Applied Geochemistry 23 (2008) 2724–2734

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Electrochemical study of hydrothermal and sedimentary pyrite dissolution

Ran Liu a, Amy L. Wolfe b, David A. Dzombak a,*, Colin P. Horwitz c, Brian W. Stewart b,
Rosemary C. Capo b
a
Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA 15213, USA
b
Department of Geology and Planetary Science, University of Pittsburgh, Pittsburgh, PA 15260, USA
c
Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA

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

Article history: The dissolution of pyrite is of interest in the formation of acid mine drainage and is a com-
Received 26 January 2008 plex electrochemical process. Being able to measure the rate of dissolution of particular
Accepted 9 June 2008 pyrite samples under particular conditions is important for describing and predicting rates
Available online 22 June 2008
of AMD generation. Electrochemical techniques offer the promise of performing such mea-
Editorial handling by B. Kimball
surements rapidly and with small samples. The oxidation of pyrite and the reduction of
Fe3+ ions and/or O2 half reactions involved in the pyrite dissolution process were investi-
gated by cyclic voltammetry and steady-state voltammetry using three pyrite materials
formed in both sedimentary and hydrothermal environments. For each sample, two kinds
of pyrite working electrodes (conventional constructed compact solid electrode, and car-
bon paste electrode constructed from fine-grained pyrite particles) were employed. Results
indicated that for both the hydrothermal and sedimentary pyrite samples the oxidation
and reduction half reactions involved in dissolution were governed by charge transfer pro-
cesses, suggesting that hydrothermal and sedimentary pyrites obey the same dissolution
mechanism despite their different formation mechanisms. In addition, the results showed
that it is feasible to use a C paste electrode constructed from fine-grained or powdered pyr-
ite to study the pyrite dissolution process electrochemically and to derive approximate rate
expressions from the electrochemical data.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction of pyrite and the reduction of Fe3+ ions or dissolved O2.

These half reactions are the oxidation of pyrite:
Pyrite is the most abundant sulfide mineral in the
earth’s crust and commonly occurs in coals, hydrothermal
FeS2 ðsÞ þ 8H2 O ! Fe2þ þ 2SO2 þ
4 þ 16H þ 14e

ð1Þ
veins, contact metamorphic deposits and sedimentary and the reduction of dissolved O2 or Fe 3+
ions:
rocks. Oxidative dissolution of pyrite has been extensively þ 
studied because this process leads to formation of H2SO4 O2 þ 4H þ 4e ! 2H2 O ð2Þ
and Fe(OH)3(s) in mine drainage waters, a significant envi-
ronmental problem in all mining regions. Fe3þ þ e ! Fe2þ ð3Þ
The dissolution of pyrite is an oxidation–reduction reac- In aqueous systems, these reactions occur simulta-
tion, as the pyrite is oxidized and the Fe3+ ions and/or O2 neously on the surface of the dissolving pyrite at rates that
are reduced at the pyrite surface. The overall reaction can satisfy the condition that the net production of electrons is
be written in terms of the half reactions for the oxidation zero. The relative contribution of O2 or Fe3+ as the electron
acceptor (Eqs. (2) and (3)) in pyrite dissolution depends on
* Corresponding author. Tel.: +1 412 268 2946; fax: +1 412 268 7813. the abundance of each under the particular aqueous
E-mail address: dzombak@cmu.edu (D.A. Dzombak). conditions.

