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Int. J. Miner. Process. 86 (2008) 1 17

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A critical review of the surface chemistry of acidic ferric sulphate

dissolution of chalcopyrite with regards to hindered dissolution
C. Klauber
Parker CRC for Integrated Hydrometallurgy Solutions, CSIRO Division of Minerals, PO Box 7229, Karawara, WA 6152, Australia
Received 17 July 2006; received in revised form 26 September 2007; accepted 27 September 2007
Available online 5 October 2007

Abstract

The present understanding of the surface chemistry of acidic ferric sulphate dissolution of chalcopyrite is critically reviewed
with regard to hindered dissolution and how the hydrometallurgical limitations, especially for microbial heap leaching operations,
might be overcome. In particular the surface science investigations of what surface phases might be responsible for hindered
dissolution are reviewed. Some other mechanistic issues are also considered which require further investigation. The possible phase
candidates for hindered dissolution are examined, with most discussion focussed on elemental sulphur and jarosites. Phases such as
polysulphides are rejected as candidates. The physical reality of metal-deficient sulphides is also questioned.
A conceptual 4-stage model is proposed which explains all the general dissolution behaviour that is widely observed, i.e. of an
induction period and a parabolic rate curve that may or may not be followed by linear rate behaviour. The general conclusion is that
thick over-layers of sulphur cause the initial parabolic behaviour, and a thin systemic sulphur layer is responsible for the rate-
limiting step, even in the linear region. Depending upon solution conditions, either unhindered near linear dissolution may occur, or
jarosite precipitation that will cause a second parabolic region. Sulphur formation remains a systemic phase in the context of heap
bioleaching but is not a problem of any consequence for mixed culture systems unlike jarosites. Suggestions are made as to a low-
cost jarosite precipitation pond for iron removal and advantages that could result.
Crown Copyright 2007 Published by Elsevier B.V. All rights reserved.

Keywords: Chalcopyrite; Leaching; Dissolution; Passivation; Metal-deficient sulphides; Polysulphides; Jarosite; XPS; Surface analysis

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Matrix of mechanistic issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Potential problems with surface analysis methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. Role of electrochemistry issues of concern . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5. Question of galvanic coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
6. Hindered dissolution or rate-limiting step(s) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
7. Role of ferrous a curious observation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Tel.: +61 8 9334 8060; fax: +61 8 9334 8001.

E-mail address: craig.klauber@csiro.au.

0301-7516/$ - see front matter. Crown Copyright 2007 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2007.09.003
2 C. Klauber / Int. J. Miner. Process. 86 (2008) 117

8.Hindered dissolution or passivation candidates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

8.1. Metal-deficient sulphides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
8.2. Polysulphides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
8.3. Elemental sulphur allotropes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
8.4. Jarosite formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
9. Conceptual 4-stage dissolution model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
10. Iron control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
11. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

1. Introduction mechanistic investigations, the electrochemical papers

Substantial work has been undertaken to examine the
chemistry behind the acidic ferric sulphate dissolution
of chalcopyrite in order to recover the copper value. This
is the most promising low-cost hydrometallurgical
route, particularly in view of the parallel chemistry
that occurs in a microbiologically mediated situation,
such as heap bioleaching, where the rate of the ferrous to
ferric ion conversion is massively enhanced. The
general bioleaching of sulphide ores has been exten-
sively reviewed by Watling (2006). In this narrower
review the surface chemistry and the phases that form
during chalcopyrite dissolution that could lead to
hindering of the mineral's complete dissolution are
specifically examined. This has most commonly been
referred to as passivation of the chalcopyrite.
Although the term passivation is still being used
with respect to chalcopyrite (e.g. Yin et al., 2000; Abed
and Dreisinger, 2003), passivation (in the corrosion
sense) is normally understood to be the formation of a
surface film that inhibits further corrosion or attack.
Often such films form spontaneously or can be made to
form by a treatment method, and are usually only a few
atomic layers thick. Such films would normally only be
directly detectable by the sensitive surface analysis
methods such as X-ray photoelectron spectroscopy (XPS
or ESCA), Auger electron spectroscopy (AES or SAM)
or secondary ion mass spectrometry (SIMS). Thin-film
techniques like infra-red, Raman and the microprobe
methods are usually not capable of detecting true
passivation. However, in the case of hindered dissolution
or reduced mass transport due to over-layers, e.g. by
particle encapsulation due to a by-product precipitation,
both the surface science and thin-film techniques are
capable of providing insight. Electrochemical methods
can also detect the presence of passivation layers and
also provide insight into their nature, although care needs
to be employed in interpretation as the evidence is often
indirect, hence they are not reviewed in detail. In terms of
nonetheless represent the largest category.
Although the review emphasis is on the surface
chemistry studies, this is not at the exclusion of the
wider investigations that have been undertaken. A number
of surface studies have concentrated on the virgin mineral
surface or chalcopyrite oxidation under conditions other
than that of acidic ferric sulphate. A particular emphasis
also exists on the surface chemistry relating to selective
froth flotation or depression, usually under non-leaching
conditions. These have generally not been cited unless
they impact on the interpretation of ferric leached systems,
in particular the question of hindered dissolution. A large
number of peripheral studies looking at other aspects of
the chalcopyrite system could not be included.
One way of looking at passivation is that the passive
layer is a consequence of the thermodynamics of the
system and is inevitable under the appropriate conditions.
This is a simpler situation than would be experienced with
hindered dissolution. Over-layer formation, in contrast,
could be dependent upon precipitation kinetics, a seed
crystal form or a solubility product that is dependent upon
side reactions or, in the case of an ore, the behaviour of the
gangue. That is, hindered dissolution could have multiple
causes; moreover copper recovery in a hindered dissolu-
tion case should continue to increase monotonically,
whereas for passivation conditions it should plateau.
Experimentally the different investigations exhibit quite
varied behaviour.
This review additionally considers some mechanistic
issues that impact upon the dissolution of chalcopyrite to
explore what variants in the hydrometallurgical route
might possibly be employed in order to enhance copper
recovery. The scope is mainly constrained to chalcopy-
rite oxidative leaching chemistry under acidic ferric
(sulphate) conditions and some unpublished work of the
author. The various hindered dissolution or passivation
candidates are then considered in turn with a view to
concluding the principal elements. The general chemistry
involved in the acidic ferric leach (though not the
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
mechanistic detail) is well understood, as well as that of
the general microbial role. The technical challenge is thus
maximising rates and recoveries by a strategy of heap
chemistry control plus strain development.
Prior empirical investigations of acidic ferric sul-
phate dissolution are usually some combination of:
Chemical leaching.
Electrochemically controlled leaching (stationary or
rotating working electrode).
Single crystal chalcopyrite.
Multi-crystal massive chalcopyrite.
Ground massive chalcopyrite.
Flotation concentrate.
Solution agitation by stirring, shaking or bottle rolling.
Usually dissolved Cu, Fe2+, Fe3+, pH, Eh, dissolved
oxygen (DO) and temperature (T) are monitored, and
some of those parameters are also controlled to a given
level. The chalcopyrite varies from high purity natural
material through to concentrates with varying gangue
minerals and may be of n-type or p-type. Also some
attempts at using synthetic material (Dutrizac et al., 1969;
Dutrizac and MacDonald, 1973; Biegler and Swift, 1976)
have been undertaken. The dissolved Cu level behaviour
with time indicates whether hindered dissolution may be
occurring. Recovery as a percentage of the actual copper
available is most useful, though that makes sense only
where the feed material is particulate. For dissolution of
massive material, especially in an electrochemical set-up,
the unit of moles cm 2 h 1, or similar Coulombic
integrals, is less useful unless electrode mass changes are
recorded. Clearly with particulate studies, size range
distribution and surface area become an issue. Both
approaches suffer from surface morphologies that may
not represent actual heap-leach ores. The author's
chalcopyrite surface work (Klauber et al., 2001; Parker
et al., 2001; Klauber, 2003a,b; Parker et al., 2003a, 2003b)
has relied upon polished massive samples and froth
flotation concentrates, with either abiotic or microbial
environments, and rest chemical potentials. Sample
preparation issues are dealt with in the above papers.
