, 0.6, and 0.8
Copper(II), mM 2.5, 5, 10, and 20
Temperature, ºC 25, 30, 40, and 50
Rotation speed, rpm 200, 300, 400, and 500
Solid-liquid ratio, % 20, 30, 40, and 50
Particle size fraction, µm -125+106, -106+75, -75+38, -38

171
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

Figure 7.1 illustrates the procedure undertaken on the weathered ore to achieve the
objectives of this section.

Gold ore

Crushing

Grinding

Classification

-125 + 106 µm -106 + 75 µm -75 + 38 µm -38 µm

-106 µm

XRD analysis

Elemental analysis

Leaching

Open Closed
vessel vessel

Gold analysis

Pregnant Wash Residue

solution solution

Figure 7.1: The procedure of gold ore leaching experiments.

172
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

7.2 Quantitive XRD Analysis

According to the experimental procedure shown in Chapter 4, the gold ore
was classified into weathered and unweathered ore samples. A sample of the
weathered ore was crushed, milled, and sieved into four size fractions of -38, -75+38,
-106+75, and -125+106 µm. The rest of the weathered sample and the entire
unweathered ore sample were crushed, milled, and sieved at 106 microns to produce
a -106 micron fraction. Quantitative X-Ray Diffraction (XRD) was used to determine
the mineralogy for the size fractions and the -106 micron samples for both weathered
and unweathered ore.
Figure 7.2 shows the distribution of minerals found in each size fraction
which indicates that albite, quartz, and muscovite are the dominant minerals in all
size fractions. The highest mass percent of albite (63.4%) was found in the
unweathered sample of size -106 µm and the lowest percent of muscovite (3.5%).

7.3 Elemental Analysis

The elemental analysis for each size fraction was performed by Ultra-trace
Laboratories located in Perth, Western Australia. A list of the main elements
analysed is shown in Figure 7.3. The elemental analysis was carried out by the
digestion of the ore samples followed by ICP-OES determination. From the data
shown in Figure 7.3, it can be seen that silicon is the most abundant element and
aluminium, iron, and sodium are found as minor constituents in all the size fractions.
It can also be seen that there is no difference between the weathered and
unweathered samples according in the constituents of these abundant elements.

173
 mass, % mass, % mass, %

0
5
10
15
20
25
30
35
40
45
50
0
5
10
15
20
25
30
35
40
45
50

Q Q

-2.5
2.5
7.5
12.5
17.5
22.5
27.5
32.5
37.5
42.5
47.5
52.5
Q ua ua
ua rtz rtz
rtz

Al Al
Al bit bit
bit e e
e
M M
M us us
us co co
co v it v it
v it e e
e

Ca Ca Ca
l ci l ci
l ci
te te te
m m m
i cr i cr i cr
oc oc oc
l in l in l in
e e e
Ni Ni Ni
ni ni

µm
ni ng ng
ng er er
er it e it e
it e
G G G
up up up
eii eii eii
te te te

gold ore samples.

c) +75-106
a) -38 µm

py py py
ri t ri t ri t
e e e
An An An
ke ke ke
rit rit rit

e) -106 µm (weathered)
e e e

mass, % mass, % mass, %

0
5
10
15
20
25
30
35
40
45
50
55
60
65
0
5
10
15
20
25
30
35
40
45
50
0
5
10
15
20
25
30
35
40
45
50

Q Q Q
ua ua ua
rtz rtz rtz

Al Al Al
bit bit
e e bit
e
M M M
us us us
co co co
v it v it
e e v it
e
Ca Ca Ca
l ci l ci l ci
te te
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

te
m m m
i cr i cr i cr
oc oc oc
l in l in l in
e e e
Ni Ni Ni
ni ni ni
ng ng ng
er er er
it e it e it e
G G G
up up up
eii eii eii
te te te

py py
d) +106-125µm

ri t ri t py
e e ri t
e
An An
b) +38-75 µm

ke ke An

Figure 7.2: Quantitative XRD analysis of mineralogy of different size fractions of

rit rit ke
e e

f) -106 µm (unweathered)
rit
e

174
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

70 70
65 65

60 a) -38 µm 60 b) +38-75 µm
55 55

50 50
45 45

40 40
mass, %

mass, %
35 35
30 30

25 25
20 20

15 15
10 10

5 5
0 0
Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,% Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,%
ppm ppm

70 70

65 65

60
c) +75-106 60 d) +106-125 µm
55 µm 55

50 50

45 45

40 40
mass, %

mass, %

35 35

30 30

25 25

20 20

15 15

10 10

5 5

0 0
Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,% Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,%
ppm ppm

70 70
65 65

60
e) -106 µm (weathered) 60 f) -106 µm (unweathered)
55 55

50 50

45 45

40 40
mass, %

mass, %

35 35

30 30

25 25

20 20

15 15

10 10

5 5
0 0
Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,% Au, Si, % Al, % Ca, % Fe, % K, % Mg,% Na, % P, % S, % Ti, % Mn,%
ppm ppm

Figure 7.3: Elemental analysis of different size fractions of gold ore samples.

175
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

7.4 Ore Sample Leaching (standard conditions)

The suitability of weathered Sukari Gold Mine ore for thiosulfate leaching
was determined first under standard conditions (section 7.4). Once the suitability was
established then reagent concentrations and leaching parameters were optimised
(section 7.5). The suitability of the weathered ore ground passing 106 µm for
thiosulfate leaching was found by determining gold extraction and thiosulfate
consumption in both open and closed vessels. To examine thiosulfate leaching of ore,
individual size fractions of the weathered ore (Table 7.1) was subjected to leaching
under standard conditions in a closed vessel.
The leaching of gold ore samples was conducted using 100 g of the ground ore
(-106 µm weathered) put into a 1L glass vessel described in the experimental setup
shown in Figure 4.4 (Chapter 4). A 400 mL solution containing 0.2 M sodium
thiosulfate, 10 mM Cu(II), and 0.4 M ammonia was used and ore added to give a
solid/liquid ratio to 20% (100 g ore and 400 mL solution). The temperature and
rotation speed were adjusted to 30 ºC and 300 rpm respectively. Unless specified, the
leaching experiment had a duration of 24 hours.

7.4.1 Gold Extraction using Open and Closed Vessels

Using the initial standard leaching condition as specified in section (7.4), gold
ore leaching experiments in open and closed vessels were conducted by the method
and procedure described in Chapter 4. Figure 7.4 shows the amount of gold extracted
from both open and closed vessels. It is clear that there is a slight increase of gold
extraction from the closed compared to the open vessel during the first 3 hours of
leaching. After 24 hours, gold extraction from the closed vessel is higher than the
open vessel by nearly 5.8%. This result may be explained by increased copper(II)
reduction due to ammonia losses from the open vessel as demonstrated by ammonia
analyses in sections 5.2.1.2 and 5.3.1.2 (Chapter 5). This explanation is consistent
with Breuer (2002) who noted the importance of maintaining sufficient ammonia in
thiosulfate solutions to minimise the rate of copper reduction, consequently
maximising gold extraction.

176
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

Closed vessel
90
Open vessel
Gold extraction, %
80

70

60

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.4: Gold extraction using open and closed vessels. Experimental initial
conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
20% S/L ratio.

7.4.2 Thiosulfate Consumption in Open and Closed Vessels

Figure 7.5 shows the effect of ambient air and hence oxygen on the amount of
thiosulfate consumed in open and closed vessels. The data in Figure 7.5 indicates that
there is a slight difference between the amount of thiosulfate consumed in an open
vessel compared to a closed vessel. This result is similar with what has been shown
in gold disc leaching experiments (Chapter 5). The relatively high consumption of
thiosulfate in the open vessel is due to thiosulfate oxidation by oxygen from the
ambient air.

177
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

35

Closed vessel
30
Open vessel

Thiosulfate consumption, Kg/t 25

20

15

10

0
0 5 10 15 20 25 30
Time, hour

Figure 7.5: Thiosulfate consumption in closed and open vessels. Experimental initial
conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm,
20% S/L ratio.

7.4.3 Gold Extraction from Screen Size Fractions

The weathered ore sample was used to evaluate how different screen size
fractions responded with regard to gold extraction. About one kilogram of the ground
ore sample was split into four size fractions (-38, -75+38, -106+75, -125+106 µm).
The gold extraction results for these fractions are presented in Figure 7.6. The finer
fractions had higher gold extraction while the course size fraction had the lowest
gold recovery after 24 hours of leaching (Figure 7.6). This is a usual trend for gold
ores, with the only link that can established between gold recovery and the
mineralogy and chemical analysis being that the largest size fraction had the most
silica in the ore and may have had more gold locked in silica particles and not
accessible to the leaching reagent. The upward trend of the recovery versus time
curves indicates that leaching was not complete for any size fraction and reagent
concentrations and leach parameters need to be optimised to achieve maximum gold
recovery within 24 hours.

