Journal of Geochemical Exploration 84 (2004) 65 76

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A review on pyrrhotite oxidation

Nelson Belzile *, Yu-Wei Chen, Mei-Fang Cai, Yuerong Li
Department of Chemistry and Biochemistry, Laurentian University, Ramsey Lake Road, Sudbury, Ontario, Canada P3E 2C6
Received 21 July 2003; accepted 29 March 2004
Available online 14 May 2004

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

iron precipitation and an increased mobility of trace

metals in drainage waters (Alpers and Blowes, 1994;
Belzile et al., 1997a; Johnson et al., 2000). This paper
reviews the recent literature on the oxidation of pyrrhotite, presents the main factors affecting the process
and discusses the mechanisms proposed for the oxidation of pyrrhotite. When possible, a comparison is
made with pyrite.

2. Structure and solubility

Pyrrhotite is found in a wide range of hydrothermal
deposits. It is often associated with mafic intrusive
and volcanic rocks and found in massive sulphide
deposits associated with pyrite, sphalerite, galena and
chalcopyrite.The name pyrrhotite covers a wide range
of minerals and synthetic iron sulphur phases based
on the NiAs structure (Becker et al., 1997). Pyrrhotite

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N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

shows a non-stoichiometric composition as Fe1
xS,

where x varies from 0 (FeS) to 0.125 (Fe7S8). The
non-stoichiometry is due to a system of ordered
vacancies within the Fe lattice (Vaughan and Craig,
1978; Pofsai and Dodonay, 1990; Thomas et al., 2000,
2001). The formula can also be expressed as Fen
1Sn
with n z 8 to give structures from Fe7S8 to Fe11S12.
The least Fe-deficient forms have hexagonal and
orthorhombic (FeS) structures whereas those with
greater iron deficiency have monoclinic symmetry
(Arnold, 1967; Janzen et al., 2000; Thomas et al.,
2001). The Fe S distance is in the range of 0.237
0.272 nm with an average of 0.250 nm (Vaughan and
Craig, 1978). The iron content ranges between 46.5%
and 46.8% in Fe (on a mole basis) in monoclinic
pyrrhotite and between 47.4% and 48.3% in hexagonal forms (Ward, 1970). Monoclinic pyrrhotite is
ferromagnetic at room temperature (Becker et al.,
1997). Pyrrhotite is an important iron sulphide waste
mineral in many mining environments. It is often
found as a gangue mineral in Cu Ni deposits, associated with valuable minerals. Massive sulphide
deposits containing pyrrhotite can be found all around
the world, more specifically in Russia, China, Australia and Canada.
Because of its sulphidic nature, pyrrhotite can be
dissolved rapidly under acidic conditions and generate
Fe2 + and H2S according to reaction (1) or (2) or more
slowly via oxidative dissolution according to reactions
(3) and (4):
Fe1
x S 2H Z 1
xFe2 H2 S

for x 0
1

Surface > S2
2H Z H2 S

Surface > S2
4H2 O Z SO2

4 8H 8e

However, Thomas et al. (1998) report that an

induction period during which a slow release of Fe
and little or no production of H2S is observed before
the rapid dissolution of pyrrhotite can occur under
anoxic acidic (1 M HClO4) and acid-consuming
conditions. The onset of non-oxidative dissolution
and production of H2S (reaction 1) can increase the
rate of oxidative dissolution by three orders of magnitude from 10
8 to 10
5 mol m
2 s
1. The main
factors controlling the length of the induction period
were identified as the amount of surface oxidation
products on the mineral surface, the acid strength (no
apparent induction in 0.05 M acid) and the temperature. The authors present a four-step dissolution
process and use X-ray photoelectron spectroscopy
(XPS) to study the initially oxidized surface of pyrrhotite samples and identify changing sulphur (e.g.
S2
, S22
, Sn2
) and iron (e.g. Fe(III)S, Fe(II)S,
Fe(III)O) species at the different stages of dissolution.
In a more recent paper, Thomas et al. (2001) refine the
model by proposing the trapping of electrons in
metastable chemical states (e.g. polysulfides) during
the oxidative dissolution of pyrrhotite before the
production of H2S according to:


2

S2

n 2n
1e Z nS

It is then proposed that not all electrons are lost to

an oxidizing agent and that some accumulation of
electrons in a crystal-wide surface space-charge surface region of pyrrhotite may occur particularly at
temperature of 40 jC and above. The overall mechanism is a non-oxidative dissolution with Fe2 + leaving the surface without the release of electrons,
followed by the reduction of polysulphides to sulphides according to reaction (5) and then production
of negative charges as HS
.
The true oxidative dissolution of pyrrhotite under
acidic conditions does not involve the production of
H2S. At low pH, the rate of acidic dissolution will
compete with the oxidative dissolution.

together with: 2O2 4H2 O 8e
Z 8OH
or 8Fe3

8e
Z 8Fe2

3. Oxidation of pyrrhotite and oxidation products

It should be mentioned that Eq. (4) will neutralize acid

produced in Eq. (3).