2. Matrix of mechanistic issues
In terms of trying to address hindered dissolution in
heap leaching, the main mechanistic points that are
likely to be of interest are:
Direct or indirect microbial action, or both?
How well do the various bioleaching models compare?
The Ag catalysis effect is there something to learn?
3
Galvanic coupling, especially relevant in a mineral
processing heap.
Do we need to be cautious in incorporating the
mechanistic/kinetic results from electrochemical
investigations?
How best to tackle the passivation or hindered
dissolution question?
We might also gain some insight from those hydro-
metallurgical processing variants that are all aimed at im-
proved rates of recovery. Generally, they involve ways of:
Increasing energy input to the system (to increase rate)
Increasing the oxidation potential (to increase rate)
By-passing passivation (fresh surface, removing
passivating agents)
Changing the dissolution mechanism (catalysis)
Examples would be:
Microwave energy, radio-frequency (RF) induction
Sonication
Pressure oxidation (POX), ozone
Mechanochemical activation, grinding activation,
high shear
Co-solvents (usually organic to tackle elemental
sulphur)
Ammoniacal lixiviants
Surface detergents/surfactants
The Ag catalytic effect
Galvanic catalysis
It is immediately obvious that only a few of these
examples could even be applicable, let alone practical,
in a low-cost heap-leach situation. These fall into the
class of either surface activators or catalytic agents.
The silver (and other metal ions) catalysis question has
been well looked at e.g. Ballester et al. (1992) but in a low
grade heap environment the point is moot, as silver is
unlikely to be a cost effective catalyst, although it may be
present naturally in some ores. Without effective re-
cycling similar conclusions would apply to surface-active
reagents. The key to knowing how to best tackle the
passivation question for abiotic or microbial heap
leaching, is to first agree on the passivation candidate or
candidates, identify the extent of their intractability and
then suggest a low-cost, remedial action to minimize or
eliminate their formation. The following four candidates
are most often proposed:
Metal-deficient sulphides
Elemental sulphur S8
4 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
Polysulphides XSn
Jarosites XFe3(SO4)2(OH)6
The main thrust of this review is to look at these
candidates in turn and see what has been learnt,
especially from the application of surface analysis
methods to the problem. As will be seen, sound
evidence for hindered dissolution can only be found
for the elemental sulphur and the jarosites. This idea is
placed in the context of a conceptual 4-stage dissolution
model. It is proposed that elemental sulphur is actually a
non-issue and the best avenue for improved heap-leach
function is a pathway involving iron control.
3. Potential problems with surface analysis methods
The common surface analytical methods such as XPS
and AES are singularly powerful in giving direct
information as to the likely composition of surface
phases. Unlike the inferences that need to be drawn from
electrochemical or solution data in order to speculate as
to the surface composition, the spectroscopies give
direct evidence. The requirement for ultra-high vacuum
means that the methods are invariably ex situ. This is a
disadvantage, but provided the consequences are
understood, it does not limit the usefulness of the
techniques. Contrary to what might be supposed, the
surface phases are not fully dehydrated by the vacuum
and considerable double-layer like water is generally
retained. Nonetheless, volatile components can be lost,
e.g. elemental multi-layer sulphur will simply evaporate
unless the sample temperature is kept very low.
Experience has shown that most errors are made in the
interpretation of the spectra, assuming that the experi-
mental data are acquired under good conditions. XPS is
the most easily quantifiable of the two electron spectro-
scopies but it is not an exact science. The spectra are
often complicated, for example by various splitting and
electron relaxation processes, which prevent a straight-
forward analysis. Leaving aside the quantification issues,
basic errors can still be made in oxidation state assign-
ments. XPS is a comparative spectroscopy. Presently
there is no ab initio method to accurately calculate the
observed final state binding energy (BE) for an atom in a
given chemical environment. The best that can be done is
a spectral comparison with known solid-state phases and
an educated interpolation as to what might be expected.
For this reason, there is no substitute for a good suite of
standard compounds. For example, in the case of poly-
sulphides, assignment in a number of instances is
speculative. If the sequential chain of literature citation
events is followed, it can be seen that some of the original
work is taken out of context, especially the attempt to
assign a polysulphide identification on just one S 2p BE
value rather than the necessary two values (Kougianos
et al., 2000, Parker et al., 2003a).
4. Role of electrochemistry issues of concern
In terms of the number of investigations, the appli-
cation of electrochemistry is the most popular avenue by
which to address the mechanistic questions, including
the cause(s) of hindered dissolution. Electrochemical
methods are very powerful due to the potential control
and the quantitative nature of assessing net charge flows
and corresponding reaction rates. However, they are not
good in complex situations for identifying surface
phases. The nature of the method also raises concerns
such as:
Corrosion at high anodic potentials above some
critical dissolution potential.
Interpretation of currenttime decay curves after
long polarization times.
The issue of multiple cyclic voltammetry and the
impact upon surface morphology.
It should be noted that cyclic voltammetry of a
chalcopyrite electrode is not a reversible process in
terms of the surface structure, as is well illustrated by
Velsquez et al. (1998) under alkaline conditions.
Indeed for a ternary compound it would be surprising
if reversibility were observed.
In keeping with most other techniques in the case of
chalcopyrite, researchers also use limited and unchar-
acterised crystal orientations. This results from the often
non-characteristic crystal habit of chalcopyrite and its
conchoidal fracture. Rotating disk electrodes (RDE's) of
massive chalcopyrite, for instance, may display 23
crystals (or more) of ill-defined orientation. Chalcopy-
rite-carbon paste electrodes go to the other extreme.
Such issues need to be considered with any quantitative
inter-study comparison. Gross rate studies on flotation
concentrate eliminate this by averaging over a large
sample (much larger surface area) but have the
disadvantage of varied mineralogy (e.g. other phases
contributing to rate indicators and galvanic interactions).
The ToF-SIMS and SEM study of the reactivity of
chalcopyrite fracture surfaces by Al-Harahsheh et al.
(2006a,b) followed by acidic ferric sulphate exposure at
90 C illustrates the differences in fracture surface
reactivity, although the fracture planes are not identified.
Fresh (air) fractured chalcopyrite exhibited two very
distinct surfaces; one oxidized and rich in Sn and SOx
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
species and ambient hydrocarbon contamination and the
other effectively pristine. Some aspects of the surface
behaviour are masked due to the extensive hydrocarbon
contamination, but the findings remain interesting.
Although not conclusive the suggestion from the
published micrographs is that the distinctly behaving
fracture surfaces may be orthogonal.
The more recent electrochemical studies of chalco-
pyrite in acidic ferric sulphate undertaken by Vira-
montes-Gamboa et al. (2006, 2007) are of interest as they
demonstrate that to reproduce the passivation potential
observed in actual leaching tests the anodic curves must
be generated at slow scanning rates. This opens the
window for productively studying the response of the
passivation region but also generates questions over
earlier work.
5. Question of galvanic coupling
The ores and concentrates, as might typically be used
in a hydrometallurgical leach operation, are likely to
have active gangue mineralization, irrespective of what
behaviour may be determined for high purity chalcopy-
rite or well-characterized concentrates. Apart from
copper mineralization, such as chalcocite Cu2S, covel-
lite CuS and bornite Cu5FeS4, a very common phase is
pyrite FeS2. Mixed mineralization raises the question of
a galvanic corrosion mechanism (Dutrizac et al., 1969).
Berry et al. (1978) demonstrate that, as separate non-
contacting phases, pyrite dissolves more rapidly than
chalcopyrite but, when the phases are in galvanic
contact, the chalcopyrite dissolves more rapidly, pro-
tecting the pyrite. A follow-up study looked at the
phenomenon more generally (Mehta and Murr, 1983).