178
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90
Gold extraction, %
80

- 38 um
70
-75 + 38 um
-106 + 75 um
60
-125 +106 um

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.6: The effect of particle size fraction on gold extraction using a closed
vessel. Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 10
mM Cu(II), 30 ºC, 300 rpm, 20% S/L ratio.

7.5 Effect of Reagent Concentration and Leaching Parameters

In order to optimise and evaluate the effect of various leaching reagents and
parameters on gold extraction and thiosulfate consumption, the weathered ore ground
to -106 µm was used in a series of tests. One of the reagents or parameters was
varied while all the others were kept constant at the initial standard conditions of 0.2
M (S2O3)2-, 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm, 20% solid/liquid (S/L) ratio
and natural pH of the solution (pH 11.4).

7.5.1 Effects of Thiosulfate Concentration on Gold Extraction

The effect of sodium thiosulfate concentration ranging from 0.1 to 0.4 M on
gold extraction was studied as shown in Figure 7.7. With an increase of thiosulfate
initial concentration from 0.1 M to 0.4 M, gold extraction increased from 74.5% to
96% after 24 hours of leaching. Initial gold extraction over the first three hours was
fast but then slowed. The final recovery after 24 hours for 0.2 to 0.4 M thiosulfate
was approximately the same, but much less for 0.1 M thiosulfate.

179
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80
Gold extraction, %

70
thiosulfate
60 0.1 M
0.2 M
0.3 M
50 0.4 M

40
0 5 10 15 20 25 30
Time, hour

Figure 7.7: The effect of thiosulfate concentration on gold extraction. Experimental

initial conditions: 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300 rpm, 20% S/L
ratio.

7.5.2 Effect of Thiosulfate Concentration on Thiosulfate Consumption

Figure 7.8 shows the effects of initial thiosulfate concentration on thiosulfate
consumption (kg/t-ore) after 24 hours of leaching for the experiments described in
section 7.5.1. It can be seen that the initial thiosulfate concentration has an
insignificant effect on thiosulfate consumption with consumption ranging from about
28 to 31 kg/t, consistent with results of Arima (2003).
As high thiosulfate concentration increases the extraction rate of gold but
does not increase consumption, the possibility of using high concentration of
thiosulfate and recovering and reusing the excess is available.

180
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

32.5

Thiosulfate consumption, kg/t

30.0

27.5

25.0
0.1 0.2 0.3 0.4
Thiosulfate concentration, M

Figure 7.8: The effect of initial sodium thiosulfate concentration on its consumption.
Experimental initial conditions: 0.4 M NH3, 10 mM Cu(II), 30 ºC, 300
rpm, 20% S/L ratio.

7.5.3 Effect of Copper Concentration on Gold Extraction

Copper(II) has been shown (Arima, 2003; Breuer & Jeffrey, 2003a,b; Wan &
LeVier, 2003; Breuer & Jeffrey, 2000) to be essential in thiosulfate leaching
solutions as an oxidising agent. In this section, the influence of copper(II)
concentration on gold extraction was studied and evaluated in the range of 2.5 – 20
mM Cu(II). Figure 7.9 shows that gold extraction is enhanced from 85% to 96% after
24 hours of leaching by increasing copper concentration from 2.5 mM to 20 mM.
From the 3 hour leaching extraction in Figure 7.9, copper(II) concentration has a
significant effect on the initial gold extraction rate.
After 24 hours, the effect of increasing copper(II) concentration on gold
extraction is not as pronounced due to high copper(II) concentration experiments
approaching maximum gold extraction. A portion of the decrease in extraction rate
may be due to an increase in the copper catalysed thiosulfate oxidation to
tetrathionate as shown in Equation 7.1.
12 S 2 O32− + 4[Cu ( NH 3 ) 4 ] 2+ → 2 S 4 O62− + 4[Cu ( S 2 O3 ) 2 ]3− + 16 NH 3 (7.1)

181
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

95

85
Gold extraction, %
75

Copper(II)
65
2.5 mM

55 5 mM
10 mM
45 20 mM

35
0 5 10 15 20 25 30
Time, hour

Figure 7.9: The effect of initial copper(II) concentration on gold extraction.

Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M NH3, 30 ºC,
300 rpm, 20% S/L ratio.

7.5.4 Effect of Copper Concentration on Thiosulfate Consumption

Figure 7.10 shows that an increase in copper(II) concentration has a detrimental
effect on thiosulfate consumption as, by increasing the concentration of copper(II)
from 2.5 mM to 20 mM, thiosulfate consumption increased from 22.5 to 44.6 kg/t-
ore. Thiosulfate was reduced by copper(II) as shown in the simplified overall
reaction in Equation 7.2 (Byerley et al., 1973a).
2Cu 2+ + 2S 2 O32− → 2Cu + + S 4 O62− (7.2)
Other researchers (Zhang & Dreisinger, 2002; Byerley et al., 1975; Byerley et
al., 1973b) have also reported that copper has a considerable affect on the stability of
thiosulfate in solution due to copper-catalyzed thiosulfate oxidation and the
formation of copper sulfides or hydroxides, depending on the leaching conditions.

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

60

Thiosulfate consumption, kg/t 50

40

30

20
2.5 5 10 20
Copper(II) concentration, mM

Figure 7.10: The effect of initial copper(II) concentration on thiosulfate

consumption. Experimental initial conditions: 0.2 M (S2O3)2-, 0.4 M
NH3, 30 ºC, 300 rpm, 20% S/L ratio.

7.5.5 Effect of Ammonia Concentration on Gold Extraction

Ammonia is required in thiosulfate solutions in order to stabilize the copper(II)
ion as a cupric tetra amine complex, [(Cu(NH3)4]2+ hence, minimising the
decomposition of thiosulfate by its reduction to tetrathionate, as indicated in
Equation 7.1.
Figure 7.11 shows the effect of ammonia concentration on gold extraction. In
the absence of ammonia only 11.5% of gold can be dissolved in 24 hours but, with a
concentration of 400 mM ammonia gold extraction increased to 96%, however, by
increasing the concentration of ammonia to 800 mM, gold extraction decreased. This
result might be attributed to higher pH values at high ammonia concentration and
thus, the reduced thermodynamic stability of Cu ( S 2 O3 ) 52− and Cu (NH 3 ) 24+ with
increased stability of solid copper species such as CuO and Cu2O resulting in lower
gold extraction (Arslan et al., 2008; Abbruzzese et al., 1995).

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80

70
Gold extraction, %

60

50
ammonia
40 0 mM
30 100 mM
400 mM
20
800 mM
10

0
0 5 10 15 20 25 30
Time, hour

Figure 7.11: The effect of initial ammonia concentration on gold extraction.

Experimental initial conditions: 0.2 M (S2O3)2-, 10 mM Cu(II), 30 ºC,
300 rpm, 20% S/L ratio.

7.5.6 Effect of Ammonia Concentration on Thiosulfate Consumption

Figure 7.12 shows the effect of ammonia concentration on thiosulfate
consumption. In the absence of ammonia, the copper(II) ion is free in solution to
react with thiosulfate consuming 70% of the initial 0.2 M thiosulfate. As the
concentration of ammonia increases the increased stability of copper as the copper
amine species leads to reduced thiosulfate consumption.

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

Thiosulfate consumption, kg/t 80

70

60

50

40

30

20
0 100 400 800
Ammonia concentration, mM

Figure 7.12: The effect of initial ammonia concentration on thiosulfate consumption.

Experimental initial conditions: 0.2 M (S2O3)2-, 10 mM Cu(II), 30 ºC,
300 rpm, 20% S/L ratio.