Oxygen is the ultimate oxidant of sulphide minerals in natural surface waters and the direct oxidant at

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

pH>4 (Nordstrom and Alpers, 1999). At pH below 4,

sulphides are oxidized by ferric iron. In most mine
wastes, oxygen is the primary oxidizing agent of
ferrous iron to ferric, which implies that sulphide
oxidation generally occurs only in areas where dissolved or gaseous oxygen is present (Benner et al.,
2000).
As is the case for pyrite (Lowson, 1982; Bierens de
Haan, 1991; Belzile et al., 1997a), oxygen and ferric
iron are generally the two important oxidants for
pyrrhotite. When O2 is the primary oxidant, the
oxidation reaction can proceed as follows (Nicholson
and Scharer, 1994):
Fe1
x S 2
1=2xO2 xH2 O Z 1
xFe2

SO2

4 2xH

The oxidation of ferrous iron produces ferric ions

that can precipitate out of solution to form ferric
hydroxide, if pH is not too low. Fe2 + is oxidized
and precipitated as ferric oxyhydroxides, principally
ferrihydrite and goethite.
Fe2 1=4O2 2H Z Fe3 1=2H2 O

Fe3 3H2 O Z FeOH3s 3H

Ferric iron can in turn oxidize more pyrrhotite and

generates more acidity in the system according to the
following reaction:
Fe1
x S 8
2xFe3 4H2 O Z 9
3xFe2

SO2

4 8H

If reaction (7) occurs under acidic conditions, a

significant quantity of Fe3 + will remain in solution
and maintain a cyclic reaction with reaction (9) where
ferric iron is the oxidant.
There is evidence from field and laboratory studies
that the oxidation may not be complete and instead
generates elemental sulphur (e.g. Steger, 1982; Jam-

67

bor, 1986; Ahonen and Tuovinen, 1994) according to

an acid-consuming reaction:
Fe1
x S 1=21
xO2 21
xH Z1
xFe2
S0 1
xH2 O
Fe1
x S 2
2xFe3 Z 3
3xFe2 S0

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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N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

detected with pyrrhotite dissolution in the presence or

absence of bacteria (Bhatti et al., 1994). The presence
of jarosite and iron oxyhydroxides occurring as goethite with traces of ferrihydrite was confirmed in an
Ontario mine tailings impoundment (Johnson et al.,
2000). Wetting drying treatment of synthetic hexagonal pyrrhotite results in the formation of a-FeOOH
(goethite) and elemental sulphur on the surface of
mineral grains as confirmed by diffuse reflectance
FTIR (Kalinkin et al., 2000). A more detailed discussion of the mechanism that could explain the
oxidation and the occurrence of oxidation products
is presented in Section 4.
3.1. Factors affecting oxidation
As suggested by reactions (6) to (11), the oxidation
of pyrrhotite is affected by several factors that determine the rate of the process. Some of the factors
presented below can play a determining role in the
nature of the oxidation products.
3.1.1. Crystal structure
Various studies indicate that specific surface values of various size fractions of museum-grade pyrrhotite samples (determined by BET surface area
analysis) are f 2 10 times higher than those observed for crystalline pyrite and 6 40 times greater
than the theoretical values based on spherical geometry (Kwong, 1995; Janzen et al., 2000). This difference can partially be attributed to surface roughness
and extended fractures into pyrrhotite grains. The
modification of mineral structures due to the pressures and stresses associated with the milling of ore
can increase the reactivity of pyrrhotite in mine
tailings and its susceptibility to oxidation processes
(Pratt et al., 1996). Compared to pyrite, 20 100
times faster oxidation rate of pyrrhotite can also be
related to lower crystal symmetry due to the vacancy
of iron atoms in the crystal structure (Nicholson and
Scharer, 1994). Although it has been suggested that
the crystal structure of pyrrhotite can affect its
oxidation rate (Yakhontova et al., 1983; Orlova et
al., 1989), the results of the study by Janzen et al.
(2000) report no apparent correlation between pyrrhotite oxidation by oxygen or ferric iron and crystal
structure. More recent results from our research group
suggest that monoclinic pyrrhotite could be less

reactive than the hexagonal form (Belzile et al.,

unpublished).
3.1.2. Oxygen and moisture
Reaction (1) indicates the required presence of
water when pyrrhotite is oxidized by oxygen (air).
The effect of humidity was studied by Steger (1982)
and his results indicate a direct increase of the
oxidation rate with increasing relative humidity (Table
1). A study using XPS (Knipe et al., 1995) confirm
that oxygen is the primary oxidant as no evidence of
oxidation could be shown when pyrrhotite is exposed
to deoxygenated water. No systematic studies relate
the effect of oxygen content to pyrrhotite oxidation
but the oxidation rate is expected to be related to the
concentration or partial pressure of O2. The rate is
shown to be proportional to the square root of the O2
partial pressure for pyrite by McKibben and Barnes
(1986) and Williamson and Rimstidt (1994) in Eqs.
(12) and (13), respectively, but different coefficients
for pyrrhotite are expected:
r 10
6:77 O2 0:5

