Applied Geochemistry 41 (2014) 1–10

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Applied Geochemistry
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Pyrrhotite dissolution in acidic media

Paul Chiritßă a,⇑, J. Donald Rimstidt b
a
University of Craiova, Department of Chemistry, Calea Bucuresßti, 107I, Craiova 200512, Romania
b
Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, United States

a r t i c l e i n f o a b s t r a c t

Article history: Non-oxidative dissolution rates for hexagonal pyrrhotite (Fe1xS) were measured for pH values ranging
Received 2 June 2013 from 0 to 1.3 and temperatures ranging from 25 to 70 °C. These results showed that pyrrhotite dissolution
Accepted 27 November 2013 rate increases with decreasing pH or increasing temperature.
Available online 3 December 2013
The 16 new rate data from this study were combined with 46 data taken from the literature (1 datum
Editorial handling by K.S. Savage
was discarded) to develop a rate equation for non-oxidative pyrrhotite dissolution
65;900 1
rHþ ðmol=m2 sÞ ¼ 1:58  107 e R ð Þ M1:46
T þ
H

This fit spans a range of pH values from 0 to 5 and temperatures from 20 to 90 °C. It is most reliable for
low pH (62.75), where most rate data were measured. This equation reasonably predicts rates for all pyr-
rhotite (Fe1xS) compositions regardless of the value of x, including monoclinic pyrrhotite, hexagonal pyr-
rhotite and troilite (FeS).
In addition, an equation that expresses pyrrhotite rate as a function of temperature and PO2 was devel-
oped using 35 rate data taken from the literature
30;200 1
rO2 ðmol=m2 sÞ ¼ 1:10  102 e R ð Þ P0:352
T
O2

and an equation that expresses the rate of oxidation of pyrrhotite as a function of temperature and Fe(III)
concentration was developed using 48 previously published data
33;600 1
rFeðIIIÞ ðmol=m2 sÞ ¼ 0:516e R ð Þ M0:368
T
FeðIIIÞ

The correlation coefficients for these regression models were relatively low due the narrow range of
experimental conditions, relatively few data, and possible uncontrolled variables. These equations predict
similar rates for all three reactions near pH 2 where many of the experiments were carried out leading to
concerns that some of the experiments may have measured combined rates. For natural conditions, the
rates of the H+ and Fe(III) reactions are predicted to be relatively fast and similar at pH < 3. The O2 reaction
is dominant at higher pH > 3.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Pyrrhotite (Fe1xS) is the second most abundant sulfide mineral
in the Earth’s crust (Belzile et al., 2004; Cai et al., 2005). It is found
disseminated in many igneous and metamorphic rocks and is
highly concentrated in certain ore deposits, such as massive sul-
fides like Ducktown, Tennessee, USA, where it is the dominant sul-
fide phase (Laurence, 1965; Craig and Vokes, 1993).
Pyrrhotite has been a raw material for the production of sulfuric
acid (Lin, 1997; Quinn, 1993) and at times it has been used to man-
ufacture copperas (also known as green vitriol), which is synthetic
melanterite (FeSO47H2O) (Hammarstrom et al., 2005; Johnsson,
⇑ Corresponding author. Tel.: +40 788849387.
E-mail addresses: paulxchirita@gmail.com (P. Chiritßă),
(J.D. Rimstidt).
2002; Karpenko and Norris, 2002). At the present time other
sources for sulfuric acid and copperas are more economic so that
pyrrhotite is considered gangue and is disposed in mine wastes
and in mill tailings where it typically oxidizes to produce acid mine
drainage (AMD). Very fine-grained pyrrhotite can cause problems
inside mines and mills because pyrrhotite oxidation is strongly
exothermic. When the oxidation process is very fast, build up of
heat can lead to spontaneous fires. This process also releases large
amounts of noxious SO2 into the air.
Exposing pyrrhotite to the atmosphere and water leads to a
variety of reactions that eventually convert it to iron oxyhydrox-
ides and sulfuric acid. This process is complicated (Pratt and Nes-
bitt, 1997; Mycroft et al., 1995; Belzile et al., 2004), consisting of
parallel and consecutive elementary reactions, with multiple reac-
jdr02@vt.edu
tion steps. Full comprehension of the nature of the overall process
requires a detailed knowledge of each rate. Because pyrrhotite

