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Abstract
The non-stoichiometric compounds of iron sulphide named pyrrhotite (Fe1 xS) are often associated with pyrite (FeS2) in
sulphidic ores and their waste products. The factors affecting pyrite and pyrrhotite oxidation are similar but the latter has
received much less attention. As it is the case for pyrite, an increase in temperature has an increasing effect on the oxidation of
pyrrhotite and the process follows the Arrhenius behaviour. Both ferric iron and bacteria act as catalysts in the oxidation
reactions and play a significant role in the oxidation kinetics. Several spectroscopic techniques are used to study the oxidation
mechanisms and products of pyrrhotite oxidation. This paper presents and discusses the main factors controlling pyrrhotite
oxidation and the proposed mechanisms of oxidation under normal conditions of temperature and pressure.
D 2004 Elsevier B.V. All rights reserved.
Keywords: Pyrrhotite; Oxidation rate; Iron sulphide; Acid generation; Oxidation mechanism
1. Introduction
After pyrite, pyrrhotite is the most common iron
sulphide in nature. A better understanding of the
reactivity and oxidation of pyrrhotite is needed for
improved mineral processing and recovery and to
prevent the production of acid mine drainage (AMD)
from iron sulphides in mine waste. AMD is a major
environmental problem causing acidification, ferric
Abbreviations: AES, Auger electron spectroscopy; AMD, acid
mine drainage; EPR, electron paramagnetic resonance; FTIR,
Fourier transform infrared; NL, non-equilibrium layer; SEM,
secondary electron microscopy; SLS, sequential layer sputtering;
ToF SIMS, time of flight-secondary electron mass spectrometry;
XES, X-ray electron spectrometry; XRD, X-ray diffraction; XPS,
X-ray photoelectron spectrometry.
* Corresponding author. Tel.: +1-705-675-1151x2114; fax: +1705-675-4844.
E-mail address: nbelzile@laurentian.ca (N. Belzile).
0375-6742/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2004.03.003
66
for x 0
1
Surface > S2 4H2 O Z SO2
4 8H 8e
Oxygen is the ultimate oxidant of sulphide minerals in natural surface waters and the direct oxidant at
SO2
4 2xH
SO2
4 8H
67
10
11
Steger and Desjardins (1978) report the predominant oxidation products of pyrrhotite to be goethite
and elemental sulphur (reactions (8), (10) and (11)) as
well as smaller amounts of ferric sulphate and various
sulphooxyanions. Using XPS, Buckley and Woods
(1985a) show that the exposure of pyrrhotite to air
leads to the consecutive formation of iron(II) oxide, an
iron(III) hydroxy-oxide or hydrated iron(III) oxide.
This is confirmed by Fe(2p) and Fe(3p) spectra that
indicate the diffusion of iron from the outermost
layers of the mineral lattices to form the observed
oxidation products. Based on an S(2p) spectrum,
Buckley and Woods (1985b) detect the presence of
elemental sulphur together with sulphate and irondeficient sulphide when a hydrogen peroxide solution
was used as an oxidant. They suggest that the oxidation of pyrrhotite proceeds via a series of iron-deficient sulphides and possibly polysulphides through to
elemental sulphur, these steps being acid-consuming.
Metastable intermediates of sulphate including thiosulphate (Steger and Desjardins, 1977; 1978), polythionate and S4O62 are also reported (Plysunin et al.,
1990; Mikhlin et al., 2002), the presence of these
intermediates being likely related to the conditions of
oxidation. The suggested mechanisms will be discussed later.
The biological leaching of pyrrhotite by Thiobacillus ferrooxidans leads to an acid-consuming step
with the formation of elemental sulphur, followed by
an acid-producing phase with the formation of Kjarosite [KFe3(SO4)2(OH)6], goethite (a-FeOOH), and
schwertmannite [(Fe8O8(OH)6SO4] as solid products
(Bhatti et al., 1993). The evolution of H2S gas could
be noticed during the initial stages of pyrrhotite
bioleaching (Ahonen and Tuovinen, 1994), likely
indicative of a non-oxidative dissolution process as
shown by reaction (1). Elemental sulphur could be
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12
13
69
Table 1
Oxidation rate and activation energy of pyrrhotite
Samples
Oxidant
Monoclinic
Air
(Falconbridge, Ontario)
Monoclinic
Air
(Wards Scientific)
Conditions
Rate (mol m 2 s 1)
based on the release of
Iron
Sulphate
pH not given,
68% r.h.a, 52 jC
pH not given,
62% r.h.