12

r 10
8:19 O2 0:5 =H 0:11

13

Rates are expressed in mol of pyrite cm
2 min
1 for

Eq. (12) and in mol m
2 s
1 for Eq. (13).
3.1.3. Ferric iron
Oxidation rates are significantly increased when
Fe3 + is present (Janzen, 1996; Janzen et al., 2000).
The oxidation of pyrrhotite by ferric iron differs under
oxic and anoxic conditions ranging from zero order
for anoxic to half order under oxic conditions
(Kwong, 1995). In the presence of oxygen, the reaction was first order with respect to Fe3 + concentration.
The same author reports both molecular oxygen and
ferric iron to be inefficient in oxidizing sulphide
sulphur to sulphate. A linear effect of ferric iron
concentration expressed on a log scale could be
observed on the reaction rates also expressed as log
values (Janzen et al., 2000). They suggest an adsorption-type mechanism with a Freundlich- or Langmuirtype isotherm similar to that proposed by Nicholson et
al. (1988) and Williamson and Rimstidt (1994) or the

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

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

Air flow reactor pH = 2.0 6.0

10 jC
22 jC
33 jC
Fe3 + f 10
3 M 22 jC, pH = 2.0
Air flow reactor Abiotic 22 jC
pH = 2.0
Abiotic 35 jC
pH = 2.0
pH = 3.0
pH = 4.0
Biotic 22 jC
Biotic 35 jC
pH = 2.0
pH = 4.0
Air flow reactor pH = 2.75;
25 jC
Fe3 +
pH = 2.75;
Fe3 + = 0.2 mM
pH = 2.50;
Fe3 + = 0.2 mM
pH = 2.50;
Fe3 + = 1.0 M
Chemical and
pH = 2.0
bioleaching
30 jC
Fe3 +
0 200 mM

Museum-grade
samples from
N. America

Several locations
in N. America
(12 samples)

Pyrrhotite ore, Bolivia

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

2.28  10
9 8.51  10
10

2.87  10
9
3.86  10
9
2.51  10
9
6.74  10
9 6.97  10
9 13.3
8.76  10
9
6.91  10
9
4  10
9
2  10
10
3.5  10
8

47.7 62.5d,
79.1 106.0e
22.8 63.0d

Janzen et al., 2000

f 100

Beolchini and Veglio,

1999; Veglio et al., 2000

3.1  10
8
6.8  10
8

r.h. for relative humidity.

Estimated mean using an average particle specific surface area from Janzen et al. (2000).
c
Average value of oxidation rates.
d
Based on iron release.
e
Based on sulfate release.
b

Reference

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N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

dual-site adsorption model of Zheng et al. (1986) for

pyrite oxidation. The rate limiting sequence is electron
transfer reactions from ferric iron to an activated
complex of Fe3 +, decomposition to a Fe2 + activated
complex, decomposition to a Fe2 + ion and desorption
of the ferrous ion from the surface. Janzen (1996)
proposes a multi-solute Fritz and Schluender (1974)
sorption isotherm to describe the dissolution of pyrrhotite by ferric iron (Eq. (14)):

rFe1
xS

k1 Fe3  k2 10
apH
1 k1 Fe3  k2 10
apH k3 Fe2 1=2
14

where k represents adsorption equilibrium constants

and a the activity.
With either mechanism, the apparent rate of solid
dissolution at low Fe3 + concentration and constant
Fe2 + and pH level is close to half order with respect to
Fe3 +. At an Fe3 + concentration of 0.2 mM, the author
reports fractional order of dependence ranging from
0.45 to 0.66 but at a higher initial Fe3 + concentration
of 10 mM, a zero order dependence on ferric concentration was observed suggesting a more complex rate
dependence.
Recent studies (Beolchini and Veglio, 1999; Veglio
et al., 2000) on the chemical leaching of pyrrhotite ore
by ferric iron show that sulphur present in pyrrhotite is
only partially oxidized to elemental sulphur. The
authors also demonstrate that the process kinetics
are controlled by the chemical reaction with an
activation energy of 99 kJ mol
1 and they present a
mathematical model which takes into account both
direct (bacteria as the primary oxidant) and indirect
(bacteria regenerating ferric iron through the oxidation
of Fe2 +) mechanisms to describe the kinetics as a
differential equation of the following type (Beolchini
and Veglio, 1999; Veglio et al., 2000):