0883-2927/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apgeochem.2013.11.013
2 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10
Nomenclature
A preexponential factor in rate equation, mol/m2 s
Ageo specific surface area calculated from grain diameter, m2/g
b initial rate (i.e., rate at t = 0), mol/L s
De effective grain diameter, m
Dmax maximum grain diameter, m
Dmin minimum grain diameter, m
Ea activation energy, J/mol
k rate constant, s1
Mi concentration of species i, mol/L
oxidation reactions produce hydrogen ions, non-oxidative dissolu-
tion reactions, which consume these hydrogen ions, are potentially
important in the overall pyrrhotite weathering process. Pyrrhotites
(po) are iron deficient and their non-oxidative dissolution can pro-
duce zero valence sulfur that appears in the reaction products as
disulfide, polysulfide, or elemental sulfur (Jones et al., 1992; Pratt
et al., 1994a; Mycroft et al., 1995; Thomas et al., 1998; Mikhlin
et al., 2000,2003; Chirita et al., 2008; Chirita, 2009; Harries et al.,
2013).
Fe1x SðpoÞ þ 2ð1  xÞHþ ¼ ð1  xÞFe2þ þ ð1  xÞH2 S þ xS0
H2S released by non-oxidative dissolution appears to play an impor-
tant role in the self-heating and spontaneous combustion of pyr-
rothite. Somot and Finch (2010) detected H2S in self-heating
sulfide masses by its reaction with copper sulfate (so that black
amorphous copper sulfides are formed) or metallic copper (so that
covellite and some digenite and chalcocite are formed).
Spectroscopy studies (Pratt et al., 1994a; Mycroft et al., 1995;
Mikhlin and Tomashevic, 2005; Skinner et al., 2004) suggest that
the charge deficiency due to the missing Fe2+ in the pyrrhotite
structure is accommodated by the presence of Fe3+. That means
that the pyrrhotite chemical formula could be written as
FeIIð13xÞ FeIII
ð2xÞ S and the dissolution reaction in acidic solution based
on this stoichiometry might release both Fe2+ and Fe3+ into
solution.
FeIIð13xÞ FeIII þ 2þ
þ ð2xÞFe3þ
ð2xÞ SðpoÞ þ 2H ¼ H2 S þ ð1  3xÞFe
This reaction does not explain the accumulation of zero and
intermediate valence sulfur associated with the sulfur rich layer.
However, a subsequent reaction between Fe3+ and H2S (Asai
et al., 1990; Ebrahimi et al., 2003; Gholami et al., 2009) could pro-
duce zero valence sulfur.
xH2 S þ ð2xÞFe3þ ¼ ð2xÞFe2þ þ 2xHþ þ xS0
Eqs. (2) and (3) add to give reaction (1) which could produce
zero valence sulfur. Alternatively, oxidation of the pyrrhotite sur-
face by Fe3+ could produce a sulfur rich layer (SRL) composed from
disulfide, polysulfide and elemental sulfur (Pratt et al., 1994a; My-
croft et al., 1995; Chirita and Schlegel, 2012). The SRL can be fur-
ther covered by an outermost layer containing ferric
oxyhydroxides (Pratt et al., 1994b).
This scenario is further complicated by an oxidative leaching
reaction in which Fe3+ reacts with pyrrhotite to form marcasite
(mc) (Fleet, 1978).
2Fe1x S þ 2ð1  2xÞFe3þ ¼ FeS2 ðmcÞ þ 3ð1  2xÞFe2þ
3+ 2
In this reaction the Fe extracts electrons from S in the pyr-
rhotite and the loss of those electrons converts the sulfide anions
to S2
2 . Charge balance is maintained by releasing Fe
2+
into the solu-
tion. This reaction is important under oxidizing conditions where
n reaction order with respect to the concentration of H+
R gas constant, 8.314 J/mol K
q density of mineral, g/cm3
ri rate for reaction involving species i, mol/m2 s
T temperature, K
t time, s
the oxidation and bio-oxidation of Fe2+ produce large amounts of
Fe3+. The FeS2 produced by the oxidative leaching of pyrrhotite,
called ‘‘Zwischenproduckt’’ by Ramdohr (1980), is recognized by
its ‘‘birds eye’’ texture under the ore microscope. Pratt et al.
(1994a) and Mycroft et al. (1995) explain the initial stage of this
process. It is not clear how much of the Zwischenproduckt ob-
served in nature is the result of Fe3+ released by non-oxidative dis-
solution and how much is produced by oxidation reactions.
Non-oxidative dissolution reactions (1) and (2) cannot occur
unless there is a source of hydrogen ions and hydrogen ions are
ð1Þ only produced by oxidation reactions. Pyrrhotite persists for geo-
logic time spans in the subsurface as long as it is isolated from oxy-
gen. However, when it is exhumed and exposed to air a complex