In both abiotic and microbial leach situations the
presence of pyrite was found to enhance copper release,
even to the point of overriding the initial parabolic
dissolution curve and going straight into apparently
linear behaviour. This obviously suggests a possible
method of enhancing copper recovery rates, but should
also serve to remind that, in cases of poor galvanic
contact (e.g. high quartz gangue), the pyrite reactivity
would initially result in a higher iron release hence
the initial high iron release studies need to be considered
in this context. The work of Holmes and Crundwell
(1995) elaborates further on galvanic effects.
6. Hindered dissolution or rate-limiting step(s)
The observed rate behaviour or copper dissolution
curves fall into one of three types; (i) parabolic with time,
(ii) linear with time or (iii) initially parabolic followed by
5
linear. Experimentally, the parabolic-only are described
as hindered dissolution, with the dissolution becoming
very slow, but not actually ceasing (e.g. Munoz et al.,
1979). In cases where the linear dissolution curve is
observed, dissolution is implied to go to completion,
though this is not necessarily confirmed by actually
achieving 100% recovery. Some studies go over time
periods of 10100 hours, others up to 55 days. These
issues are briefly reviewed elsewhere (Hirato et al.,
1987). In all likelihood the various investigations are not
displaying true differences in the chalcopyrite behaviour,
but rather a case of the different experimental methods
and conditions giving such an impression. For example,
in Hirato et al. (1987), in which parabolic-linear
behaviour is observed, the hindered parabola is associ-
ated with a dense sulphur layer; this peels leaving a
roughened surface and a higher linear rate with no thick
sulphur layer observed. The conclusion here is that initial
hindered dissolution is due to the sulphur layer. Hirato
et al. (1987) endeavour to place their observed sulphur in
the context of sulphur observed by other workers and
that produced by ferric chloride attack.
Divergent views as to the rate-limiting process (e.g.
early brief review of Munoz et al., 1979) have been held
for some time. There is no consistent evidence across the
investigations for a single hindering phase. Either the
dissolution is surface reaction controlled or limited by
transport diffusion by either the ferrous or ferric ions
through some layer (e.g. the elemental sulphur). Munoz
et al. (1979) concludes that it is the electron transport
through the sulphur that is the problem. The Munoz
reasoning is quite cogent, especially the similarity of the
measured activation energy of the dissolution process
with the known activation energy dependence for
electron transport through elemental sulphur. Tempering
this is the knowledge that the sulphur morphology is
highly variable, which would also raise questions for the
conductivity comparison and the general reliability of
any Arrhenius activation energy. Reliability is necessary
for comparison between investigations (as opposed to
relative values for an individual investigation). For
example, the Eact for the initial (sulphur free) region
determined by Munoz is 33.5 kJ mol 1, but a value of
83.7 kJ mol 1 is obtained for the analysed parabolic
region (assuming the transport limiting model). This
might appear in stark contrast to the range of 76.87 to
87.7 kJ mol 1 determined by Hirato et al. (1987)
specifically for the linear rate region (successive
leaching method), but that is not necessarily the case.
The successive leaching method of rinsing, plus fresh
solution and then carrying on, appears to avoid the
growing bulk sulphur layer responsible for the parabolic
6 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
rate, but it would not necessarily remove atomically thin
sulphur layers (which would also not be EDAX
detectable). Making that assumption simplifies the
understanding of the apparent differences determined.
The initial parabolic region gives a high rate followed by
an ever-decreasing rate, then, in some cases, followed
by an open ended linear region of high consistent rate.
For long dissolution times (e.g. Jones and Peters, 1976)
and a linear form, any initial parabolic region appears
simply as an induction period. Providing circumstances
prevent massive sulphur encapsulation, the linear form
remains and Eact then represents electron transport
through a thin sulphur layer and some steady state
composition reaction interface.
Interestingly, sonication appears not to be able to
disrupt the cause of initial hindered dissolution. Abed
and Dreisinger (2003) find sonication to have a dramatic
catalytic-like effect on the dissolution, with rates 2 to
3 times higher at the same nominal temperature.
However, based on KMnO4 consumption to follow the
oxidative dissolution, the initial parabolic rate behaviour
occurred with or without sonication, implying that the
sonication rate gains were simply due to particle
fragmentation rather than any layer removal.
Realistically the relevance of the initial reaction
phase can be questioned. Many mineral systems fracture
to produce re-constructed surfaces that relate to the bulk
phase, but are actually different. Certainly, the surface
analysis of freshly prepared chalcopyrite surface (both
fractured and polished) is indicative of a non-chalcopy-
rite surface (Klauber, 2003a,b). This could explain high
rate low Eact for the initial period, and perhaps some of
the strange electrochemical responses observed for the
initial reaction. However, such reconstructions are not
sensible candidates for hindered dissolution, as the
acidic ferric sulphate chemical environment is radically
different to the fracture or polishing environment. The
recent paper of Farquhar et al. (2003) adds relatively
little to the hindered dissolution question and could
benefit from a proper peak analysis. However, the tie-up
of XPS with atomic force microscopy (AFM) is useful
as it shows the significant morphological problems
associated with chalcopyrite polishing as a means of
electrode preparation, backing up the chemical changes
evident from XPS (Klauber, 2003a,b).
7. Role of ferrous a curious observation
The role of the ferrous ion in the presence of cupric is
postulated in the Hiroyoshi et al. (1997, 2000) series of
papers. These are a curious set of results in which, for four
different sourced chalcopyrite samples, the ferrous ion
was found to be a far more effective system for dissolving
chalcopyrite than the ferric ion. Based on copper
dissolution correlating with a drop in pH and the cessation
of reaction in the absence of oxygen, an overall reaction is
postulated based on the reduction of oxygen to water,
oxidation of the sulphide to sulphur and the release of
cupric and ferrous. Although contrary to overwhelming
evidence for ferric based leaching, some follow-up
investigation of the ferrous system would be worthwhile.
Two models for the role of ferrous ions are proposed. One
model has ferrous ion acting as a catalyst and the second,
more plausible model is that the dissolved oxygen
converts ferrous to ferric ion at the chalcopyrite surface
and the reaction proceeds as expected. It is possible that
the doubly charged ferrous ion has surface access
advantages over the triply charged ferric ion and the
associated hydrolysis issues. Note that copper extraction
observed in all cases is linear.
In a different, but supporting approach, Sandstrm
et al. (2005) looked both at abiotic chemical leaching
and bioleaching (Sulfolobus metallicus) at two different
redox potentials of 420 and 600 mV (Pt vs Ag|AgCl) at
6567 C and a pH of 1.5. The chalcopyrite
concentrates used contained 1415% pyrite. At the
lower redox potential the chalcopyrite leached most
rapidly, dropping with pyrite competition at the higher
redox value. The chemical leachate was initially acidic
ferrous-cupric sulphate and both redox control and
ferrous oxidation was achieved by KMnO4 titration, the
consumption of which served to indicate iron dissolu-
tion rates. The conclusions drawn from the XPS of
leached concentrate was that elemental sulphur (even
when formed in large quantities) did not passivate, but
jarosite formation did. Of particular interest however,
the authors argue for an autocatalytic effect with
solution ferrous and cupric being the active leaching
species. Although a surface intermediate of chalcocite
Cu2S is implicit in this model the very intense Cu(I) 2p
emission from the underlying chalcopyrite would
preclude its easy identification. A shortcoming in this
case is the use of a concentrate with a high pyrite level
and the complicating role of the permanganate. This
relates to the question of galvanic coupling previously
considered in Section 5. Several cathodic pyrite half-cell
reactions might be envisaged which could all lead to
enhanced anodic dissolution of the chalcopyrite. This
makes autocatalysis difficult to establish.
8. Hindered dissolution or passivation candidates
Four candidates are commonly cited as causing
hindered chalcopyrite dissolution: metal-deficient
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
sulphides, polysulphides, elemental sulphur and
jarosites. They will be considered in order.
8.1. Metal-deficient sulphides
Metal-deficient sulphide is most commonly cited as a
characteristic surface phase sometimes it is also
branded as the possible reason for the passivation.
