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A Review on Pyrrhotite Oxidation

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DOI: 10.1016/j.gexplo.2004.03.003

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 Journal of Geochemical Exploration 84 (2004) 65 – 76
www.elsevier.com/locate/jgeoexp

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 iron precipitation and an increased mobility of trace

metals in drainage waters (Alpers and Blowes, 1994;
After pyrite, pyrrhotite is the most common iron Belzile et al., 1997a; Johnson et al., 2000). This paper
sulphide in nature. A better understanding of the reviews the recent literature on the oxidation of pyr-
reactivity and oxidation of pyrrhotite is needed for rhotite, presents the main factors affecting the process
improved mineral processing and recovery and to and discusses the mechanisms proposed for the oxi-
prevent the production of acid mine drainage (AMD) dation of pyrrhotite. When possible, a comparison is
from iron sulphides in mine waste. AMD is a major made with pyrite.
environmental problem causing acidification, ferric

2. Structure and solubility

Abbreviations: AES, Auger electron spectroscopy; AMD, acid
mine drainage; EPR, electron paramagnetic resonance; FTIR,
Fourier transform infrared; NL, non-equilibrium layer; SEM, Pyrrhotite is found in a wide range of hydrothermal
secondary electron microscopy; SLS, sequential layer sputtering; deposits. It is often associated with mafic intrusive
ToF SIMS, time of flight-secondary electron mass spectrometry; and volcanic rocks and found in massive sulphide
XES, X-ray electron spectrometry; XRD, X-ray diffraction; XPS, deposits associated with pyrite, sphalerite, galena and
X-ray photoelectron spectrometry.
* Corresponding author. Tel.: +1-705-675-1151x2114; fax: +1- chalcopyrite.The name pyrrhotite covers a wide range
705-675-4844. of minerals and synthetic iron – sulphur phases based
E-mail address: [email protected] (N. Belzile). on the NiAs structure (Becker et al., 1997). Pyrrhotite

0375-6742/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.gexplo.2004.03.003
66 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76

shows a non-stoichiometric composition as Fe1
xS, However, Thomas et al. (1998) report that an
where x varies from 0 (FeS) to 0.125 (Fe7S8). The induction period during which a slow release of Fe
non-stoichiometry is due to a system of ordered and little or no production of H2S is observed before
vacancies within the Fe lattice (Vaughan and Craig, the rapid dissolution of pyrrhotite can occur under
1978; Pofsai and Dodonay, 1990; Thomas et al., 2000, anoxic acidic (1 M HClO4) and acid-consuming
2001). The formula can also be expressed as Fen
1Sn conditions. The onset of non-oxidative dissolution
with n z 8 to give structures from Fe7S8 to Fe11S12. and production of H2S (reaction 1) can increase the
The least Fe-deficient forms have hexagonal and rate of oxidative dissolution by three orders of mag-
orthorhombic (FeS) structures whereas those with nitude from 10
8 to 10
5 mol m
2 s
1. The main
greater iron deficiency have monoclinic symmetry factors controlling the length of the induction period
(Arnold, 1967; Janzen et al., 2000; Thomas et al., were identified as the amount of surface oxidation
2001). The Fe– S distance is in the range of 0.237 – products on the mineral surface, the acid strength (no
0.272 nm with an average of 0.250 nm (Vaughan and apparent induction in 0.05 M acid) and the tempera-
Craig, 1978). The iron content ranges between 46.5% ture. The authors present a four-step dissolution
and 46.8% in Fe (on a mole basis) in monoclinic process and use X-ray photoelectron spectroscopy
pyrrhotite and between 47.4% and 48.3% in hexago- (XPS) to study the initially oxidized surface of pyr-
nal forms (Ward, 1970). Monoclinic pyrrhotite is rhotite samples and identify changing sulphur (e.g.
ferromagnetic at room temperature (Becker et al., S2
, S22
, Sn2
) and iron (e.g. Fe(III)S, Fe(II)S,
1997). Pyrrhotite is an important iron sulphide waste Fe(III)O) species at the different stages of dissolution.
mineral in many mining environments. It is often In a more recent paper, Thomas et al. (2001) refine the
found as a gangue mineral in Cu –Ni deposits, asso- model by proposing the trapping of electrons in
ciated with valuable minerals. Massive sulphide metastable chemical states (e.g. polysulfides) during
deposits containing pyrrhotite can be found all around the oxidative dissolution of pyrrhotite before the
the world, more specifically in Russia, China, Aus- production of H2S according to:
tralia and Canada.
Because of its sulphidic nature, pyrrhotite can be