series of oxidation reactions occur (Gunsinger et al., 2006). The
overall process produces goethite and 1 mol of sulfuric acid for
every mole of pyrrhotite oxidized.
Fe1x S þ ðð9  3xÞ=4ÞO2 þ ðð3  xÞ=2ÞH2 O
¼ ð1  xÞFeOOH þ 2Hþ þ SO2
4 ð5Þ
Under the acid conditions found in acid mine drainage, this
reaction requires the participation of Acidithiobacillus ferrooxidans
and related microbes that oxidize the Fe2+ to Fe3+ because the abi-
otic Fe2+ oxidation rate is too slow to be important (Williamson
et al., 2006; Singer and Stumm, 1970). When these microbes are
not active because of low water activity, low oxygen concentra-
tions, or high temperature, pyrrhotite oxidizes to a mixture of fer-
ð2Þ
rous sulfate and sulfuric acid.
Fe1x S þ ðð4  xÞ=2ÞO2 þ xH2 O ¼ ð1  xÞFe2þ þ 2xHþ þ SO2
4 ð6Þ
This reaction seems to be important under confined conditions with
limited water and oxygen availability. Under these conditions pyr-
rothite can convert to melanterite (FeSO47H2O) (Jerz and Rimstidt,
ð3Þ 2003). Regardless of whether reaction (5) or (6) predominates, the
rate of hydrogen ion diffusion ðDHþ ¼ 9:3  109 m2 =sÞ (Li and Greg-
ory, 1974) into granular pyrrhotite masses is about four times faster
than dissolved O2 ðDO2 ¼ 2:2  109 m2 =sÞ (Ferrell and Himmelblau,
1967). This means that some combination of reactions (1)–(4)are
potentially important in the interior of the pyrrhotite granular
masses where they are likely to be the first stage of the pyrrhotite
weathering process. The relative importance of each of these reac-
tions will depend upon its relative rate, which in turn depends upon
solution composition, especially pH, and temperature.
Pyrrhotite dissolution involves multiple reactions and pro-
cesses, which vary in their contribution depending upon the reac-
tion conditions. Deriving rate equations for the key reactions is a
ð4Þ
reasonable first step toward achieving a quantitative understand-
ing of pyrrhotite reactivity. This paper focuses on developing a rate
equation for reaction (1) as a function of pH and temperature.
Some rate data are already available in the literature (Bugajinski
and Gamsjager, 1982; Gleisner, 2005; Janzen et al., 2000; Thomas
 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10
et al., 2000, 2001). These were supplemented with additional mea-
surements and these new data were combined with the literature
data to develop a rate equation that describes pyrrhotite non-oxi-
dative dissolution rates as a function of pH and temperature. This
reaction was chosen for study because of its relative simplicity
compared to the oxidation reactions and because the available data
appear to be reasonably reliable. In order to evaluate the impor-
tance of the non-oxidative reaction, rate equations for the oxida-
tion of pyrrhotite by Fe(III) and by O2 were also developed from
published rates. Side by side comparison of these three rate equa-
tions is a first step toward untangling the complex and competing
processes that occur during pyrrhotite weathering.
2. Experimental procedure
2.1. Materials
A sample of natural pyrrhotite, described by Chirita et al.
(2002), was used in this study. Electron microprobe analysis
(MBT, accelerating voltage 25 kV and beam current 20.13 nA) of
the sample gave 47.03 at.% Fe and 52.80 at.% S, respectively. The
composition (Fe0.89S) is consistent with that of hexagonal pyrrho-
tite. X-ray powder diffraction (XRD) analysis of pyrrhotite sample
with Co radiation generated at 40 kV and 25 mA confirmed the
presence of hexagonal pyrrhotite. No Ni, Cu, or Pb was detected
by microprobe analysis. The Co concentration is 0.04 at.%; the Zn
concentration is 0.01 at.%; and the As concentration is 0.12 at.%.
The pyrrhotite was crushed in an agate mortar and separated
into 80–150 lm, 50–80 lm, and 25–50 lm size fractions by dry
screening. The effective grain diameter (De, m) for each fraction
was calculated from the relationship given by Tester et al. (1994).
Dmax  Dmin
De ¼  
ln DDmax
min
The effective diameter and the density of pyrrhotite (q = 4.88 g/
cm3 calculated from the molar volume and molecular weight given
by Robie and Hemingway (1995)) was used to calculate the geo-
metric surface area for each size fraction (Kimball et al., 2010).
 