7.5.7 Effect of Temperature on Gold Extraction

Temperature is one of the most important factors in thiosulfate leaching of gold
as the gold oxidation rate, copper(II) reduction, thiosulfate oxidation, and the
stability of ammonia in the solution depend on temperature. The effect of
temperature ranging from 25 to 50 ºC on gold extraction is shown in Figure 7.13.
After an initial 3 hours of leaching gold extraction can be seen to increase with
increasing temperature. However, the initial fast leaching rate at 50 ºC declines and
after 24 hours of leaching, the amount of gold extracted at 50 ºC is the lowest.
The decrease in leaching rate over time at high temperatures (above 40 ºC) can
be attributed to two mechanisms. Passivation of the gold surface is proposed due to
the formation of cupric sulfide as described in the unbalanced equation of Arslan et
al., (2008) and Abbruzzese et al. (1995) (Equation 7.3) but the mechanism is likely to
be more complicated than this reaction.
Cu 2+ + S 2 O32− + H 2 O → CuS + SO42− + 2OH − (7.3)
The second mechanism is that an increase in the reduction of copper(II) to
copper(I) and the oxidation of thiosulfate and polythionate compounds occurs at
higher temperatures as shown in Equation 7.4 (Breuer, 2002). Both of these

185
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

mechanisms would be supported by an increase in thiosulfate consumption with

increasing temperature, which is investigated in the following section (7.5.8).
2Cu 2+ + 2S 2 O32− → 2Cu + + S 4 O62− (7.4)

100

90

80
Gold extraction, %

25 ºC
70
30 ºC
40 ºC
60 50 ºC

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.13: The effect of temperature on gold extraction from -106 µm weathered
gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3,
10 mM Cu(II), 300 rpm, 20% S/L ratio.

7.5.8 Effect of Temperature on Thiosulfate Consumption

The effect of temperature on thiosulfate consumption is presented in Figure
7.14 for the experiments described in section 7.5.7. As the temperature increased, the
amount of thiosulfate consumed increased. An increase in temperature will increase
the leaching rate of gold but above about 40 ºC, the detrimental effects of passivation
of the gold surface and increased consumption of reagents may outweigh this
advantage.

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

50

Thiosulfate consumption, kg/t

40

30

20
25 30 40 50
Temperature, ºC

Figure 7.14: The effect of temperature on thiosulfate consumption while leaching -

106 µm weathered gold ore. Experimental initial conditions: 0.2 M
(S2O3)2-, 400 mM NH3, 10 mM Cu(II), 300 rpm, 20% S/L ratio.

7.5.9 Effect of Air Injection on Gold Extraction

The effect of air and oxygen on gold oxidation and thiosulfate decomposition
has been studied and evaluated by many authors (Arima, 2003; Breuer & Jeffrey,
2003b; Chu et al., 2003; Molleman & Dreisinger, 2002). Most of the published work
recommends that air or oxygen should be controlled in thiosulfate leaching solutions.
In this section the effect of airflow on gold extraction was evaluated with the results
shown in Figure 7.15. The results show that for the Sukari Gold Mine weathered ore
that gold leaching in thiosulfate solutions should be undertaken without the injection
of oxygen or air. Gold extraction reaches more than 95% without air injection
whereas it decreases when air is passed into the solution. This result is consistent
with those of Breuer and Jeffrey (2003b) and Muyunda (1996).

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90
Gold extraction, %

80

70 Airflow, cm3/min
None
60
5

10
50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.15: The effect of airflow on gold extraction using -106 µm weathered gold
ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3, 10
mM Cu(II), 300 rpm, 20% S/L ratio.

7.5.10 Effect of Air Injection on Thiosulfate Consumption

It is important to evaluate why gold extraction decreased when air flow was
increased into the thiosulfate leach solution. This section evaluates the effect of
airflow on thiosulfate consumption after 24 hours of leaching from the experiments
described in section 7.5.9. From the data shown in Figure 7.16, thiosulfate loss after
24 hours is 75% of the initial thiosulfate concentration with air injection of 10
cm3/min, while the loss does not exceed 15% without air injection. The results
indicate that the decrease in gold dissolution with air injection is due to the
consumption of most of the thiosulfate in the system. This finding is supported by
Breuer (2002) who evaluated the effect of high rates of airflow (1000 cm3/min) on
thiosulfate oxidation, and showed that most of the thiosulfate was consumed after
only one hour of leaching.

188
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

0.25

Initial thiosulfate concentration

0.2
15% loss 55% loss 75% loss
Thiosulfate concentration, M

0.15

0.1

0.05

0
0 5 10
Airflow, cm3/min

Figure 7.16: The effect of airflow on thiosulfate consumption using -106 µm

weathered gold ore. Experimental initial conditions: 0.2 M (S2O3)2-,
400 mM NH3, 10 mM Cu(II), 30 ºC, 300 rpm, 20% S/L ratio.

7.5.11 Effect of Pulp Density on Gold Extraction

Figure 7.17 shows the results of a series of experiments conducted to determine
gold extraction at different pulp densities ranging from 20% to 50%. Gold extraction
percentages increased with lower pulp density and hence, extraction is inversely
proportional to the solid/liquid ratio. The trends shown in Figure 7.17 are consistent
with leaching systems where a defined amount of reagent is required to dissolve
metal from the ore, hence, the total amount of metal extracted increases with
increased percent solids but, the extraction efficiency as a percentage decreases.

189
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80

Gold extraction, % 70

60

50
Pulp density
40
20%
30
30%
20 40%
50%
10

0
0 5 10 15 20 25 30
Time, hour

Figure 7.17: The effect of pulp density on gold extraction using -106 µm weathered
gold ore. Experimental initial conditions: 0.2 M (S2O3)2-, 400 mM NH3,
10 mM Cu(II), 30 ºC, 300 rpm.

7.5.12 Effect of Agitation on Gold Extraction

The effect of agitation measured as impellor rotation speed (RPM) can play a
major role in determining the rate of gold extraction. If the reaction is diffusion
controlled increased agitation will decrease the thickness of the surface boundary
layer speeding the diffusion of reactant ions to the ore’s surface. On the other hand,
agitation does not affect the reaction itself if it is chemically controlled but, may
more efficiently suspend the particles allowing uniform contact with the leaching
solution. Figure 7.18 shows the results of a series of experiments conducted at
different impellor rotation speeds to determine the effect of agitation on gold
dissolution, which slightly increased with a higher rotation speed. This result is
supportive that gold leaching in thiosulfate solutions is a chemically controlled
reaction as observed by Jeffrey (2001) and Muyunda (1996).

190
Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80
Gold extraction, %

70 200 RPM
300 RPM
60 500 RPM
600 RPM

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.18: The effect of rotation speed (RPM) on gold extraction using -106 µm
weathered gold ore. Experimental initial conditions: 0.2 M (S2O3)2-,
400 mM NH3, 10 mM Cu(II), 30 ºC, 20% S/L ratio.

7.5.13 Effect of Ore Weathering on Gold Extraction

Two types of ore were obtained from Sukari Gold Mine, one from shallow
surface drill holes (weathered) and the other from deep holes (unweathered).
Leaching experiments were conducted on -106 µm ore for both weathered and
unweathered ore samples under standard leaching conditions. From the results shown
in Figure 7.19 the percentage of gold extracted is slightly higher for the weathered
ore. However from the chemical analysis the weathered ore had a lower gold content.
The XRD analysis shows that the mass percent of albite and microcline
decreased during the weathering process and the percentage of muscovite increased.
The weathering process breaks down the original minerals, liberating the gold, such
that the leach solution can easily penetrate the ore particles and extract the gold. This
process increased the gold recovery from about 87% in the unweathered ore to 92%
in the weathered ore.

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80
Gold extraction, %

70
Weathered ore
Unweathered ore
60

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.19: The effect of weathering on gold extraction. Experimental initial

conditions: 0.2 M (S2O3)2-, 400 mM NH3, 10 mM Cu(II), 30 ºC, 300
rpm, 20% S/L ratio.

7.5.14 Ore Leaching in Thiosulfate Compared to Cyanide Solutions

A comparison of gold dissolution in thiosulfate and cyanide solutions was
carried out. From the investigation of different reagent concentrations and leaching
conditions, it was found that the optimum conditions are very close to the selected
standard conditions with thiosulfate concentration in a range of 0.2 - 0.4 M, rotation
speed in a range of 300 – 500 rpm and ammonia concentration in a range of 0.4 -0.6
M. Therefore, a thiosulfate solution containing 0.2 M S2O32-, 400 mM NH3 and 10
mM Cu(II), at 30 ºC, 300 rpm, 20% S/L ratio, and the natural pH of the solution was
used. For comparison, a cyanide solution containing 1.5 g NaCN/L, 20% S/L ratio, in
an open vessel at pH =11 was used to leach -106 µm weathered ore. The results are
shown in Figure 7.20. Gold extraction using thiosulfate is very close to that obtained
using cyanide. The difference of gold extraction in cyanide solution (96%) and in
thiosulfate solution (~ 95%) was around 1%. This insignificant difference shows that
thiosulfate leaching is efficient in leaching gold from ore from the Sukari Gold Mine,
Eastern Desert, Egypt and competes well with cyanide in terms of gold recovery.