Strictly speaking the metal-deficient sulphide is a
transformed surface phase, unlike the other candidates
considered below, which can all be regarded as oxidation
products or precipitation from resultant solution chemis-
try. Most authors have valid reasons for suggesting the
metal-deficient sulphide as being present, usually be-
cause of initial non-stoichiometric dissolution, usually of
iron. Although most experiments are run in a single batch
mode, this non-stoichiometric metal release is also
supported by the long-term flow-through experiments of
Acero et al. (2007) designed to simulate acid-mine or
acid-rock drainage. For both the sulphuric and hydro-
chloric acid leaches undertaken, in which dissolved
oxygen (DO) is the oxidant, the long-term Fe:Cu leach
ratio averages out at 2.2 over a range of both DO and
temperature. Clearly an iron-deficient residue is left
behind, but under the leach conditions of Acero et al.
(2007) this phase is found to be not inhibitory.
Unfortunately, although solution stoichiometry
might suggest a metal-deficient sulphide, it is difficult
to directly prove or disprove its existence, so in some
circumstances it has become a convenient candidate, or
set of candidates, to postulate. Non-stoichiometric solid-
state phases are well known, but they are invariably
cases of small deviations in which the requirement of
electroneutrality can be satisfied with either substitu-
tional impurities and/or mixed oxidation states. Such
small deviations are beyond the quantitative accuracy of
either XPS or AES, although a divergent chemical state
might well be detectable and such a phase could be
inferred. By contrast, the extent of metal deficiency
implied in the context of chalcopyrite leaching is
typically up to 20%. It should be possible to measure
such a deviation directly but quantification is not
straightforward. The problem with the surface electron
spectroscopies is that they rely on their surface
sensitivity being due to the rapid extinction (via inelastic
scattering) of characteristic electron intensity in the 100
to 1000 eV kinetic energy range. A consequence of this
rapid extinction with depth is that a variety of very
different surface phase arrangements (e.g. combinations
of layer ordering, island formation, etc.) can be
conceived which all yield very similar electron
intensities. Although the simplest solution to a problem
7
is generally the best course, invoking a metal-deficient
sulphide requires a larger burden of proof than is
typically seen. For an iron containing ternary sulphide
and an iron-based leachant this is far from trivial.
For example, Hackl et al. (1995) use Auger evidence
to demonstrate that the iron leaches preferentially to the
copper to form an iron-deficient sulphide and that this
phase is responsible for the chalcopyrite passivation.
In this case the surfaces were briefly sputter cleaned
prior to analysis (implied for the leached samples as
well) and preferential ion sputtering, leading to an
altered surface stoichiometry, is a well-established
artefact. Also the Auger spectra were collected in
derivative mode dN / dE and the quantification is based
on peak-to-peak heights in the derivative spectra,
whereas it should be based on a double integral of the
dN / dE spectrum. This is especially true if the integral
feature's width broadens, as peak-to-peak height is a
reflection of peak sharpness and not intensity. The XPS
Fe 2p spectra could not be used for quantification in this
case, as the spectrum (even for the unleached surface)
was complicated by extensive oxidation.
The work of Buckley and Woods (1984) is an early
proposal of a metal-deficient sulphide, namely Cu0.8S2
forming on chalcopyrite in acidified peroxide media.
This followed on from the determination of a sulphur
rich CuS2 for an air-exposed sample of chalcopyrite.
One advantage of a fresh-fractured surface that is
allowed to oxidize on air exposure is that the metal
atoms are constrained. In the case of the Buckley and
Woods work, the Fe 2p definitely indicates an iron oxide
forming. No sulphate is evident, so whatever the lattice
transformation, it is clear that iron is removed from the
chalcopyrite lattice and the observed Cu 2p and S 2p
spectra need to be explained. The Cu 2p spectra are not
shown but they are reported as indicating Cu(I). The S
2p is quite reasonably fitted to two sulphur components,
a chalcopyrite sulphide peak plus a high BE shoulder at
1.7 to 1.9 eV higher. This 1.8 eV shifted peak is ascribed
to the sulphur rich CuS2 phase. The implication is that
the shift is due to the iron deficiency. This can be looked
at in one of two ways. Either there is a nominal CuS23
moiety (the unbalanced negative charge responsible for
the large BE increase) or, alternatively, the sulphur
atoms are more directly oxidized. As air oxidation
implies O2 (with possibly a water involvement), the
need to reduce the oxygen makes the CuS23 moiety an
unnecessary construct and the sulphur must presumably
be modified by electron loss. Buckley and Woods
(1984) maintain that there is no reconstruction to form
pyritic S22 dimers. The arguments surrounding dimers
are more fully detailed elsewhere (Klauber, 2003a,b)
8 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
and also briefly by Harmer et al. (2004). Essentially
chalcopyrite lattice sulphide at 161.2 eV and bulk pyrite
at 162.6 eV would indicate that a likely 1.4 eV BE shift
would be observed. In the chalcopyrite fracture induced
reconstruction work (Klauber, 2003a,b) a sulphur dimer
at 161.9 eV or a 0.7 eV shift is identified. This would
then raise the interesting question as to the true identity
of the 1.8 eV shifted S 2p3/2 component. Buckley and
Woods reject elemental sulphur as a candidate, as the
feature was not lost on sample warming. Whilst this is
true for multi-layer sulphur, there is no reason to expect
that the initial monolayer sulphur would be so easily
lost. The author's XPS work has consistently found
volatilisable elemental sulphur at 163.5 eV. The
Buckley and Woods feature would be expected at
163.0 eV. The Harmer surface polymer is also
observed at 161.88161.90 eV, although the authors
note that this is in the dimer range, they contend that the
peak width indicates a longer oligomer. The problem
with this interpretation is that, as outlined in Section 8.2,
longer charged oligomers should display a defined
charge distribution (Parker et al., 2003a).
There are at least two alternative spectroscopic
explanations to the Cu0.8S2 metal-deficient sulphide
model; it could easily be (i) initial monolayer sulphur
which is in intimate contact with a semi-conductor so
increased extra-atomic relaxation decreases the ob-
served BE or (ii) the sulphur state is the S linear
chain sulphur (see Section 8.3). These are simpler
explanations than Cu0.8S2. The copper would then be as
cuprite Cu2O and not actually distinguishable from the
Cu(I) within the chalcopyrite.
On closer examination of thorough investigations,
such as that of Buckley and Woods, the metal-deficient
sulphide case is not clear-cut. A worthwhile contrast is
the work of Yin et al. (1995) that examines atmospheric
and electrochemical oxidation of chalcopyrite, but not
specifically the acidic ferric sulphate system. The
authors put forward that, under acid conditions, a
passive film of CuS2 forms at low potential and then
elemental sulphur at higher potentials, the asterisk for
the CuS2 indicating an uncharacterised metastable
phase existing at the electrode surface with a compo-
sition of Cu:2S. It is important to note that the XPS for
the low potential CuS2 region was from 1 M HClO4 at
pH 9.2 and bears no resemblance to the acidic ferric ion
case. Moreover, other than the relative increase in
surface Cu:Fe ratio, the surface actually shows no sign
of oxidation. Indeed, the S 2p (if anything) shows some
broadening plus a slight reduction shift in BE. This is
not consistent with the CuS2 phase proposed as the Cu
2p photoemission observed has no cupric satellite struc-
ture so is demonstrably Cu(I). This would imply the
unlikely oxidation of the sulphur from the sulphide state
in chalcopyrite to something quasi-S2. The observed
results do not entirely support the interpretations.
Mikhlin et al. (2004) argue strongly for reaction
layers of amorphous, variable composition, metal-
depleted sulphides; moreover that these layers are up
to several m in thickness. Despite the implied thickness
of the metal deficiency the authors reflect that the
electronic structure of the metal-deficient layer is similar
to the original chalcopyrite, e.g. the small changes in the
metal L-edge X-ray absorption. Conceptually an
amorphous metal-deficient phase should have a dra-
matically different electronic structure to the ionic-
covalent chalcopyrite. From the XPS the copper is
observed to remain as Cu(I) but the same spectra exhibit
contradictorily decreasing electronic conductivity with
acidic reaction. Irrespective of the nature of this layer the
authors observed no passivation.