6  106 m2
Ageo ¼
De q g Initial dissolution rates were determined by the method de-
Although reaction rates are often expressed in terms of BET sur-
face area, geometric surface area is equally valid and is more con-
venient to measure and to use to model field conditions as
explained in Rimstidt et al. (2012). Each pyrrhotite fraction was
ultrasonically cleaned in ethanol to remove the fine particles
adhering to the larger particles (Descostes et al., 2004). The frac-
tions were stored in an evacuated desiccator until use.
Distilled oxygen-free water and analytical grade purity HCl
were used for the experiments. Oxygen-free water was prepared
by bubbling ultra high purity nitrogen through water for at least
2 h. Metallic tin (99.5%) (Sn(0)) or SnCl22H2O (Sn(II)) was added
to most of the experiments in order to consume any traces of oxy-
gen, which were not removed by nitrogen bubbling along with
Fe3+, which might participate in reactions (3) or (6).
2.2. Dissolution experiments
The dissolution experiments were performed in a sealed 0.5 L
glass reactor under an atmosphere of ultra high purity nitrogen.
For each experiment metallic tin (0.20–0.25 g) and 0.25 g of pyr-
rhotite were added to 250 mL oxygen-free, acidic solutions (0.05
to 1 mol/L HCl), which had been thermally equilibrated to desired
temperature (25–70 °C). Each experiment lasted 4 h. The cover of
3
Fig. 1. Schematic representation of the experimental setup.
the reactor contained holes for a condenser, a gas (nitrogen) inlet,
a thermometer and a central shaft driven by a motor. The reactor
was plugged into a flask containing KOH, which acted as a H2S trap,
through a condenser and a safety flask, half filled with oxygen-free
water. Fig. 1 shows the experimental setup. Before adding the pyr-
rhotite, the reactor was filled with HCl solution and purged for an
hour with high purity nitrogen in order to remove oxygen and CO2.
To prevent secondary precipitation reactions produced by H2S(aq),
the reaction system was continuously purged with high purity
nitrogen. No attempt was made to determine the amount of
evolved H2S because some of it reacted with the dissolved Sn(II)
(Liteanu, 1971; Alexeyev, 1969) released by Sn(0) dissolution. Tin
residues were always found in the reactor at the end of experi-
ments, indicating that reducing conditions were preserved during
dissolution.
ð7Þ
Periodically, a 2 mL solution sample was withdrawn from the
reactor, filtered with 0.22 lm pore size membrane, and analyzed
for total dissolved iron using Atomic Absorption Spectroscopy
(AAS). The detection limit was 5 lmol/L. Iron was used as the reac-
tion progress variable to calculate the dissolution rate.
2.3. Determination of the initial rate
ð8Þ
scribed in Rimstidt and Newcomb (1993). For each experiment,
the concentration of iron released at each sample time was fitted
to a second order polynomial.
MFe ¼ a þ bt þ ct 2 ð9Þ
The derivative of this equation is
dMFe
¼ b þ 2ct ð10Þ
dt
The coefficient b is the rate at t = 0, i.e. the initial rate (mol/L s). The
b coefficients were divided by the surface area of the grains (m2/g)
and multiplied by the volume of solution to find the dissolution rate
in mol/m2 s.
2.4. Deriving the rate equation
In order to develop a rate equation for non-oxidative pyrrhotite
dissolution it is desirable to use a large number of data. In order to
obtain these data, we scrutinized the literature to gather 47 addi-
tional dissolution rates from five previously published papers
(Table 1). These data were combined with the 16 rate data
obtained in this study to develop a rate equation. The data set
spanned the pH range from 0 to 5 and temperatures from 20 to
4 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10

