Journal of Cleaner Production 14 (2006) 1158e1167

www.elsevier.com/locate/jclepro

Review article

Alternatives to cyanide in the gold mining industry: what

prospects for the future?
Gavin Hilson a, A.J. Monhemius b,*
a
School of City and Regional Planning, Cardiff University, Glamorgan Building, King Edward VII Avenue,
Cardiff CF10 3WA, Wales, UK
b
Department of Earth Science and Engineering, Royal School of Mines, Imperial College, London SW7 2BP, UK
Received 5 May 2004; received in revised form 28 September 2004; accepted 29 September 2004
Available online 24 May 2005

Abstract

This paper reviews a series of alternative lixiviant systems for the recovery of gold from ores and concentrates. For over 100
years, cyanide has been the leach reagent of choice in gold mining because of its high gold recoveries, robustness and relatively low
costs. The environmental damages resulting from its mismanagement, however, have initiated widespread research aimed at
identifying and developing less toxic leaching agents. The most widely-researched alternative lixiviants for gold ores are examined in
this paper, but it is evident that none has yet made any significant inroad into the dominant position of cyanide as the reagent of
choice at the vast majority of gold mines worldwide.
Ó 2005 Published by Elsevier Ltd.

Keywords: Cyanide; Gold; Alternatives; Thiourea; Thiosulphate; Thiocyanate

1. Introduction called ‘‘cyanidation’’, received immediate industrial

The debate surrounding the use of cyanide in the
mining industry has fuelled considerable investigation
into the development of more environmentally benign
alternatives. For over 100 years, cyanide has featured
prominently as a leach reagent at gold mines because of
its high efficiency and relatively low cost. Although
Hagen first discovered that gold was soluble in cyanide
in 1806, it was not until the work of John Stewart
MacArthur in the 1880s that the value of cyanide as
a leach reagent for gold ore treatment was finally
realised. A chemical metallurgist, MacArthur was
granted British Patent No. 14174, Process of Obtaining
Gold and Silver from Ores, in 1887. This technology,
* Corresponding author. Tel.: C44 207 594 7329; fax: C44 207 594
7444.
E-mail address: j.monhemius@imperial.ac.uk (A.J. Monhemius).
success in New Zealand in 1889 and South Africa in
1890. Gold worth US$14 million was recovered by
cyanidation over the first five-year period of operation
of the process [1], which eventually replaced chlorina-
tion processing outright. By 1907, global annual pro-
duction of gold had doubled because of an increased use
of cyanide; it continues to this day to be the primary
leaching method in the gold mining industry [2].
Today, over one million metric tonnes of cyanide e
representing 80% of total production e are used
annually by the chemical industry for the production
of organic chemicals such as nitrile, nylon, and acrylic
plastics. The remaining 20% is used to manufacture
sodium cyanide, a solid form of cyanide, of which 90%
(i.e. 18% of total production) is used in mining
operations around the world for gold recovery purposes
[3]. Typically, dilute solutions of sodium cyanide
(NaCN), normally in the range of 0.01e0.05% cyanide

0959-6526/$ - see front matter Ó 2005 Published by Elsevier Ltd.

doi:10.1016/j.jclepro.2004.09.005
 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
(100e500 parts per million), are used in tank leaching
and heap leaching processes. Cyanide ions (CN
) are
the active ingredients in the gold leaching process, which
dissolve the gold contained in the ore by complexation
(see below), forming a ‘‘pregnant solution’’ from which
gold is later extracted.


