Minerals Engineering 19 (2006) 883895

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The inuence of pyrite pre-oxidation on gold recovery by cyanidation

J. Li a, B. Dabrowski a, J.D. Miller
a

a,*

, S. Acar b, M. Dietrich b, K.M. LeVier b, R.Y. Wan

Department of Metallurgical Engineering, University of Utah, 135 S. 1460 E. Room 412, Salt Lake City, UT 84112-0114, United States
b
Newmont Mining Co., 10101 E. Dry Creek Road, Englewood, CO 80112, United States
c
Metallurgy Consultant, 9634 Kalamere Court, Highlands Ranch, CO 80126, United States
Received 11 April 2005; accepted 18 September 2005
Available online 17 November 2005

Abstract
The inuence of pyrite pre-oxidation in alkaline solutions on gold recovery by cyanidation from Twin Creek refractory gold ore in
which pyrite was identied as the major sulde mineral has been investigated with the aid of electrochemical measurements, leaching
experiments, and direct analysis of reaction products for selected residues. It was found that gold recovery by cyanidation in bottle roll
experiments mainly depended on the extent of pyrite pre-oxidation. The rate of pyrite oxidation in alkaline solutions measured by electrochemical measurements, including chronoamperometry and linear sweep voltammetry, increased with an increase in pH, potential,
and temperature. All alkaline reagents used for the electrochemical measurements, NaOH, NH4OH, Na2CO3 and Ca(OH)2, showed
a similar eect on pyrite oxidation kinetics. However, the results of alkaline pre-oxidation for pyrite of the Twin Creek refractory gold
ore suggested that NaOH and Na2CO3/Ca(OH)2 were superior to Ca(OH)2. Without pre-oxidation, cyanide leachable gold was found to
be only 20% which could be increased to 70% under appropriate pre-oxidation conditions. At the same time, cyanide consumption
decreased from 2.5 kg/t ore to 1.5 kg/t ore.
Selected residues after pre-oxidation and cyanidation were examined by X-ray diraction. Backscattered electron images of pyrite
particles in these residues were taken. The reaction products at the surface of pyrite particles were found to be iron-, silicon-, and calcium-bearing compounds with variable amounts of sulfur as determined by X-ray energy dispersion analysis. Additionally, some mineral
nes, such as aluminum and/or potassium-bearing minerals, were found to be present at the partially oxidized pyrite surface.
 2005 Elsevier Ltd. All rights reserved.
Keywords: Sulde ores; Gold ores; Hydrometallurgy; Oxidation; Cyanidation

1. Introduction
With depletion of the oxidized free-milling gold reserves
close to the earths surface, most of the important new
deposits being mined today do not respond to direct cyanidation. It is found that the gold is very nely disseminated
and encapsulated in host matrices that are inert and/or
impermeable to the cyanide solution. In this case, it is necessary to rst break down the host matrices and then it is
possible to leach the liberated gold. In many cases, the host
matrices are sulde minerals, which exhibit a strong association with nely disseminated gold particles in many ore
*

Corresponding author. Tel.: +1 801 581 5160; fax: +1 801 581 4937.
E-mail addresses: jli@mines.utah.edu (J. Li), jdmiller@mines.utah.edu
(J.D. Miller).
0892-6875/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.09.052

bodies. Of these suldes, pyrite is one of the most important

minerals. Therefore, a knowledge of pyrite leaching behavior is very important for the development of improved technology for the treatment of refractory gold ores.
The electrochemistry of pyrite and the kinetics of pyrite
oxidation in dierent systems have been extensively studied. The anodic dissolution behavior of pyrite has been
investigated by various techniques (Brion, 1980; Hamilton
and Woods, 1981; Buckley and Woods, 1987; Buckley
et al., 1988; Ahlberg et al., 1990). It was found that pyrite
is the most noble sulde mineral and a good electrocatalyst
for oxygen reduction (Biegler et al., 1975) and for hydrogen
evolution (Peters, 1976). This property can aect the
behavior of other sulde minerals through galvanic coupling, in which pyrite serves as a cathode and thus enhances
the oxidation of other sulde minerals, as might occur