Table 1
Summary of the literature sources for the pyrrhotite dissolution rate data.

Identifier reference Experimental Run material Reactor Rate determination Activation energy, Number of
conditionsa type method kJ/mol data
Bu 82 (Bugajinski and 40–90 °C Monoclinic pyrrhotite BR IRM 59 22
Gamsjager, 1982)
pH 1
Ja00 (Janzen et al., 2000) 25 °C Monoclinic and hexagonal BR IRM – 12
pyrrhotite
pH 2.75
Gl05 (Gleisner, 2005) 25 °C Pyrrhotite from unoxidized CE RDFCE – 3
tailings
pH 4 and 5
Th00 (Thomas et al., 2000) 50 °C Synthetic hexagonal BR RPT – 1
pyrrhotite
pH 1
Th01 (Thomas et al., 2001) 50 °C Polished natural hexagonal BR RPT – 9
pyrrhotite
pH 1

BR = batch reactor; CE = column experiments. IRM = initial rate method; RDFCE = rates derived from column experiments; RPT = rate at particular time.
a
pH and temperature for each experiment can be found in Table S1.

Table 2
Summary of the literature sources for the pyrrhotite oxidative dissolution rate data.

Identifier Experimental Run material Oxidantb Reaction progress Reactor Rate Activation Number
Reference conditionsa variables type determination energy, kJ/mol of data
method
Ja00 (Janzen 25 °C Monoclinic and O2 and Iron and sulfate BR IRM 47.7–62.5c 47
et al., 2000) hexagonal pyrrhotite Fe3+
d
pH 2.50 and 2.75 22.8–63.0
Be04 (Belzile 22–35 °C Museum grade O2 and Iron and sulfate Unreported Unreported – 5
et al., 2004) pyrrhotite Fe3+
pH 2–4
Ca05 (Cai et al., 10–40 °C Monoclinic and O2 and Iron and sulfate BR IRM – 12
2005) hexagonal pyrrhotite Fe3+
pH 2
Ch08 (Chirita 25–45 °C Monoclinic pyrrhotite O2 Iron and H+ BR IRM 41.6 4
et al., 2008)
pH 2.75–3.45
Ro12 (Romano, 4–35 °C Monoclinic pyrrhotite O2 Iron BR IRM 40.26 15
2012)
pH 1.97–3.9

BR = batch reactor; CE = column experiments; IRM = initial rate method.

a
pH and temperature for each experiment can be found in Table S3.
b
Oxidant for each experiment can be found in Table S3.
c
Based on iron release in the presence of dissolved oxygen.
d
Based on iron release in the presence of Fe3+.