4AuC8CN
CO2 C2H2 OZ4AuðCNÞ2 C4OH

A series of recent environmental accidents at various
gold mines around the world, however, has precipitated
widespread concern over the use of cyanide as a leach
reagent. In the majority of these cases, cyanide from
processing operations entered the environment either
by leakage through tears and/or punctures in protective
heap leach liners, or by spillage from overflowing
solution ponds or tailings storage areas [4]. For
example, in Guyana, some 2.9 million m3 of cyanide-
laced tailings and wastewater was released by a collapse
of the tailings dam at the Omai mine on the night of
August 19, 1995, polluting the Omai River. A disaster
similar in scale occurred on January 30, 2000 in Baia
Mare, Romania, where the tailings dam of Aurul S.A.
was breached, resulting in the discharge of wastewater
containing as much as 100 t of cyanide that eventually
reached the Danube River. (See Table 1 for additional
examples of cyanide spills and resulting impacts.).
Although cyanide is not regarded as a persistent
toxin, it is nevertheless a deadly poison in high con-
centrations, posing a serious health threat to a wide
range of ecological entities. In fact, the contention that
cyanide is not persistent and does not give rise to
chronic health or environmental problems [3] is some-
what misleading. As Moran [5] explains, the CN
ion,
which is ubiquitous in nature, tends to react readily with
innumerable chemical agents and molecules to form
hundreds of different compounds, many of which are
lethal to organisms. To determine the persistence and
toxicity of the chemical, chemists have traditionally
distinguished ‘‘weak’’ from ‘‘strong’’ cyanide complexes.
Weak cyanide complexes, often referred to as ‘‘weak
Table 1
Examples of recent cyanide-related mine accidents and resulting environmental impacts [6]
Company/Mine Location and date
Galactic Resources Ltd.’s Colorado, USA, 1992
Summitville Mine
Pegasus Corporation’s Montana, USA, 1997
ZortmaneLandusky Mine
Echo Bay’s McCoy/Cove Nevada, USA, 1989
Gold Mine and 1990
Kumtor Mine Kyrgyzstan, 1998
Cambior Mining Company’s Guyana, 1995
Omai Mine
1159
acid dissociable’’ or WAD cyanide, break down, re-
leasing free cyanide ions when the pH is lowered. WAD
cyanide includes cyanide complexes of cadmium,
copper, nickel, silver, and zinc, all of which can dis-
associate in acid conditions and produce environmentally-
significant quantities of toxic cyanide ions. Strong
cyanide complexes are more stable than WAD cyanide,
thus degrading much more slowly under natural
conditions. These include cyanide complexes containing
gold, cobalt, and iron, which are more stable in solution
[3,7]. The toxicity of cyanide varies, with free cyanide
being the most toxic, and cyanide complexes being less
or non-toxic [8].
In excessive quantities, cyanide can be lethal to
humans and to animal species because it binds to the
iron-carrying enzymes required for cells to use oxygen,
thus inhibiting bodily tissues from extracting oxygen
from the blood (Table 2). The body then rapidly exhibits
symptoms of oxygen starvation and suffocation. Symp-
toms of cyanide poisoning include irregular heartbeat,
convulsions, chest pains and vomiting [7]. Many species
of migratory birds can come to grief at gold mine
heap leaching facilities, some dying immediately after
consuming cyanide-contaminated water. Signs of acute
poisoning to livestock, including initial muscle tremors,
salivation, lacrimation, defecation, urination and la-
boured breathing, usually occur within 10 min; death can
follow quickly [4,9e11]. In the aquatic environment,
young, freshwater fish such as salmonoids are particularly
susceptible to cyanide poisoning.
It is against the background of these environmental
impacts that indigenous groups and representatives of
the NGO community in particular have lobbied for the
mining industry to develop alternative, less toxic, leach
reagents. The purpose of this article is to review the most
widely-researched alternative leach reagents to cya-
nide. Several substitutes have been proposed (Table 3)
but generally, the non-cyanide lixiviants thiourea,
thiocyanate and thiosulphate are regarded as being the
most realistic substitutes. These, along with a number of
other possible alternatives, including halides and the
Impacts
Caused severe environmental problems along
a 17-mile stretch of the Alamosa River
Severe contamination of groundwater;
substantial wildlife deaths
Eight cyanide leaks over a two-year period
released almost 900 lbs of cyanide into the
environment
Almost 2 t of sodium cyanide was accidentally
released into surface waters
Released more than 860 million gallons of
cyanide-laden tailings into a major river
1160 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167

Table 2 (1) inexpensive and recyclable;