S2

n þ 2ðn
1Þe Z nS
2

ð5Þ
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 It is then proposed that not all electrons are lost to
(3) and (4): an oxidizing agent and that some accumulation of
electrons in a crystal-wide surface space-charge sur-
face region of pyrrhotite may occur particularly at
Fe1
x S þ 2Hþ Z ð1
xÞFe2þ þ H2 S ðfor x ¼ 0Þ temperature of 40 jC and above. The overall mech-
ð1Þ anism is a non-oxidative dissolution with Fe2 + leav-
ing the surface without the release of electrons,
followed by the reduction of polysulphides to sul-
Surface > S2
þ 2Hþ Z H2 S ð2Þ phides according to reaction (5) and then production
of negative charges as HS
.
The true oxidative dissolution of pyrrhotite under
Surface > S2
þ 4H2 O Z SO2
þ
acidic conditions does not involve the production of
4 þ 8H þ 8e ð3Þ
H2S. At low pH, the rate of acidic dissolution will
compete with the oxidative dissolution.
together with: 2O2 þ 4H2 O þ 8e
Z 8OH
or 8Fe3þ
þ 8e
Z 8Fe2þ ð4Þ 3. Oxidation of pyrrhotite and oxidation products

It should be mentioned that Eq. (4) will neutralize acid Oxygen is the ultimate oxidant of sulphide miner-
produced in Eq. (3). als in natural surface waters and the direct oxidant at
 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76 67

pH>4 (Nordstrom and Alpers, 1999). At pH below 4, bor, 1986; Ahonen and Tuovinen, 1994) according to
sulphides are oxidized by ferric iron. In most mine an acid-consuming reaction:
wastes, oxygen is the primary oxidizing agent of
ferrous iron to ferric, which implies that sulphide
oxidation generally occurs only in areas where dis- Fe1
x S þ 1=2ð1
xÞO2 þ 2ð1
xÞHþ Zð1
xÞFe2þ
solved or gaseous oxygen is present (Benner et al., þ S0 þ ð1
xÞH2 O ð10Þ
2000).
As is the case for pyrite (Lowson, 1982; Bierens de
Haan, 1991; Belzile et al., 1997a), oxygen and ferric Fe1
x S þ ð2
2xÞFe3þ Z ð3
3xÞFe2þ þ S0 ð11Þ
iron are generally the two important oxidants for
pyrrhotite. When O2 is the primary oxidant, the
oxidation reaction can proceed as follows (Nicholson Steger and Desjardins (1978) report the predomi-
and Scharer, 1994): nant 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
Fe1
x S þ ð2
ð1=2ÞxÞO2 þ xH2 O Z ð1
xÞFe2þ sulphooxyanions. Using XPS, Buckley and Woods
þ
þ SO2

4 þ 2xH ð6Þ (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.
The oxidation of ferrous iron produces ferric ions This is confirmed by Fe(2p) and Fe(3p) spectra that
that can precipitate out of solution to form ferric indicate the diffusion of iron from the outermost
hydroxide, if pH is not too low. Fe2 + is oxidized layers of the mineral lattices to form the observed
and precipitated as ferric oxyhydroxides, principally oxidation products. Based on an S(2p) spectrum,
ferrihydrite and goethite. Buckley and Woods (1985b) detect the presence of
elemental sulphur together with sulphate and iron-
deficient sulphide when a hydrogen peroxide solution
Fe2þ þ 1=4O2 þ 2Hþ Z Fe3þ þ 1=2H2 O ð7Þ was used as an oxidant. They suggest that the oxida-
tion of pyrrhotite proceeds via a series of iron-defi-
cient sulphides and possibly polysulphides through to
Fe3þ þ 3H2 O Z FeðOHÞ3ðsÞ þ 3Hþ ð8Þ elemental sulphur, these steps being acid-consuming.
Metastable intermediates of sulphate including thio-
sulphate (Steger and Desjardins, 1977; 1978), poly-
Ferric iron can in turn oxidize more pyrrhotite and thionate and S4O62
are also reported (Plysunin et al.,
generates more acidity in the system according to the 1990; Mikhlin et al., 2002), the presence of these
following reaction: intermediates being likely related to the conditions of
oxidation. The suggested mechanisms will be dis-
cussed later.
Fe1
x S þ ð8
2xÞFe3þ þ 4H2 O Z ð9
3xÞFe2þ The biological leaching of pyrrhotite by Thioba-
þ SO2
þ cillus ferrooxidans leads to an acid-consuming step
4 þ 8H ð9Þ
with the formation of elemental sulphur, followed by
an acid-producing phase with the formation of K-
If reaction (7) occurs under acidic conditions, a jarosite [KFe3(SO4)2(OH)6], goethite (a-FeOOH), and
significant quantity of Fe3 + will remain in solution schwertmannite [(Fe8O8(OH)6SO4] as solid products
and maintain a cyclic reaction with reaction (9) where (Bhatti et al., 1993). The evolution of H2S gas could
ferric iron is the oxidant. be noticed during the initial stages of pyrrhotite
There is evidence from field and laboratory studies bioleaching (Ahonen and Tuovinen, 1994), likely
that the oxidation may not be complete and instead indicative of a non-oxidative dissolution process as
generates elemental sulphur (e.g. Steger, 1982; Jam- shown by reaction (1). Elemental sulphur could be
68 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76