da
99  103 1
1

4
1440:0  10 e



dt
T 298
R

0:47
27  103 a
CFe3

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

m
3), R the universal gas constant (J mol
1 K
1),

and T the temperature (K).
3.1.4. pH
Very few studies mention the pH effect although it
appears clearly that low pH is required to prevent the
precipitation of Fe3 + and maintain the activity of the
Thiobacilli-type acidophilic bacteria. Nicholson and
Scharer (1994) report an inconsistent effect of pH
between 2.0 and 6.0 at three different temperatures. A
similar observation is made by Kwong (1995) who
does not observe a real trend in the abiotic oxidation
of pyrrhotite associated to pH and the major pH effect
being on the control of bacterial activity below 4.5. A
study of the pH influence on oxidation of pyrrhotite
by ferric iron also shows inconsistent results and
suggests a competing effect of the proton with Fe3 +
and possibly Fe2 + for adsorption sites on the surface
(Janzen, 1996) as suggested by Eq. (14) representing a
model for the reaction rate of oxidation. As it has been
mentioned in the introduction, the non-oxidative dissolution of pyrrhotite can occur at low pH and
liberates H2S.
3.1.5. Temperature
A significant increase in the oxidation rate of
pyrrhotite with increasing temperature is presented
by Steger (1982); the effect is more obvious when
the rate is calculated on the basis of iron release
(Table 1). The effect of temperature is reported to be
more significant than that of pH with the reaction
rate doubling between 25 and 35 jC (Kwong, 1995)
or increasing by 3 5 times for a 20 jC increase with
oxygen as oxidant and by 2 11 times for a 30 jC
increase with ferric iron as the oxidant (Janzen,
1996). In both studies, the oxidation process follows
Arrhenius behaviour. Abiotic activation energy between 58.1 kJ mol
1 (pH = 2.0) and 100.4 kJ mol
1
(pH = 6.0) and biotic activation energy at pH 2.0 of
only 13.3 kJ mol
1 are reported (Kwong, 1995).
Activation energies for pyrrhotite oxidation by oxygen range from 48 to 63 kJ mol
1 based on iron
release and from 79 to 124 kJ mol
1 based on
sulphate release (Janzen, 1996; Janzen et al., 2000).
Similar values are presented by the same authors for
oxidation by ferric iron (Table 1). For comparison,
values of activation energy originating from various
studies on the order of 50 80 kJ mol
1 are reported

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

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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N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

interface based on the interpretation of Fe(2p), Fe(3p)

and S(2p) spectra.
4Fe1
x S 3yO2 2yH2 O Z 2yFe2 O3 H2 O
or 4yFeOOH 4Fe1
x
y S
with y < (1
x).
When a H2O2 solution is used, the presence of
elemental sulphur and sulphate can be detected using
XPS (Buckley and Woods, 1985b). Further studies
using voltammetry and XPS show that the initial
oxidation products for pyrrhotite and pyrite oxidation
include metal-deficient sulphides rather than elemental sulphur (Buckley et al., 1988). The presence of
sulphate species, iron(III) oxide/hydroxides and irondeficient sulphide species including a tetragonal Fe2S3
reaction product is also noticed when ground pyrrhotite is oxidized by air and water as confirmed by XPS
and XRD (Jones et al., 1992). An extensive study of
the mechanism of air oxidation based on XPS and
AES (Pratt et al., 1994a) identifies for the first time
Fe(III) bonded to sulphur in fresh pyrrhotite where the
latter is present as monosulphide (S2
), along with
minor amounts of disulphide (S22
) and polysulphide
(Sn2
). After 6.5 h of air exposure, Fe(III) is bonded to
oxygen and most of the remaining Fe(II) remains
bonded to sulphur with some of the initial monosul-

phide being converted into a range of compounds

including sulphite, elemental sulphur, polysulphides
and predominantly disulphides. The authors propose a
sequential layer sputtering (SLS) model with which
AES depth profiles can be calculated. After 50 h of air
oxidation, the model suggests an oxygen-rich and

sulphur-depleted outermost layer of less than 10 A

(1 nm), covering an Fe-deficient, S-rich layer displaying a continuous and gradual decrease in S/Fe from
the outer layer to the unaltered inner layers of pyrrhotite with a sequential composition of FeO1.5, FeS2,
Fe2S3 and Fe7S8 (Fig. 1). They propose a mechanism
where molecular oxygen is adsorbed onto the surface
of pyrrhotite and reduced to O2
and reacts with
Fe(III) bonded to sulphur to form Fe(III) O bonds
and Fe(III) oxyhydroxides. The establishment of
subsequent ferric oxyhydroxide layers is realized
through the diffusion of Fe from pyrrhotite, which
causes a depletion of iron in the zones immediately
below the oxyhydroxide layer and a rise of S/Fe
ratios. A similar chemical stratification can also be
obtained when pyrrhotite is oxidized in sulphuric acid
solutions at pH 3.0 (Pratt et al., 1994b).
The model proposed by Pratt et al. (1994a) was
further refined by Mycroft et al. (1995) who confirm
by angle-resolved XPS that ferric oxyhydroxides
requiring the presence of water are the only species
to form during the initial stages of air oxidation of

Fig. 1. Model illustrating the sequence of oxidation products at the surface of pyrrhotite.