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J. Li et al. / Minerals Engineering 19 (2006) 883895

during pre-oxidation processes for exposure of gold particles from suldes matrices.
For pressure oxidation in alkaline solutions, the rate of
pyrite oxidation was found to be surface-reaction controlled (Lowson, 1982; Brown and Jurinak, 1989; Ciminelli
and Osseo-Asare, 1995a,b). Some authors observed that
the oxidation rate increases with an increase of pH, reagent
concentration, and temperature (Brown and Jurinak, 1989;
Nicholson et al., 1988, 1990; Ciminelli and Osseo-Asare,
1995a,b; Envangelou et al., 1998). With more extensive
alkaline oxidation of pyrite, higher gold recovery is generally observed (Souza and Ciminelli, 1992).
The kinetics of pyrite oxidation in alkaline solutions
have been found to be aected by the nature of the reagents
used to control the pH of the systems. Among the reagents,
sodium carbonate/bicarbonate was claimed to be particularly eective in enhancing pyrite decomposition in aerated
solutions (Wheelock, 1981; Guay, 1981a,b; Souza and
Ciminelli, 1992). However, there still is some controversy
regarding this position. For instance, Warren (1956) found
that the addition of small amount of calcium carbonate for
pH adjustment caused a drastic reduction in the pyrite
decomposition rate. Warren (1956) explained the reduction
in rate as a consequence of the formation of a growing
iron-oxide lm on pyrite particles, the oxidation rate then
becoming controlled by diusion in the product layer. In
contrast, Guay (1981a,b) suggested that sodium carbonate
enhanced the rate of pyrite oxidation by favoring the
removal of the iron-oxide coating, thus increasing the
exposure of fresh surfaces to oxidation.
Caldeira et al. (2003) recently reported the product layer
constituents and morphology from pyrite oxidation by
molecular oxygen in alkaline solutions. In sodium hydroxide solutions, hematite was the main phase identied in the
product layer. In carbonate solutions, the main constituent
was ferrihydrite. In calcium hydroxide solutions, only calcium carbonate was detected on the surface of oxidized
pyrite in an amount that increased when the system was
opened to the atmosphere. The morphology of the product
layers demonstrated that in NaOH solutions the pyrite particles were initially covered by a thin oxide layer and then
the oxide layer fractured after longer reaction times. Pyrite
oxidation in Na2CO3/NaHCO3 solutions resulted in particles that were initially covered by a discontinuous oxide
coating that grew with reaction time, thus increasing the
overall pyrite surface coverage.
Upon review of the literature, the kinetics and products
of pyrite decomposition in alkaline solutions under oxidative conditions are dependent on many variables, such as
oxidation potential, temperature, solution composition,
whether the system is open to the atmosphere, etc. (Buckley
and Woods, 1987; Buckley et al., 1988; Ahlberg et al., 1990;
Kathe et al., 1993; Caldeira et al., 2003). Generally, it is
accepted that the oxidation of pyrite is described by the following overall reactions, in which the ferric ion precipitates
on the pyrite surface or reports to the solution in suspension as ferric hydroxide