detected with pyrrhotite dissolution in the presence or reactive than the hexagonal form (Belzile et al.,
absence of bacteria (Bhatti et al., 1994). The presence unpublished).
of jarosite and iron oxyhydroxides occurring as goe-
thite with traces of ferrihydrite was confirmed in an 3.1.2. Oxygen and moisture
Ontario mine tailings impoundment (Johnson et al., Reaction (1) indicates the required presence of
2000). Wetting –drying treatment of synthetic hexag- water when pyrrhotite is oxidized by oxygen (air).
onal pyrrhotite results in the formation of a-FeOOH The effect of humidity was studied by Steger (1982)
(goethite) and elemental sulphur on the surface of and his results indicate a direct increase of the
mineral grains as confirmed by diffuse reflectance oxidation rate with increasing relative humidity (Table
FTIR (Kalinkin et al., 2000). A more detailed dis- 1). A study using XPS (Knipe et al., 1995) confirm
cussion of the mechanism that could explain the that oxygen is the primary oxidant as no evidence of
oxidation and the occurrence of oxidation products oxidation could be shown when pyrrhotite is exposed
is presented in Section 4. to deoxygenated water. No systematic studies relate
the effect of oxygen content to pyrrhotite oxidation
3.1. Factors affecting oxidation but the oxidation rate is expected to be related to the
concentration or partial pressure of O2. The rate is
As suggested by reactions (6) to (11), the oxidation shown to be proportional to the square root of the O2
of pyrrhotite is affected by several factors that deter- partial pressure for pyrite by McKibben and Barnes
mine the rate of the process. Some of the factors (1986) and Williamson and Rimstidt (1994) in Eqs.
presented below can play a determining role in the (12) and (13), respectively, but different coefficients
nature of the oxidation products. for pyrrhotite are expected:

3.1.1. Crystal structure

Various studies indicate that specific surface val- r ¼ 10
6:77 ½O2 0:5 ð12Þ
ues of various size fractions of museum-grade pyr-
rhotite samples (determined by BET surface area
r ¼ 10
8:19 ½O2 0:5 =½Hþ 0:11 ð13Þ
analysis) are f 2– 10 times higher than those ob-
served for crystalline pyrite and 6– 40 times greater
than the theoretical values based on spherical geom- Rates are expressed in mol of pyrite cm
2 min
1 for
etry (Kwong, 1995; Janzen et al., 2000). This differ- Eq. (12) and in mol m
2 s
1 for Eq. (13).
ence can partially be attributed to surface roughness
and extended fractures into pyrrhotite grains. The 3.1.3. Ferric iron
modification of mineral structures due to the pres- Oxidation rates are significantly increased when
sures and stresses associated with the milling of ore Fe3 + is present (Janzen, 1996; Janzen et al., 2000).
can increase the reactivity of pyrrhotite in mine The oxidation of pyrrhotite by ferric iron differs under
tailings and its susceptibility to oxidation processes oxic and anoxic conditions ranging from zero order
(Pratt et al., 1996). Compared to pyrite, 20 – 100 for anoxic to half order under oxic conditions
times faster oxidation rate of pyrrhotite can also be (Kwong, 1995). In the presence of oxygen, the reac-
related to lower crystal symmetry due to the vacancy tion was first order with respect to Fe3 + concentration.
of iron atoms in the crystal structure (Nicholson and The same author reports both molecular oxygen and
Scharer, 1994). Although it has been suggested that ferric iron to be inefficient in oxidizing sulphide
the crystal structure of pyrrhotite can affect its sulphur to sulphate. A linear effect of ferric iron
oxidation rate (Yakhontova et al., 1983; Orlova et concentration expressed on a log scale could be
al., 1989), the results of the study by Janzen et al. observed on the reaction rates also expressed as log
(2000) report no apparent correlation between pyr- values (Janzen et al., 2000). They suggest an adsorp-
rhotite oxidation by oxygen or ferric iron and crystal tion-type mechanism with a Freundlich- or Langmuir-
structure. More recent results from our research group type isotherm similar to that proposed by Nicholson et
suggest that monoclinic pyrrhotite could be less al. (1988) and Williamson and Rimstidt (1994) or the
 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76 69