28 jC
35 jC
43 jC
50 jC
50 jC
37% r.h.
50% r.h.
55% r.h.
75% r.h.
pH = 1,
25 80 jC
1.5 10 8
6.0 10 10
3.9 10 9
5.0 10 9
6.3 10 9
8.9 10 9
6.5 10 10
7.1 10 10
7.8 10 10
8.4 10 10
3.2 10 9
4.4 10 9
5.2 10 9
1.1 10 8
8.0 10 10
9.1 10 10
9.1 10 10
9.0 10 10
Monoclinic and
hexagonal
Eletrochemical
Museum-grade
Museum-grade
samples from
N. America
Several locations
in N. America
(12 samples)
Activation energy
(kJ mol 1)
Steger and
Desjardins, 1978b
Steger, 1982b
50.21
46.23
34.48
22.97
3.1 10 9
8.5 10 9
3.3 10 8
1.44 10 8 2.05 10 9
(mono),
Orlova et al., 1989
(hexa),
([Fe] = 0.54 M),
([Fe] = 0.90 M)
Nicholson and
58.1 (pH = 2)
Scharer, 1994c
52.4 (pH = 4)
100.4 (pH = 6)
same as Nicholson
Kwong, 1995
and Scharer, 1994
47.7 62.5d,
79.1 106.0e
22.8 63.0d
f 100
3.1 10 8
6.8 10 8
Reference
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rFe1xS
k1 Fe3 k2 10apH
1 k1 Fe3 k2 10apH k3 Fe2 1=2
14
1 a2=3
15
RT
1000
where a is the pyrrhotite conversion, t the time (days),
CFe3+ the concentration of ferric iron in solution (mol
by Williamson and Rimstidt (1994) and a temperature dependence following Arrhenius behaviour with
an activation energy of 88 kJ mol 1 is given in
Nicholson et al. (1988). A study on the oxidation of
sulphide minerals at high temperature (120 jC) and
high oxygen pressure (855 kPa) showed that pyrrhotite could oxidize much more rapidly at pH 2.7 than
all the other sulphides considered in the study
(Majima and Peters, 1966). The same study indicates
that the oxidation of pyrrhotite is considerably reduced at neutral and alkaline pH values. Steger
(1982) also reports that an increase in temperature
can enhance the rate of O2 diffusion and therefore
the formation of ferric oxide and ferric sulphate
products. It can be speculated that the mechanism
of ferric oxide formation as well as the mineralogical
composition of these oxides will be different under
different temperatures.
3.1.6. Trace metal content
A trend of decreasing reaction rates with increasing trace metal content is noticed (Kwong, 1995;
Janzen et al., 2000) but no statistically significant
effect on the oxidation rate can be established for
individual trace metal (Co, Cu, Mn, Ni) or total trace
metal content. More research needs to be done to
clarify the effect of trace metal on the oxidation of
pyrrhotite.
3.1.7. Bacteria
Thiobacilli can oxidize ferrous to ferric iron and
inorganic sulphur compounds to sulphuric acid
(Suzuki, 1974; Suzuki et al., 1994). The autotrophic
bacteria T. ferrooxidans play a catalytic role in the
oxidative dissolution of sulphide minerals and the
effect is generally attributed to the increased supply
of Fe3 + in solution resulting from bacterial activity
(Nordstrom and Southam, 1997). The essential role of
bacteria in the oxidation of pyrite and pyrrhotite,
especially in coal, is well established and the bacterial
oxidation of pyrrhotite is more effective than that of
pyrite (Pinka, 1991). The biotic oxidation of pyrrhotite appears to be three times faster than the abiotic
one at pH 2 and 4 (Kwong, 1995). It seems more
difficult to put an exact number on the influence of
bacteria on pyrite oxidation but most studies refer to a
significant catalytic effect of bacteria (Nordstrom and
Southam, 1997). Thiobacilli are most active in tem-
71
peratures ranging from 20 to 55 jC and T. ferrooxidans is the dominant organism at temperatures below
40 jC. Most strains have optimum growth at 25 35
jC (Tuovinen and Kelly, 1972) with some Canadian
strains showing optimum strength at 20 jC (Mason
and Rice, 2002). T. ferrooxidans is most active in the
pH range 1.0 2.5 deriving its energy from redox
reactions where Fe2 + or reduced sulphur compounds
serve as electron donor and oxygen as electron
acceptor.