There is general agreement in the electrochemical and
other studies on the initial non-stoichiometric release
ratio of Fe:Cu, typically varying from 2:1 (Linge,
1976) to something in the order of 4 or 5:1 (Biegler and
Swift, 1979; Holliday and Richmond, 1990). This is also
observed in other work on concentrate dissolution and is
used to additionally support the idea of metal-deficient
(generally iron-deficient) sulphides. Long dissolution
times tend to show no difference in the Fe:Cu release, i.e.
stoichiometric release, hence the implication is one of an
intermediate phase that co-exists during the dissolution.
This is probably a batch limitation as the flow-through
study of Acero et al. (2007) finds a long-term ratio of
3.3:1 for sulphuric at pH 3. Experimentally, as pointed
out by Linge (1976), a major problem is accurately
determining changes in iron level in a ferric leaching
medium. Generally, the metal-deficient sulphide propo-
sition is speculative. Parker et al. (1981) conclude that
the early stages of oxidation are limited by mass
transport through an unstable film of metal-deficient
polysulphide. The evidence supports a film, but the
polysulphide remains supposition. The authors only
make uncited references to polysulphides like CuS2 or
CuFeS4. Holliday and Richmond (1990) propose initial
rate-limiting steps involving either the formation of FeS2
or CuS and elemental sulphur. They favour the pyrite
version but speculate on a copper deficient sulphide
Cu0.8S2.
Lazaro and Nicol (2003) have revisited investigation
of the transient anodic pre-wave for chalcopyrite that
had been observed previously (e.g. Biegler and Swift,
1979; Holliday and Richmond, 1990). The study
excludes bornite and covellite as possible intermediates,
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
but reinforces the concept of an initial iron-deficient and
copper-rich surface. They conclude that dissolution is
inhibited (implying passivation) by the slow solid-state
diffusion of both copper and iron through that layer. The
subsequent reasoning is unclear. There is an uncited
reference to the apparent alloy nature of chalcopyrite (of
Cu2S, FeS and FeS2) that is then conjoined with work on
a metallic coppergold alloy to conclude that the layer is
so thin that it is undetectable by surface analytical
methods. As these are all sub-monolayer-capable
techniques it is not clear exactly what so thin to be
undetectable represents. The authors disagree with
elemental sulphur as a hindering product and propose
thiosulphate as a soluble sulphur intermediate. This runs
contrary to the majority of observations and fails to take
account of sulphur allotropy. In a follow-up study
(Lazaro and Nicol, 2006) reaffirm the thiosulphate as a
pre-elemental sulphur intermediate but ignore passiv-
ation and the previously proposed alloy concept.
Clearly the apparent paradigm for a metal-deficient
sulphide, especially in the electrochemical literature, is
as a remnant surface phase after a component is
preferentially leached. This view is akin to a 2-phase
composite in which one phase is leached leaving behind
a second skeletal or sponge-like phase via which the first
phase must continue to leach. For non-liberated mixed
minerals systems this is a perfectly valid macroscopic
model. However, for leaching from a single-phase
system this is a misleading picture. In the case of the
ternary sulphide chalcopyrite, the preferential removal
of either iron or copper destroys the lattice. A deficient
chalcopyrite can be no more than a limited surface
monolayer model (certainly not several m), beyond
that the structure would be expected to breakdown. If
the overall leach is non-stoichiometric then the remnant
metal-deficient phase should simply be viewed as an
insoluble product of the leach reaction. This is likely to
be amorphous and possibly also a mixture of phases; but
logically the phase or phases would individually be near
stoichiometric systems. This model resolves the entire
dilemma in which some studies show leach ratios of Fe:
Cu of b1 and others ratios of N 1. The leach process is
essentially the same in both cases, merely that the Eh
pH or solubility product conditions are such that a
remnant phase or mixture forms, e.g. the Eh can be
above the stability zone of CuFeS2, but sufficiently low
to favour CuS or Cu2S or sufficiently high to enable full
cupric dissolution or higher still to favour jarosites.
The common view of the extended metal-deficient
sulphide should be questioned. Nava and Gonzlez
(2006) refer to a passive Cu1 rFe1 sS2 t non-stoichio-
metric polysulphide that then decomposes to a non-
9
passive porous non-stoichiometric polysulphide Cu1
xFe1 yS2 z.
Neither r, s and t nor x, y and z are quantified
beyond s N r and y N x. The pertinent question is not that
the experiment cannot accurately quantify a preferential
dissolution of the iron over the copper, nor the existence of
some surface structure with a passive character. The
problem is that phases such as Cu1 rFe1 sS2 t make
no physical sense. For example, if a fraction of the
sulphide anions oxidatively oligomerize, thereby reduc-
ing the overall negative charge to compensate for the
cation loss of Cu+ and Fe3+, then there is a physically large
anionic entity occupying an extended lattice vacancy
previously occupied by the metal cations. One version of
this phase is passive, another is concluded to be porous. A
serious challenge would be to prove the existence of a
structural analogue that can be characterized by other
means. The electrochemistry is clearly reproducible over
a number of years, but it appears metal-deficient phases
have transformed from a convenient accounting model to
belief in a physical existence. In the earlier work of Warren
et al (1982) intermediates such as Cu1 xFe1 yS2 z are
employed, but the low anodic passive and high anodic
non-passive are described in terms of physically realistic
phases such as bornite and covellite.
In the context of this review, due to the absence of
consistent evidence, metal-deficient sulphides are not
considered a hindered dissolution candidate. Moreover
their physical reality is open to question.
8.2. Polysulphides
As the name indicates, polysulphides are a general
class of compounds in which sulphur is polymerised and
reduced, generally of the form M2Sn (n N 2). Typically n
is no more than 6. They consist of a chain of sulphur
atoms with an overall negative charge of 2 balanced by
monovalent metal cations. The chain length is usually
limited, so oligomers would be a better description.
Importantly, polysulphides longer than two units would
be expected to contain non-equivalent sulphur atoms,
i.e. unequal charge distribution and hence be amenable
to XPS determination. Earlier work by Termes et al.
(1987) on the bidentate polysulphido complexes (which
can be considered very approximate analogues of the
alkali metal polysulphide) does suggest (1 ) terminal
sulphur charge and charge for the penultimate sul-
phur atoms. The charge distribution between the sulphur
atoms is also considered in the work of Smart et al.
(1999). In order to determine the surface speciation for
chalcopyrite during dissolution more rigorously, a variety
of alkali metal polysulphides have been synthesized and
characterized (Kougianos et al., 2000; Parker et al.,
10 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
2003a). This work conclusively shows a very character-
istic charge distribution. Within the polysulphide anions,
irrespective of the oligomeric anions length, only S[1] or
S[0] oxidation states could be identified with a binding
energy separation, averaging out to 1.6 eVover the seven
polysulphide compounds examined. No BE correlation
with chain length is observed. Importantly, in order to
determine the presence or absence of polysulphides using
XPS a more careful analysis would be required than has
typically been applied in earlier work. Both elemental
sulphur S8 and the dimer S22 would also contribute to
these oxidation states. The consistent S[0] and S[1]
separation and overlapping peak positions would limit
speciation identification if multiple polysulphide species
happened to be present, but the limited chain length
(hence relative ratio) could allow a unique identification if
one species dominated.
What is additionally clear (Kougianos et al., 2000;
Parker et al., 2003a) is that the polysulphide compounds
examined are all extremely reactive. They readily
oxidize to elemental sulphur upon exposure to air,
especially in the presence of moisture. It is difficult to
conceive of these compounds forming any overlayer
capable of hindering chalcopyrite dissolution. The
bidentate polysulphido complexes of Termes et al.
(1987) are, by contrast, very stable compounds and
should not be regarded as valid XPS standards for true
polysulphides (Parker et al., 2005).
Attempts by the author and co-workers to synthesize
a bulk copper polysulphide were completely unsuccess-
ful. It would seem that the highly electropositive
monovalent alkali atom is a necessary pre-condition
for a (albeit limited) stable metal polysulphide. As a
quasi-noble metal, copper would be very easily reduced
by the polysulphide anion that, in turn, is thermody-
namically unstable with respect to its elemental sulphur
form, i.e. the copper analogue is very unlikely to exist.