0883-2927/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2008.06.005
 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
The kinetics and the mechanisms of pyrite dissolution
in water have received considerable attention. The rate of
pyrite dissolution has been most often studied by monitor-
ing aqueous phase concentrations of Fe or S species re-
leased under various ambient pressure and temperature
conditions (Lowson, 1982; McKibben and Barnes, 1986;
Moses et al., 1987; Moses and Herman, 1991; Williamson
and Rimstidt, 1994; Paschka and Dzombak, 2004; Liu
et al., 2007). In general, the rate of pyrite oxidation in-
creases with the concentration of Fe3+ ions and dissolved
O2, and decreases with the concentrations of Fe2+and H+
ions in solution. Various empirical expressions for the rate
of pyrite dissolution have been proposed by different
researchers in laboratory studies (Table 1). Electrochemical
measurements, especially cyclic voltammetry and steady-
state voltammetry (Peters and Majima, 1968; Biegler and
Swift, 1979; Meyer, 1979; Ahlberg and Broo, 1997; Lin
and Say, 1999) combined with surface analytical tech-
niques (Turcotte et al., 1993; Kelsall et al., 1999; Chernysh-
ova, 2004), have been employed to study the oxidation of
pyrite. These studies focused on pyrite oxidative dissolu-
tion products under various aqueous conditions: SO2 4 ,
Fe(OH)3(s), Fe2+ and Fe3+ have been identified as the reac-
tion products in aqueous solutions, with elemental S and
other polysulfides as intermediates on the pyrite electrode
surface. The reaction products were found to vary with ap-
plied potentials, electrolyte composition, and solution pH.
Because the three half reactions given in Eqs. (1)–(3)
can occur independently, they can be studied separately
in an electrochemical cell, and rate expressions for the
individual half reactions can be established according to
electrochemical kinetic theory (Bard and Faulkner, 2001).
Holmes and Crundwell (2000) used the electrochemical
approach, which involves studying pyrite oxidation and
reduction half reactions separately, to examine the kinetics
of pyrite oxidation. The rate expressions derived in their
paper were consistent with the reported empirical rate
expressions for oxidative dissolution of pyrite by both
Fe3+ ions and O2. A kinetic expression for the rate of the
overall reaction can be derived from the rate expressions
for the half reactions by setting up the condition that the
net production of electrons is zero at the mixed potential.
Compared to traditional batch reactor dissolution experi-
ments used to provide the basis for empirical rate expres-
Table 1
Empirical rate expressions for the dissolution of pyrite obtained by previous batch reactor studies
Study pH Temperature
Smith and Shumate (1970) 2–10 20–35 °C
Mathews and Robins (1974) 0.1–1.2 30–70 °C
McKibben and Barnes (1986) 2–4 20–40 °C
Williamson and Rimstidt (1994) 0.5–3 25 °C
Ciminelli and Osseo-Asare (1995) 1.5–12.5 50–80 °C
Paschka (2001) 3–6 25 °C
Liu et al. (2007) 3–6 25 °C
Garrels and Thompson (1960) 0–2 33 °C
Mathews and Robins (1972) 0–1.5 30–70 °C
Wiersma and Rimstidt (1984) 2 25–50 °C
Rimstidt and Newcomb (1993) 2 25 °C
2725
sions for pyrite dissolution, the electrochemical technique
has the advantage of requiring less experimental time and
not requiring a large amount of pyrite material.
Most electrochemical studies of pyrite dissolution have
used hydrothermal pyrite samples because they are readily
available and well characterized. However, sedimentary
pyrite is the dominant form of pyrite found near and in
coal-bearing strata and is the major contributor to acid
mine drainage (AMD) generation in coal mining regions.
Moreover, most previous electrochemical studies of pyrite
dissolution have been conducted using solid electrodes,
with the pyrite electrode prepared by cutting a cubic sub-
sample of solid pyrite from a large sample and mounting
the subsample into epoxy resin. Such studies have not been
conducted with sedimentary pyrite, as a sufficiently large
sample typically is not available to make the electrode.
In this study, the oxidation and reduction half reactions
of three pyrite samples from both hydrothermal and sedi-
mentary origins were investigated using the electrochem-
ical approach and the results were used to derive
dissolution rate expressions for each material under the
conditions studied. Sedimentary pyrite usually consists of
fine-grained materials that must be separated from parent
rock. Lazaro et al. (1995) and Almeida and Giannetti
(2002a,b) developed a practical carbon paste electrode by
using powdered mineral material which can reproduce
data obtained from conventional constructed compact
crystal electrodes. In the present study, C paste electrodes
for pyrite powders were fabricated and their performance
compared to that of conventional solid electrodes to exam-
ine the feasibility of the C paste electrode for use in pyrite
dissolution studies. By comparison of these rate expres-
sions to the empirical rate expressions for the same mate-
rial obtained by fitting batch reactor data (Liu et al., 2007),
the feasibility of the electrochemical approach for routine
study of the rate of dissolution of particular pyrite samples
under particular conditions was examined.
2. Experimental materials and methods
2.1. Materials
Three massive pyrite samples (one hydrothermal and
two sedimentary) were used in the present study. The
Rate law: r FeS2 ¼  d½FeS
dt
2
Oxidation by dissolved oxygen Oxidation by ferric iron
0:70 þ 0:10
k½O2  ½H  –
k½O2 0:81 –
0:49
k½O2  k½Fe3þ 0:50 ½Hþ 0:50
k½O2 0:50 ½Hþ 0:11 k½Fe3þ 0:30 ½Fe2þ 0:47 ½Hþ 0:32
k½O2 0:50 ½Hþ 0:1 –
k½O2 0:5 ½Hþ 0:43 k½Fe3þ 0:3 ½Fe2þ 0:6 at pH 3
k½O2 0:5 ½Hþ b (b varied from –
0.21 to 0.14 with different samples used)
– k½Fe3þ f½Fe3þ  þ ½Fe2þ g1:0
– k½Fe3þ f½Fe3þ  þ ½Fe2þ g1:0 ½Hþ 0:44
– k½Fe3þ 
– k½Fe3þ 0:62
2726 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
hydrothermal pyrite, Hy_3 was obtained from Great South
Gems & Minerals, Inc. in Ellenwood, Georgia and it origi-
nated in Logrono, Spain. Sedimentary pyrite sample
Sed_2 was obtained from the Carnegie Mineral Show, Pitts-
burgh, PA (2004) and it originated by fossil replacements in
New Albany Shale in Manon County, Indiana. The other
sedimentary pyrite sample, Sed_coal_1, originated within
coal seams in Westmoreland County, Pennsylvania. X-ray
diffraction analysis confirmed all three samples to be