Table 1
Oxidation rate and activation energy of pyrrhotite
Samples Oxidant Conditions Rate (mol m
2 s
1) Activation energy Reference
based on the release of (kJ mol
1)
Iron Sulphate
Monoclinic Air pH not given, 1.5  10
8 6.0  10
10 Steger and
(Falconbridge, Ontario) 68% r.h.a, 52 jC Desjardins, 1978b
Monoclinic Air pH not given, Steger, 1982b
(Wards Scientific) 62% r.h.
28 jC 3.9  10
9 6.5  10
10
35 jC 5.0  10
9 7.1  10
10
43 jC 6.3  10
9 7.8  10
10
50 jC 8.9  10
9 8.4  10
10
50 jC
37% r.h. 3.2  10
9 8.0  10
10
50% r.h. 4.4  10
9 9.1  10
10
55% r.h. 5.2  10
9 9.1  10
10
75% r.h. 1.1  10
8 9.0  10
10
Monoclinic and Eletrochemical pH = 1, 50.21 (mono), Orlova et al., 1989
hexagonal 25 – 80 jC 46.23 (hexa),
34.48 ([Fe] = 0.54 M),
22.97 ([Fe] = 0.90 M)
Museum-grade Air flow reactor pH = 2.0 – 6.0 Nicholson and
10 jC 3.1  10
9 58.1 (pH = 2) Scharer, 1994c
22 jC 8.5  10
9 52.4 (pH = 4)
33 jC 3.3  10
8 100.4 (pH = 6)
Museum-grade Fe3 + f 10
3 M 22 jC, pH = 2.0 1.44  10
8 2.05  10
9 same as Nicholson Kwong, 1995
samples from Air flow reactor Abiotic 22 jC and Scharer, 1994
N. America pH = 2.0 2.28  10
9 8.51  10
10
Abiotic 35 jC
pH = 2.0 2.87  10
9
pH = 3.0 3.86  10
9
pH = 4.0 2.51  10
9
Biotic 22 jC 6.74  10
9 6.97  10
9 13.3
Biotic 35 jC
pH = 2.0 8.76  10
9
pH = 4.0 6.91  10
9
Several locations Air flow reactor pH = 2.75; 4  10
9 2  10
10 47.7 – 62.5d, Janzen et al., 2000
in N. America 25 jC 79.1 – 106.0e
(12 samples) Fe3 + pH = 2.75; 3.5  10
8 22.8 – 63.0d
Fe3 + = 0.2 mM
pH = 2.50; 3.1  10
8
Fe3 + = 0.2 mM
pH = 2.50; 6.8  10
8
Fe3 + = 1.0 M
Pyrrhotite ore, Bolivia Chemical and pH = 2.0 f 100 Beolchini and Veglió,
bioleaching 30 jC 1999; Veglió et al., 2000
Fe3 +
0 – 200 mM
a
r.h. for relative humidity.
b
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.
70 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76