This would best be proven by a comparison of reduction
potentials. An electrochemical investigation of the Au
S system under alkaline conditions by Buckley et al.
(1987) could infer surface polysulphide production from
the electrochemistry. However the XPS of the AuS
system in this case is not that clear. Interestingly the Eh
pH diagram calculated for the sulphurwater system at
25 C clearly shows the polysulphide species only to be
stable in the alkaline region and reverting to elemental
sulphur at high oxidation potentials.
One polysulphide species that is of some interest due
to the divalent cation present is calcium polysulphide.
Known also as limesulphur, it has been in widespread
use for a century as a plant fungicide, although it is not
well characterized. There are no reported structural
determinations and the consensus is that it is a mixture
of water, the thiosulphate CaS2O3 and the tetra and penta
sulphides CaS4 and CaS5; an interpretation unchanged
from earlier work e.g. Valensi, (1948). Neither the tetra
nor the penta sulphides have been structurally character-
ized and the tetra sulphide has been reported as unstable
by Lutz and Kostic (1966). The purpose of limesulphur
is simply to allow for water-based dispersion of sulphur.
Note that calcium polysulphide should not be confused
with CaS that is structurally a galena analogue.
The work by Hackl et al. (1995) is also interesting in
terms of the traceability of polysulphide assignment via
XPS. Although an oxygen pressure leach study is
presented, the authors point out that the chemistry is
similar to both acidic ferric sulphate and microbial
leaching and conclude, both from XPS and Auger studies,
that the passivation layer is a thin copper-rich (relative
to iron) layer (b 1 m) thought to be a copper polysulphide
CuSn where n N 2. This is based on an S 2p3/2 assignment
at 163.3 eV in what appears a problematic fit. The
justification for a polysulphide assignment is based on
prior work by Pratt et al. (1994) that reports polysulphide
in a tail fit to pyrrhotite S 2p structures. That work, in turn,
relies on Hyland and Bancroft (1989) but appears to
misquote the results. Pratt et al. (1994) state 163.7 eV as
being a polysulphide species and assign 163.01 and
163.25 eV features to polysulphide on vacuum-fractured
and air-oxidized pyrrhotite. The 163.7 eV is actually
Hyland and Bancroft's elemental sulphur value. The
evidence chain is blurred as Hyland and Bancroft (1989)
quote Buckley et al. (1987), citing three states in order to
support their findings. However, those states occurred
together in Buckley et al. in only one case in which an
original two sulphur state surface eventually transformed
in vacuum. Nonetheless, the Hyland and Bancroft work is
very interesting. They used highly reactive Au(III) as
KAuCl4 solution (acidified) as an oxidizing agent for
several sulphide minerals. They concluded that a set of
three polysulphide features were evident; 161.5 eV for
MSS, 162.2 eV for MSS and 163.1 eV for
SS. This implies the identification of sulphur atoms
that would then be at the end of the chain. Further, the high
and low energy separation matches the BE of 1.6 eV
observed for those polysulphides directly synthesized
(Kougianos et al., 2000; Parker et al., 2003a). Clearly,
sulphur polymerisation is occurring in the Hyland and
Bancroft investigation, but it would seem the highly
reactive oxidant system could be producing polysulphido
complexes rather than polysulphides. The other curious
feature is that, on pyrite, the S22 dimer would appear to be
reduced as well, with the 161.5 eV feature some 0.9 eV
lower in BE, although this agrees well with the set of
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
seven alkali polysulphides that average to 161.66 eV for
the terminal sulphur atom (Kougianos et al., 2000) (and
163.22 eV for the central atoms).
Note also that the author's XPS work, (e.g. Klauber
et al., 2001), specifically associates S 2p3/2 structure at
163.5 eV with elemental sulphur. This assignment is
confirmed by showing the expected volatilisation losses
at that energy along with increased bulk photoemission,
plus the fact that the binding energy is what would be
expected considering the easily assigned BE values for
bulk sulphide and surface sulphate. Moreover, the S 2p
difference spectra clearly show the 163.5 eV state to be
single state and true polysulphides consistently have two
oxidation states. This debate will no doubt continue, e.g.
Uhlig et al. (2001) assign a single 163.2 eV feature on
marcasite (observed at a very low temperature range of
2075 K) to the trimer S32. It is nonetheless clear that a
single peak argument for polysulphide assignment is
inadequate. Mikhlin et al. (2004) endeavour to interpret
Sn2 oligomers (where n ranges 3 to 4) on the basis of
terminal and non-terminal sulphur atom BE values but
the spectral signal-to-noise makes the assignment
problematic. Species detected by Uhlig et al. may well
be a neutral S-polymer. A better understanding of
sulphur's behaviour is very important.
Harmer et al. (2006) conducted chalcopyrite leaching
and subsequent surface studies under acidic conditions
but with the use of (initially) ferric-free perchloric acid for
experimental reasons instead of acidic ferric sulphate. It is
worth noting that the acid change completely changes the
dissolution process; the leach becoming acid consuming
and with no indication of surface sulphates or jarosites.
The authors propose a very complex mechanism starting
with an oxidation step requiring ferric as the oxidant,
followed by ferrous as a reductant and/or ferric again as an
oxidant. Moreover the extent of polysulphide Sn2 formed
is proposed to be a function of the percentage of copper
and iron released. Neither the complex redox proposed
nor the stoichiometry implied is cogent.
In principal, if not in practice, many of these
questions should be answerable by SIMS investigations.
As noted above Al-Harahsheh et al. (2006a,b) found one
chalcopyrite surface particularly reactive with strong
evidence for a likely S2O32 surface species, but could
not identify polymerisation beyond a general Sn.
8.3. Elemental sulphur allotropes
Elemental sulphur is observed consistently and can
be considered a systemic product in the acidic ferric
sulphate dissolution of chalcopyrite. Clearly different
morphologies are capable of forming (Dutrizac, 1989)
11
although morphology, for example based on SEM
micrographs, may reflect surface tension and chalcopy-
rite roughness issues rather than innate sulphur types.
Importantly, the complete encapsulation of small
(b40 m) chalcopyrite particles by a coherent sulphur
layer has been observed, hence hindered dissolution.
Moreover, even at 95 C the acidic ferric sulphate
chemical environment does not significantly attack the
sulphur. This would be a problem for a low temperature,
low shear, hydrometallurgical route, but for a mixed
culture heap bioleach the microbial sulphur oxidation
through to acid solves the problem and additionally
increases acid levels.
The chemistry of elemental sulphur is complex and it is
worthwhile considering the possibilities concerning the
nature of sulphur and the variety of allotropic modifica-
tions that elemental sulphur can exist in. These vary in
solubility, density and crystal form. More importantly, the
allotropy is dynamic so that the various allotropes are
always in equilibrium (The Sulphur Institute, 1997). S
(the characteristic 8-member sulphur ring, also referred to
as Sr/8) is the dominant stable solid sulphur allotrope, and
S (long polymerised chains of elemental sulphur) the
less stable, eventually converting to S. Behavioural
differences can be marked, for example the chain polymer
allotrope S is not CS2 soluble, whereas the S is CS2
soluble so solvent removal based experiments are
intrinsically flawed. What is known about sulphur derives
mainly from studies of liquidsolid transformation.
However, it is reasonable to expect that incipient
elemental sulphur would pass through the short chain
S form and then the polymerised chain, that is, it would
act as a liquid even at the low temperatures (below a
nominal melting point) employed in the dissolution
experiments. Debate over dense and porous elemental
sulphur forms, whilst interesting, is also a major
distraction. It will have some impact on mass and solution
transport, depending on coverage and continuity, and
could then have a variable effect on the nature of the initial
parabolic rate. This probably explains the wide variation
in reported Arrhenius activation energies in Hirato et al.