FeS2 + 3H2 O = Fe(OH)3 + 2S0 + 3H + 3e

or
FeS2 + 3OH = Fe(OH)3 + 2S0 + 3e

1
2

and at higher potentials


FeS2 11H2 O FeOH3 2SO2
4 19H 15e

or

FeS2 19OH FeOH3 2SO2
4 8H2 O 15e

Besides the aforementioned phenomena, other issues

have also been considered: (1) whether elemental sulfur is
involved as an intermediate during formation of sulfate;
and (2) which component of pyrite is preferentially oxidized
(Sato, 1960; Peters and Majima, 1968; Biegler and Swift,
1979; Hamilton and Woods, 1981; Goldhaber, 1983; Buckley and Woods, 1985; Buckley and Woods, 1987; Chander
and Briceno, 1987; Kathe et al., 1993). It is due to the system complexity that a detailed mechanism of pyrite oxidation has not been well established (Hayes et al., 1987;
Ahlberg et al., 1990; Caldeira et al., 2003). Consequently,
in the current research, the behavior of pyrite oxidation in
alkaline solutions was investigated by electrochemical measurements under conditions for industrial applications at
ambient pressure. The variables tested, in experiments open
to the atmosphere, included pH, potential, temperature,
and alkaline reagent. Based on these fundamental results
as a point of reference, other experiments were initiated
for alkaline pre-oxidation of the Twin Creek refractory gold
ore, and to determine the inuence of pre-oxidation conditions on sulde oxidation and gold recovery by subsequent
cyanidation from the oxidized residues. In addition, characteristics of the solid products after alkaline pre-oxidation
and cyanidation for gold recovery were made for selected
samples by X-ray diraction (XRD), backscattered electron
(BSE) images, and X-ray energy dispersion (EDS) analysis.
2. Electrochemical experiments
Pyrite is a semiconductor and known to support electrochemical reactions. Therefore, some electrochemical measurement techniques can be utilized to determine the rate
of anodic pyrite oxidation. In this respect, it was decided
to do a systematic electrochemical research on the kinetics
of pyrite oxidation in alkaline solutions in order to provide
supporting information for the alkaline pre-oxidation
experiments. The electrochemical techniques used in the
current research included chronoamperometry and linear
sweep voltammetry. The rate of anodic pyrite oxidation
in alkaline solutions under certain conditions and the inuence of important factors on the rate were determined by
electrochemical measurements. The experimental methods
and results are presented in the following sections.
2.1. Pyrite electrode preparation
A natural massive specimen of pyrite of unknown
source was provided by Newmont Mining Corporation.

J. Li et al. / Minerals Engineering 19 (2006) 883895

885

Fig. 1. Eect of applied potential (EAP) on the rate of pyrite oxidation by chronoamperometry at pH 11 and ambient temperature with a stationary pyrite
electrode, magnetically stirred solution (0.2 M Na2SO4, 500 rpm), and dierent alkaline reagents: NaOH, NH4OH, Na2CO3, and Ca(OH)2.

The massive pyrite specimen was cut into a parallelepiped

with dimensions of 14 13 8 mm and then attached to
a copper wire (2.0 mm in diameter) using silver conducting
glue. The pyrite electrode was molded in epoxy, exposing
one side to the solution.
2.2. Electrochemical procedures
Before each experiment, the pyrite electrode was ground
with silicon carbide papers (800 and 2400 mesh) successively, rinsed with ethanol and deionized water, respectively. The electrode was immediately put into the test
solution in an electrochemical cell. During the experiment,
the solution was open to the atmosphere. The volume of
the test solution was 250 mL. The pH was adjusted by
addition of concentrated solutions of dierent alkaline
chemicals. The potential was measured and referenced
against the saturated calomel electrode (SCE),
E0SCE 0:242 V vs. SHE. Most experiments were performed at ambient temperature (24 C) with the stationary
pyrite electrode, solution being stirred (500 rpm) with a
magnetic bar (8.0 mm in diameter and 38.0 mm in length).
Sodium sulfate was added as an indierent electrolyte

(0.2 M). Variations from these conditions can be noted in

the text and in the gure captions.
A typical three-electrode system was employed for these
measurements. The pyrite electrode was used as the working electrode, a graphite rod was used as the counter electrode, and the SCE was used as the reference electrode.
Potential measurements between the working electrode
and the reference electrode were made through a Luggin
capillary. The current densities for anodic pyrite oxidation
or decomposition were obtained with an EG&G Princeton
Applied Research, Potential-Galvanostat (Model 273).
2.3. Experimental results and discussion
The current density determined by chronoamperometry
for pyrite oxidation under specic conditions in this paper
is the average of anodic current densities within a certain
experimental time, for example, after 5 min, during which
time the current density reaches a relatively stable level.
When the anodic current densities are available, the following equation can be used to calculate the rates (mol/
cm2 min) of pyrite oxidation from the corresponding anodic current densities.