Single dose toxicity of sodium cyanide (in mg NaCN kg
1 body (2) selective;
weight), selected species [13]
(3) non-toxic; and
Species Oral LD50 (95% (4) compatible with downstream recovery processes.
confidence limits)
Mallard 2.7 Box 1 highlights additional criteria which must be
Human 3.0
American kestrel 4.0
considered for gold lixiviants.
Coyote 4.1 For over a century, sodium cyanide has been the
Black vulture 4.8 predominant leach reagent for gold because of its
Lab rat 5.1 excellent performance with a great variety of ores and
Little brown bat 8.4 its relatively low cost [15]. Moreover, despite being
Eastern screech owl 8.6
Japanese quail 9.4
a potentially deadly poison if ingested in high doses,
Domestic chicken 21 cyanide does not give rise to chronic health or
White footed mouse 28 environmental problems if present in low concentrations
[3]. It is ubiquitous in nature, produced by a wide
range of micro-organisms and over 2500 plant species as
recently-developed coaleoil agglomeration process, part of their normal metabolisms [7]. The low concen-
are reviewed individually in the discussion that trations of cyanide used in gold milling and heap leach-
follows. ing are quickly degradable: cyanide is nowhere near as
harmful as other naturally occurring toxins (e.g. tetanus,
strychnine) because it is readily transformed by natural
2. The challenges to developing alternatives for cyanide physical, chemical, and biological processes, into less or
non-toxic forms.
The main challenge to developing substitutes for The primary challenge in devising a suitable sub-
cyanide rests in ensuring that the particular metallurgi- stitute for cyanide in gold processing, therefore, lies in
cal processes selected for the extraction of gold matches developing an equally effective and degradable leach
the characteristics of the ore. Alternative lixiviants or reagent, which is not a persistent environmental toxin.
leaching agents should also be [12]: As gold cyanidation rates are relatively slow, the industry

Table 3
Suggested alternatives to cyanide [14]
Reagent type Concentration pH range Basic Research Extent of
range chemistry level commercialisation
Ammonia High 8e10 Simple Low Pilot tests, C100  C
Ammonia/cyanide Low 9e11 Simple Extensive Applied to Cu/Au ores
Ammonium thiosulphate High 8.5e9.5 Complex Extensive Semi-commercial
Slurry CN-electrolysis Low 9e11 Simple Historical Limited historical
Sodium sulphide High 8e10 Simple Low Geological interest only
Alpha-hydroxynitriles Moderate 7e8 Fairly simple Fairly popular None
Malononitrile Moderate 8e9 Fairly complex Low None
Alkali cyanoform Poorly defined 9? Poorly defined Low None
Calcium cyanide Poorly defined 9? Poorly defined Low none
Alkaline polysulphides High 8e9 Poorly defined Low None
Hypochlorite/chloride High chloride 6e6.5 Well defined Extensive Historical and modern
Bromocyanide High 6e7 Poorly defined Historical Historical
Iodine High 3e10 Poorly defined Low None
Bisulphate/sulphur dioxide High 4e5 Fairly simple Low None
Bacteria High 7e10 Fairly complex Low, growing None
Natural organic acids High 5e6 Fairly complex Low None
DMSO, DMF Poorly defined 7 Poorly defined Very low None
Bromine/bromide High 1e3 Well defined Low Historical
Thiourea High 1e2 Well defined Fairly popular Some concentrates
Thiocyanate Low 1e3 Well defined Low None
Aqua regia High Below 1 Well defined Low Analytical and refining
Acid ferric chloride High Below 1 Well defined Low Electrolytic Cu slimes
Ethylene thiourea High 1e2 Poorly defined Very low None
Haber process Poorly defined Proprietary One entity None
‘‘Bio-D leachant’’ Poorly defined Proprietary One entity None
High temperature chlorination High 6e7 Simple historical Historical
 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
Box 1. Criteria which should be considered for
gold lixiviants [16]
Economic considerations
 Capital outlay
 Extraction costs
 Availability
 Detoxification/recycling costs
Toxicity
 Emissions
 Handling
 Environmental toxicity
Process applicability
 Limitations (e.g. ore type, selectivity,
control, separation, etc.)
 Recyclability
 Detoxifiability
 Feasibility at a large scale
has been searching for faster gold leaching reactions
capable of facilitating high metal recovery rates.
Although there has been significant research undertaken
to develop plausible substitutes, driven mainly by
economics, the list of effective options is limited, as most
are addressed to refractory ores and are not amenable to
simple cyanide leaching [15]. The discussion that follows
reviews the most promising alternatives.
3. Thiourea leaching of gold
3.1. Overview
The use of thiourea (NH2CSNH2) as a gold extrac-
tion agent has shown considerable promise. In acidic
conditions, thiourea dissolves gold, forming a cationic
complex; the reaction is rapid and gold extractions of up
to 99% can be achieved [15]. The anodic reaction
follows the equation:
ÿ
C
AuC2CSðNH2 Þ2 ZAu CS½NH2 2 2 Ce