(1987) and also emphasizes that rate data from limited
laboratory experiments in the case of chalcopyrite is of
very limited value, especially if used to predict heap-leach
dynamics. The Hirato et al. approach is just to consider the
second linear stage and to arrive at long leach times by the
successive leaching method in which the leach solution
is regularly changed in order to avoid the effect of reaction
products. Again, such data is of limited value in order to
predict heap-leach behaviour, but as an aside it is a good
method to determine an Arrhenius activation energy
(for example to determine the true influence of semi-
12 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
conductor type) or to determine the reaction order
dependency.
Equally fascinating is the difference between chemi-
cally produced and microbially produced sulphur. A
simple phase dispersion test by Janssen et al. (1999)
dramatically illustrates the difference between sulphur
produced by microbial activity and that produced
chemically. This is shown in Fig. 1 (reproduced with
permission). In this case, the sulphur arises from the
microbial oxidation of H2S. The sulphur sol is both
hydrophilic and stable, and, with a density of 1.22 g cm 3,
it is substantially lower than the amorphous to crystalline
range of normal solid sulphur of 1.92 to 2.07 g cm 3; in
fact it is lower than the liquid sulphur density of 1.80 g
cm 3 at 125 C (The Sulphur Institute, 1997). Interest-
ingly, H2S(aq) is speculated to be a precursor to sulphur
production in the abiotic system (Dutrizac, 1989).
Microbially-derived elemental sulphur is most likely a
nucleus of S8 with an outer hydrophilic character
polythionate coatings have been suggested and rejected.
Janssen et al. (1999) suggest a biological protein
excretion. Either way, the microbial sulphur may be
even less of a hindered dissolution issue than the sulphur
resulting from the direct chemical pathway.
Fig. 1. Sulphur partition test with hexadecane (top) and water (bottom).
Microbially produced sulphur is hydrophilic and is dispersed through the
water phase (tube 1), whereas standard hydrophobic sulphur remains in
the hexadecane phase (tube 2). Janssen et al. (1999), reproduced with
permission.
Linge (1976) dismisses the sulphur film as being the
cause of the parabolic rate; this is based on a porous
sulphur film phase and a pore diffusion model with a
tortuosity assumption. This reasonably rejects the pore
diffusion possibility, but cannot be used to reject a sulphur
film per se. Whatever the sulphur phase, it would be more
appropriate to consider any thin-film as a phase that
allows mass transport by elastic lattice deformation, rather
than a rigid pore structure. This model variation could
give the observed lower mass transport rate. It would also
be an interesting molecular modelling exercise.
Parker et al. (1981), recognized the production of
elemental sulphur, but dismissed it as the passivating
film, because its removal did not enhance the dissolution
rate. In their work, removal involved dipping the
electrode in CS2. As already noted, the elemental
polysulphur (not sulphide) S is actually not soluble in
CS2, so the efficacy of sulphur removal via solvents is
open to debate. Parker used the sulphur rejection to
support the metal-deficient polysulphide proposition.
Parker et al. (2003c,d) have applied in situ Raman
spectroscopy to chalcopyrite leaching coupled with
electrochemical control. Although Raman sensitivity is
poor, the results are of interest, as under acidic ferric
sulphate conditions, apparently little elemental sulphur
was found, though bands consistent with SS pairs were
observed. A major disadvantage is that the laser power
can significantly disrupt the surface being examined. No
conclusions were drawn as to hindered dissolution. In
follow-up work Parker et al. (2005) and Hope et al.
(2006) found that gold decoration could usefully enable
the surface enhanced Raman effect to be employed.
Both acidic ferric sulphate and acidic ferric chloride
studies indicate that a disordered surface phase is
formed containing SS bonds, which aged to a fibrous
sulphur phase, though only room temperature condi-
tions were examined. The absence of bending modes
exclude rhombic sulphur as an initial product but laser-
induced recrystallization was a problem. The low
temperature meant the conditions precede the onset of
hindered dissolution. No polysulphide species or
oxysulphur anions were detected (Hope et al., 2006).
Logically, the intermolecular Sr/8 dispersion bonding
forces would lead to rapid agglomeration for the
chemically produced sulphur. Hence globules would
be expected rather than extensive coatings (especially at
the higher temperatures). It may be that the coating
sulphur in the Dutrizac (1989) work relates to the initial
S sulphur. Certainly in this author's chemical and
microbial leach studies, on both massive and float
concentrate, elemental sulphur has been present to a
varying extent, primarily as macroscopic globules.
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
Fig. 2. EhpH diagram for the FeSKOH system at a temperature
of 25 C (after Bigham et al. (1996)).
8.4. Jarosite formation
There are extensive studies on jarosite chemistry,
particularly the work of Dutrizac. It is not the intent to
review that work, simply to summarize some character-
istics salient to the heap-leach situation. In the author's
chalcopyrite investigations, the precipitation of jarosites
is typically found to be an inevitable consequence of
long leach times. XPS investigation identified an
intermediate ferric sulphate surface phase that forms
on the chalcopyrite surface which is proposed as a
jarosite nucleation trigger. This phase is possibly the
jarosite precursor phase of schwertmannite Fe8O8
(OH)6SO4 (Bigham et al., 1996). The formation of
jarosite is T, pH & Eh dependent and characteristically:
3Fe2 SO4 3 K; Na; H3 O2 SO4
12H2 O2K; Na; H3 OFe3 SO4 2 OH6
6H2 SO4
Rate of formation increases dramatically with T.
Rate is very slow below 60 C.
Rate is at a maximum at pH 2.
Formation is increasingly depressed at pH b 1,
pH N 3, i.e. outside of a narrow pH range.
Note that the pH region favouring jarosite formation
is also the generally accepted ideal region for
bioleaching in terms of microbial activity. Illustrating
this is the EhpH diagram for the FeSKOH system
at 25 C shown in Fig. 2. Importantly the rate of jarosite
13
precipitation is enhanced by jarosite seed (Fig. 3). This
kinetic enhancement is important, as the conditions for
jarosite formation could exist in a heap without it
apparently forming. Jarosite would thus appear a benign
issue until massive precipitation occurred.
XPS studies from the author's own work (e.g. Fig. 4)
show that jarosite precipitation occurs very suddenly, both
attenuating the underlying sulphide photoemission and
reducing the concentrate's electrical conductivity. This
behaviour indicates an effectively contiguous (and hence
hindering) coating. Note that such a coating would not be
visible with conventional microprobe analysis. The
various jarosites are characterized by monovalent cations,
typically K+, Na+, H3O+ NH4+, giving rise to potassium,
sodium, hydronium and ammonium jarosites. Each has
particular relative stabilities and, in a well-controlled
leach environment, it is possible to delay the onset and
type of jarosite formation.
9. Conceptual 4-stage dissolution model
In general terms, the dissolution of chalcopyrite could
be explained in terms of four discrete stages (as also
shown in Fig. 5):
Stage 1 An initial reaction of a fresh chalcopyrite
surface which is dependent upon surface prep-
aration history. Reaction has a high rate and a
low Eact.
Stage 2 Thick elemental sulphur layer hinders dissolu-
tion, electron transport causes reaction to have a
low rate and a high Eact. If conditions do not
favour removal of the thick sulphur layer the
parabolic rate curve continues.
Fig. 3. Illustration of the significant enhancement of the rate of jarosite
precipitation found in the presence of jarosite seed. Note that the
activation energy of the process is unaltered (after Dutrizac (1996)).
14 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
Fig. 4. (a) Sulphur 2p spectra from concentrate leached in the presence
of S. metallicus at 65 C for periods varying from 12 to 108 h in nutrient
media with varying K+ level (after Parker et al. (2003b)). (b) Iron 2p
spectra from concentrate leached in the presence of S. metallicus at
65 C for periods varying from 12 to 108 h in nutrient media with
varying K+ level (after Parker et al. (2003b)).
Stage 3 Conditions favour peeling of the thick sulphur
layer and reaction rate increases to display the
open linear rate curve. Reaction has a high rate
and a high Eact. If both ferric concentration and
pH conditions preclude jarosite formation then
the linear rate curve continues.