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J. Li et al. / Minerals Engineering 19 (2006) 883895

Fig. 2. Eect of pH on the rate of pyrite oxidation by chronoamperometry

at applied potential (EAP) 0.258 V (SCE), and ambient temperature with a
stationary pyrite electrode, magnetically stirred solution (0.2 M Na2SO4,
500 rpm), and dierent alkaline reagents: NaOH and Na2CO3.

Ia
60 s= min
A=cm2
96 490 C=mol  na
1000
where R is the rate of pyrite oxidation (mol/min cm2), Ia is
the anodic current density of pyrite oxidation (mA/cm2)
and na is the number of electrons transferred for pyrite
oxidation.
However, it is expected that the products from anodic
pyrite oxidation vary, for example, ferrous ion or ferric
ion and elemental sulfur or sulfate etc., depending on
experimental conditions. Because of the dierent reactions
that can occur, the na value cannot be dened unambiguously. For this case, the anodic current densities for pyrite
decomposition will be used as an indication of the rate for
pyrite oxidation in order to compare the inuence of some
important variables on pyrite oxidation rate.
R

2.3.1. Stirring speed

In order to investigate the reaction characteristics for
anodic pyrite oxidation, it is necessary to examine many
dierent variables, including stirring speed. The inuence
of magnetically stirring speed on the anodic current density
for pyrite oxidation was examined at potential 0.258 V
(SCE) and pH 11 (Ca(OH)2). It was found that when the

Fig. 3. Eect of pH on the rate of pyrite oxidation by chronoamperometry

at applied potentials (EAP) 0.258 V and 0.370 V (SCE), and ambient
temperature with a stationary pyrite electrode, magnetically stirred
solution (0.2 M Na2SO4, 500 rpm), and alkaline reagent Ca(OH)2.

Fig. 4. Examination of pH (Ca(OH)2) eect on the rate of pyrite oxidation

by linear sweep voltammetry at ambient temperature and potential
scanning rate 2 mV/s with a stationary pyrite electrode, magnetically
stirred solution (0.2 M Na2SO4, 500 rpm), and alkaline reagent Ca(OH)2.

J. Li et al. / Minerals Engineering 19 (2006) 883895

solution was stationary, the current density was much

lower than that at the stirring speed of 250 rpm; when
the stirring speed was above 250 rpm, the current density
was found to be almost independent of the stirring speed.
These results indicate that when the stirring speed is above
250 rpm the reaction rate for pyrite oxidation is no longer
limited by aqueous phase transport processes. Thus, the
speed was kept at 500 rpm for all of the following
experiments.
2.3.2. Eect of potential
Examination of the inuence of the oxidation potential
on the rate of pyrite oxidation was made by chronoamperometry at the potentials of 0.258 V and 0.370 V (SCE) with
dierent alkaline reagents to adjust the solution pH, including sodium hydroxide, ammonium hydroxide, sodium carbonate, and calcium hydroxide. These results are
presented in Fig. 1, which clearly demonstrate that the rate
of anodic pyrite oxidation is signicant at these potentials.
The rate at 0.370 V is much higher than at 0.258 V. A similar phenomenon can be observed from the results determined by linear sweep voltammetry presented in Fig. 4.
For example, it is evident that the oxidation rate increases
with an increase in the oxidation potential at each pH level.
2.3.3. Eect of pH
The eect of pH on the rate of pyrite oxidation using
dierent alkaline reagents for adjustment of the solution
pH was measured by dierent electrochemical measurements. The results determined by chronoamperometry are
shown in Fig. 2 using NaOH and Na2CO3 at potential of
0.258 V, and in Fig. 3 using Ca(OH)2 at potentials of
0.258 V and 0.370 V. The results determined by linear
sweep voltammetry are shown in Fig. 4 using Ca(OH)2.
These results suggest that the oxidation rate increases with

Fig. 5. Reaction order determination by plot of the logarithm of anodic

current density (Ia) vs. pH. Data taken from Fig. 3 at potentials of 0.258 V
and 0.370 V (SCE).