The reagent, however, has to be used under relatively
restricted conditions, as it is fairly stable thermodynam-
ically in acid and neutral mediums, but decomposes
rapidly in basic solutions [17]. Leaching is normally
carried out in the pH range of 1e2, and its successful
application is contingent upon careful optimisation and
control of pH, redox potential, thiourea concentration,
and leaching time. The critical parameters for thiourea
leaching are as follows [18]:
1161
pH: 1.4 adjusted accordingly with
H2SO4
Redox potential: Max 250 mv; Min 150 mv
Thiourea concentration: 1%
Thiourea consumption: 2 kg/t
Leach time: 10e15 min
It is claimed in a number of sources [15,19,20] that
the work of the Soviet scientists Plastin and Kozukhova
[21,22] was the pioneering research in this field, but the
potential of thiourea for gold dissolution was recognised
much earlier by Moir [17] who, in 1906, published
a paper entitled ‘‘Thiocarbamide e a new solvent for
gold’’ [23]. Moir reported the results of experiments in
which he dissolved pieces of gold leaf in thiourea (then
called thiocarbamide) solutions. He showed that acid
conditions were necessary and that the reaction was
rapid in the presence of suitable oxidants. At that time,
however, cyanide was already established as the reagent
of choice for gold ore treatment and so Moir’s discovery
lay neglected for over half a century. Thiourea has only
received serious consideration as an alternative to
cyanide in the past 20 years [12]. It is an attractive
option for treating refractory ores and floatation
concentrates, although it is hoped that with further
research, it can be adopted to treat lower grade ores [18].
3.2. The thiourea process and potential benefits
In a comprehensive review, Pyper and Hendrix [24]
identified the following about thiourea kinetics:
 The use of ferric ion in sulphuric acid is the most
effective system;
 The rate of leaching is contingent upon thiourea and
oxidant concentrations;
 The ferric ion ties up thiourea in ironethiourea
complexes; and
 The rate of gold dissolution is strongly determined
by pH.
Generally, gold can be recovered from thiourea via
cementation (using iron powder, or aluminium), or by
absorption on activated carbon, or by electrowinning, or
by the use of ion-exchange resins. Compared to cyanide,
thiourea has certain advantages, including low sensitiv-
ity to base metals (Pb, Cu, Zn, As); low sensitivity to
residual sulphur in calcines; high gold recovery from
pyrite and chalcopyrite concentrates; and satisfactory
recovery of gold from carbonaceous (refractory) ores
[15]. It also poses less of a threat environmentally
[25,26]. On its own, thiourea has a lower toxicity and
higher rate of gold and silver dissolution than cyanide
[27]. Moreover, if using cyanide to treat refractory
sulphide gold-containing ores, which have been pre-
oxidised to release the gold, the highly acidic solutions
1162 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
produced must be neutralised prior to cyanidation,
whereas thiourea can be used directly, since gold
leaching occurs in acidic solutions [28].
Despite the proven effectiveness of thiourea as a gold
leach reagent [27,29,30], there are still few full-scale
operations in existence. Its commercial adoption has
been hindered by the following three factors [31]:
(1) It is more expensive than cyanide;
(2) Its consumption in gold processing is high; and
(3) The gold recovery step requires more development.
Reagent consumption is exceedingly high because
thiourea is readily oxidised in solution, and as Presad
et al. [18] implies, the high costs attached to leaching are
likely due to the thiourea process still being in an
infancy stage. Past attempts to adopt this reagent have
led to over-consumption and increased production
costs. There is also an emerging concern about its
environmental impact. Despite claims that thiourea is
less toxic than cyanide, it is a suspected carcinogen, and
thus must be treated with caution [12].
3.3. Experimental work and commercial
developments
The effectiveness of thiourea as a substitute for
cyanide has been verified through substantial experi-
mental work. As Monhemius [17] reports, in terms of its
feasibility as a leach reagent, Shultz originally argued in
his work that the addition of sulphur dioxide during
thiourea leaching prevents it from degrading chemically,
thus resulting in lower consumptions of the reagent
[32,33]. The author proposed that the bubbling of
sulphur dioxide during the thiourea leaching of precious
metals prevents decomposition of formamidine disul-
phide, which can lead to the coating of gold surfaces by
fine adhesive sulphur, a decomposition product.
More recently, Abbruzzese et al. [34] carried out
further laboratory evaluations to assess the feasibility of
thiourea leaching. Gold was recovered from leaching
solutions by adsorption onto activated carbon; gold was
eluted from the carbon using water/alcohol mixtures,
and the final recovery of gold from the elution solutions
was accomplished via electrowinning. The authors
reported an overall gold yield of 82% with a low
consumption of reagents (based upon a gold extraction
of 85% at room temperature, and a 99% recovery after