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

73

pyrrhotite. The air oxidation of pyrrhotite forces Fe to

diffuse from the interior to the surface and to combine
with oxygen. This removal of Fe results in an S
enrichment in the zone below and promotes the
formation of disulphide bonds and the reorganization
of the pyrrhotite structure towards a marcasite (FeS2)
structure. This last step requires oxidation of monosulphide ions to disulphides and polysulphides. An
increase in S S bonding is also observed after the
oxidation of pyrrhotite when using time of flightsecondary ion mass spectrometry ToF-SIMS (Smart
et al., 2000). In another study based on XPS, Knipe et
al. (1995) show no evidence of oxidation when
pyrrhotite and pyrite are exposed to deoxygenated
water.
The formation of a non-stoichiometric non-equilibrium or metastable layer (NL) as a result of
preferential release of iron relative to sulphur in the
oxidation or dissolution of pyrrhotite has been further
studied by Russian researchers (Mikhlin, 2000; Mikhlin et al., 1998, 2000, 2001, 2002; Kuklinskii et al.,
2001) through a combination of spectroscopic techniques (XRD, FTIR, XPS, XES, EPR, Mossbauer,
etc). These studies provide more information on the
composition and reactivity of the metal-deficient
layer and on the mechanisms involved in the complex
transformations of sulphide species (formation of
elemental sulphur and sulphoxy compounds) and
alterations of the oxidation and spin state of iron
(Mikhlin et al., 2002). The oxidation kinetics and
products depend on the environment humidity and on
the crystalline structure of pyrrhotite. The same
authors suggest that the partially oxidized, disordered
NL may be passive.

sludge or compost) that could prevent the diffusion of

oxygen and also maintain some reducing conditions
when organic amendments are used (e.g. Nicholson et
al., 1989; Blowes et al., 1994; Belzile et al., 1997a).
Wet covers are also efficient in reducing the oxidation
of sulphidic wastes because of the lower concentration
and lower diffusion rate of oxygen in water compared
to those in air (Belzile et al., 1997a). For preventing
AMD, a technology by which sulphidic minerals are
coated with ferric phosphate in presence of H2O2 can
be used to form a stable mineral at the surface of
pyrrhotite (Evangelou, 1994; Georgopoulou et al.,
1996). Natural phosphate rock can be used and a
biofilm induced by the presence of microbes feeding
on phosphate can be formed (Ueshima et al., 2003).

5. Prevention and remediation

6. Concluding remarks

Pyrrhotite is oxidized by O2 and the oxidation

products are generally protons, ferrous ions, sulphate
ions and free sulphur, the oxidation to elemental
sulphur being acid-consuming. Several engineered
devices have been proposed for the remediation and
prevention of acid drainage and metal solubilization.
One logical approach consists in preventing or limiting the contact between pyrrhotite and oxygen (air). It
can be done by applying different types of dry and
organic covers (clay, soil, peat, hay, straw, sawdust,

The oxidation of pyrrhotite depends on several

biotic and abiotic factors. Most studies confirm the
importance of surficial and adsorptive reactions in the
oxidation mechanisms, which could explain why
crystal structure and surface defects, the presence of
catalysts such as bacteria, and to a lesser extent,
temperature can be considered as the most important
factors in pyrrhotite oxidation studies. Two of these
factors are indirectly controlled by pH as the presence
of high Fe3 + concentrations and acidophilic bacteria

Fe1
x S 3:5H2 O2 1
xH2 PO

4

! 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

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

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

and bactericidal additives. In: Smith, R.W., Misra, M. (Eds.),

Proc. Conf. Mineral Bioprocessing, The Minerals, Metals and
Materials Society, pp. 389 400.
Arnold, R.G., 1967. Range in composition and structure of 82
natural terrestrial pyrrhotites. Can. Mineral. 9, 31 50.
Becker, U., Munz, A.W., Lennie, A.R., Thornton, G., Vaughan, D.J.,
1997. The atomic and electronic structure of the (001) surface of
monoclinic pyrrhotite (Fe7S8) as studied using STM, LEED and
quantum mechanical calculations. Surf. Sci. 389, 66 87.
Belzile, N., Goldsack, D., Maki, S., McDonald, A., 1997a. Acid
mine drainage in the Sudbury area, Ontario. In: Eyles, N. (Ed.),
Environmental Geology of Urban Areas. Geological Association of Canada, St. Johns, Canada, pp. 223 226.
Belzile, N., Maki, S., Chen, Y.-W., Goldsack, D., 1997b. Inhibition
of pyrite oxidation by surface treatment. Sci. Total Environ. 196,
177 186.
Benner, S.G., Gould, W.D., Blowes, D.W., 2000. Microbial populations associated with the generation and treatment of acid mine
drainage. Chem. Geol. 169, 435 448.
Beolchini, F., Veglio, F., 1999. Kinetic modelling of pyrrhotite ore
leaching by ferric iron and related statistical analysis. Ind. Eng.
Chem. Res. 38, 3296 3299.
Bhatti, T.M., Bigham, J.M., Carlson, L., Tuovinen, O.H., 1993.
Mineral products of pyrrhotite oxidation by Thiobacillus ferrooxidans. Appl. Environ. Microbiol. 59, 1984 1990.
Bhatti, T.M., Bigham, J.M., Vuorinen, A., Tuovinen, O.H., 1994.
Alteration of mica and feldspar associated with the microbiological oxidation of pyrrhotite and pyrite. In: Alpers, C.N.,
Blowes, D.W. (Eds.), Environmental Geochemistry of Sulfide
OxidationACS Symposium Series, vol. 550, pp. 90 105. Washington, DC.
Bierens de Haan, S., 1991. A review of the rate of pyrite oxidation in
aqueous systems at low temperature. Earth-Sci. Rev. 31, 1 10.
Blowes, D.W., Ptacek, C.J., Jambor, J.L., 1994. Remediation and
prevention of low-quality drainage from tailings impoundments.
In: Jambor, J.L., Blowes, D.W. (Eds.), The Environmental Geochemistry of Sulfide Mine Wastes. Mineralogical Association of
Canada, Ottawa, Canada, pp. 365 379.
Buckley, A.N., Woods, R., 1985a. X-ray photoelectron spectroscopy of oxidized pyrrhotite surfaces: I. Exposure to air. Appl. Surf.
Sci. 22/23, 280 287.
Buckley, A.N., Woods, R., 1985b. X-ray photoelectron spectroscopy
of oxidized pyrrhotite surfaces: I. Exposure to aqueous solutions.
Appl. Surf. Sci. 20, 472 480.
Buckley, A.N., Hamilton, I.C., Woods, R., 1988. Studies of the
surface oxidation of pyrite and pyrrhotite using X-ray photoelectron spectroscopy and linear potential sweep voltammetry.
In: Richardson, P.E., Woods, R. (Eds.), Proc. Int. Symp. on
Electrochemistry in Mineral and Metal Processing II. The Electrochemical Society, vol. 88-21, pp. 234 246.
Evangelou, V.P., 1994. Potential micro-encapsulation of pyrite artificial inducement of FePO4 coating. 3rd Int. Conf. on the
Abatement of Acidic Drainage. Bureau of Mines, SP-obB-g4,
pp. 96 103.
Fritz, W., Schluender, E.U., 1974. Simultaneous adsorption equilibria of solutes in dilute aqueous solutions on activated carbon.
Chem. Eng. Sci. 29, 1279 1282.