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

100

90

80
Gold extraction, %

70
Thiosulfate
Cyanide
60

50

40
0 5 10 15 20 25 30
Time, hour

Figure 7.20: Gold extraction from thiosulfate and cyanide solutions using -106 µm
weathered gold ore. Experimental initial conditions for the thiosulfate
solution: 0.2 M (S2O3)2-, 400 mM NH3, 10 mM Cu(II), 30 ºC, 300
rpm, closed vessel, 20% S/L ratio, and natural pH of the solution and
for the cyanide solution : 1.5 g NaCN/L, 20% S/L ratio, open vessel,
pH =11).

7.6 Summary
In this chapter, the effect of utilising various reagent concentrations and
parameter conditions on gold extraction and thiosulfate consumption in a closed
vessel, a comparison between gold ore leaching in a closed vessel to an open vessel,
and in thiosulfate and cyanide solutions were studied and evaluated. The results
showed that there is a slight increase in gold recovery from a closed vessel compared
to an open one and gold recovery from the closed vessel is higher than from an open
vessel by nearly 5.8%. Increasing copper(II) concentration from 2.5 mM to 20 mM,
increased gold recovery from 85% to 96% after 24 hours of leaching, but thiosulfate
consumption increased from 22.5 to 44.6 kg/t-ore. With an increase in thiosulfate
concentration up to 0.4 M, gold extraction increased to 96% and initial thiosulfate
concentration had an insignificant effect on thiosulfate consumption. At the
beginning of leaching (after 3 hours), it was found that gold recovery increased by
raising the temperature, but over time gold recovered decreased at 50 ºC to be the
lowest after 24 hours, the optimum temperature being 30 ºC. Thiosulfate

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Chapter 7: Thiosulfate leaching of gold ore in a closed vessel

consumption also increased significantly with increasing temperatures. Lower

solid/liquid ratio gave higher recovery of gold from the ore. The agitation speed had
an insignificant effect on gold recovery. It has been shown that the gold extraction
percentage using thiosulfate is very close to that extracted using cyanide. The results
showed that the thiosulfate leaching system is efficient to leach the selected gold ore.
Finally, from the results of this chapter, the optimum conditions to leach the ore were
determined to be 0.2 – 0.4 M thiosulfate, 400-600 mM NH3, 10-20 mM Cu(II), 30
ºC, 300 rpm, no air supplied, solid/liquid ratio 20% at a particle size of < -106 µm.

194
Chapter 8 Dissolution of mercury in thiosulfate and cyanide
solutions: an environmental problem

8.1 Introduction
Mercury (Hg) is frequently associated with gold and silver minerals. One of
the main problems in gold processing plants is that cyanide leach solutions dissolve
gangue minerals as well as gold and silver. One of these gangue minerals can be
metalic mercury and others may be mercury compounds. Mercury forms a strong
complex with cyanide which subsequently adsorbs on carbon with gold or silver in
carbon-in-column, carbon-in-pulp, and carbon-in-leach (Washburn & Hilldoi, 2003)
adsorption circuits. Mercury is then partially recovered with gold and silver in the
elution circuit and electroplates in the electrowinning process. When gold is
recovered using the zinc-precipitation (Merrill-Crowe) process, mercury precipitates
along with gold. Mercury contained in the Merrill-Crowe precipitate and in the
electrowinning sludge can result in environmental and industrial problems if a retort
is not used to capture it during smelting.
The loss of mercury from the tailings to the surrounding environment can
occur through two main processes: (i) the leaching of soluble mercury to the
groundwater in the form of Hg–CN complexes; and (ii) the diffusion of mercury gas
(Hg0) into the atmosphere (Shaw, 2006).
In this chapter, the solubility of mercury and mercury compounds in
thiosulfate and cyanide solutions is evaluated. The effect that mercury has on gold
and copper loading from thiosulfate solutions onto ion exchange resin is investigated.
Other experimental work using ion exchange resin columns was conducted to elute
gold, copper, and mercury in order to evaluate the possibility of gold loading and
recovery using ion-exchange resins.

8.2 Mercury Dissolution in Thiosulfate and Cyanide Solutions

In the following sections, the dissolution of metallic mercury and mercury
compounds in thiosulfate and cyanide solution is reported.
The mercury sources used in this study were: metallic mercury (Hg0),
mercury chloride (HgCl2), mercurous chloride (Hg2Cl2), and mercury sulfide (HgS).

195
The thiosulfate and cyanide solution tested were:
2.5 g/L NaCN, pH 12;
50 mM ATS, 400 mM NH3, 10 mM Cu2+, pH 11.4;
50 mM ATS, 1 mM Cu2+, pH 10;
50 mM ATS, 10 mM Tu, 12.5 mM Oxalate, 5 mM FeCl3, pH 5.5; and
50 mM ATS, 10 mM Tu, 5 mM Ferric-ethylenediaminetetraacetic (Fe-EDTA), pH 7.

8.2.1 Mercury Stability in the Collected Samples

Before the dissolution of mercury in thiosulfate and cyanide leach solutions
could be tested a method to stabilise mercury in the samples extracted for analyses
had to be determined. Section 8.2.1 describes the experiments and results conducted
to determine the stability of mercury in leach samples.
As mercury chloride (HgCl2) is known for its high solubility in water, it was
dissolved to obtain a known concentration of mercury (100 mg/L) in a range of leach
solutions. Then a 10 mL filtered sample from each solution was treated with 1 mL of
0.1 M tetra-sodium EDTA. The samples of known mercury concentration were
analysis for mercury by ICP-OES. The measured mercury concentration and the
composition of each leach solution are shown in Table 8.1. All the results are very
close to 100 mg/L indicating that adding tetra-sodium EDTA stabilises the mercury
in these leach solutions and can be used as a method to stabilise samples for analyses
from leaching tests. Hence EDTA was added to all leach tests sample to stabilize
them until analysed.

Table 8.1: The concentration of dissolved mercury in each solution stabilized with
tetra-sodium EDTA at room temperature after 48 hours.

Solution Hg, mg/L

2.5 g/L NaCN 100.2
50 mM ATS, 400 mM NH3, 10 mM Cu2+ 100.5
2+
50 mM ATS, 1 mM Cu 98.5
50 mM ATS,10 mMTu, 12.5 mM Oxalate, 5 mM FeCl3 98.4
50 mM ATS,10 mMTu, 5 mM FeEDTA 97.9

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

8.2.2 Effect of Tetrathionate on the Mercury Thiosulfate Complex

Stability
In this section the effect of tetrathionate on the stability of the mercury
thiosulfate complex was evaluated using potassium tetrathionate (K2S4O6). Two
solutions (100 mL) were tested: 1) 50 mM of ammonium thiosulfate with either low
tetrathionate (1 mM); or 2) high tetrathionate (10 mM). Mercury chloride (HgCl2)
were weighed to form 100 mg/L Hg in each solution. The experiments were
conducted using the bottle roll technique with samples taken after 5, 24, and 48
hours, stabilised with tetra-sodium EDTA, and analysed for mercury. The pH of each
solution was monitored at sample times. From the data in Table 8.2, tetrathionate did
not effect the stability of the mercury thiosulfate complex with all analyses results
within 2% of the actual value. Also, the decrease in pH in the solution, possibility
due to the decomposition of thiosulfate, did not affect the stability of the mercury
thiosulfate complex.

Table 8.2: The dissolved mercury in thiosulfate solutions containing tetrathionate

after 0, 5, 24, and 48 hours.

Tetrathionate (S4O6)2- concentration, mM

Time, hour 1 mM 10 mM
Hg (mg/L) pH Hg (mg/L) pH

0 99.1 6.39 101.85 5.85

5 98.50 5.84 99.71 5.66
24 98.84 5.40 99.25 4.95
99.01
48 4.88 101.10 4.09

8.2.3 The Dissolution of Mercurous Chloride (Hg2Cl2)

The dissolution of mercurous chloride (Hg2Cl2) in thiosulfate and cyanide leach
solutions was tested using the bottle roll technique under the conditions described in
section 8.2. Solid mercurous chloride was added to each leach solution to give 200
mg/L of Hg. Samples were taken after 5, 24, and 48 hours of leaching with the
percentage mercury dissolution shown in Figure 8.1. The amount of dissolved

197
Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
mercury in the cyanide, copper-ammonia, and FeEDTA solutions is much higher
than in the ferric oxalate (FeOX) and ATS with 1 mM Cu2+ solutions. About 78% of
the mercury was dissolved after 48 hours in the cyanide and FeEDTA solutions.