pyrite, FeS2(s), with no traces of marcasite. However,
Sed_coal_1 contained a small amount of quartz, while
Hy_3 and Sed_2 were relatively pure pyrite.
For the construction of the solid electrodes, each pyrite
sample was cut into about 0.5 cm  0.5 cm  0.5 cm cubic
shape, and one side of the cube was affixed to a bare Cu
wire with Ag conductive glue (Electron Microscopy Sci-
ence, Hatfield, PA). The cube was then mounted in epoxy
resin with one surface exposed.
For the construction of C paste electrodes, pyrite sam-
ples were ground and wet sieved to isolate a desired size
fraction using the method described in Wolfe et al.
(2007). Particles less than 45 lm in diameter were em-
ployed to construct C paste electrodes using a modified
version of the procedure of Almeida and Giannetti
(2002b). A Cu rod with diameter 6.4 mm was immersed
in a mixture of 1.0 g graphite and 1.2 g paraffin wax heated
at 70 °C. Then 20.0 mg of powdered pyrite was placed in a
Teflon cavity with diameter 9.0 mm and the extremity of
the rod covered with the hot mixture was immediately
pressed on the pyrite particles placed in the mould. The re-
sult was a pyrite disk with diameter nearly 7.0 mm, which
covered the graphite surface almost completely. The lateral
parts of the electrode were then covered with Teflon tape
to prevent contact with solution. Schematic representa-
tions of the solid and C paste electrode construction can
be found in Almeida and Giannetti (2002b) and in Appen-
dix C of Liu (2007).
Analytical grade reagents were used in the experiments.
Ultrapure water (P17.2 mX) was used to prepare all the
solutions. Ultra high purity N2 and O2 gases were used.
2.2. Apparatus
Pyrite oxidation and reduction half reactions and kinet-
ics were studied by cyclic voltammetry and steady-state
voltammetry measurements carried out in a standard 3 –
electrode cell. The cell consisted of a pyrite working elec-
trode, a Pt wire counter electrode, and a saturated calomel
reference electrode. The calomel reference electrode was
placed in a Luggin-Haber capillary (Bard and Faulkner,
2001). All potentials were referenced to the saturated calo-
mel electrode (SCE). The three electrodes and the electro-
lyte solution were placed in a glass beaker on a hot/
magnetic-stir plate, which provided constant temperature
control and continuous agitation of the solution. An Eco
Chemie Autolab (Eco Chemie B.V., Utrecht, The Nether-
lands) PGSTAT100 potentiostat/galvanostat system con-
trolled by General Purpose Electrochemical System (GPES)
software (Eco Chemie B.V., Utrecht, The Netherlands) was
used to perform the voltammetry. The electrode potential
and current were recorded with the GPES software.
2.3. Electrochemical experimental procedures
The solid pyrite electrodes were prepared by sequen-
tially polishing with 300, 600 and 1200 grade silicon car-
bide paper. After polishing, the electrodes were rinsed in
deionized water and washed with acetone to remove any
species that may have remained on the electrode surfaces.
The electrodes were then further polished with a 0.5 lm
alumina polishing compound and rinsed with deionized
water before placing in the electrochemical cell. The C
paste electrodes were rinsed with deionized water, ace-
tone, and deionized water again before placement in the
electrochemical cell.
The electrochemical behavior of each electrode was
investigated using cyclic voltammetry. The procedure for
cyclic voltammetry measurements consisted of (1) prepar-
ing a fresh H2SO4 solution at the desired concentration, (2)
placing the solution and the electrodes in the electrochem-
ical cell, (3) de-aerating the solution by passing high purity
N2 gas through the solution for at least 15 min, and (4) car-
rying out the electrochemical measurements. The three
electrodes were connected to the PGSTAT100 potentiostat,
and then the applied potential range was set at desired val-
ues and a scan rate of 20 mV/s was used.
The current–voltage behavior of the individual half
reactions was investigated using steady-state voltamme-
try. The procedures for the steady-state voltammetry mea-
surements were similar to those used for cyclic
voltammetry: after connecting the three electrodes to the
potentiostat, the applied potential was set at the desired
value and held for at least 2 min. This measurement was
increased in small increments over the desired potential
range, and the corresponding current was recorded at
these potentials.
2.4. Microscopy techniques
A scanning electron microscope (PhilipsXL30 FEGSEM,
FEI Company, Hillsboro, Oregon) was used to examine
the surface of pyrite solid electrodes after polishing, as well
as the surface of the pyrite C paste electrodes before and
after oxidation. Fig. 1 shows the SEM micrographs of the
solid electrode and of the C paste electrode containing pyr-
ite particles less than 45 lm for sample Sed_2 before and
after 1 h of oxidative dissolution in 1 mM H2SO4 solution
at 0.8 V vs. SCE. Note that the amount of exposed area of
graphite/paraffin binder in the C paste electrode exposed
is minimal for both before and after the 1 h duration of
the electrochemical dissolution. The surface of the C paste
electrode was almost fully covered by pyrite particles both
before and after the 1 h dissolution. This means the pyrite
particles immobilized on the graphite/paraffin mixture
were mechanically stable and could endure during the
electrochemical measurements.
2.5. Pyrite electrode surface area estimation
SEM micrographs (Fig. 1) showed that the surface of
polished pyrite solid electrode (SE) was relatively smooth
and flat, while the surface of C paste electrode (CPE) was
rough, containing numerous small particles and voids.
 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
Fig. 1. SEM micrographs of SED_2 pyrite electrode surfaces: (a) polished
solid electrode (SE), (b) carbon paste electrode (CPE, with particles
<45 lm) before 1 h oxidation in 1 mM H2SO4 at 0.8 V vs. SCE and (c) CPE
after 1 h oxidation in 1 mM H2SO4 at 0.8 V vs. SCE. Note: all the grains
shown in (b) and (c) are pyrite particles.
Thus, the geometric surface area of a C paste electrode was
larger than that of a solid electrode, although the differ-
ence could not be evaluated quantitatively from an SEM
micrograph. However, the effective surface area of an elec-
trode is considered to be the electrochemically active sur-
face area that affects the kinetics of reactions at electrodes.