Stage 4 Absence of iron and pH control allows the
spontaneous formation of jarosites. These may
self-nucleate or precipitate independent of the
remaining chalcopyrite and the linear rate
curve again continues; alternatively they may
coat the remaining chalcopyrite causing a
parabolic rate curve to reappear, this time due
to mass transport and/or reduced surface area.
This simple 4-stage conceptual model of the steps
involved in chalcopyrite dissolution can logically tie
together all the known experimental observations. The
induction period would be viewed as Stage 1 or Stage 1
and 2 depending upon the length of the reaction time.
Clearly, solution conditions, particularly Fe3+, pH and
T, impact on whether Stages 3 and 4 come into final
play. The model does not address the individual
mechanistic steps variously proposed for the dissolution
reaction. Beyond Stage 1, there is, at all times, an
elemental sulphur layer present. As pointed out by
Munoz et al. (1979), this would preclude a direct
interaction of the hydrated ferric ion with the surface.
Rather, the hydrated species forms at the sulphur-
solution interface and cupric, ferrous and electrons
would diffuse through the thin elemental sulphur layer.
The 4-stage model is not meant to apply in cases of
galvanic coupling (as might be observed in a concen-
trate) nor for the silver catalysed system (which is not
dealt with here, but is clearly a very different reaction
system). This intervening sulphur layer should not be
considered as a major barrier to the oxidative dissolution;
the ferric ion is a powerful oxidant and the driving force
is the abstraction of the electron from the chalcopyrite.
Moreover, as noted, sulphur oxidation itself is not a
problem for microbial systems. Note that the ferric ion
hydration is critical, as the oxygen atom content of the
sulphate unit is proven to originate from the water
molecule (Reedy et al., 1991) in the case of ferric
oxidation of pyrite. If Stage 4 occurs this represents a
final hindered dissolution situation in which complete
copper recovery becomes an increasingly lengthy task.
In addition to the likelihood of jarosite precipitation
eventually coating any remaining chalcopyrite compo-
nent in a heap, jarosite represents a significant molar
volume expansion over the original chalcopyrite phase
of 17.5% (based on iron content). Typical of most
corrosion products its precipitation will, even if not
coating chalcopyrite particles, occur in pore structures so
as to (i) reduce the porosity of the heap and (ii) change
Fig. 5. A conceptual 4-stage model describing chalcopyrite dissolution.
Although the deposition and peeling of elemental sulphur layers impacts
on copper release, the evidence suggests that preventing encapsulating
jarosite precipitation is the final key to maximum copper recovery.
 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
the leachant pathway. Although the heap has no physical
constraints (i.e. it can expand) the jarosites would be
expected to reduce access to the copper value. The extent
of this problem will be dependent not only on
chalcopyrite content but more critically on pyritic
gangue (e.g. the jarosite's iron molar volume expansion
over pyrite is very high at 214%) and the enhanced
ferric concentration.
10. Iron control
There are three in-principal ways to tackle jarosite in
a heap-leach situation:
Prevent jarosite formation.
Induce jarosite to self-precipitate and not coat the
chalcopyrite.
Remove iron (and hence jarosite potential) from heap
circuit.
Preventing jarosite precipitation and still maintaining
an ideal environment for oxidative dissolution is
challenging. Although a low pH is required for jarosite
formation, a very low pH is known to inhibit formation.
This can be seen from the EhpH diagram for the FeS
KOH system at 25 C in Fig. 2. Possible alternatives
would be to operate the heap at either pH b 1 or pH N 3.
This would necessitate the development of alternate
microbial strains away from the present ideal of just below
a pH of 2. In the presence of gangue a consistent pH b 1 is
not likely to be practical. The activated nature of jarosite
formation also means that, as jarosites are favoured at
higher temperatures, running a mesophile biased heap
would help, even if not the preferred option in terms of
rates of recovery. Of course, controlling the leachant in a
heap is not the same as in a reactor. Even if an average pH
and T were targeted, local variations could occur which
favoured jarosite formation.
A much simpler concept is to control iron concentra-
tion. The leachate is continually re-cycled and tapped off
for copper recovery. Two of the key jarosite characteristics
(elevated precipitation in the presence of seed and at
higher temperatures) could be employed in a simple low-
cost iron control circuit via a solar jarosite precipitation
pond. Before leachate or raffinate is re-cycled to the heap
it would be heated in the presence of jarosite seed. This
could be viewed negatively by the industry as it represents
the inclusion of an extra unit operation in what should be a
very low technology set-up to begin with, but, in the
presence of hindered copper recoveries, it would reduce
the time required for recovery of the copper value.
However, this need not be a large cost burden. Deliberate
15
jarosite precipitation outside of the heap could also have
two additional advantages. If the heap gangue is an acid
consumer the jarosite precipitation generates substantial
extra acid. Also, depending upon environmental rehabil-
itation requirements, the removal of the jarosite may
present easier remediation/disposal options. If the heap
were originally constructed with a view to capping, in
accordance with current acid-mine drainage (AMD)
practice, there may be a significant reduction in future
liability by acid control during the life of the heap; or
indeed the leached heap may not actually require AMD
remediation. Some jarosites have commercial value as
fertilizer additives, though product from a heap is unlikely
to be sufficiently pure.
Conceptually, the solar jarosite precipitation circuit
would be a black plastic lined pond of a calculable area,
perhaps with a staged weir design for concentration
control and to impart some turbulence to encourage
further precipitation. It would be expected that the only
maintenance required would be periodic jarosite remov-
al. The pond would operate at an elevated temperature
above the core of the heap and the leachate would only
require a residence time of a few hours in the pond.
Other iron control strategies, such as those used in zinc
circuits (Dutrizac, 1979, 1982) could be used but these
would be at a significantly high cost. Note that all the
chalcopyrite dissolution studies concur on a common
point that there is no advantage to run at excessively
high ferric concentrations, as the rate of the dissolution
is not increased; for example anything above 0.1 M Fe2
(SO4)3 is unnecessary (an iron level equivalent to 11.2 g/
L) (Parker et al., 1981). In summary, the potential
advantages for the iron control circuit would be:
Removal of jarosite problem entirely from the heap.
Improved copper recovery (rate and amount).
Additional acid release into leachate circuit if required.
Lower iron levels in copper recovery circuit.
Possibly lower final environmental rehabilitation costs.
11. Conclusions
This review has focussed on the surface chemistry of
acidic ferric sulphate dissolution of chalcopyrite with
regards to hindered dissolution. Although much of
the literature appears to come to different conclusions,
especially in terms of rate behaviour, this can be ge-
neralized easily in terms of a four-stage dissolution model,
the stages being dependent upon the leaching conditions in
question rather than some intrinsic behaviour of the
chalcopyrite. This explains the general dissolution
behaviour observed of an induction period and a parabolic
16 C. Klauber / Int. J. Miner. Process. 86 (2008) 117
rate curve that may or may not be followed by a linear rate
behaviour. True passivation of the chalcopyrite does not
occur, but hindered dissolution is commonly observed.
The possible causes have been examined. There is no
compelling evidence for either the metal-deficient sul-
phides or the polysulphides, but clear evidence for
elemental sulphur and jarosite playing roles. Initially, the
systemic presence of sulphur causes some hindered
dissolution but in a microbially-mediated heap bioleach
environment, only the jarosites would be expected to cause
a true hindered dissolution problem. The advantages of an
iron removal circuit in a heap-leach situation for jarosite
control have been discussed, with a simple solar jarosite
precipitation pond being a practical solution. This utilizes
the jarosite properties of elevated precipitation rates in the
presence of seed and at higher temperatures. Removal
would not only lead to improved copper recovery (rate and
amount) but could also have advantages of additional acid
release into leachate circuit (if required), lower iron levels
in copper recovery circuit and the possibility of lower final
environmental rehabilitation costs.
Acknowledgements
This work forms part of the Base Metals Research
Program of the Parker Cooperative Research Centre for
Integrated Hydrometallurgy Solutions. The financial
support of the Australian Commonwealth Government
is gratefully acknowledged.
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