90
80
70
Hg dissolution, %

60

50
40 Solution A
Solution B
30
Solution C
20 Solution D
10 Solution E
0
0 10 20 30 40 50 60
Time, hour

Figure 8.1: The dissolution of mercurous chloride (Hg2Cl2) in thiosulfate and

cyanide solutions. Leaching conditions: Solution A, 50 mM ATS, 1 mM
Cu2+, pH 10; Solution B, 50 mM ATS, 400 mM NH3, 10 mM Cu2+, pH
11.4; Solution C, 2.5 g/L NaCN solution, no air, pH 12; Solution D, 50
mM ATS, 10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5, and
Solution E, 50 mM ATS, 10 mM Tu, 5 mM FeEDTA, pH 7.

8.2.4 The Dissolution of Mercury Sulfide (HgS)

The dissolution of mercury sulfide (HgS) in thiosulfate and cyanide solutions
was tested using the bottle roll technique under the conditions described in section
8.2. Solid mercury sulfide was added to each solution to give a 100 mg/L of Hg. The
percent mercury dissolved after 48 hours is shown in Table 8.3. The maximum
mercury dissolution is 10.9% in 2.5 g/L NaCN solution whereas the maximum
mercury dissolved from thiosulfate solutions was 3.4%. Mercury sulfide does not
dissolve as easily in all the leach solutions tested as mercurous chloride.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

Table 8.3: The percentage of mercury dissolved from mercury sulfide in thiosulfate
and cyanide solutions after 48 hours.

Solution Hg, %
2.5 g/L NaCN 10.9
50 mM ATS, 400 mM NH3, 10 mM Cu2+ 3.4
50 mM ATS, 1 mM Cu2+ 0.4
50 mM ATS, 10 mMTu, 12.5 mM Oxalate, 5 mM FeCl3 0.3
50 mM ATS, 10 mMTu, 5 mM FeEDTA 0.2

8.2.4.1 Effect of Ammonium Thiosulfate Concentration on the Dissolution of

Mercury Sulfide
In this section, the effects of ammonium thiosulfate concentration on the
dissolution of mercury sulfide (HgS) in thiosulfate solutions was investigated using
the bottle roll technique. The selected ATS concentrations were 50, 100, and 200
mM.

• Solution A:
The mercury sulfide dissolution as a function of ATS concentration in
solution A (ATS, 1 mM Cu2+, pH 10) is shown in Figure 8.2. Increasing the ATS
concentration from 50 mM to 200 mM, increases the amount of dissolved mercury
with the maximum percentage of mercury dissolved after 48 hours not exceed 1.5%.

199
Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

2
50 mM ATS
100 mM ATS
1.5 200 mM ATS
Hg dissolution, %

0.5

0
0 10 20 30 40 50 60
Time, hour

Figure 8.2: The effects of thiosulfate concentration on mercury dissolution in

solution A: (ATS, 1 mM Cu2+, pH 10).

• Solution B:
The effects of ammonium thiosulfate concentration on mercury sulfide
dissolution in solution B (ATS, 400 mM NH3, 10 mM Cu2+, pH 11.4) is shown in
Figure 8.3.

10

8
50 mM ATS
100 mM ATS
Hg dissolution, %

6 200 mM ATS

0
0 10 20 30 40 50 60
Time, hour

Figure 8.3: The effect of thiosulfate concentration on mercury leaching in solution

B: (ATS, 400 mM NH3, 10 mM Cu2+, pH 11.4).

200
Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
Solution D:
Mercury sulfide dissolution as a function of ATS concentration in solution D
(ATS, 10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5) is shown in Figure 8.4.
Mercury dissolution in this solution is much lower than in solution B and only about
1.2% of mercury dissolved in 48 hours.

1.5
Hg dissolution, %

1
50 mM ATS
100 mM ATS
200 mM ATS
0.5

0
0 10 20 30 40 50 60
Time, hour

Figure 8.4: The effect of thiosulfate concentration on mercury leaching in solution D

(ATS, 10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5).

Solution E:
The effects of the ATS thiosulfate concentration on mercury dissolution in
solution E (ATS, 10 mM Tu, 5 mM FeEDTA, pH 7) are shown in Figure 8.5. When
the ATS concentration increased from 50 mM to 200 mM, the mercury dissolution
after 48 hours increased from 0.3% to 2.6%.

201
Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

2.5

Hg dissolution, %
2
50 mMAT S
100 mMAT S
1.5
200 mMAT S
1

0.5

0
0 10 20 30 40 50 60
T ime, hour

Figure 8.5: The effects of thiosulfate concentration on mercury dissolution in

solution E (ATS, 10 mM Tu, 5 mM FeEDTA, pH 7).

It was found that increasing the concentration of ammonium thiosulfate to 200

mM, increases the amount of dissolved mercury from mercury sulfide in all the
thiosulfate solutions but the amount of mercury dissolved was always less than that
dissolved by cyanide.

8.2.5 The Dissolution of Mercury Metal (Hg0)

The dissolution of metallic mercury (Hg0) in thiosulfate and cyanide solutions
was tested using the bottle roll technique using the conditions described in section
8.2. Mercury metal (about 0.865g as an average value) was added to each solution
and samples taken after 5, 24, and 48 hours of leaching and analysed for mercury
with the results shown in Figure 8.6. Mercury dissolution in the thiosulfate-copper-
ammonia, Fe-Oxalate (FeOX), and cyanide solutions are higher than in FeEDTA and
ATS with 1 mM Cu2+ solutions. The maximum dissolution of mercury metal was
20.9% after 48 hours of leaching in the thiosulfate-copper- ammonia solution
(solution B).

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

25
Solution A
Solution B
20
Solution C
Hg dissolution, %
Solution D
15 Solution E

10

0
0 10 20 30 40 50 60
Time, hour

Figure 8.6: The dissolution of mercury metal (Hg0) in thiosulfate and cyanide
solutions. Experimental conditions: Solution A, 50 mM ATS, 1 mM
Cu2+, pH 10; Solution B, 50 mM ATS, 400 mM NH3, 10 mM Cu2+, pH
11.4; Solution C, 2.5 g/L NaCN solution, pH 12; Solution D, 50 mM
ATS,10 mM Tu, 12.5 mM oxalate, 5 mM FeCl3, pH 5.5, and Solution
E, 50 mM ATS, 10 mM Tu, 5 mM FeEDTA, pH 7.

The dissolution of mercury from mercurous chloride, mercury sulfide and

mercury metal in a variety of thiosulfate leaching solutions was determined and
compared with a cyanide solution. There was no advantage in terms of decreased
mercury dissolution from mercurous chloride or mercury metal when using
thiosulfate compared with cyanide solutions. However, mercury dissolution from
mercury sulfide was lower for all thiosulfate solutions tested than for the cyanide
leach solution.
The finding that thiosulfate solutions also dissolve mercury, as does cyanide,
is a factor to be considered if thiosulfate has a future industrial application in the
leaching of gold.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
8.3 Effect of Mercury on Gold Loading and Recovery from
Thiosulfate Solutions Using Anion-Exchange Resins
8.3.1 Introduction
Ion exchange is a technique for chemical separation, and it is to this field that it
has made some of its most remarkable contributions (Rodriques, 1986). The process
of ion exchange consists of two main steps: (1) sorption of a metal ion from the
pregnant solution onto the ion exchange resin and then (2) elution in which a solution
is used to remove the metal ions from the resin. Ion exchange applications can be
useful to (1) treatment of wastewaters (2) non metallic anions such as halides,
sulfates, nitrates, and cyanides; and (3) water-soluble, ionic organic compounds.
The first attempts to apply ion exchange for metal recovery were in connection
with recovery of copper from waste solutions of the cuprammonium rayon and brass
industry, silver from photographic film manufacturing wastes, and chromium from
electroplating wastes. Uranium was the first metal to be recovered from leach
solutions by ion exchange on a large scale (Habashi, 1970).
Gold and silver production fundamentally consists of two main steps: (1)
leaching of metals from its ore or concentrate and (2) recovery of the metal from the
leach solution. The leaching of gold and silver can be achieved using different
reagents such as cyanide, thiosulfate, thiourea, ammonia, halides, and many others.
The metal recovery can be achieved by precipitation, electrowinning, solvent
extraction, carbon absorption or ion exchange resin absorption.
Leaching of gold using thiosulfate is considered to be one of the most
promising alternatives to cyanide. However, it is difficult to recover the gold
thiosulfate complex as (Gallagher et al., 1990) the gold thiosulfate complex is not
adsorb effectively onto activated carbon. The precipitation methods are not highly
favoured, as they suffer from high zinc consumption, are less selective and are likely
to precipitate most metals from solution in addition to the difficulty of recycling the
leach liquor (Gross et al., 2003; Deschenes & Ritcey, 1990). Some success has been
achieved using ion exchange resin in gold recovery from thiosulfate solution (Jeffrey
& Brunt, 2007; Zhang & Dreisinger, 2004 & 2002; Fleming et al., 2001).
In this section, the recovery of gold, copper, and mercury from ammonium
thiosulfate (ATS) solutions using a strong ion-exchange resin has been studied and
evaluated. A commercially available ion-exchange resin, Purolite A500/2788, was

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
obtained in its wet form and used without conditioning. Table 8.4 presents the
physical and chemical properties of Purolite A500/2788 resin.