In the present study, the effective surface areas of the pyr-
ite solid electrodes and the pyrite C paste electrodes were
estimated by varying cyclic voltammetric scan rates in
2 mM ferrocene carboxylic acid solution and calibrating
against a glass C electrode with known surface area. (Ferro-
cene carboxylic acid exhibits reversible oxidation–reduc-
2727
tion processes on various electrodes in aqueous
phosphate buffer around pH 7. In cyclic voltammograms,
the peak current is directly proportional to an electrode’s
effective surface area. By comparing the peak currents of
a pyrite electrode and a glass C electrode, the effective sur-
face area of a pyrite electrode can be determined. Details
are given in Liu (2007), Appendix E). The results were as
follows: 0.23 cm2 for Hy_3 SE, 0.22 cm2 for Sed_2 SE,
0.11 cm2 for Sed_coal_1 SE, 0.08 cm2 for Hy_3 CPE,
0.22 cm2 for Sed_2 CPE, and 0.21 cm2 for Sed_coal_1 CPE.
These results indicated that the electrochemically active
areas for the C paste electrodes were in the same range
as those of the solid electrodes. These areas were used to
obtain current density values in the cyclic voltammetry
and steady-state voltammetry measurements.
3. Results
3.1. Cyclic voltammetry of solid electrodes and carbon paste
electrodes
Cyclic voltammograms obtained from the solid elec-
trodes and C paste electrodes of pyrite samples Hy_3,
Sed_2, and Sed_coal_1 in 20 mM H2SO4 at 25 °C are shown
in Fig. 2. The results indicate that within the electrode po-
tential region of 0.6 to 0.6 V vs. SCE, both the oxidation
and reduction rates were very slow, with observed cur-
rents less than 1 mA. Above 0.6 V vs. SCE, the oxidation
rates increased. These results are consistent with several
other studies (Flatt and Woods, 1995; Kelsall et al., 1999;
Almeida and Giannetti, 2002a,b; Antonijevic et al., 2005)
and can be explained by the two-step oxidation reaction
model proposed by Lin and Say (1999): the first reaction
step involves the oxidation of pyrite to S starting at
0.36 V vs. SCE (0.6 V vs. SHE (Standard Hydrogen Elec-
trode)), and the second reaction step is the oxidation of
the S to ðSO4 2 starting at 0.66 V vs. SCE (0.9 V vs. SHE).
In the Lin and Say (1999) study, an oxidation peak around
0.61 V to 0.71 V vs. SCE (0.75–0.95 V vs. SHE), depending
on the scan rate, was observed and was interpreted as
the oxidation of the S film on the pyrite surface, a product
of the first reaction step. Although in this study there was
no distinguishable oxidation peak below 0.6 V vs. SCE for S
film formation, due to the high stability of the pyrite sur-
face in this region, the relatively high currents observed
upon increasing the voltage beyond 0.6 V vs. SCE is sugges-
tive of oxidation of a surface film formed at lower poten-
tials (Ahlberg and Broo, 1997). The reduction peak
between 0.4 V and 0.2 V vs. SCE can be interpreted as
two possible reactions: (1) the reduction of S formed elec-
trochemically during the oxidation scan, and (2) the reduc-
tion of FeS2(s) to form FeS(s) and H2S (Hamilton and
Woods, 1981; Giannetti et al., 2001).
Comparing the results for the two kinds of electrodes,
the overall shape of the curve obtained from the C paste
electrode of each pyrite sample was very similar to that ob-
tained from its solid electrode, with little difference in the
values of the oxidation and reduction currents. Comparing
the three pyrite materials, the shape of the voltammo-
grams for Sed_coal_1 differed from those for Hy_3 and
2728 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
Fig. 2. Cyclic voltammograms of solid electrodes (SE) and carbon paste
electrodes (CPE) in 20 mM H2SO4 and 33 mM Na2SO4, pH = 2.02, at 25 °C
and scan rate 20 mV/s: (a) Hy_3, (b) Sed_2, and (c) Sed_coal_1.
Sed_2, which will be discussed later. Despite the differ-
ences noted, in general the results obtained with the C
paste electrode for each pyrite material successfully repro-
duced the electrochemical behavior obtained with the con-
ventional solid electrode constructed with the same
material.
3.2. Oxidation of pyrite
The current–potential characteristics of the oxidation of
pyrite Hy_3, given by Eq. (1), are presented in Fig. 3 as a
function of applied potential under various pH conditions.
These results show that the current increased exponen-
tially with applied potential, with a Tafel slope range of
0.103–0.131 V/decade for the solid electrode and 0.094–
0.184 V/decade for the C paste electrode. The exponential
relationship between the current and the applied potential
indicates the oxidation of pyrite is controlled by chemical
kinetics (Holmes and Crundwell, 2000; Bard and Faulkner,
2001). The apparent transfer coefficient, aFeS2 (which incor-
Fig. 3. The current due to the oxidation of Hy_3 pyrite as a function of
applied potential in 33 mM Na2SO4, at 35 °C, N2 sparged: (a) Hy_3 SE, and
(b) Hy_3 CPE.
porates the number of electrons transferred in reaction (1))
of the oxidation reaction can be calculated from the Tafel
slope via the following relationship:
2:303RT
Tafel slope ¼ ð4Þ
aFeS2 F
where R is the gas constant, T is temperature (308 K in this
study) and F is the Faraday constant. Average aFeS2 values of
0.53 and 0.50 were obtained for the Hy_3 solid electrode
and C paste electrode, respectively. These results are in
agreement with those in the literature (Peters and Majima,
1968; Biegler and Swift, 1979; Meyer, 1979; Holmes and
Crundwell, 2000). The current–potential behaviors of the
oxidation of Sed_2 and Sed_coal_1 solid electrodes and C
paste electrodes exhibited similar characteristics as Hy_3
(additional figures in Liu (2007), Appendix F).
Table 2 summarizes the Tafel slope range and average
aFeS2 for all the electrodes of the three pyrite materials.
The apparent transfer coefficients aFeS2 for Sed_coal_1 solid
and C paste electrodes were smaller than those of Hy_3
and Sed_2.
The effect of pH on the oxidation of the Hy_3 solid elec-
trode and C paste electrode is shown in Fig. 4, in which the
dependence of anodic current density on pH is depicted.
The slopes of the log current density vs. pH plots indicate
that, for the Hy_3 SE, an increasing order of 0.28 to
0.12 with respect to H+ as the applied potential varies
from 0.6 V to 0.7 V vs. SCE. These results are not consistent
with the results of Holmes and Crundwell (2000), in which
 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734 2729