dual-site adsorption model of Zheng et al. (1986) for m
3), R the universal gas constant (J mol
1 K
1),
pyrite oxidation. The rate limiting sequence is electron and T the temperature (K).
transfer reactions from ferric iron to an activated
complex of Fe3 +, decomposition to a Fe2 + activated 3.1.4. pH
complex, decomposition to a Fe2 + ion and desorption Very few studies mention the pH effect although it
of the ferrous ion from the surface. Janzen (1996) appears clearly that low pH is required to prevent the
proposes a multi-solute Fritz and Schluender (1974) precipitation of Fe3 + and maintain the activity of the
sorption isotherm to describe the dissolution of pyr- Thiobacilli-type acidophilic bacteria. Nicholson and
rhotite by ferric iron (Eq. (14)): Scharer (1994) report an inconsistent effect of pH
between 2.0 and 6.0 at three different temperatures. A
k1 ½Fe3þ  þ k2 10
apH similar observation is made by Kwong (1995) who
rFeð1
xÞS ¼ does not observe a real trend in the abiotic oxidation
1 þ k1 ½Fe3þ  þ k2 10
apH þ k3 ½Fe2þ 1=2 of pyrrhotite associated to pH and the major pH effect
ð14Þ being on the control of bacterial activity below 4.5. A
study of the pH influence on oxidation of pyrrhotite
where k represents adsorption equilibrium constants by ferric iron also shows inconsistent results and
and a the activity. suggests a competing effect of the proton with Fe3 +
With either mechanism, the apparent rate of solid and possibly Fe2 + for adsorption sites on the surface
dissolution at low Fe3 + concentration and constant (Janzen, 1996) as suggested by Eq. (14) representing a
Fe2 + and pH level is close to half order with respect to model for the reaction rate of oxidation. As it has been
Fe3 +. At an Fe3 + concentration of 0.2 mM, the author mentioned in the introduction, the non-oxidative dis-
reports fractional order of dependence ranging from solution of pyrrhotite can occur at low pH and
0.45 to 0.66 but at a higher initial Fe3 + concentration liberates H2S.
of 10 mM, a zero order dependence on ferric concen-
tration was observed suggesting a more complex rate 3.1.5. Temperature
dependence. A significant increase in the oxidation rate of
Recent studies (Beolchini and Veglió, 1999; Veglió pyrrhotite with increasing temperature is presented
et al., 2000) on the chemical leaching of pyrrhotite ore by Steger (1982); the effect is more obvious when
by ferric iron show that sulphur present in pyrrhotite is the rate is calculated on the basis of iron release
only partially oxidized to elemental sulphur. The (Table 1). The effect of temperature is reported to be
authors also demonstrate that the process kinetics more significant than that of pH with the reaction
are controlled by the chemical reaction with an rate doubling between 25 and 35 jC (Kwong, 1995)
activation energy of 99 kJ mol
1 and they present a or increasing by 3 –5 times for a 20 jC increase with
mathematical model which takes into account both oxygen as oxidant and by 2 –11 times for a 30 jC
direct (bacteria as the primary oxidant) and indirect increase with ferric iron as the oxidant (Janzen,
(bacteria regenerating ferric iron through the oxidation 1996). In both studies, the oxidation process follows
of Fe2 +) mechanisms to describe the kinetics as a Arrhenius behaviour. Abiotic activation energy be-
differential equation of the following type (Beolchini tween 58.1 kJ mol
1 (pH = 2.0) and 100.4 kJ mol
1
and Veglió, 1999; Veglió et al., 2000): (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 oxy-
da
4 99  103 1 1
¼ 1440:0  10 e

gen range from 48 to 63 kJ mol
1 based on iron
dt R T 298
 0:47 release and from 79 to 124 kJ mol
1 based on
27  103 a CFe3þ sulphate release (Janzen, 1996; Janzen et al., 2000).
þ ð1
aÞ2=3 ð15Þ
RT 1000 Similar values are presented by the same authors for
oxidation by ferric iron (Table 1). For comparison,
where a is the pyrrhotite conversion, t the time (days), values of activation energy originating from various
CFe3+ the concentration of ferric iron in solution (mol studies on the order of 50 –80 kJ mol
1 are reported
 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76 71