Table 8.4: Typical physical and chemical characteristics of Purolite A500/2788

resin.

Characteristic Ionic form Value

Total Capacity (min.) Cl- 1.15 eq/L
Moisture Retention Cl- 53-58%

Particle Size 800-1300 µm 92%

Reversible Swelling (max.) Cl- → OH- 15%
Specific Gravity 1.08 g/mL
Shipping Weight (approx.) 670-700 g/L
Temp Limit OH- 60 °C
Temp Limit Cl- 100 °C
pH Limits 0-14 (Stability)

The loading and recovery of gold, copper, and mercury from thiosulfate
solution was carried out using two different methods: (1) loading and then stripping
using sodium perchlorate (NaClO4. H2O) in batch tests and (2) loading and then
elution using a solution composed of 2 M NaCl and 0.2 M Na2SO3 in elution
columns. The experimental procedures for both methods have been described in
Chapter 4, sections 4.4.1 and 4.4.3.

Loading-Stripping Batch Tests

The recovery of mercury, gold, and copper from a synthetic thiosulfate leach
solution at different mercury concentrations (0, 2, 3, 5, 7, 10, 15, and 20 mg/L Hg as
HgCl2) was studied. The reagent concentrations of the synthetic leach solution were
100 mM ammonium thiosulfate (ATS), 4 mM trithionate ( S 3O6 ) 2− , 1 mM copper

sulfate, and 5 mM gold (Au) as gold thiosulfate Au ( S 2 O3 ) 32− . Resin was loaded using
the synthetic leach solution and stripped in batch tests.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
Loading-Elution Column Tests
In the loading-elution experiments, gold, copper, and mercury were eluted from
loaded resins utilising an ion exchange column. A 1.5 L synthetic thiosulfate leach
solution containing 100 mM ATS, 4 mM trithionate, 1 mM copper sulfate, 5 ppm
gold as gold thiosulfate, and 5 mg/L mercury as (HgCl2) was contacted overnight
with 6 g of the strong ion-exchange resin. The loaded resin was then stripped in
column tests.

8.3.2 Loading and Recovery of Gold

The amount of gold loaded on 0.667 g of resin from 250 mL of synthetic leach
solution is shown in table 8.5 as a function of mercury concentration. The loaded
resin was batch stripped twice with 25 mL of 0.5 M sodium perchlorate (NaClO4.
H2O) for half an hour each. The gold stripped from the resin is shown in table 8.5.
The results showed that gold loading and recovery is not affected significantly by the
presence of mercury in the solution. On average, the percentage of the gold in the
solution loaded onto the resin is about 76%. From the differences between the
amount of gold loaded on the resin and the amount stripped it can be seen that most
of the loaded gold is recovered from the resin by using sodium perchlorate as an
eluant. The presence of mercury, up to 20 mg/L, has no influence on the gold loading
and recovery.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

Table 8.5: The amount of gold loaded on resin and stripped from the resin as a
function of mercury concentration in a synthetic leach solution.

Gold, kg-Au/t-resin
Hg, conc., Deviation, %
mg/L Gold loaded Gold stripped

0 2.60 2.78 6.9

2 2.57 2.73 6.1
3 2.47 2.51 1.4
5 2.58 2.74 6.1
7 2.44 2.47 1.3
10 2.48 2.49 0.5
15 2.53 2.54 0.5
20 2.52 2.72 7.7

8.3.3 Loading and Recovery of Copper

Copper might be present in thiosulfate solutions when it used to treat gold ores
containing copper or when it is added as a catalyst for gold leaching. The amount of
copper loaded on 0.667 g of resin from 250 mL of synthetic leach solution containing
100 mM ammonium thiosulfate (ATS), 4 mM trithionate (S3O62-), 1 mM
CuSO4.5H2O, and 5 mM gold (Au) as gold thiosulfate Au ( S 2 O3 ) 32− is shown in table
8.6 as a function of mercury concentration. The loaded resin was batch stripped twice
with 25 mL of 0.5 M sodium perchlorate (NaClO4. H2O) for 30 minutes each. The
copper stripped from the resin is also shown in table 8.6. The percentage of copper
from solution loaded on the resin is low with the maximum being around 18.5%
when no mercury was added into the loading solution.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
Table 8.6: The amounts of copper loaded on resin and stripped from resin as a
function of mercury concentration in a synthetic leach solution.

Copper, kg-Cu/t-resin
Hg, conc.,
Deviation, %
mg/L Copper loaded Copper stripped

0 8.07 7.77 3.7

2 7.91 7.67 3.1
3 6.91 6.97 0.9
5 7.92 7.70 2.8
7 6.80 6.87 1.1
10 6.34 6.84 7.7
15 6.50 6.96 7.0
20 7.84 7.66 2.4

8.3.4 Loading and Recovery of Mercury

The amount of mercury loaded on 0.667 g of resin from 250 mL of synthetic
leach solution is shown in table 8.7 for different initial mercury concentrations. The
loaded resin was batch stripped twice with 25 mL of 0.5 M sodium perchlorate
(NaClO4 H2O) for half an hour each. The mercury stripped from the resin is also
shown in Table 8.7. It was found that the amount of mercury stripped was about 75%
of the mercury loaded on the resin for all initial mercury concentrations.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
Table 8.7: The percentages of mercury loaded on resin and stripped from resin as a
function of initial mercury concentration. Possible loading is the loading
if all of the mercury was removed from solution and loaded on the resin.

Possible Hg Hg loaded and stripped, %

loading, kg-
Hg/t-resin Mercury loaded as Mercury Stripped as
a % of possible a % of possible
loading. loading
0 0 0
1.36 56.3 42.3
4.16 60.4 46.8
6.13 61.8 48.4
9.09 63.8 49.7
11.81 62.0 43.9

Figure 8.7 shows the mercury loaded on resin and stripped from resin as a
function of initial mercury concentration. The amount of mercury loaded and
stripped is influenced by the initial mercury concentration in the loading solution
with increasing initial mercury concentration increasing the amount of loaded and
recovered mercury.

8
Hg loaded and recovered, kg-Hg/t-resin

6 Loading based
Stripping based

0
0 2 4 6 8 10 12 14 16 18 20
Initial Hg concentration, mg/L

Figure 8.7: The amount of mercury loaded on resin and stripped from resin at
different initial mercury concentrations.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
8.3.5 Polythionate Speciation
For each loading-stripping experiment after 5 hours loading, the barren solution
was analysed to determine the quantities of thiosulfate and polythionate species using
a Waters 2695 HPLC separation module. The loaded resin was then stripped twice
for 30 minutes each using 25 mL of 0.5 M sodium perchlorate and the polythionate
speciation analysis carried out for each stripping batch. The measured speciation of
the barren loading and stripping solutions are shown in Tables 8.8 and 8.9
respectively. From these tables, the thiosulfate, trithionate, tetrathionate, and
pentathionate that is loaded and stripped from the resin at different mercury
concentrations can be seen.

Table 8.8: Thiosulfate and polythionate speciation of the barren loading solution
(Initial loading solution containing:100 mM ammonium thiosulfate
(ATS), 4 mM trithionate (S3O62-), 1 mM CuSO4.5H2O, and 5 mM gold
(Au) as gold thiosulfate).

Barren solution
Species
0 ppmHg 5 ppmHg 10 ppm Hg 15 ppm Hg

Thiosulfate 93.89 mM 93.92 mM 89.51 mM 90.62 mM

Trithionate 2.75 mM 2.75 mM 2.63 mM 2.56 mM
Tetrathionate 0.36 mM 0.44 mM 0.58 mM 0.57 mM
Pentathionate 0.01 mM 0.01 mM - -

Table 8.9: Thiosulfate and polythionate speciation of the stripping solution (25 mL
of 0.5 M sodium perchlorate (NaClO4. H2O).