Table 2
Summary of the Tafel slope range and the apparent transfer coefficient values for all the pyrite electrodes

Electrode ID Oxidation of FeS2 Reduction of ferric ions Reduction of dissolved oxygen

Tafel slope (V/decade) Average aFeS2 Tafel slope (V/decade) Average aFe3þ Tafel slope (V/decade) Average aO2
Hy_3 SE 0.103–0.131 0.55 ± 0.05 0.091–0.145 0.52 ± 0.10 0.106–0.153 0.52 ± 0.08
Hy_3 CPE 0.094–0.184 0.52 ± 0.13 0.086–0.142 0.53 ± 0.11 0.082–0.182 0.57 ± 0.17
Sed_2 SE 0.148–0.203 0.35 ± 0.05 0.084–0.185 0.52 ± 0.15 0.101–0.113 0.57 ± 0.03
Sed_2 CPE 0.104–0.174 0.52 ± 0.10 0.094–0.166 0.52 ± 0.11 0.132–0.147 0.44 ± 0.02
Sed_coal_1 SE 0.257–0.295 0.23 ± 0.01 0.080–0.212 0.49 ± 0.20 0.120–0.136 0.48 ± 0.03
Sed_coal_1 CPE 0.246–0.268 0.24 ± 0.01 0.092–0.171 0.52 ± 0.17 0.101–0.142 0.51 ± 0.07