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

Georgopoulou, Z.J., Fytas, K., Soto, H., Evangelou, B., 1996. Feasibility and cost of creating an iron-phosphate coating on pyrrhotite to prevent oxidation. Environ. Geol. 28, 61 69.
Gould, W.D., Bechard, G., Lortie, L., 1994. The nature and role
of microorganisms in the tailings environment. In: Jambor,
J.L., Blowes, D.W. (Eds.), The Environmental Geochemistry
of Sulfide Mine Wastes. Mineralogical Association of Canada,
Ottawa, Canada, pp. 185 199.
Hamilton, I.C., Woods, R., 1981. An investigation of surface oxidation of pyrite and pyrrhotite by linear potential sweep voltametry. J. Electroanal. Chem. 118, 327 343.
Hmidi, N., Amaratunga, L.M., 1998. Stabilization of reactive pyrrhotite tailings for backfill using cold-bond agglomeration process. In: Rao, S.R., Amaratunga, L.M., Richards, G.G., Kondos,
P.D. (Eds.), Proc. 3rd International Symp. on Waste Processing
and Recycling in Mineral and Metallurgical Industries. 37th
Annual Conference of Metallurgists, Calgary, Canada.
Jambor, J.L., 1986. Detailed mineralogical examination of alteration products in core WA-20 from Waite Amulet tailings.
CANMET Division Report MSL 86-137(IR). Dept. Energy
Mines Resources, Canada.
Janzen, M.P., 1996. Role of ferric iron, trace metal content, and
crystal structure on pyrrhotite oxidation. MSc thesis. University
of Waterloo. Canada. 175 pp.
Janzen, M.P., Nicholson, R.V., Scharer, J.M., 2000. Pyrrhotite reaction kinetics: reaction rates for oxidation by oxygen, ferric
iron, and for nonoxidative dissolution. Geochim. Cosmochim.
Acta 64, 1511 1522.
Johnson, R.H., Blowes, D.W., Robertson, W.D., Jambor, J.L., 2000.
The hydrogeochemistry of the Nickel Rim mine tailings impoundment, Sudbury, Ontario. J. Contam. Hydrol. 41, 49 80.
Jones, C.F., Lecount, S., Smart, R.St.C., White, T., 1992. Compositional and structural alteration of pyrrhotite surfaces in solution: XPS and XRD studies. Appl. Surf. Sci. 55, 65 85.
Kalinkin, A.M., Forsling, W., Makarov, D.V., Makarov, V.N., 2000.
Surface oxidation of synthetic pyrrhotite during wetting drying
treatment. Environ. Eng. Sci. 17, 329 335.
Knipe, S.W., Mycroft, J.R., Pratt, A.R., Nesbitt, H.W., Bancroft,
G.M., 1995. X-ray photoelectron spectroscopic study of water
adsorption on iron sulphide minerals. Geochim. Cosmochim.
Acta 59, 1079 1090.
Kuklinskii, A.V., Mikhlin, Yu.L., Pashkov, G.L., Kargin, V.F., Asanov, I.P., 2001. Conditions for the formation of a nonequilibrium
nonstroichiometric layer on pyrrhotite in acid solutions. Russ. J.
Electrochem. 37, 1269 1276.
Kwong, E.C.M., 1995. Abiotic and biotic pyrrhotite dissolution.
MASc thesis. University of Waterloo, Waterloo, Ontario.
Lalvani, S.B., DeNeve, B.A., Weston, A., 1990. Passivation of
pyrite due to surface treatment. Fuel 69, 1567 1569.
Lalvani, S.B., DeNeve, B.A., Weston, A., 1991. Prevention of pyrite dissolution in acidic media. Corrosion 47, 55 61.
Lan, Y., Huang, X., Deng, B., 2002. Suppression of pyrite oxidation
by iron 8-hydroxyquinoline. Arch. Environ. Contam. Toxicol.
43, 168 174.
Lowson, R.T., 1982. Aqueous oxidation of pyrite by molecular
oxygen. Chem. Rev. 82, 461 497.
Majima, H., Peters, E., 1966. Oxidation rates of sulfide minerals by