90 °C. All rate data are found in Table S1 in the Supplementary
material.
These data were fit to a generalized rate equation that relates
the rate to hydrogen ion molarity, which is hereafter expressed
in terms of pH (assuming that the activity coefficient for H+ is near
one), and temperature.
n
r ¼ kMHþ ¼ ðAeEa =RT ÞM nHþ
This equation was transformed to a linear form by taking the
logarithm of both sides.
Ea 1 mined from each pyrrhotite dissolution experiment. The concen-
log r ¼ log A   npH
2:303R T
Log r was fitted as a function of pH and 1/T using the multiple linear
module in JMP version 9.0.0 statistical software from SAS Institute
Inc., Cary, NC. T-tests were used to determine the significance of
the fitted parameters and residual plots were examined to identify
outliers in the data set. The uncertainty in the fitted parameters is
reported as 1 standard error. Data for the rate of pyrrhotite oxida-
tion by Fe(III) and O2 were also collected from the literature
(Table 2) and fit to linearized rate equations with the form of Eq.
(12) but with MHþ replaced either by MFe(III) or by P O2 .
3. Results
ð11Þ
3.1. Experimental results
Table 3 shows the experimental conditions and the rates deter-
ð12Þ tration of total iron in solution (MFetotal) versus time data for
these experiments are given in the Supplementary material
(Table S2). Representative plots of MFetotal as a function of time
are shown in Fig. 2.
The effect of two different reducing agents on pyrrhotite disso-
lution was investigated at 40 °C, pH 1, 700 rpm and particles diam-
eter in range 50–80 lm. The first experiment (#R02) was
 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10 5

Table 3
Experimental conditions and measured rates. Sn(0) was present in all experiments except R01, which contained no reducing agent, and R02, which was performed with a
0.01 mol/L Sn(II) solution.

Experiment # Grain size, lm Ageo, m2/g Stirring, rpm pH T, °C Rate, mol/m2 s

T01 50–80 0.0205 700 1.00 25 6.23  106
T02 50–80 0.0205 700 1.00 40 8.30  106
T03 50–80 0.0205 700 1.00 50 9.76  106
T04 50–80 0.0205 700 1.00 55 1.21  105
T05 50–80 0.0205 700 1.00 70 1.71  105
F01 80–150 0.0118 700 1.00 40 9.12  106
F02 25–50 0.0363 700 1.00 40 7.37  106
P01 50–80 0.0205 700 1.30 40 5.24  106
P02 50–80 0.0205 700 0.30 40 2.60  105
P03 50–80 0.0205 700 0.10 40 4.00  105
P04 50–80 0.0205 700 0.00 40 5.60  105
S01 50–80 0.0205 400 1.00 40 7.47  106
S02 50–80 0.0205 500 1.00 40 8.30  106
S03 50–80 0.0205 800 1.00 40 8.98  106
R01 50–80 0.0205 700 1.00 40 4.24  106
R02 50–80 0.0205 700 1.00 40 6.85  106

The effect of the temperature on the rate of pyrrhotite dissolu-

tion was determined using several experiments conducted at tem-
peratures from 25 to 70 °C (experiments #T01-T05). As expected
the pyrrhotite dissolution rate increases when reaction tempera-
ture increases from 25 °C to 70 °C.
The initial pH was varied over the range of 0–1.3. This had a
very significant effect on the dissolution rate so that the dissolu-
tion rate increases from 5.24  106 mol/m2 s to 5.60  105 mol/
m2 s as the hydrogen ion concentration increases from 0.05 to
1 mol/L.