where kFeS2 is the rate constant. The effect of pH on the oxi-

dation (parameter a) of all pyrite samples is summarized in
Table 3. The Hy_3 C paste electrode, Sed_2 solid electrode
and C paste electrodes exhibited characteristics similar to
those of the Hy_3 solid electrode: as the applied potential
increased, the oxidation half-reaction order with respect to
pH decreased. However, the effect of pH on oxidation of
the C paste electrodes was about three orders of magnitude
higher than on the solid electrodes for Hy_3 and Sed_2. For
Sed_coal_1, both the solid and C paste electrodes exhibited
a weak pH effect on their oxidation, and the pH depen-
dence did not vary much with the applied potential. XRD
analysis indicated that Sed_coal_1 material contained a
small amount of quartz, and this impurity could affect its
oxidation reaction rate, thus resulting in the discrepancy
in the observations.

3.3. The reduction of ferric ions on pyrite

The observed current–potential relationships for the

Fig. 4. The effect pH on the oxidation of (a) Hy_3 SE and (b) Hy_3 CPE
pyrite at different applied potentials in 33 mM Na2SO4, at 35 °C, N2
sparged.
a constant dependence of 0.50 on H+ across the similar
applied potential range was obtained. The pH-dependent
variation indicated that the observed current densities
(as well as the pyrite oxidation rates) were more sensitive
to the applied potentials for lower pH solutions compared
to higher pH solutions. As shown in Fig. 3 for the pH 1.27
solution, the current densities increased about 3–4 orders
of magnitude as applied potential increased from 0.4 V to
0.7 V vs. SCE; while in the pH 3.64 solution, the current
density only increased about 1–2 orders of magnitude over
the same potential range.
The results presented in Figs. 3 and 4 indicate that the
current density due to oxidation of pyrite, iFeS2 , is depen-
dent on the applied potential, E, and the concentration of
H+ and is given by the general current–potential
relationship
 
ð1  aFeS2 ÞFE
iFeS2 ¼ kFeS2 ½Hþ a exp
RT
reduction of Fe3+ ions on Sed_coal_1, given by Eq. (3), are
shown in Fig. 5 as a function of applied potential and at
various Fe3+ concentrations. In order to avoid the contribu-
tion of the oxidative dissolution of pyrite to the total cur-
rent, the reduction of Fe3+ ions was studied at potentials
that were always more negative than 0.55 V vs. SCE. At
low values of the cathodic current, the current was expo-
nentially dependent on the applied potential, indicating
that the reaction was controlled by kinetics. As the catho-
dic current increased, the current became independent of
the applied potential (especially at low Fe3+ concentra-
tions), indicating that the reaction becomes mass transfer
controlled, which is in agreement with the results of
Holmes and Crundwell (2000). The Tafel slopes for the
reduction of Fe3+ ions on Sed_coal_1 ranged between
0.080–0.212 V/decade for the solid electrode and 0.092–
0.171 V/decade for the C paste electrode. From the Tafel
slopes for each electrode, as shown in Eq. (4), the overall
average aFe3þ values of 0.49 and 0.52 were obtained for so-
lid electrode and C paste electrode, respectively.
The current–potential characteristics of the reduction of
Fe3+ ions on the other two materials, Hy_3 and Sed_2, were
similar to those of Sed_coal_1 (data provided in Liu, 2007,
Appendix F). The Tafel slopes and the average values of
aFe3þ for each electrode are summarized in Table 2. All
the values of the apparent transfer coefficient aFe3þ were
close to 0.5, consistent with the results of Holmes and
Crundwell (2000). As the reduction of Fe3+ ions is the reaction
ð5Þ
of aqueous solution species (Fe3+) on the pyrite electrode
2730 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734

Table 3
Summary of the effect of pH on the oxidation of pyrite (parameter a in Eq. (5)) for both the solid and carbon paste electrodes at different potentials

Applied potential Parameter a

Hy_3 SE Hy_3 CPE Sed_2 SE Sed_2 CPE Sed_coal_1 SE Sed_coal_1 CPE
0.70 V vs. SCE 0.12 0.36 0.13 0.27 0.21 0.17
0.65 V vs. SCE 0.23 0.55 0.16 0.48 0.20 0.17
0.60 V vs. SCE 0.28 0.70 0.21 0.64 0.18 0.16
Average 0.21 ± 0.08 0.54 ± 0.17 0.17 ± 0.04 0.46 ± 0.19 0.20 ± 0.02 0.17 ± 0.01

Fig. 5. The reduction of ferric ions on Sed_coal_1 pyrite as a function of

applied potential at various concentrations of ferric ions in 200 mM
Fig. 6. The reduction of dissolved oxygen on Sed_2 pyrite as a function of
H2SO4 and 100 mM FeSO4, at 35 °C, N2 sparged, 250 rpm: (a) Sed_coal_1
applied potential at various concentrations of dissolved oxygen in
SE, and (b) Sed_coal_1 CPE.
200 mM H2SO4, at 35 °C: (a) Sed_2 SE, and (b) Sed_2 CPE.