by Williamson and Rimstidt (1994) and a tempera- peratures ranging from 20 to 55 jC and T. ferroox-
ture dependence following Arrhenius behaviour with idans is the dominant organism at temperatures below
an activation energy of 88 kJ mol
1 is given in 40 jC. Most strains have optimum growth at 25 –35
Nicholson et al. (1988). A study on the oxidation of jC (Tuovinen and Kelly, 1972) with some Canadian
sulphide minerals at high temperature (120 jC) and strains showing optimum strength at 20 jC (Mason
high oxygen pressure (855 kPa) showed that pyrrho- and Rice, 2002). T. ferrooxidans is most active in the
tite could oxidize much more rapidly at pH 2.7 than pH range 1.0– 2.5 deriving its energy from redox
all the other sulphides considered in the study reactions where Fe2 + or reduced sulphur compounds
(Majima and Peters, 1966). The same study indicates serve as electron donor and oxygen as electron
that the oxidation of pyrrhotite is considerably re- acceptor.
duced at neutral and alkaline pH values. Steger The intermediate steps of oxidation (from S2
to
(1982) also reports that an increase in temperature S, SO32
and SO42
including thionates and poly-
can enhance the rate of O2 diffusion and therefore thionates) along with the enzymes responsible for the
the formation of ferric oxide and ferric sulphate individual reactions are presented by Suzuki et al.
products. It can be speculated that the mechanism (1994). Other microorganisms are associated with the
of ferric oxide formation as well as the mineralogical oxidation of sulphides and the generation of acid
composition of these oxides will be different under mine drainage (Gould et al., 1994; Benner et al.,
different temperatures. 2000).

3.1.6. Trace metal content

A trend of decreasing reaction rates with increas- 4. Oxidation mechanisms
ing trace metal content is noticed (Kwong, 1995;
Janzen et al., 2000) but no statistically significant A relatively abundant literature exists on the
effect on the oxidation rate can be established for mechanisms involved during the alteration or oxida-
individual trace metal (Co, Cu, Mn, Ni) or total trace tion of the pyrrhotite surface. Information has been
metal content. More research needs to be done to obtained using X-ray techniques such as electron
clarify the effect of trace metal on the oxidation of (XES), photoelectron (XPS) and Auger electron
pyrrhotite. spectroscopy (AES), X-ray powder diffraction
(XRD) as well as from Mössbauer spectroscopy
3.1.7. Bacteria and secondary electron microscopy (SEM). Although
Thiobacilli can oxidize ferrous to ferric iron and a clear mechanism has yet to be defined, many
inorganic sulphur compounds to sulphuric acid studies agree on a progressive enrichment of the
(Suzuki, 1974; Suzuki et al., 1994). The autotrophic surface with respect to sulphur when pyrrhotite is
bacteria T. ferrooxidans play a catalytic role in the oxidized. Taylor (1970) and Taylor and Mao (1971)
oxidative dissolution of sulphide minerals and the use XRD and optical microscopy to detect the
effect is generally attributed to the increased supply conversion of pyrrhotite into a more S-rich phase
of Fe3 + in solution resulting from bacterial activity named smythite (Fe3.25S4). The electrochemical ox-
(Nordstrom and Southam, 1997). The essential role of idation of pyrrhotite at pH 4.6, 9.2 and 13.0 produ-
bacteria in the oxidation of pyrite and pyrrhotite, ces mainly sulphur and significant quantities of
especially in coal, is well established and the bacterial sulphate in the alkaline solutions and the oxidation
oxidation of pyrrhotite is more effective than that of of pyrrhotite is strongly inhibited under alkaline
pyrite (Pinka, 1991). The biotic oxidation of pyrrho- conditions due to the passivation of the surface by
tite appears to be three times faster than the abiotic ferric oxides (Hamilton and Woods, 1981).
one at pH 2 and 4 (Kwong, 1995). It seems more In an oxidation study of pyrrhotite by air using
difficult to put an exact number on the influence of XPS, Buckley and Woods (1985a) propose the diffu-
bacteria on pyrite oxidation but most studies refer to a sion of iron from the outermost layers of the solid
significant catalytic effect of bacteria (Nordstrom and lattice to form, via an iron(II) oxide, an iron(III)
Southam, 1997). Thiobacilli are most active in tem- hydroxyl-oxide or hydrated oxide at the air/solid
72 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76