75

aqueous oxidation at elevated temperatures. Trans. Metall. Soc.

AIME 236, 1409 1413.
Mason, L.J., Rice, N.M., 2002. The adaptation of Thiobacillus
ferrooxidans for the treatment of nickel iron sulphide concentrates. Min. Eng. 15, 795 808.
McKibben, M.A., Barnes, H.L., 1986. Oxidation of pyrite in low
temperature acidic solutions: rates laws and surface texture.
Geochim. Cosmochim. Acta 50, 1509 1520.
Mikhlin, Yu., 2000. Reactivity of pyrrhotite surfaces: an electrochemical study. Phys. Chem. Chem. Phys. 2, 5672 5677.
Mikhlin, Yu.L., Tomashevich, Ye.V., Pashkov, G.L., Okotrub, A.V.,
Asonov, I.P., Mazalov, L.N., 1998. Electronic structure of the
non-equilibrium iron-deficient layer of hexagonal pyrrhotite.
Appl. Surf. Sci. 125, 73 84.
Mikhlin, Yu.L., Varnek, V., Asonov, I.P., Tomashevich, Ye.V., Okotrub, A.V., Livshits, A., Selyutin, G., Pashkov, G.L., 2000. Reactivity of pyrrhotite (Fe9S10) surfaces: spectroscopic studies.
Phys. Chem. Chem. Phys. 2, 4393 4398.
Mikhlin, Yu.L., Kuklinskii, A.V., Pashkov, G.L., Asonov, I.P.,
2001. Pyrrhotite electrooxidation in acid solutions. Russ. J.
Electrochem. 37, 1277 1282.
Mikhlin, Yu.L., Kuklinskii, A.V., Pavlenko, N.I., Varnek, V.A., Asonov, I.P., Okotrub, A.V., Selyutin, G.E., Solovyev, L.A., 2002.
Spectroscopic and XRD studies of the air degradation of acidreacted pyrrhotite. Geochim. Cosmochim. Acta 66, 4057 4067.
Mycroft, J.R., Nesbitt, H.W., Pratt, A.R., 1995. X-ray photoelectron
and auger electron spectroscopy of air-oxidized pyrrhotite: distribution of oxidized species with depth. Geochim. Cosmochim.
Acta 59, 721 733.
Nicholson, R.V., Scharer, J.M., 1994. Laboratory studies of pyrrhotite oxidation kinetics. In: Alpers, C.N., Blowes, D.W. (Eds.),
Environmental Geochemistry of Sulfide Oxidation. ACS Symposium Series, vol. 550, pp. 14 30. Washington, DC.
Nicholson, R.V., Gillham, R.W., Reardon, E.J., 1988. Pyrite oxidation in carbonate-buffered solution: I. Experimental kinetics.
Geochim. Cosmochim. Acta 52, 1077 1085.
Nicholson, R.V., Gillham, R.W., Cherry, J.A., Reardon, E.J., 1989.
Reduction of acid generation in mine tailings through the use of
moisture-retaining cover layers as oxygen barriers. Can. Geotech. J. 26, 1 8.
Nordstrom, D.K., Alpers, C.N., 1999. Geochemistry of acid mine
waters. In: Plumlee, G.S., Logston, M.D. (Eds.), The Environmental Geochemistry of Mineral Deposits: Part A. Processes, Methods, and Health Issues. Society of Economic
Geologists, Littleton, CO., Reviews in Economic Geology,
vol. 6A, pp. 133 160.
Nordstrom, D.K., Southam, G., 1997. Geomicrobiology of sulfide
mineral oxidation. Mineralogical Society of America Reviews in
Mineralogy, vol. 35, pp. 361 382.
Orlova, T.A., Stupnikov, V.M., Krestan, A.L., 1989. Mechanism of
oxidative dissolution of sulphides. Zhurnal Prikladnoi Khimii
61, 2172 2177.
Pinka, J., 1991. Bacterial oxidation of pyrite and pyrrhotite. Erzmetall 44, 571 573.
Plysunin, A.M., Mironov, A.G., Belomestrova, N.V., Chernigova,
S.Y., 1990. Laboratory studies on gold-bearing sulfide oxidation. Geokhimiya 1, 51 60.