surface, it appears that the different pyrite materials and
the different kinds of electrode preparations did not affect
electrochemical reduction behavior. Similar ranges of Tafel
slopes and similar transfer coefficients were obtained for
all the pyrite electrodes.
3.4. The reduction of dissolved oxygen on pyrite
The current–potential characteristics of the reduction of
dissolved O2 on Sed_2 pyrite, given by Eq. (2), are pre-
sented in Fig. 6 as a function of applied potential under
various concentrations of dissolved O2. Results indicate
that the reduction reaction is controlled by reaction kinetic
considerations at low cathodic currents, and by mass
transfer processes at high cathodic currents on both the so-
lid and C paste electrodes. In the region of potentials in
which pyrite dissolution occurs, the reduction of dissolved
O2 at the pyrite electrode is described by kinetically con-
trolled reactions (Holmes and Crundwell, 2000). The Tafel
slope for the reduction of dissolved O2 on Sed_2 ranged be-
tween 0.101 and 0.113 V/decade for the solid electrode and
between 0.132 and 0.147 V/decade for the C paste elec-
trode under the dissolved O2 concentration range of 3.5–
13.5 mg/L. An average value of 0.57 for the apparent trans-
fer coefficient, aO2 of the dissolved O2 reduction on the so-
lid electrode was obtained from the Tafel slopes using Eq.
(4), and a value of 0.44 for the C paste electrode.
The current–potential characteristics of the reduction of
dissolved oxygen on the other two materials, Hy_3 and
Sed_coal_1, were similar to those of Sed_2 (data provided
in Liu, 2007, Appendix F). The Tafel slope range and the
average values of aO2 for each electrode are summarized
in Table 2. All the values of the apparent transfer coeffi-
cient aO2 were close to 0.5, consistent with the results of
Holmes and Crundwell (2000). These results showed that
the different pyrite materials and the different kinds of
electrode preparations did not affect the electrochemical
reduction behavior of dissolved O2 in water.
The reduction of dissolved O2 on Sed_coal_1 C paste
electrode was weakly dependent on the pH, as shown in
 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734 2731

Sed_2 have n-type semiconductor characteristics (Morim-

Fig. 7. The effect of pH on the reduction of dissolved oxygen on
Sed_coal_1 (CPE) pyrite electrode at various applied potentials in
33 mM Na2SO4 and 9.5 mg/L dissolved oxygen at 35 °C.
Fig. 7. The current density due to the reduction of dissolved
O2 on the pyrite surface, iO2 , is described by
 
aO2 FE
iO2 ¼ kO2 ½O2 ½Hþ c exp
RT
where kO2 is the rate constant. The order of the reduction
half reaction with respect to H+ (parameter c) was from
0.66 to 0.69 as the applied potential increased from 0.00
to 0.15 V vs. SCE. The summary of the effect of pH on the
reduction of dissolved O2 on all the electrodes at 9.5 mg/
L dissolved O2 concentration is presented in Table 4.
4. Discussion
4.1. Electrochemical behavior of the hydrothermal and
sedimentary pyrite samples
As shown in Fig. 2, the shapes of cyclic voltammograms
obtained for Hy_3 and Sed_2 pyrite materials were the
same in H2SO4 solution under the applied potential range
of 0.6 to 0.8 V vs. SCE. Only one reduction peak between
0.4 V and 0.2 V vs. SCE appeared, and it can be assigned
as the reduction of S or the decomposition of pyrite yield-
ing H2S (Giannetti et al., 2001). Sed_coal_1 exhibited a
slightly different electrochemical behavior as a second
reduction peak occurred around 0.0 V vs. SCE. This peak
could be due to the reduction of Fe(III) hydroxide, pro-
duced during polishing/grinding (Giannetti et al., 2001).
Previous studies (Liu et al., 2007) on the trace element con-
tent in these pyrite samples have shown that Sed_coal_1
has p-type semiconductor characteristics, while Hy_3 and
oto, 1992). Because the carriers of electric currents are
different for different types of semiconductors (electrons
for n-type and positively charged holes for p-type), the
semiconducting properties of a pyrite sample may affect
the pyrite oxidation pathways and are likely responsible
for the different electrochemical behaviors between
Sed_coal_1 and the other two pyrite materials.
Previous batch dissolution studies (Liu et al., 2007) on
these pyrite samples showed that the dissolution rate of
Sed_coal_1 was an order of magnitude higher than those
of Hy_3 and Sed_2. Although the three materials were all
obtained as massive pyrite samples, Sed_coal_1 was ac-
quired from within a coal seam and found to have a much
larger specific surface area and a darker color than the
other two pyrites. The presence of quartz in the Sed_coal_1
pyrite may help produce more surface defects in the disso-
lution process, thus resulting in a faster dissolution rate.
The larger specific surface area and presence of impurities
in Sed_coal_1 pyrite may also have contributed to produce
more Fe(III) hydroxide production during the in-reactor
ð6Þ electrode preparation period, resulting in a noticeable
Fe(III) hydroxide reduction peak on Sed_coal_1 cyclic
voltammograms.
The differences between Sed_coal_1 and the other two
pyrite samples were also reflected in their oxidation pro-
cesses. Sed_coal_1 exhibited larger Tafel slopes and smal-
ler values of average apparent transfer coefficient, aFeS2 .
For a redox elementary reaction, the formal charge transfer
coefficient a is the basic electrochemical parameter char-
acterizing the mechanism of an electrode reaction or elec-
tron-transfer step and typically is found to have a value of
0.5 (Bard and Faulkner, 2001). The formal transfer coeffi-
cient a provides insight into the way the transition state
is influenced by the applied potential. A value of 0.5 means
that the transition state behaves midway between the
reactants and products in response to applied potential.
The formal transfer coefficient is related to properties of
the electrode (Rice et al., 1983), reaction mechanism
(Zakharchuk et al., 2000), and phase composition and crys-
tallinity of the sample (Grygar, 1997; Domenech-Carbo
et al., 2001).
Pyrite oxidation involves a complex series of elemen-
tary reactions. Basolo and Pearson (1967) pointed out that
elementary steps of redox reactions almost always involve
the transfer of only one electron at a time, so that the oxi-
dation of pyrite must require up to seven elementary steps,
depending on how elementary steps are defined (Rimstidt
and Vaughan, 2003). In this study, non-elementary pyrite

Table 4
Summary of the effect of pH on the reduction of dissolved oxygen (parameter c in Eq. (6)) on both solid and carbon paste pyrite electrodes at different potentials
with 9.5 mg/L dissolved oxygen