887

an increase in pH, which is expected by examination of the

reactions (1)(4) for pyrite oxidation and is similar to the
results reported by other authors (Brown and Jurinak,
1989; Nicholson et al., 1988, 1990; Ciminelli and OsseoAsare, 1995a,b; Envangelou et al., 1998).
Plots of the logarithm of anodic current density vs. pH
for pyrite oxidation at potentials of 0.258 V and 0.370 V
are presented in Fig. 5. The data are taken from Fig. 3.
The slopes of 0.584 for 0.258 V and 0.586 for 0.370 V presented in Fig. 5 demonstrate that the oxidation rate is
approximately half order with respect to hydroxide ion
concentration. The half order may indicate that the reaction for anodic pyrite decomposition or pyrite oxidation
in alkaline solution would be a multiple-step process, which
needs to be further studied in future research. In addition,
the close values of the slopes indicate that the oxidation

Fig. 6. Examination of chemical eect on the rate of pyrite oxidation by

chronoamperometry at applied potentials (EAP) of 0.258 V and 0.370 V
(SCE), pH 11, and ambient temperature with a stationary pyrite electrode
and magnetically stirred solution (0.2 M Na2SO4, 500 rpm).

Fig. 7. Voltammogram for pH eect on the rate of pyrite oxidation using

dierent alkaline reagents at ambient temperature and potential scanning
rate 2 mV/s with a stationary pyrite electrode and magnetically stirred
solution (0.2 M Na2SO4, 500 rpm).

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J. Li et al. / Minerals Engineering 19 (2006) 883895

reaction at the dierent potentials may have the same ratelimiting step and/or produce the same products under these
circumstances.
2.3.4. Alkaline reagents
It can be noted from review of the literature that the
kinetics of pyrite oxidation in alkaline solutions are dependent not only upon pH, potential and whether the system is
open to the atmosphere, but also upon the solution composition or reagents used to adjust the solution pH (Lowson,
1982; Brown and Jurinak, 1989; Nicholson et al., 1990;
Ciminelli and Osseo-Asare, 1995a,b; Caldeira et al., 2003).
In the current research, the inuence of dierent alkaline
reagents on pyrite oxidation kinetics, including sodium
hydroxide, ammonium hydroxide, sodium carbonate, and
calcium hydroxide, was examined by chronoamperometry

Fig. 8. Eect of temperature on the rate of pyrite oxidation by

chronoamperometry at applied potential (EAP) of 0.258 V (SCE), and
pH 11 (NaOH or Na2CO3) with a stationary pyrite electrode, magnetically
stirred solution (0.2 M Na2SO4, 500 rpm).

Fig. 10. Eect of pH on the rate of pyrite oxidation by chronoamperometry at elevated temperature (45 C and 65 C), and applied potential
0.258 V (SCE) with a stationary pyrite electrode and magnetically stirred
solution (0.2 M Na2SO4, 500 rpm).

Fig. 11. Inuence of purging N2 on the rate of pyrite oxidation by

chronoamperometry at ambient temperature, applied potentials (EAP) of
0.258 V and 0.370 V (SCE), and pH 11 (Na2CO3) with a stationary pyrite
electrode and magnetically stirred solution (0.2 M Na2SO4, 500 rpm).

Fig. 9. Arrhenius plot of the natural logarithm of anodic current density

(Ia) for pyrite oxidation vs. 1/T. Data taken from Fig. 8.

at potentials of 0.258 V and 0.370 V (Fig. 6) and by linear

sweep voltammetry at pH values of 10, 11 and 12 (Fig. 7).