Stripping solution
Species
0 ppmHg 5 ppmHg 10 ppm Hg 15 ppm Hg

Thiosulfate 202.4 mM 202.6 mM 195.4 mM 203.5 mM

Trithionate 353.7 mM 350.9 mM 340.9 mM 347.7 mM
Tetrathionate 66.3 mM 59.7 mM 62.2 mM 65.5 mM
Pentathionate 6.0 mM 5.1 mM 3.4 mM 3.1 mM

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
8.3.6 Gold, Copper and Mercury Recovery Using an Elution Column
The elution of gold, copper, and mercury from a loaded resin was carried out
with an eluant solution composed of 2 M NaCl and 0.2 M Na2SO3. An automatic
fraction collector was adjusted to collect 8 mL fractions (1 bed volume, BV). All the
sample fractions were analysed for gold, copper, and mercury with a suitable method
for each metal using ICP-OES. From the amount of gold, copper, and mercury
loaded and eluted, the elution efficiency for each metal was calculated. The
following sections present the amount of gold, copper, and mercury eluted and the
elution efficiencies.

8.3.6.1 Gold Recovery

Figure 8.8 shows the concentration of gold (mg/L) eluted with each BV of
solution (Elution Profile) and the elution efficiency (%). The cumulative values of
the bed volumes (BV) of eluant are plotted on the x-axis. It can be seen that gold was
eluted from the resin very fast and the maximum concentration of gold in the eluant
was at about 2.1 BV. Most of the gold loaded was eluted completely after about 5
BV at which time the gold concentration in the eluant was less than 0.01 mg/L and
the elution efficiency was 99.2%.

140 120

120 100
Gold concentration, mg/L

100
80
Elution efficiency, %

80 Elution Profile
Elution Efficiency 60
60
40
40

20 20

0 0
0 2 4 6 8 10 12 14
Bed Volume

Figure 8.8: Gold eluted and elution efficiency from 8 mL of the loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3.

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem
8.3.6.2 Copper Recovery
Figure 8.9 shows the amount of copper (mg/L) eluted with each BV of
solution and the elution efficiency (%). It can be seen from a comparison between
Figures 8.8 and 8.9 that the elution of copper is faster than that of gold. The
maximum concentration of copper in the eluant was in the first BV and most of the
loaded copper was eluted by about 3 BV at which time the elution efficiency was
100% (Figure 8.9).

800 120

100
Copper concentration, mg/L

Elution efficiency, %
600
Elution Profile 80
Elution Efficiency
400 60

40
200
20

0 0
0 2 4 6 8 10 12 14
Bed Volume

Figure 8.9: Copper eluted and the elution efficiency from 8 mL of loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3.

8.3.6.3 Mercury Recovery

The amount of mercury eluted and the elution efficiency are plotted in Figure
8.10, which shows the maximum concentration of mercury in the eluant was at about
1.3 BV, but the difference between the elution of mercury and the elution of both
gold and copper is that the elution of mercury is slower than for gold and copper.
Complete mercury elution was achieved at about 10 BV compared with gold (5 BV)
and copper (3 BV).

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Chapter 8: Dissolution of mercury in thiosulfate and cyanide solutions: an
environmental problem

100 120

100

Mercury concentration, mg/L

80

Elution efficiency, %
80
60
Elution Profile 60
Elution Efficiency
40
40

20
20

0 0
0 2 4 6 8 10 12 14
Bed Volume

Figure 8.10: Mercury eluted and the elution efficiency from 8 mL of loaded resin
(Purolite A500/2788) using an eluant containing 2 M NaCl and 0.2 M
Na2SO3.

8.4 Summary
In this chapter, the solubility behaviour of mercury compounds (elementary
mercury (Hg0), mercuric chloride (HgCl2), mercurous chloride (Hg 2Cl2), and
mercury sulfide (HgS)) in ammoniacal thiosulfate leaching solutions and cyanide
solutions was evaluated. The effect that mercury has on gold and copper loading
from thiosulfate solution onto ion exchange resin has also been investigated. Finally,
gold, copper, and mercury elution was examined using ion exchange resin columns
in order to evaluate the recovery of gold and copper in the presence of mercury. It
has been found that thiosulfate solutions dissolve mercury similar to cyanide, which
would need to be considered when thiosulfate is used to leach gold. Mercuric
chloride was the most soluble of the mercury salts tested with the order of the rate of
dissolution in thiosulfate solutions being HgS < Hg0 < Hg2Cl2<HgCl2.
The results show that the presence of mercury does not have a significant
effect on both gold loading and recovery. Finally, gold, copper and mercury were
eluted using a solution composed of 2 M NaCl and 0.2 M Na2SO3. The results
showed that gold and copper were eluted faster than mercury and that complete
mercury elution was achieved at 10 BV compared to gold (5 BV) and copper (3 BV).

213
Chapter 9 Conclusions and Recommendations

9.1 Conclusions
The outcomes presented in this work show a significant achievement in the
understanding of gold leaching with thiosulfate and the environmental impacts of
mercury and cyanide in the field of gold production. The gold dissolution process
using thiosulfate solutions was intensively studied in several ways: (1) gold was
leached in thiosulfate solution in both closed and open vessels (kinetic and
environmental comparison); (2) the metallurgical optimum thiosulfate leaching
conditions for pure gold and pure silver were evaluated and the research extended to
gold silver alloys (4, 8, 20 and 50 wt% silver); (3) the electrochemical nature of
leaching was studied using gold, silver, and gold/silver alloys with linear sweep
voltammetry and coulometric electrochemical techniques at fixed potential values;
(4) the leaching of gold from ore samples supplied from the Centamin Egypt Limited
Company was optimised, and (5) finally, the possibility of mercury dissolution in
thiosulfate solutions and gold, copper, and mercury loading onto and recovered from
ion-exchange resins was studied.

9.1.1 Gold leaching in open and closed vessels

The leaching of gold and silver in solutions containing copper(II), ammonia
and thiosulfate in a closed vessel maintains optimum leaching conditions and
enhances the leaching kinetics compared with an open vessel. The leaching rate of
gold and silver in the closed vessel was greater than that obtained in the open vessel
by 30% and 45% respectively. Silver leaching rates were found to be more sensitive
to temperature and ammonia concentration than gold. Higher temperatures increased
the volatilization rate of ammonia during leaching in the open vessel which is not
desirable kinetically and environmentally. Copper (II) reduction increased in the
open vessel with increasing temperature. Thiosulfate decomposition was also greater
in an open vessel compared to the closed one and increased with increasing
temperature. Temperature should be minimized in the thiosulfate system to avoid
ammonia losses and the consumption of thiosulfate. In brief, gold and silver leaching
in thiosulfate solutions is preferable kinetically and environmentally if conducted in a
closed vessel system.

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Chapter 9: Conclusions and Recommendations

9.1.2 Optimum thiosulfate leaching characteristics of pure gold, pure

silver and gold/silver alloys
From the kinetic study of the dissolution of gold, silver and gold-silver alloys in
solutions containing copper (II), ammonia and thiosulfate with standard experimental
conditions: 10 mM Cu(II), 0.4 M NH3, 0.2 M S2O32-, 30 ºC, 300 rpm, pH 11.5, it is
concluded that :
 Pure silver dissolution rate is around 6.89 times more than pure gold
 The dissolution rate of pure gold is higher than that from 4 and 8 wt% Ag alloys,
but the dissolution rate of gold in 20 and 50% silver alloys is more than that obtained
for pure gold.
 The average dissolution rate of pure gold and pure silver after 8 hours are 45 and
36% respectively of the dissolution rates after 1 hr. The average total metal
dissolution rate decreased over time for all gold-silver compositions tested.
 By increasing the initial thiosulfate concentration, the average total dissolution
rate after 8 hr increased for all gold–silver compositions tested.
 Silver dissolution rate is more sensitive to thiosulfate concentration than gold.
 The silver dissolution rate is sensitive to copper(II) concentration being 1.67 x
10 mol.m-2.s-1 at an initial copper(II) concentration of 1.25 mM and 6.6x10-5 mol.m-
-5

2 -1
.s at an initial copper(II) concentration of 10 mM.
 Silver dissolution is more sensitive to ammonia than gold. The pure silver
dissolution rate with 0.2 M ammonia was very low while its maximum rate was
15.29 x 10-5 mol.m-2.s-1 with 0.8 M ammonia. For pure gold the maximum
dissolution rate was 1.63 x 10-5 mol.m-2.s-1 with 0.6 M ammonia which decreased to
1.25 x 10-5 mol.m-2.s-1 with 0.8 M ammonia.