3.2. Rate equation for the H+ reaction

Sixteen rate measurements from this study were combined

Fig. 2. Graphs illustrating concentration of total iron (MFetotal) versus time for some
typical experiments.
performed with a 0.01 mol/L Sn(II) solution, the second (#T02) was
conducted in the presence of metallic tin. A control experiment
without the reducing agents (#R01) was carried out under similar
reaction conditions. When the reducing agents were added to the
reactor pyrrhotite dissolution rates were slightly higher,
6.85  106 mol/m2 s for #R02 and 8.30  106 mol/m2 s for
#T02, compared to the control experiment’s (#R01) rate of
4.24  106 mol/m2 s. These results might reflect a minor rate ef-
fect caused by the reduction of ferric iron on pyrrhotite surface
and in its lattice (Hsieh et al., 2002).
In order to investigate the effect of stirring speed on the rate
of pyrrhotite dissolution a series of experiments (#S01-S04 and
#T02) was carried out in the presence of Sn(0) at 40 °C, pH 1,
and stirring rates ranging from 400 to 800 rpm. The rate of pyr-
rhotite dissolution was essentially unaffected by the stirring
speeds greater than 400 rpm. This finding suggests that the
mass transfer in solution is not the rate-determining step. A
stirring speed of 700 rpm was chosen for the rest of the
experiments.
To study the effect of particle size on pyrrhotite dissolution,
three particle size fractions (25–50, 50–80 and 80–150 lm) were
exposed to acidic solutions, in the presence of Sn(0), at 40 °C and
pH 1. It was found that the rate of iron release from pyrrhotite in-
creased as the particle size decreased. According to Mudunkotuwa
et al. (2012), when the diameter of the particles decreases surface
area and the number of kinks, edges and defect site density in-
crease creating hot spots of dissolution.
with 47 rate data taken from the literature (see Table 1 for the data
sources) to create a set of 63 independent measurements. These
data spanned pH values from 0 to 5 and temperatures from 20 to
90 °C. An initial regression model found that one datum fell 5.7
standard deviations away from the best-fit line. This point was re-
moved from the data set and the remaining 62 data were regressed
to produce:
log rHþ ¼ 7:20ð0:59Þ  1:46ð0:04ÞpH
3443ð194Þ
 ðR2
T
¼ 0:98Þ ð13Þ
The numbers in parentheses are one standard error of the
parameter estimate. An example of the method to forward propa-
gate these errors to find the error in log r is given in the Supple-
mental materials for this paper. Fig. 3 shows the distribution of
data and the goodness of the fit. The reaction order with respect
to the concentration of H+ is 1.46 and the activation energy is
65.9 kJ/mol. Because diffusion coefficients have activation energy
values near 15 kJ/mol, this high activation energy is further confir-
mation that the reaction is not limited by ion transport through
solution.
3.3. Rate equations for the oxidation reactions
To highlight the role of non-oxidative dissolution of pyrrhotite
in the oxidative process we collected rate data from literature
sources listed in Table 2. These data were used to develop rate
equations for oxidative dissolution of pyrrhotite by reaction with
O2 or Fe(III). The rate data are listed in Table 3S and details about
6 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10

Fig. 3. (a) Comparison of log r values predicted by Eq. (13) with the measured values (62 data) (R2 = 0.984). (b) Residual plot showing the difference between the predicted
and measured values of log r versus log r (predicted). (c) Leverage plot showing the effect of pH on log r. (d) Leverage plot showing the effect of 1/T on log r. The dashed
horizontal line in each graph is the average of the dependent variable and the dashed lines surrounding the solid regression lines shows the confidence interval for the fit. If
the horizontal line lies entirely within the confidence interval, the regression variable does not significantly affect the dependent variable. The legend refers to the data
sources listed in Table 1.

Fig. 4. (a) Comparison of log r values predicted by Eq. (14) with the measured values (35 data) (R2 = 0.207). (b) Residual plot showing the difference between the predicted
and measured values of log r versus log r (predicted). Leverage plot showing the effect of 1/T on log r. (d) Leverage plot showing the effect of log P O2 on log r. (c) The dashed
horizontal line in each graph is the average of the dependent variable and the dashed lines surrounding the solid regression lines shows the confidence interval for the fit. If
the horizontal line lies entirely within the confidence interval, the regression variable does not significantly affect the dependent variable. The legend refers to the literature
sources listed in Table 2.
 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10 7

Fig. 5. (a) Comparison of log r values predicted by Eq. (15) with the measured values (48 data) (R2 = 0.390). (b) Residual plot showing the difference between the predicted
and measured values of log r versus log r (predicted). (c) Leverage plot showing the effect of log MFe(III) on log r. (d) Leverage plot showing the effect of 1/T on log r. The dashed
horizontal line in each graph is the average of the dependent variable and the dashed lines surrounding the solid regression lines shows the confidence interval for the fit. If
the horizontal line lies entirely within the confidence interval, the regression variable does not significantly affect the dependent variable. The legend refers to the literature
sources listed in Table 2.

the literature sources and experimental conditions are given in Ta-
ble 2. Multiple linear regression of these data showed that pH has
no significant effect on the rates for either reaction so the rates
were fit as functions of temperature and oxidant concentration
or pressure. For the 35 data for O2 oxidation the resulting rate
equation is:
log r O2 ¼  1:96ð2:6Þ þ 0:352ð0:162Þ log P O2
1575ð675Þ
 ðR2 ¼ 0:21Þ
T us to develop an acceptable rate equation.
The reaction order for O2 is 0.35 and the activation energy is
30.1 kJ/mol. For the 48 data for Fe(III) oxidation the rate equation
is:
reactions discussed in the Introduction must be occurring, the sim-
plicity of the rate equation suggests that one of them dominates the
overall dissolution process giving us hope that the reaction process
is relatively simple. The scatter of the rates around the regression
model is much larger than would be expected by forward propaga-
tion of measurement errors but it is typical of mineral dissolution
rate data (see Rimstidt et al. (2012) for a discussion of this problem).
Fortunately, the relatively large number of rate data spanning a
wide range of temperatures and pH offsets this problem allowing
ð14Þ
An interesting comparison can be made between pyrrhotite and
troilite non-oxidative dissolution at 50 °C (Fig. 6). In order to deter-
mine rate of troilite dissolution, the data from Chirita and

log r FeðIIIÞ ¼  0:278ð1:7Þ þ 0:368ð0:089Þ log M FeðIIIÞ

1753ð494Þ
 ðR2 ¼ 0:39Þ ð15Þ
T
The reaction order for Fe(III) is 0.37 and the activation energy is
33.6 kJ/mol. The numbers in parentheses are one standard error of
the parameter estimate. Figs. 4 and 5 show the distribution of data
and the goodness of the fit.