J. Li et al. / Minerals Engineering 19 (2006) 883895

These results suggest that the rate of pyrite oxidation

under dierent conditions is independent of the alkaline
reagents used under the conditions studied. However, it
should be pointed out that, in the current research, the anodic current densities for pyrite decomposition as determined
by these electrochemical measurements only represent the
initial rates of pyrite oxidation. The eect of these alkaline
reagents needs to be further examined by actual pre-oxidation tests. Especially, the oxidation rate may be aected by
the reaction products formed at the pyrite surface with different alkaline reagents in actual pre-oxidation systems.
2.3.5. Temperature
The eect of temperature on the anodic current density
for pyrite oxidation was examined by chronoamperometry
in NaOH and Na2CO3 solutions at pH 11 and potential
0.258 V (SCE). The results are presented in Fig. 8. A logaTable 1
Chemical analysis of Twin Creek refractory ore
Au (g/t)

S-total
(%)

S-sulfate
(%)

S-sulde
(%)

C-total
(%)

C-org.
(%)

Fe
(%)

As
(%)

2.49

3.45

0.39

3.06

0.60

0.61

4.52

0.20

889

rithm of the anodic current density is then plotted against

reciprocal of the absolute temperature in Fig. 9. According
to the Arrhenius theory (EAct/R = 4150), the apparent activation energy was found to be 8.20 kcal/mol (34.5 kJ/mol),
which indicates that, under the conditions studied, the rate
of pyrite oxidation is limited by surface reaction control or
by mixed control.
Additionally, the inuence of pH on the kinetics of alkaline pyrite oxidation at elevated temperatures of 45 C and
65 C was investigated by chronoamperometry in sodium
carbonate/sodium hydroxide solutions and the results are
presented in Fig. 10. It can be seen from these results that
the rate of pyrite oxidation signicantly increases with an
increase in pH value from pH 10 to pH 11, and that when
the pH exceeds pH 11 the initial rate seems to become not
signicantly dependent of pH under the conditions studied.
At the elevated temperatures and with the consideration of
alkaline reagent consumption, control at pH 11 is suitable
for pyrite oxidation for an actual pre-oxidation process.
2.3.6. Purging with nitrogen
In the current research, all solutions were open to the
atmosphere. In most fundamental studies by other authors,
the systems generally were isolated from the atmosphere by

Table 2
Summary of baseline cyanide/CIL test results
Test

Sulde
oxidation
(%)

Au in
residue
(g/t ore)

Au
recovery
(%)

NaCN
consumption
(kg/t ore)

1
2

6.2
14.4

2.0
1.68

19.9
32.4

2.5
2.7

Table 3
Alkaline pre-oxidation tests at 60 C for 6 h followed by cyanide/CIL
Test

Reagent

pH

Sulde
oxidation
(%)

Au
extraction
(%)

3
4
5
6
7

NaOH

Ca(OH)2

Na2CO3
Ca(OH)2

10
11
10
11
10

26.1
67.6
17.3
28.4
23.8

38.4
63.1
32.9
37.0
41.1

14.6
62.7
18.2
41.1
48

1.6
1.2
1.2
1.3
1.3

11

67.9

54.4

147.5

0.7

Alkaline
reagent
(kg/t)

NaCN
(kg/t)

Fig. 12. Eect of the pre-oxidation slurry pH on gold extraction from the
oxidized residues by cyanide/CIL (Test 2 as a reference: gold extraction
32% for the pre-oxidation without addition of alkaline reagent).

Table 5
XRD analysis of Twin Creek refractory gold ore and pre-oxidation
residues (%)a

Table 4
Eect of lime addition in grinding circuit
Test

Lime in
grinding
(g/kg)

pH

Sulde
oxidation
(%)

CIL Au
Extraction (%)

9
10
11
12
13a
14a

5
5
10
10
5
5

10
11
10
11
10
11

49.6
79.6
37.1
71.8
48.4
88.0

62.9
71.4
47.6
63.3
62.8
69.8

Alkaline reagent used: Na2CO3/Ca(OH)2 (molar ratio 1:1).

a
Addition of Pb(NO3)2 in cyanide/CIL.