9.1.3 Electrochemical studies of gold, silver, and gold/silver alloys in

thiosulfate solutions
Electrochemical experimental work was carried out in two different ways:
linear sweep voltammetry and coulometric electrochemical experiments at a fixed
potential value. The experiments were performed at a rotation speed of 300 rpm and
at a temperature of 30 ºC for 30 minutes.
From the linear sweep voltammetry experiments, an increase in ammonium
thiosulfate concentration resulted in an increase in the produced current due to the
oxidation of gold and/or silver. Gold was found to oxidise faster in ammonium

215
Chapter 9: Conclusions and Recommendations

thiosulfate solutions than sodium thiosulfate solutions. An increase of silver percent

in the alloy resulted in an increase of the total current density from both gold and
silver oxidation in thiosulfate solution over the whole range of applied potentials. In
the absence of ammonia gold and silver oxidation is very slow however, in solutions
containing high ammonia concentration, gold oxidation occurs rapidly. The most
important finding from the electrochemical and kinetic results (Chapter 6) is that the
addition of thiourea into the thiosulfate solution retards the oxidation of silver and
the lowest silver oxidation occurs at high thiourea concentrations. From this
observation, the results suggest that choosing thiourea as an oxidant in the thiosulfate
solution should be limited if the gold mineral is mixed with silver which, is usually
the case with most native gold found alloyed with silver.
From the coulometric electrochemical experiments at fixed potential values of
0.22, 0.256, 0.292, and 0.35V (relative to standard hydrogen electrode (SHE)) in
thiosulfate solutions, it was found that an increase in the pure gold dissolution rate
can be achieved by increasing the potential. The gold dissolution rate started slowly
at a low potential and increased with increasing potential in thiosulfate-thiourea
solutions. The highest total (gold/silver) dissolution rate is obtained from the
thiosulfate–thiourea solutions when there is a low percentage silver in the alloys.
When the silver percent was increased up to 20 and 50%, the total leach rate
decreased significantly. In thiosulfate-ammonia and thiosulfate-ammonia-copper
solutions, the total dissolution rate increased significantly with increasing percentage
of silver in the alloy.

9.1.4 Thiosulfate leaching of gold ore samples

The effect of thiosulfate concentration, ammonia, copper(II), temperature, and
solid-liquid ratio on gold ore leaching was studied. The results showed that there is a
slight increase in gold recovery from a closed vessel compared to an open one during
the first 3 hours of leaching. After 24 hours, gold recovery from the closed vessel is
higher than from an open vessel by nearly 5.8%. By increasing copper(II)
concentration from 2.5 mM to 20 mM, gold recovery increased from 85% to 96%
after 24 hours of leaching, but thiosulfate consumption increased from 22.5 to 44.6
kg/t-ore. With an increase in thiosulfate concentration up to 0.4 M, gold extraction
increased to 96% and initial thiosulfate concentration had little effect on thiosulfate
consumption. At the beginning of the leach (after 3 hours), it was found that gold

216
Chapter 9: Conclusions and Recommendations

recovery increased by raising the temperature, but as time passed, it was found that
the amount of gold recovered at 50 ºC was the lowest, the optimum temperature
being 30 ºC. Thiosulfate consumption also increased significantly with increasing
temperature. Lower Solid/liquid ratio gave higher recovery of gold from the ore. The
agitation speed has insignificant effect on gold recovery. Finally, the study found the
optimum conditions to leach the ore to be 0.2 – 0.4 M thiosulfate, 400 mM NH3, 10 -
20 mM Cu(II), 30 ºC, 300 rpm, no air supplied, solid/liquid ratio 20 %, and a particle
size of -106 µm.

9.1.5 Mercury dissolutions in thiosulfate solutions and gold, copper, and

mercury recovery from ion-exchange resins
The dissolution of different mercury forms in thiosulfate and cyanide solutions
was carried out. The results showed that mercury dissolves in thiosulfate and in
cyanide solutions. The order of the dissolution rates of different mercury forms in
these solutions was HgS2 < Hg0 < Hg2Cl2<HgCl2. Mercury chloride (HgCl2)
dissolved completely in all the solutions tested. The cyanide solution sparingly
leaches mercury sulfide with 10.9% dissolved after 24 hours while, the amount of
mercury dissolved from the thiosulfate solution did not exceeds 3.4 % after two days
of leaching.
Gold, copper, and mercury loading and stripping experiments were conducted
using a strong basic ion-exchange resin. The results showed that the presence of
mercury does not have a significant effect on gold loading and stripping. The study
also showed that the amount of mercury stripped from the resin was about 75% of
the mercury loaded at different initial mercury concentrations.
Finally, gold and copper were loaded in the presence of mercury in the
loading solution and then eluted. A solution composed of 2 M NaCl and 0.2 M
Na2SO3 was used as the eluant. The results suggested that gold and copper were
eluted faster than mercury and that mercury eluted at 10 BV compared to gold (5
BV) and copper (3 BV). The presence of mercury did not have any affect on the
loading or recovery of gold.

217
Chapter 9: Conclusions and Recommendations

9.2 Recommendations
The study offers several recommendations for future research work directed
at thiosulfate leaching of gold. First of all, the leaching of gold and silver in a closed
system should be more intensively studied to evaluate the leaching kinetics of gold in
the presence of low percents of silver. The environmental advantages of using a
closed system in thiosulfate leaching needs to be studied on a semi-industrial scale to
evaluate the amount of ammonia evaporated into the environment and that left in the
final solution and its environmental impacts. Secondly, further studies should be
undertaken to evaluate the effect of silver content (gold/silver as alloys and ores) on
gold leaching from thiosulfate solutions containing thiourea as an oxidant. An
important finding from this work is that in the presence of thiourea, the oxidation
current of gold and silver decreased and the oxidation current from pure gold after
the standard potential for gold oxidation (150 mV) is higher than the total oxidation
current from gold-silver alloys. In the future work, the kinetic and electrochemical
effects of silver content on gold leaching rate in thiosulfate solutions containing
thiourea should be studied.
Finally, mercury forms with cyanide a strong complex which is adsorbed on
carbon with gold or silver during the recovery processes and this causes a serious
problem in the elution circuit and in the electrowinning process. An important future
project suggested by this work is to study the leaching, loading, and recovery of gold
in thiosulfate solutions from gold ore minerals containing different contents of
mercury. The effect of mercury dissolved on gold loading and recovery should then
be evaluated kinetically and environmentally.

218
Chapter 10: References

Chapter 10 References

Abbruzzese, C., Fornyari, P., Massidda, R., Veglio, F. and Ubaldini, S., 1995,
“Thiosulphate leaching for gold hydrometallurgy”, Hydrometallurgy, 39, 265-276.

ACGIH, 1997, “Threshold limit values for chemical substances and physical agents
and biological exposure indices”, American Conference of Governmental Industrial
Hygienists, Cincinnati, Ohio.

Akcil, A., 2003, “Destruction of cyanide in gold mill effluents: biological versus
chemical treatments”, Biotechnology Advances, 21, 501-511.

Alabaster, J.S., Shurben, D.G. and Mallett, M., 1983, “The acute lethal toxicity of
mixtures of cyanide and ammonia to smolts of salmon, Salmo salar L. at low
concentrations of dissolved oxygen”, Journal of Fish Biology, 22, 215-222.

Angelidis, T.N., Kydros, K.A and Matis, K.A., 1993, “A fundamental rotating disk
study of gold dissolution in iodine-iodide solutions”, Hydrometallurgy, 34 (1), 49-64.

Anhong, C., 1997, “An investigation of optimum conditions for gold extraction from
ores using ammonium thiosulfate”, California, California State University.

Anonymous, 2000, “Colorado cyanide ban fails to make November ballot”, Mining
Engineering, 52, 36.

Arima, H., 2003, “Gold extraction and recovery by using ammonium thiosulfate
solution”, Department of mining engineering. Kingston, Ontario, Canada, Queen’s
University.

Arima, H., Fujita, T. and Yen, W.T., 2004, “Using nickel as a catalyst in ammonium
thiosulfate leaching for gold extraction”, Materials Transactions, 45, 516-526.

219
Chapter 10: References

Arslan, F., Sayiner, B. and Scedil, S., 2008, “Extraction of gold and silver from
Turkish gold ore by ammoniacal thiosulphate leaching”, Mineral Processing and
Extractive Metallurgy Review, 29, 68 - 82.
Aylmore, M.G. and Muir, D.M., 2001a, “Thiosulfate leaching of gold - a review”,
Minerals Engineering, 14, 135-174.

Aylmore, M.G. and Muir, D.M., 2001b, “Thermodynamic analysis of gold leaching
by ammoniacal thiosulfate using eh/ph and speciation diagrams”, Minerals and
Metallurgical Processing, 18, 221-227.

Aylmore, M.G., 2001, “Treatment of a refractory gold-copper sulfide concentrate by

copper ammoniacal thiosulfate leaching”, Minerals Engineering, 14, 615-637.

Baghalha, M., 2007, “Leaching of an oxide gold ore with chloride/hypochlorite

solutions”, International journal of Mineral processing, 82 (4), 178-186.

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