The intermediate steps of oxidation (from S2 to
S, SO32 and SO42 including thionates and polythionates) along with the enzymes responsible for the
individual reactions are presented by Suzuki et al.
(1994). Other microorganisms are associated with the
oxidation of sulphides and the generation of acid
mine drainage (Gould et al., 1994; Benner et al.,
2000).
4. Oxidation mechanisms
A relatively abundant literature exists on the
mechanisms involved during the alteration or oxidation of the pyrrhotite surface. Information has been
obtained using X-ray techniques such as electron
(XES), photoelectron (XPS) and Auger electron
spectroscopy (AES), X-ray powder diffraction
(XRD) as well as from Mossbauer spectroscopy
and secondary electron microscopy (SEM). Although
a clear mechanism has yet to be defined, many
studies agree on a progressive enrichment of the
surface with respect to sulphur when pyrrhotite is
oxidized. Taylor (1970) and Taylor and Mao (1971)
use XRD and optical microscopy to detect the
conversion of pyrrhotite into a more S-rich phase
named smythite (Fe3.25S4). The electrochemical oxidation of pyrrhotite at pH 4.6, 9.2 and 13.0 produces mainly sulphur and significant quantities of
sulphate in the alkaline solutions and the oxidation
of pyrrhotite is strongly inhibited under alkaline
conditions due to the passivation of the surface by
ferric oxides (Hamilton and Woods, 1981).
In an oxidation study of pyrrhotite by air using
XPS, Buckley and Woods (1985a) propose the diffusion of iron from the outermost layers of the solid
lattice to form, via an iron(II) oxide, an iron(III)
hydroxyl-oxide or hydrated oxide at the air/solid
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Fig. 1. Model illustrating the sequence of oxidation products at the surface of pyrrhotite.
73
6. Concluding remarks
! 1 xFePO4 SO2
4 3 xH 3H2 O
17
This iron phosphate coating can control the oxidation process of pyrrhotite by stabilizing pH around
4 and by reducing iron generation. The long-term
resistance of coating agent remains to be tested.
Pyrrhotite can be stabilized in combination with a
binder (such as cement), neutralizers, bactericides or
surfactants to form agglomerates (Amaratunga, 1991;
Hmidi and Amaratunga, 1998). It is also suspected
that the oxidation of pyrrhotite could be partially or
totally inhibited through surface treatments (coating
agents) similar to those suggested for pyrite (Lalvani
et al., 1990, 1991; Belzile et al., 1997b; Lan et al.,
2002).
74
both require low pH environments. Taking into account the variable nature of pyrrhotite compounds and
the various experimental designs, it is not surprising
to find variable results for oxidation rates and products of oxidation. However, the few studies reporting
oxidation rate of pyrrhotite seem to agree on values on
the order of 10 8 10 9 mol m 2 s 1 (Table 1),
generally based on iron release. However, a reliable
rate law similar to those presented for pyrite still needs
to be defined. The oxidation rates based on sulphate
production clearly indicate an incomplete oxidation as
elemental sulphur and sulphoxy intermediates are
formed and detected. Since oxidation to polysulphides
and elemental sulphur is acid-consuming, this represents a major difference to pyrite oxidation which
produces sulphate and is always acid producing. In
recent years, the combination of X-ray (e.g. XRD) and
spectroscopic (e.g. XPS, FTIR) techniques has been
particularly useful in improving our understanding the
mechanism of oxidation at the molecular level and the
chemical bonds formed at the surface of oxidized
pyrrhotite. More systematic studies are required to
better understand and control the oxidation of this
reactive mineral so as to improve both mineral extraction and environmental protection.
Acknowledgements
Financial support from the Natural Sciences and
Engineering Research Council of Canada and from the
Materials and Manufacturing Ontario Centre of
Excellence is acknowledged. Constructive comments
from J.E. Thomas and R.B. Herbert Jr. greatly
improved the paper.
References
Ahonen, L., Tuovinen, O.H., 1994. Solid-phase alteration and iron
transformation in column bioleaching of a complex sulfide ore.
In: Alpers, C.N., Blowes, D.W. (Eds.), Environmental Geochemistry of Sulfide Oxidation. ACS Symposium Series 550,
American Chemical Society, Washington, DC, 79 89.
Alpers, C.N., Blowes, D.W., 1994. Environmental Geochemistry of
Sulfide Oxidation. ACS Symposium Series, vol. 550. Washington, DC, 681 pp.
Amaratunga, L.M., 1991. A novel concept of safe disposal of acid
generating tailings by agglomeration and encapsulating alkaline
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