4. Discussion and conclusions

Combining rate data from other laboratories with the new data
from the experiments reported in this paper allowed us to develop a
rate equation that not only spans a wider range of conditions but is
also more reliable than those previously obtained. The R2 value of
0.98 shows that 98% of the variance of the rates is explained by
the hydrogen ion concentration and temperature. This means that
even though the experiments were carried out using different reac-
Fig. 6. Comparison of the non-oxidative dissolution rates of troilite (filled circles)
tor schemes, extents of reaction, solution chemistries and pyrrho- from Chirita and Descostes (2006) with the rates for pyrrhotite predicted by Eq. (13)
tite samples those experimental differences appear to have no (solid line). The dashed lines represent 1 standard error for the value predicted by
significant effect on the rates. Although we know that all of the Eq. (13).
8 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10

Table 4
Initial rates of non-oxidative dissolution of troilite at 50 °C based
on concentration versus time data taken from Chirita and
Descostes (2006).

M Hþ , mol/L Rate, mol/m2 s

0.2 2.95  105
0.1 2.02  105
0.06 7.60  106
0.04 6.20  106

Descostes (2006) were analyzed using the initial rate method. The
rates were derived from the slope of the regression lines for data
collected at the beginning of the experiments (0–1300 s). These
rates are given in Table 4. Fig. 6 shows that at low pH the non-oxi-
dative dissolution rates of pyrrhotite and troilite are essentially the
same. This similarity suggests that Eq. (13) is applicable to all pyr-
rhotite compositions regardless of the composition of pyrrhotite, Fig. 7. Rates of the H+, O2, and Fe(III) reactions predicted by the rate Eqs. (13)–(15)
including monoclinic pyrrhotite, hexagonal pyrrhotite and troilite. for the experimental conditions (25 °C) where the rate data were derived (shaded
areas and H+ line). The shaded rectangles represent ranges of pH and oxidant
This hypothesis is also supported by the small effect of reducing
concentrations for the rate data used to develop Eqs. (14) and (15). The overlap of
agents of Fe3+ on pyrrhotite dissolution rate in acidic media. the rates for these experimental conditions suggests that the rates determined by
Although reducing agents may change the composition of pyrrho- some of the experiments are a composite of two reactions.
tite surface by reducing the Fe3+ present the dissolution rates are
not significantly affected. narrow pH range of 2.0–2.75 (all experimental conditions lie
The regression models for the O2 and Fe(III) oxidation data are within the small rectangle) and the overlap between this range
somewhat disappointing because the correlation coefficients are and the H+ rates strongly suggest that the rates measured near
low, which means that the regression variables explain only 21% pH 2 represent a combination of rates from the H+ and Fe(III) reac-
and 39% of the variance of the rates respectively. This means that tions. Finally, the measured rates for O2 and Fe(III) reactions over-
the random and systematic errors in the data are quite large com- lap and this suggests that in O2 rich atmospheres the measured
pared to the effect of O2 or Fe(III) concentrations on the observed Fe(III) oxidation rates may contain a significant contribution from
rate. None the less, these equations represent the current best esti- O2 oxidation. These possible overlapping rates are a point of con-
mates for the effect of O2 and Fe(III) on pyrrhotite dissolution rates. cern and may help to explain the low correlation coefficients for
This lack of fit may be the result of one or more uncontrolled vari- the O2 and Fe(III) rate equations.
ables such as reactor design, extent of reaction, solution chemistry, These rate equations can also help us to interpret geochemical
pyrrhotite impurities or simply caused by the narrow range of processes. Although there are large uncertainties associated with
experimental conditions and relatively small numbers of data. the O2 and Fe(III) rate equations, they are the most reliable model-
Several previous studies have suggested that the pyrrhotite ing tools currently available and the pattern of rates versus pH
dissolution rates are limited by diffusion of reactants through a shown in Fig. 8 seem to provide a reasonable conceptual model.
SRL (Mycroft et al., 1995; Thomas et al., 1998, 2001, 2003; Mikhlin This pattern is similar to that for pyrite (Williamson et al., 2006),
et al., 2003; Chirita et al., 2008; Chirita, 2009). However, our results which is a useful comparison. In acid mine drainage settings Fe(III)
do not support that idea because the calculated activation energy concentrations tend to be controlled by the solubility of a ferric
values for the Fe(III) and O2 reactions are near 30 kJ/mol, which oxyhydroxide phase. Fig. 8 shows the Fe(III) rates recast in terms
is significantly larger than the 10 to 20 kJ/mol activation energy of Fe(III) concentrations for solutions in equilibrium with goethite
values expected for diffusion processes. More rate data for a wider and ferrihydrite. This figure shows that for pH < 2, Fe(III) oxidation
range of temperature and oxidant concentrations are needed to re- rates and H+ dissolution rates overlap. If the process of self-heating
solve this matter. Even thought the O2 and Fe(III) oxidation rate
equations could be better, the fitted parameters are the most prob-
able values based on existing data. As a result we can make at least
order-of-magnitude comparisons of reaction rates in order to gain
some sense of the relative importance of each of the reactions.
Fig. 7 compares the rates of pyrrhotite dissolution for each of
the three reactions based on the predictions of the rate Eqs.
(13)–(15). This figure allows some tentative observations regard-
ing the rate experiments. The H+ experiments spanned the pH
range from 0 to 5 and were carried out under anoxic conditions.
These results appear to be quite reliable and unaffected by O2
and Fe(III) oxidation reactions. Even though some Fe(III) was re-
leased by the anoxic dissolution process, the good correlation be-
tween the experiments, which trapped that Fe(III) using Sn
reported in this paper, and the others, which did not, suggests that
the Fe(III) did not significantly affect the observed rates. The O2
rate experiments were performed over a pH range of 1.97–3.5
(all experimental conditions lie within the large rectangle). The
rates at the low pH end of this range are similar to the H+ rates Fig. 8. Rates of the H+, O2, and Fe(III) reactions predicted by the rate equations for
and there is a reasonable possibility that those rates are a compos- field conditions (25 °C) where the Fe(III) concentrations tend to be controlled by
ite of both the H+ and O2 reactions. The Fe(III) experiments span a ferric oxyhydroxide phases and the P O2 ¼ 0:21.
 P. Chiritßă, J.D. Rimstidt / Applied Geochemistry 41 (2014) 1–10
that leads to spontaneous combustion involves pore waters that
have this very low pH, rapid oxidation and H2S generation could
co-occur and this would explain the observed H2S in self-heating
ores. Acid mine drainage solutions seldom attain pH < 2.5 because
of the sulfate-bisulfate buffer. Because of this, neither the H+ nor
the Fe(III) reaction is likely to play a significant role in acid mine
drainage production from pyrrhotite rich rocks. This contrasts with
pyrite rich rocks where the Fe(III) oxidation reaction becomes sig-
nificant near pH 4 leading to runaway acid production at lower pH.
The pyrrhotite oxidation process is dominated by the O2 reaction at
pH > 3 and runaway acid production caused by increasing Fe(III)
concentration linked to declining pH can barely begin before the
pH decline is halted by the sulfate–bisulfate buffer. An important
but unanswered question is whether the sulfur rich layer that
has been found in laboratory experiments plays a role in acid mine
drainage settings. Elemental sulfur is seldom reported by field
studies of pyrrhotite oxidation. This observation can be explained
if we consider that sulfur rich layers are related to H+ reaction,
which favors the release of iron relative to sulfur. Since H+ reaction
is not important at pH > 3 (field conditions), it appears unlikely
that layers of elemental sulfur that are thick enough to cause to dif-
fusion-limited reactions are present. Furthermore if significant sul-
fur-rich layers did form they would likely reduce the oxidation rate
to the point that pyrrhotite rich rocks would produce little or no
acid. Also, it is possible that significant sulfur rich layers do not
form because microbes consume the sulfur rich layer as quickly
as it forms. The absence of significant sulfur rich layers for field
conditions means that the rates for experiments with little or no
sulfur coating (likely the experiments at pH > 3), reported in
the literature or acquired in the future studies, could be used to de-
velop better rate equations of pyrrhotite oxidation, applicable to
natural settings.
We hope that this paper will prompt the readers to take a
thoughtful approach toward the design and interpretation of rate
experiments. Rate experiments are often carried out over a very
limited set of conditions and the resulting rate data are seldom
compared to rates reported by other sources to identify reliable
patterns and to remediate inconsistencies. This can lead to over
confidence in narrowly constrained rates and to a tendency to over
interpret them. Compilation and comparison of rate data from
multiple sources gives a fresh and broad view of a reaction pro-
cesses. The widespread use of computers and the availability of
statistical software allow for easy correlation of the data to pro-
duce rate equations that recast the experimental data into a form
that can be used to model geochemical processes.
Acknowledgements
This work was supported by a grant of the Romanian National
Authority for Scientific Research, CNDI–UEFISCDI, Project Number
51/2012. The authors thank Wayne Nesbitt for his helpful sugges-
tions. The comments of K. Savage and two anonymous reviewers
led to significant improvement of the manuscript.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apgeochem.
2013.11.013.
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