Mineral

Formula

Anatase
Calcite
Muscovite/
Illite
Pyrite
Quartz

TiO2
CaCO3
KAl2(AlSi3O10)(OH)2/
K0.7Al2(Si,Al) O10(OH)2
FeS2
SiO2

Total
a

Head

Test
4

Test
10

Test
12
1
12
22

25

26

1
13
23

6
67

2
71

2
62

2
63

100

100

100

100

All values were obtained by Rietveld analysis/whole pattern tting.

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J. Li et al. / Minerals Engineering 19 (2006) 883895

Fig. 13. BSE images of pyrite (py) in the Test 4 residue sample. Cyan arrows show EDS analysis points in rimming material, conrming S removal with Ca
and Si addition. Upper image includes an arsenopyrite (asp) grain. Right-hand pyrite in lower image has attached muscovite/illite (labeled) that shows no
eect from chemical treatment. (For interpretation of the references in colour in this gure legend, the reader is referred to the web version of this article.)

purging with an inert gas. In order to identify the dierence

for alkaline pyrite oxidation kinetics under these dierent
conditions, the inuence of N2 and O2 purging on pyrite
oxidation was examined by chronoamperometry, and comparison of these results with those open to the atmosphere
is made in Fig. 11. It can be noted that when being isolated
from oxygen in the atmosphere by purging with nitrogen,
the anodic current densities or the rates of pyrite oxidation
at potentials of 0.258 V and 0.370 V are lower than those
open to the atmosphere, and that when purging with oxygen the oxidation rates are the same as those open to the
atmosphere. These results indicate that oxygen may participate in the surface reaction during pyrite oxidation and

that more oxygen does not aect the oxidation kinetics

under the conditions studied. These phenomena need to
be investigated in future research.
3. Alkaline pre-oxidation and gold leaching
by cyanidation
A refractory suldic-carbonaceous ore from Newmonts
Twin Creek Mine (a representative for one of refractory gold
ore) was used for pre-oxidation and gold leaching tests. The
received sample was crushed to minus 10-mesh and split into
500-g charges. Prior to each test, the crushed sample was wetne ground in two stage grinding mills. Particle size distribu-

J. Li et al. / Minerals Engineering 19 (2006) 883895

891

Fig. 14. BSE images of pyrite (py) in the Test 10 (lime 5 g/kg ore) residue sample. Cyan arrows show EDS analysis points in the surrounding material,
conrming S removal with Ca and Si addition. The upper-most EDS spectrum shows evidence for a small amount of Cl. (For interpretation of the
references in colour in this gure legend, the reader is referred to the web version of this article.)

tion analysis indicated that the particle size of the ground

sample was 100% minus 45 lm and 80% minus 20 lm.
A sample of 250 g of the ne ground sample was used
for each oxidation test. The oxidation tests were performed
in a 1 L reactor at about 60 C, 30% solids slurry with
5 scfpm (standard cubic feet per minute) oxygen ow rate
for 6 h. The agitation speed was controlled at 600 rpm.
The slurry pH for the pre-oxidation was adjusted by addition of selected alkaline reagents, such as NaOH, Ca(OH)2
and Ca(OH)2/Na2CO3 (molar ratio 1:1). After the pre-oxidation test, a solution sample was taken for analysis and
the oxidized slurry was transferred into a one-gallon glass
bottle for gold leaching by cyanidation/CIL. Both leach
residue and activated carbon were analyzed. Gold extraction was calculated based on mass balance, leach residue
and feed gold assay.
3.1. Ore sample characteristics
The Twin Creek ore is highly refractory due to both gold
locking in pyrite matrix and preg-robbing activity. The
mineral constituents of the ore were identied and deter-