the adsorption, desorption and electrowinning phases).
More specific studies have been carried out such as that
of Gonen et al. [35], who examined the effects of
thiourea and oxidant type, pH, agitation time, and
particle size on gold recovery from Gumushane-Mastra
ore in Turkey. It was determined that with short
leaching times and low pH values, the amount of
oxidant and the consumption of thiourea decreased.
Gold extractions of 75% were achieved using a particle
size of 150-mesh in a mixing time of 5 h.
Miroslav et al. [36] examined the feasibility of thiourea
extraction of gold from copper slimes in Kovohutny
Krompachy, Slovenia. The authors reported that thio-
urea extracted some 80% of gold from the residues. Orgui
and Atalay [37] reported similar results. In an attempt to
extract gold from Kaymaz gold ore (4 gAu/t) using
thiourea and iron (III) sulphate as an oxidizing agent, at
room temperature, it was possible to obtain a gold
extraction of 80% in 6 h. The process has also proven to
be a successful non-toxic solvent for gold in Russia [38].
Thiourea leaches gold more rapidly than cyanide, and
is less toxic; forms cationic complexes; and can be
utilised on ores refractory to cyanide and in heap and in
situ leaching [39]. However, as previously explained,
research gaps and costs have hindered its wide-scale
adoption as a leach reagent in the gold mining industry.
Costs can be exorbitant because of the quantity of
reagent required. As Presad et al. [18] explain, the high
consumption of thiourea and low rate of dissolution are
attributable to an inhibiting coating of sulphur on the
surface of the gold particles formed because of thiourea
degradation. It has been proposed that adding sulphur
dioxide to leaching solutions would control the redox
couple between the thiourea and its first decomposition
product, formamidine sulphide, thereby keeping the
formation of sulphur to an absolute minimum.
The most significant commercial development in-
volving thiourea made to date in the Western world has
been at the New England Antimony Mines in New
South Wales, Australia, which was commissioned in
1982. As la Brooy et al. [31] explain, because of
thiourea’s tolerance to stibnite, the company was able
to recover 50e80% of the gold from a stibnite
concentrate using a thiourea leach, followed by gold
recovery onto activated carbon. More recently, Lacoste-
Bouchet et al. [40] used thiourea to leach gold from ore
containing 0.4% Cu and 5.6 g/t Au obtained from the
Val d’Or Mine in Quebec. Gold extractions of 89% were
obtained using thiourea at a rate of 3.9 g/t.
4. Thiocyanate
In 1905, White [41] first demonstrated that thiocya-
nate dissolved gold effectively in the presence of a suit-
able oxidising agent; however, work with this reagent
remained stagnant until Fleming re-opened the field in
1986 [42,43]. As Barbosa-Filho and Monhemius explain
[42], the leaching of gold with thiocyanate, if performed
between pH 1 and 2, enables the use of iron (III) as an
oxidising agent. During the dissolution of gold by iron
(III)ethiocyanate, FeIII is reduced to FeII while oxidis-
ing SCN
, producing several intermediate species,
including (SCN)
3 and (SCN)2, which can both oxidise
 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
and complex gold. In aqueous solutions, acidified
thiocyanate can dissolve gold to form both Au(I) and
Au(II) complexes [44].
In terms of relevant research, Barbosa-Filho and
Monhemius [45] describe aspects of the chemistry and
thermodynamics of thiocyanate, and Broadhurst and du
Preez [46] describe the speciation of the goldethiocya-
nate system. In subsequent experimental work un-
dertaken by Barbosa-Filho and Monhemius [47,48]
with solutions of FeIIIethiocyanate, which reduced
from FeIII to FeII with the oxidation of SCN
, it was
shown that the auto-reduction reaction produced both
(SNC)
3 and (SNC)2, which were fundamental in the
mechanism of the thiocyanate dissolution of gold. The
authors concluded that thiocyanate is an ‘‘effective
lixiviant for gold in acidic conditions, yielding dissolu-
tion rates that are comparable to those obtained with
thiourea whilst offering the advantage of much greater
stability against oxidative decomposition’’. Kholmog-
orov et al. [49] recovered over 95% of gold from weak
acidic solutions, recovering thiocyanate complexes on
carbon adsorbents and ion exchangers [49]. Further
research was performed at a laboratory scale by
Monhemius and Ball [50], who used iodide-catalysed
thiocyanate solutions to leach gold ores derived from
the Dominican Republic. These researchers concluded
that the thiocyanate system used gave results com-
parable to that of a cyanide system, and exhibited
considerably greater effectiveness than thiourea.
5. Thiosulphate leaching
Thiosulphate (S2O2
3 ), a chemical used widely in
photography and in the pharmaceutical industries, has
also been proposed as a substitute for cyanide. As
Yannopoulis [15] explains, gold dissolves slowly in
alkaline thiosulphate. The rate of dissolution is influ-
enced by the concentrations of thiosulphate and dis-
solved oxygen, the process temperature, and can be enhanced
by adding copper ions [44]. Gold forms a stable anionic
complex with thiosulphate according to the following
reaction:

3

2AuC0:5 O2 C4S2 O2

3 CH2 O/2AuðS2 O3 Þ2 C2OH
Although the gold thiosulphate complex is fairly
stable once it has formed, alkaline conditions are
necessary to prevent thiosulphate decomposition by
acid [31]. As Aylmore [51] explains, the thiosulphate
leaching process is catalysed by copper and has several
advantages over the conventional cyanidation process,
in spite of its slow rate. Acceptable gold leaching rates
using thiosulphate are achieved in the presence of
ammonia, together with copper [52]. In recent years
the reagent has been considered seriously as a potential
1163
substitute for cyanide because it generally causes fewer
environmental impacts: thiosulphate leaching exhibits
less interference from foreign cations and poses fewer
pollution concerns [53,54].
The use of thiosulphate as a leach reagent in gold
processing was first proposed during the early-1900s. As
Aylmore and Muir [55] explain, in a procedure known
as the ‘‘Von Patera Process’’, gold and silver ores, first
subjected to a chloridising roast, were leached with
thiosulphate. Before World War II, silver-rich sulphide
ores in South America and the ore at Mexico’s
LeColorado Mine were leached commercially with
thiosulphate following a chloridising roast [56,57].
Improvements were made to the procedure during the
1980s, most notably through the addition of copper ions
and stabilisation of thiosulphate by addition of SO2 or
bisulphite [18].
Several promising experimental investigations [58e
60] have since been undertaken. Most of this work has
been carried out on complex ores containing copper,
carbonaceous ores, or ores containing high concentra-
tions of lead, zinc or manganese. For example, Yen et al.
[61] used a mildly refractory gold ore containing pyrite
and chalcopyrite to determine the feasibility of thio-
sulphate as an alternative heap leaching technology. The
authors report that a gold extraction of 72% was
achieved over a period of 50 days. The US Bureau of
Mines used statistical experimental methods to de-
termine thiosulphate leaching feasibility. Gold extrac-
tions of up to 62% were achieved from the leaching of
low-grade carbonaceous ores [62].
A number of the more recent research efforts have
targeted the development of pre-treatment strategies in
order to improve recovery with thiosulphate. Balaz et al.
[63] investigated the use of a mechanically-activated
flotation concentrate from a complex coppereleadezinc
ore from Banska Hodrusa, Slovakia. Mechanical activa-
tion of the concentrate was achieved by ultra-fine grinding
and proved to have a beneficial influence on the rate of
extraction and recovery of gold using ammonium
thiosulphate in the presence of copper ions. The authors
report that 90% gold recovery was achieved in only a few
minutes, compared to the 54% extraction achieved under
equivalent conditions for untreated concentrate. Liu et al.
[64] reported that sponge gold of 99.92% purity was
produced by ammonium thiosulphate leaching, although
it was found that the addition of copper sulphate not only
accelerated the rate of gold leaching, but also increased
thiosulphate consumption. Panayotov [65] reported
similar results, indicating that a gold recovery of 91%
can be achieved using thiosulphate, if the concentrate is
pre-oxidised. In commercial practice, thiosulphate has
been used successfully by Newmont and Consolidated
Empire Gold Inc. in heap leaching of gold ore.
The principal problem with thiosulphate leaching
is the high consumption of reagent during extraction
1164 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
[54]. Moreover, the process is generally slow, although
acceptable leaching rates can be achieved in the presence
of ammonia using copper (II) as an oxidant [51,53].
Nevertheless, high reagent consumption renders most
thiosulphate systems uneconomical overall, in spite of
their potential environmental benefits. At present, no
simple and affordable method for recovering gold from
thiosulphate leach solutions exists [10].
6. Coaleoil agglomeration
The coaleoilegold agglomeration (CGA) method
has been identified as an alternative to cyanide for large-
scale operations. More recently, it has also been
promoted as an alternative to mercury amalgamation
in the small-scale (artisanal) gold mining industry.
Although the ability of oil to recover gold was known
in the early-1900s, as Calvez et al. [66] explain, it was not
until BP Australia patented the CGA process in 1986
that it began gaining recognition in the public domain as
an alternative to cyanide in the gold mining industry.
Batmen Engineering International Ltd. and Charlton