interface based on the interpretation of Fe(2p), Fe(3p) phide being converted into a range of compounds
and S(2p) spectra. including sulphite, elemental sulphur, polysulphides
and predominantly disulphides. The authors propose a
sequential layer sputtering (SLS) model with which
4Fe1
x S þ 3yO2 þ 2yH2 O Z 2yFe2 O3 H2 O
AES depth profiles can be calculated. After 50 h of air
ðor 4yFeOOHÞ þ 4Fe1
x
y S oxidation, the model suggests an oxygen-rich and
sulphur-depleted outermost layer of less than 10 Å
with y < (1
x). (1 nm), covering an Fe-deficient, S-rich layer display-
When a H2O2 solution is used, the presence of ing a continuous and gradual decrease in S/Fe from
elemental sulphur and sulphate can be detected using the outer layer to the unaltered inner layers of pyr-
XPS (Buckley and Woods, 1985b). Further studies rhotite with a sequential composition of FeO1.5, FeS2,
using voltammetry and XPS show that the initial Fe2S3 and Fe7S8 (Fig. 1). They propose a mechanism
oxidation products for pyrrhotite and pyrite oxidation where molecular oxygen is adsorbed onto the surface
include metal-deficient sulphides rather than elemen- of pyrrhotite and reduced to O2
and reacts with
tal sulphur (Buckley et al., 1988). The presence of Fe(III) bonded to sulphur to form Fe(III)– O bonds
sulphate species, iron(III) oxide/hydroxides and iron- and Fe(III) – oxyhydroxides. The establishment of
deficient sulphide species including a tetragonal Fe2S3 subsequent ferric oxyhydroxide layers is realized
reaction product is also noticed when ground pyrrho- through the diffusion of Fe from pyrrhotite, which
tite is oxidized by air and water as confirmed by XPS causes a depletion of iron in the zones immediately
and XRD (Jones et al., 1992). An extensive study of below the oxyhydroxide layer and a rise of S/Fe
the mechanism of air oxidation based on XPS and ratios. A similar chemical stratification can also be
AES (Pratt et al., 1994a) identifies for the first time obtained when pyrrhotite is oxidized in sulphuric acid
Fe(III) bonded to sulphur in fresh pyrrhotite where the solutions at pH 3.0 (Pratt et al., 1994b).
latter is present as monosulphide (S2
), along with The model proposed by Pratt et al. (1994a) was
minor amounts of disulphide (S22
) and polysulphide further refined by Mycroft et al. (1995) who confirm
(Sn2
). After 6.5 h of air exposure, Fe(III) is bonded to by angle-resolved XPS that ferric oxyhydroxides
oxygen and most of the remaining Fe(II) remains requiring the presence of water are the only species
bonded to sulphur with some of the initial monosul- 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) 65–76 73

pyrrhotite. The air oxidation of pyrrhotite forces Fe to sludge or compost) that could prevent the diffusion of
diffuse from the interior to the surface and to combine oxygen and also maintain some reducing conditions
with oxygen. This removal of Fe results in an S when organic amendments are used (e.g. Nicholson et
enrichment in the zone below and promotes the al., 1989; Blowes et al., 1994; Belzile et al., 1997a).
formation of disulphide bonds and the reorganization Wet covers are also efficient in reducing the oxidation
of the pyrrhotite structure towards a marcasite (FeS2) of sulphidic wastes because of the lower concentration
structure. This last step requires oxidation of mono- and lower diffusion rate of oxygen in water compared
sulphide ions to disulphides and polysulphides. An to those in air (Belzile et al., 1997a). For preventing
increase in S –S bonding is also observed after the AMD, a technology by which sulphidic minerals are
oxidation of pyrrhotite when using time of flight- coated with ferric phosphate in presence of H2O2 can
secondary ion mass spectrometry ToF-SIMS (Smart be used to form a stable mineral at the surface of
et al., 2000). In another study based on XPS, Knipe et pyrrhotite (Evangelou, 1994; Georgopoulou et al.,
al. (1995) show no evidence of oxidation when 1996). Natural phosphate rock can be used and a
pyrrhotite and pyrite are exposed to deoxygenated biofilm induced by the presence of microbes feeding
water. on phosphate can be formed (Ueshima et al., 2003).
The formation of a non-stoichiometric non-equi-
librium or metastable layer (NL) as a result of Fe1
x S þ 3:5H2 O2 þ ð1
xÞH2 PO

4
preferential release of iron relative to sulphur in the þ
oxidation or dissolution of pyrrhotite has been further ! ð1
xÞFePO4 þ SO2