Applied potential Parameter c

Hy_3 SE Hy_3 CPE Sed_2 SE Sed_2 CPE Sed_coal_1 SE Sed_coal_1 CPE
0.15 V vs. SCE – 0.53 0.20 0.65 0.33 0.69
0.10 V vs. SCE 0.44 0.40 0.20 0.27 0.23 0.67
0.05 V vs. SCE 0.08 0.35 0.22 0.27 0.18 0.65
0.00 V vs. SCE 0.15 0.29 0.21 0.10 0.12 0.66
Average 0.22 ± 0.19 0.39 ± 0.10 0.21 ± 0.01 0.32 ± 0.23 0.22 ± 0.09 0.67 ± 0.02
2732 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
oxidation and reduction (Eqs. (1)–(3)) were considered,
and the apparent transfer coefficient obtained thus incor-
porated the numbers of the corresponding electrons trans-
ferred in each reaction. There appears to be an inverse
relationship between average apparent transfer coefficient,
aFeS2 of the solid electrode obtained in electrochemical
experiments and the dissolution rate observed in batch
reaction dissolution experiments (Liu et al., 2007): as the
dissolution rate increases (Hy_3<Sed_2<Sed_coal_1), the
average apparent transfer coefficient, aFeS2 , decreases
(Table 2).
4.2. Electrolytes and electrode construction methods
As shown in Fig. 2, the same shape of cyclic voltammo-
grams was obtained from the solid and C paste electrodes
for each pyrite sample in 20 mM H2SO4 solution, as well as
in the other concentrations of H2SO4: 0.5–50 mM (data
provided in Liu, 2007, Appendix D). These results indicate
that C paste electrodes can successfully reproduce data ob-
tained from conventional solid electrodes under the H2SO4
solution conditions used in this study. In similar experi-
ments conducted in 10 mM HCl solution, however, the cyc-
lic voltammograms obtained from the C paste electrode
failed to reproduce the data obtained from the solid elec-
trode (details given in Liu, 2007, Appendix D). Almeida
and Giannetti (2002b) reported the same shape for cyclic
voltammograms measured with C paste electrode and so-
lid electrode for pyrite, pyrrhotite and arsenopyrite in pH
4.5 acetic acid/acetate buffer solution. Thus, electrolyte
composition affects the electrochemical behavior of pyrite
C paste and solid electrodes. When using a C paste pyrite
electrode to reproduce the data of a conventional solid elec-
trode, pre-testing is needed to choose a proper electrolyte.
As described previously, the oxidation of pyrite on both
the solid and C paste electrodes of the three pyrite samples
exhibited Tafel behavior for the applied potential range of
0.4–0.7 V vs. SCE, indicating the reaction was controlled by
chemical kinetics. Because the oxidation of pyrite involves
decomposition of the working pyrite electrode itself, the
changing surface properties of the electrodes during the
oxidation process may affect the kinetics of the reaction.
Microscopic examination by Meyer (1979) revealed that
during pyrite oxidation, portions of the solid electrode sur-
face are rapidly attacked to form pits and crevices while
the rest of the surface is comparatively unmarred. SEM
studies by McKibben and Barnes (1986) on pyrite particles
showed that chemical oxidant attack occurs preferentially
at specific sites of high excess surface energy, such as de-
fects, cleavage and fracture traces. According to Eq. (1),
H2O molecules in bulk solution need to be adsorbed on
the electrode surface for electron transfer to take place
on the electrode surface. It is possible that H2O adsorption
and the subsequent electron transfer also occur preferen-
tially at those specific sites with high excess surface en-
ergy. Surface analysis has shown that H2O molecules
bind specifically to defect sites on the FeS2(100) surface
(Strongin et al., 1997). The C paste electrode has a rough
surface, suggesting more specific sites, perhaps with high
excess surface energy compared to the polished solid elec-
trode (Fig. 1). The rough surface will also affect the mass
transfer of the oxidation products (Fe2+ and H+) from the
electrode/solution interface to the bulk solution. Therefore,
the surface roughness might be responsible for the stron-
ger pH effect (parameter a in Eq. (5)) on the oxidation of
C paste electrode than on the solid electrode, as observed
for Hy_3 and Sed_2 (Table 3). For Sed_coal_1, the presence
of non-conductive quartz as an impurity might affect the
surface morphology and the distribution of the electric
field across the surfaces of its solid electrode as the decom-
position continues, rendering its performance comparable
to the C paste electrode and resulting in a pH effect on
the oxidation reaction similar to that observed for the C
paste electrode (Table 3).
The reduction of dissolved O2 or Fe3+ ions on the pyrite
electrode can involve multiple steps, and the resulting cur-
rent can be governed by the rate of several processes (Bard
and Faulkner, 2001) such as mass transfer of molecular O2
from the bulk solution to the electrode surface, adsorption
of molecular O2 on the electrode surface, electron transfer
at the electrode surface, and desorption of the reduction
products from the electrode surface. All of these processes
will be affected by the pH at the electrode/solution inter-
face as well as by the bulk solution composition. However,
the surface properties of the pyrite electrodes will remain
unchanged during the reduction processes because the
reactants are only from the bulk solution, not from the
electrodes. Thus the pH effects on the reduction of dis-
solved O2 for the three solid electrodes are almost the same
(Table 4). The rougher surface of the C paste electrodes,
however, will influence the electric field distribution on
the electrodes, thus yielding a larger pH effect on the dis-
solved O2 reduction (Table 4).
4.3. Development of rate expressions for the dissolution of
pyrite
The rate of oxidation of pyrite is often obtained from
batch reaction experiments by monitoring the aqueous
dissolution products with time and fitting the experimen-
tal data to a rate law. Different empirical rate expressions
have been proposed for pyrite oxidation by dissolved O2
(Smith and Shumate, 1970; Williamson and Rimstidt,
1994; Ciminelli and Osseo-Asare, 1995), and the rate of
pyrite dissolution is found to be weakly dependent on
the solution pH (Table 1).
Pyrite dissolution is an electrochemical process and oc-
curs as a combination of the oxidation of pyrite and the
reduction of Fe3+ ions or O2 on the surface as given by
Eqs. (1)–(3). These three half reactions take place simulta-
neously on the entire surface of the dissolving pyrite at
rates that satisfy the condition that the net production of
electrons is zero. The potential at which this condition is
met is called the mixed potential. Holmes and Crundwell
(2000) proposed an electrochemical approach to develop
a rate expression for the dissolution of pyrite based on
mixed potential theory (Bard and Faulkner, 2001). With
use of mixed potential theory, the kinetic expression for
the rate of the overall pyrite dissolution reaction can be
derived from the rate expressions for the individual half
reactions using the condition that the net production of
electrons is zero at the mixed potential.
 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734
Table 5
Derived rate expression parameter b in Eq. (7) from the electrochemical approach vs. b obtained from empirical data in batch dissolution experiments
Parameter b, the dependence of pyrite dissolution rate on H+
b values from the present study
b values from batch dissolution experiments (Liu et al., 2007)
In this study, the rate expressions for the three pyrite
materials were developed following the approach of
Holmes and Crundwell (2000) given by
r FeS2 ¼ k½Hþ b ½O2 0:5
where k is the overall dissolution rate constant and b is the
overall pyrite dissolution rate dependence on solution pH.
The parameter b can be calculated from the parameters a
and c (b = [a + c]/2) in Tables 3 and 4 (detailed derivation
given in Holmes and Crundwell, 2000) and is summarized
in Table 5 for all the materials and electrode types. The val-
ues of parameter b for the solid electrodes of the three pyr-
ites are almost equal to zero, as a and c values for the solid
electrodes don’t vary much from each other. This result is
in agreement with those findings by Mathews and Robins
(1974), Bailey and Peters (1976) and McKibben and Barnes
(1986), where the pyrite dissolution rate is independent of
the pH. The b values for Hy_3 and Sed_2 C paste electrodes
are almost equal to each other, which is close to the find-
ings of Williamson and Rimstidt (1994), where b is equal
to 0.11. Sed_coal_1 C paste electrode exhibited a some-
what higher b value compared to all the other electrodes,
probably because of the presence of quartz impurity as dis-
cussed previously.
Table 5 also presents the b values for the three pyrites
obtained from the conventional batch reactor dissolution
study at pH 3 and 6 (Liu et al., 2007). The b values derived
from Hy_3 C paste electrode data and Sed_coal_1 solid
electrode data are closer to the values obtained from batch
reactor dissolution results. For Sed_2 material, neither the
solid electrode nor C paste electrode gave b values close to
those from batch reactor dissolution data. As the electro-
chemical studies were conducted at 35 °C and the batch
reactor studies were conducted at 25 °C, temperature
could be a cause of the differences. Considering the range
of b values (0.08 to 0.25) obtained from all the electrodes
in this study, a conclusion still can be made that pyrite dis-
solution is weakly dependent on the pH, which is consis-
tent with the results obtained from investigating eight
different pyrite materials from different geological loca-
tions (Liu et al., 2007).
The results obtained in this study show that, in general,
the electrochemical approach proposed by Holmes and
Crundwell (2000) can give an approximate description of
the relationship between pyrite dissolution rate and the
pH, no matter which kind of electrode preparation method
is used. Electrochemical experiments can be conducted
with electrodes made using different types of pyrite to ob-
tain kinetic information for the half reactions involved in
pyrite dissolution.
A disadvantage of the electrochemical approach for
deriving the rate laws for pyrite dissolution is that the
reaction rate constant kFeS2 in Eq. (5), kO2 in Eq. (6), and
2733
Hy_3 SE Hy_3 CPE Sed_2 SE Sed_2 CPE Sed_coal_1 SE Sed_coal_1 CPE
0.01 ± 0.10 0.08 ± 0.10 0.02 ± 0.02 0.07 ± 0.15 0.01 ± 0.05 0.25 ± 0.01
0.102 ± 0.028 +0.144 ± 0.013 0.002 ± 0.002
the overall dissolution rate constant in Eq. (7) cannot be
obtained directly from steady-state voltammetry studies.
Therefore, the actual dissolution rate of each pyrite sample
cannot be obtained and compared with each other as can
ð7Þ be done with batch reactor results. In a companion study
(Liu, 2007), controlled pyrite dissolution was performed
by fixing the applied potential on the pyrite electrodes,
and measuring the pyrite dissolution rate for each sample
by monitoring the concentrations of pyrite dissolution
products in solution.
5. Conclusions
This study investigated the utility and accuracy of the
electrochemical techniques of cyclic voltammetry and
steady-state voltammetry for rapidly measuring the disso-
lution rates of hydrothermal and sedimentary pyrites un-
der particular solution conditions. The electrochemical
behaviors and the kinetics of the half reactions involved
in the oxidation of three pyrite samples of different geolog-
ical origins were evaluated.
For the three hydrothermal and sedimentary pyrite
samples studied here, in the potential region below
0.60 V vs. SCE, pyrite dissolution was insignificant, perhaps
due to the formation of a S film on the pyrite electrode sur-
face; in the potential region greater than 0.60 V vs. SCE,
pyrite starts its active dissolution. The oxidative dissolu-
tion of pyrite and the reduction of Fe3+ ions and O2 was
determined to be governed by charge transfer processes
for all the pyrite material studied, indicating that pyrites
follow the same dissolution mechanism despite their dif-
ferent geological origins.
For both sedimentary and hydrothermal pyrites, a C
paste electrode constructed with fine-grained pyrite pow-
der was found to be successful in reproducing the electro-
chemical behavior obtained from conventional solid
electrodes cut from large samples of the same material.
This provides a way to study the electrochemical behaviors
of fine-grained, disseminated pyrite materials which are
often found in sedimentary environments.
The results of this study demonstrate that the electro-
chemical experimental approach proposed by Holmes
and Crundwell (2000) involving independent study of the
half reactions involved in pyrite dissolution can be used
to estimate the dissolution kinetic parameters for both
sedimentary and hydrothermal pyrites.
Acknowledgements
This work was supported by the National Science Foun-
dation under Grants EAR-0228903 (D.A.D.) and EAR-
0229019 (R.C.C./B.W.S.). The authors thank Mr. Tom Nuh-
fer for help on the SEM analysis.
2734 R. Liu et al. / Applied Geochemistry 23 (2008) 2724–2734

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