Mineral Associates Pty Ltd. have also patented varia-
tions of the CGA method.
As described by Kotze and Petersen [67], the CGA
process is based upon the recovery of hydrophobic/
oleophilic free gold particles from ore slurries; gold
grains ranging from one to 100 microns can be
recovered with ease. Oil serves as a bridge between coal
and gold particles, whilst coal acts as a carrier and
facilitates effective separation of the gold-bearing
agglomerates. The CGA method has proved to be
effective if used to process liberated/free gold particles,
such as those contained within alluvial deposits and
some process tailings.
Considerable experimental work has been undertaken
which suggests that CGA can be an effective gold ore
processing alternative. For example, findings by Bellamy
et al. [68], who tested ore samples collected from a New
Zealand beach, show that the CGA method is a quicker,
cleaner and more effective method than conventional
gold processing techniques, including cyanidation.
Bonney [69] conducted laboratory analysis on mixtures
of silica and gold powder and pilot tests on gold tailings;
the laboratory results showed that under optimum
conditions, gold recoveries of 95% could be achieved,
whilst pilot test results gave recoveries of 62e75%.
Additional experimental work has been carried out to
further validate the CGA method. For example, Mar-
ciano et al. [70] used diesel oil, kerosene and vegetable oil
as agglomerating liquids to process gold-containing
materials, achieving 90% gold recovery. Calvez et al.
[66] performed tests using synthetic gold-bearing samples
to evaluate the underlying principles by which gold is
recovered by coaleoil agglomerates, including oilecoal
ratios, agglomerateeore ratios, pH and coal particle size.
The results show that gold recovery increases with
decreasing coal particle size, an increased agglomeratee
ore ratio, and a decreased oilecoal ratio. Moses and
Petersen [71] performed similar batch tests on synthetic
(7 gAu/t) ore, demonstrating that increased oil viscosity
led to the formation of stronger agglomerates and hence,
greater gold recovery. Kotze and Petersen [67] also
achieved high gold recoveries (85%) in batch tests on
artificial gold slurry mixtures.
Although promising experimental work has been
carried out using the CGA method, it can only be used
to process free gold particles. It therefore has limited
potential on a large-scale, but as explained previously, it
could prove to be a viable alternative to amalgamation
in small-scale mining.
7. Halides
The use of halide (fluorine, chlorine, bromine, iodine
and astatine) systems for gold dissolution pre-dates
cyanidation [31]. With the exceptions of fluorine and
astatine, all halogens have been tested and/or used for
the extraction of gold [23]. Prior to the inception of
cyanide, chlorine was extensively used as a leaching
reagent for gold recovery from calcines, ores and
concentrates. Chlorine can be generated in slurries and
solutions via electrolysis of NaCl solution or by addition
of MnO2 to hydrochloric acid [15]:
MnO2 C4HCl/MnCl2 C2H2 OCCl2
Gold is leached rapidly by chlorine at low pH:
2AuC3Cl2 52AuCl3
Chlorination rates are favoured by low pH, high
chloride and chlorine levels, increased temperatures, and
high ore surface areas [15,31]. Although gold dissolution
with chlorine is substantially faster than with cyanide,
low concentrations of sulphides or other reactive
components in the ore can make reagent consumption
excessive and can reduce AuCl
4 back to metallic gold.
Several investigations have been undertaken to
determine the effectiveness of chlorine [72e77]. Histor-
ically, AuCl
4 was recovered from chloride leach
solutions as metallic gold by natural reduction on
carbon or charcoal, after which the ‘‘loaded’’ carbon
was burnt to yield the gold. Today, the gold chloride
complex is recovered on activated carbon as metallic
gold, which generally leads to the loss of gold to tailings,
due to attrition of fine gold particles from the surface of
the activated carbon particles. Chloride gold extraction
is more difficult to apply than cyanide extraction, how-
ever, for a number of reasons [4]:
 G. Hilson, A.J. Monhemius / Journal of Cleaner Production 14 (2006) 1158e1167
 special stainless steel and rubber-lined equipment is
required to withstand the highly corrosive acidic and
oxidising conditions;
 chlorine gas is highly poisonous and must be
contained both to allow optimum utilisation of the
gas and to avoid any health risk; and
 although chlorination was used for pre-treating
refractory and carbonaceous ores in several plants