4 þ ð3
xÞH þ 3H2 O
studied by Russian researchers (Mikhlin, 2000; Mikh- ð17Þ
lin et al., 1998, 2000, 2001, 2002; Kuklinskii et al.,
2001) through a combination of spectroscopic tech- This iron phosphate coating can control the oxi-
niques (XRD, FTIR, XPS, XES, EPR, Mössbauer, dation process of pyrrhotite by stabilizing pH around
etc). These studies provide more information on the 4 and by reducing iron generation. The long-term
composition and reactivity of the metal-deficient resistance of coating agent remains to be tested.
layer and on the mechanisms involved in the complex Pyrrhotite can be stabilized in combination with a
transformations of sulphide species (formation of binder (such as cement), neutralizers, bactericides or
elemental sulphur and sulphoxy compounds) and surfactants to form agglomerates (Amaratunga, 1991;
alterations of the oxidation and spin state of iron Hmidi and Amaratunga, 1998). It is also suspected
(Mikhlin et al., 2002). The oxidation kinetics and that the oxidation of pyrrhotite could be partially or
products depend on the environment humidity and on totally inhibited through surface treatments (coating
the crystalline structure of pyrrhotite. The same agents) similar to those suggested for pyrite (Lalvani
authors suggest that the partially oxidized, disordered et al., 1990, 1991; Belzile et al., 1997b; Lan et al.,
NL may be passive. 2002).

5. Prevention and remediation 6. Concluding remarks

Pyrrhotite is oxidized by O2 and the oxidation The oxidation of pyrrhotite depends on several
products are generally protons, ferrous ions, sulphate biotic and abiotic factors. Most studies confirm the
ions and free sulphur, the oxidation to elemental importance of surficial and adsorptive reactions in the
sulphur being acid-consuming. Several engineered oxidation mechanisms, which could explain why
devices have been proposed for the remediation and crystal structure and surface defects, the presence of
prevention of acid drainage and metal solubilization. catalysts such as bacteria, and to a lesser extent,
One logical approach consists in preventing or limit- temperature can be considered as the most important
ing the contact between pyrrhotite and oxygen (air). It factors in pyrrhotite oxidation studies. Two of these
can be done by applying different types of dry and factors are indirectly controlled by pH as the presence
organic covers (clay, soil, peat, hay, straw, sawdust, of high Fe3 + concentrations and acidophilic bacteria
74 N. Belzile et al. / Journal of Geochemical Exploration 84 (2004) 65–76

both require low pH environments. Taking into ac- and bactericidal additives. In: Smith, R.W., Misra, M. (Eds.),
count the variable nature of pyrrhotite compounds and Proc. Conf. Mineral Bioprocessing, The Minerals, Metals and
Materials Society, pp. 389 – 400.
the various experimental designs, it is not surprising Arnold, R.G., 1967. Range in composition and structure of 82
to find variable results for oxidation rates and prod- natural terrestrial pyrrhotites. Can. Mineral. 9, 31 – 50.
ucts of oxidation. However, the few studies reporting Becker, U., Munz, A.W., Lennie, A.R., Thornton, G., Vaughan, D.J.,
oxidation rate of pyrrhotite seem to agree on values on 1997. The atomic and electronic structure of the (001) surface of
monoclinic pyrrhotite (Fe7S8) as studied using STM, LEED and
the order of 10
8 –10
9 mol m
2 s
1 (Table 1),
quantum mechanical calculations. Surf. Sci. 389, 66 – 87.
generally based on iron release. However, a reliable Belzile, N., Goldsack, D., Maki, S., McDonald, A., 1997a. Acid
rate law similar to those presented for pyrite still needs mine drainage in the Sudbury area, Ontario. In: Eyles, N. (Ed.),
to be defined. The oxidation rates based on sulphate Environmental Geology of Urban Areas. Geological Associa-
production clearly indicate an incomplete oxidation as tion of Canada, St. John’s, Canada, pp. 223 – 226.
elemental sulphur and sulphoxy intermediates are Belzile, N., Maki, S., Chen, Y.-W., Goldsack, D., 1997b. Inhibition
of pyrite oxidation by surface treatment. Sci. Total Environ. 196,
formed and detected. Since oxidation to polysulphides 177 – 186.
and elemental sulphur is acid-consuming, this repre- Benner, S.G., Gould, W.D., Blowes, D.W., 2000. Microbial popu-
sents a major difference to pyrite oxidation which lations associated with the generation and treatment of acid mine
produces sulphate and is always acid producing. In drainage. Chem. Geol. 169, 435 – 448.
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Alteration of mica and feldspar associated with the microbio-
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