76

N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 6576

Pofsai, M., Dodonay, I., 1990. Pyrrhotite superstructures: Part I.

Fundamentals structures of the NC (N = 2, 3, 4 and 5) type.
Eur. J. Mineral. 2, 525 528.
Pratt, A.R., Muir, I.J., Nesbitt, H.W., 1994a. X-ray photoelectron
and Auger electron spectroscopic studies of pyrrhotite and
mechanism of air oxidation. Geochim. Cosmochim. Acta 58,
827 841.
Pratt, A.R., Muir, I.J., Nesbitt, H.W., 1994b. Generation of acids
from mine waster: oxidative leaching of pyrrhotite in dilute
H2SO4 solutions at pH 3.0. Geochim. Cosmochim. Acta 58,
5147 5159.
Pratt, A.R., Nesbitt, H.W., Mycroft, J.R., 1996. The increased reactivity of pyrrhotite and magnetite phases in sulphide mine
tailings. J. Geochem. Explor. 56, 1 11.
Smart, R.St.C., Jasieniak, M., Prince, K.E., Skinner, W.M., 2000.
SIMS studies of oxidation mechanisms and polysulfide formation in reacted sulfide surfaces. Min. Eng. 13, 857 870.
Steger, H.F., 1982. Oxidation of sulfide minerals: VII. Effect of
temperature and relative humidity on the oxidation of pyrrhotite.
Chem. Geol. 35, 281 295.
Steger, H.F., Desjardins, L.E., 1977. Oxidation of sulphide minerals: 3. Determination of sulphate and thiosulphate in oxidised
sulphide minerals. Talanta 24, 675 679.
Steger, H.F., Desjardins, L.E., 1978. Oxidation of sulphide minerals: 4. Pyrite, chalcopyrite and pyrrhotite. Chem. Geol. 23,
225 237.
Suzuki, I., 1974. Mechanisms of inorganic oxidation and energy
coupling. Annu. Rev. Microbiol. 28, 85 101.
Suzuki, I., Chan, C.W., Takeuchi, T.L., 1994. Oxidation of inorganic
sulfur compounds by Thiobacilli. In: Alpers, C.N., Blowes, D.W.
(Eds.), Environmental Geochemistry of Sulfide OxidationACS
Symposium Series, vol. 550, pp. 60 67. Washington, DC.
Taylor, L.A., 1970. Low temperature phase relations in the Fe S
system. Carnegie Inst. Wash. Yearb. 69, 259 270.
Taylor, L.A., Mao, H.K., 1971. Observations on the occurrence and

stability of smythite Fe3.25S4. Carnegie Inst. Wash. Yearb. 70,

290 291.
Thomas, J.E., Jones, C.F., Skinner, W.M., Smart, R.St.C., 1998.
The role of surface sulfur species in the inhibition of pyrrhotite
dissolution in acid solutions. Geochim. Cosmochim. Acta 62,
1555 1565.
Thomas, J.E., Smart, R.St.C., Skinner, W.M., 2000. Kinetics factors
for oxidative and non-oxidative dissolution of iron sulfides.
Min. Eng. 10 11, 1149 1159.
Thomas, J.E., Skinner, W.M., Smart, R.St.C., 2001. A mechanism
to explain sudden changes in rates and products for pyrrhotite
dissolution in acid solution. Geochim. Cosmochim. Acta 65,
1 12.
Tuovinen, O.H., Kelly, D.P., 1972. Biology of Thiobacillus ferrooxidans in relation to the microbiological leaching of sulphide
ores. Z. Allg. Mikrobiol. 12, 311 346.
Ueshima, M., Kalin, M., Fortin, D., 2003. Microbial effects of
natural phosphate rock (NPR) addition to mining wastes. Proc.
Sudbury 2003, Mining and the Environment III.
Vaughan, D.J., Craig, J.R., 1978. Mineral Chemistry of Metal Sulphides. Cambridge Univ. Press, Cambridge, UK. 493 pp.
Veglio, F., Beolchini, F., Nardini, A., Toro, L., 2000. Bioleaching of
a pyrrhotite ore by a sulfooxidans strain: kinetic analysis. Chem.
Eng. Sci. 55, 783 795.
Ward, J.C., 1970. The structure and properties of some iron sulphides. Rev. Pure Appl. Chem. 20, 175 206.
Williamson, M., Rimstidt, J.D., 1994. The kinetics and electrochemical rate-determining step of aqueous pyrite oxidation.
Geochim. Cosmochim. Acta 58, 5443 5454.
Yakhontova, L.K., Nesterovich, L.G., Grudev, A.P., 1983. New data
on natural oxidation of pyrrhotite. Vestnik Moskovskogo Universiteta Geologiya 38, 41 44.
Zheng, C.Q., Allen, C.C., Bautista, R.G., 1986. Kinetic study of the
oxidation of pyrite in aqueous ferric sulfate. Ind. Eng. Chem.
Process Des. Dev. 25, 308 317.