in the United States in the 1980s, few pilot or
demonstration studies have since been reported on
the use of these systems [78,79].
Bromine was first identified as a potential solvent for
gold in 1846; its rate of leaching gold is enhanced in the
presence of a protonic cation [15]. However, despite long
being recognised as a powerful gold extractant, it is only
recently that its application has been seriously consid-
ered. Bromine offers a number of advantages, including
rapid extraction, non-toxicity, and adaptability to a wide
range of pH values.
Although the high dissolution rates give it a definite
advantage over cyanide, there is often high reagent
consumption with bromine use [18], and because it can
combine with other elemental species to form toxic
compounds, the costs of construction materials to
withstand the severe conditions and resultant health
impacts can be exorbitant [4]. However, as Tran et al.
[72] explain, the bromideebromine system is receiving
increasing attention, particularly since the Great Lakes
Corporation patented its bromine-based gold leaching
process, which is based upon a proprietary dibromo-
dimethyl hydantoin compound.
Gold leaching rates in iodide solutions are also much
faster than cyanidation. Despite the fact that gold iodide
complexes are the most stable in aqueous solutions
(among halogens), iodine continues to be under-utilised
and under-researched as a gold lixiviant. This is largely
because of its cost [15].
Presently, halide systems have limited potential as
substitutes for cyanide, which itself had replaced gold
leaching agents such as chlorine in the first place. As la
Brooy et al. [31] explain, halide systems are currently
limited to analytical applications, where the capacity for
simultaneous sulphide destruction and speed of dissolu-
tion are more important than reagent consumption.
Moreover, gold halide complexes are generally unstable
and critics remain sceptical about their widespread use
because of the significant chemical and process control
required during processing to maintain gold in solution
[72,73].
8. Conclusions
This paper has reviewed the most promising alterna-
tive gold leaching agents to cyanide. Although consider-
1165
able research has been undertaken at a laboratory scale,
most, if not all, of the alternatives identified have proven
to have limitations that hinder their widespread
adoption in the gold mining industry. Thiourea, for
example, despite being a proven technology and suitable
for refractory ores, is associated with high detoxification
costs, has limited recyclability, and features process
parameters that are difficult to control. Thiosulphate
offers the same advantages, but is highly unstable and
also has high detoxification costs and limited recycla-
bility. Thiocyanate, whilst being more stable than the
former two reagents, is under researched with consider-
able obstacles to be overcome before it could be
considered as a viable alternative to cyanide. The
CGA process, developed and patented by BP during
the mid-1980s, is only suitable for processing free gold
particles, and is therefore more likely to become
a substitute for small-scale mercury amalgamation than
cyanidation. Finally, halides, which have been utilised in
this context in the past, are difficult to handle and
control, and are also expensive.
It is concluded that, in spite of the vociferous
opposition to the use of cyanide in the gold mining
industry by sections of the environmental movement,
unless further research and development makes one or
more of the alterative lixiviants economically competi-
tive, it will continue to be the only practical leach
reagent in large-scale gold extraction processes. It
should be realised, however, that much of the opposition
to the use of cyanide in the mining industry is based on
a relatively small number of well-publicised pollution
incidents, most of which were caused either by poor
design or faulty operation of gold extraction processes.
Cyanide has been used for over a century at gold mines
all over the world and the evidence is overwhelming
that in well-designed and properly managed mining
operations, it can be safely used as a gold leaching
reagent without significant risk to human life or the
environment.
Acknowledgements
The authors gratefully acknowledge financial assis-
tance for the preparation of this paper from the
European Commission through funding provided from
the INCO COPERNICUS Project ICA2-1999-10065.
Opinions expressed in the article are those of the
authors, not the Commission.
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