mined by semiquantitative XRD analysis, which indicated

that the ore is comprised of 6% pyrite, 2% anatase, 25%
muscovite/illite and about 67% quartz.
Fire assay and chemical analysis of the head sample are
given in Table 1. The ore sample contains 2.5 g Au/ton ore.
S-sulde content is about 3%. The cyanide leachable gold
assay of this ore (AuCN) is 0.39 ppm, which indicates that
only 15.7% of the gold in the ore is cyanide leachable. The
preg-robbing ability of the ore was tested. Results from
samples spiked with gold solution and cyanide leaching
returned a spike recovery only 62%, which indicates the
ore has a moderate preg-robbing characteristic. The elevated organic carbon, 0.6%, may be one important factor
causing preg-robbing. This matter needs to be investigated
in future research.
To nd maximum gold recovery after complete sulde
oxidation, a series of hot nitric acid pretreatment tests were
performed on the ne-ground samples and followed by
cyanide/CIL. After the nitric acid pretreatment, the sulde
oxidation was over 99.2%. Even with this high sulde oxidation, gold recoveries by cyanide/CIL only ranged from
78.2% to 83.7%. Results suggested that even with the oxi-

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J. Li et al. / Minerals Engineering 19 (2006) 883895

Fig. 15. BSE image of pyrite (py) in the Test 10 (lime 5 g/kg ore) residue sample surrounded in this case by mineral nes. The pyrite appears to be
disintegrating. Cyan arrows show EDS analysis points. The upper-most spectrum indicates mostly quartz with a trace amount of muscovite/illite. The
other spectra show higher quantities of Ca and Fe. The S contents at the analysis points are less than the limit of detection (0.4%). (For interpretation of
the references in colour in this gure legend, the reader is referred to the web version of this article.)

dation pretreatment, the maximum achievable gold recovery would only be about 80% due to the preg-robbing
activity of the ore sample.
3.2. Alkaline cyanide/CIL tests for gold leaching
An alkaline cyanide/CIL test was performed directly on
the ne-ground samples without pre-oxidation at ambient
temperature with 20 g/L carbon for 24 h and an initial
sodium cyanide concentration of 1 g/L. The alkaline cyanide/CIL test result (Test 1) is given in Table 2.
Table 2 also includes a pre-oxidation test followed by
cyanide/CIL (Test 2). The pre-oxidation was carried out
with oxygen at 60 C for 6 h without the addition of alkaline chemical reagent. Alkaline cyanide/CIL testing
resulted in gold recovery of 20%. After aerated with oxygen
for 6 h at the elevated temperature, the subsequent gold
extraction by alkaline cyanide/CIL increased to 32%.
3.3. Comparison of alkaline pre-oxidation at pH 10
and pH 11
Results of alkaline pre-oxidation with selected alkaline
reagents and gold leaching by cyanidation/CIL are listed

in Table 3. The alkaline reagents used were NaOH,

Ca(OH)2 and a mixture of Na2CO3/Ca(OH)2 (molar ratio
of 1:1). The pre-oxidation tests were examined at pH 10
and pH 11 for each reagent tested. It was intended to
determine the pH eect on sulde oxidation instead of minimizing the reagent dosage.
The results in Table 3 suggest that gold extraction increases with an increase in the degree of sulde oxidation and that the eect of pH on the pre-oxidation
reaction is evident. Both sulde oxidation and gold extraction are greater at pH 11 than at pH 10. The highest gold
extraction is 63%, about 40% greater than the gold extraction without pre-oxidation though the ore has some prerobbing activity. Additionally, the cyanide consumption
is signicantly reduced after sulde oxidation.
3.4. Eect of lime addition in grinding process
The inuence of lime addition during ne grinding on
the extent of sulde oxidation and gold extraction was
examined. Test results, shown in Table 4, demonstrate that
the lime addition obviously increases the extent of sulde
oxidation and the level of gold extraction. Under similar
pre-oxidation condition, an additional 15% of gold extrac-

J. Li et al. / Minerals Engineering 19 (2006) 883895

893

Fig. 16. BSE image and EDS spectra from two pyrite (py) grains in the Test 12 (lime 10 g/kg ore) residue sample. Cyan arrows show analysis points. The
upper-right pyrite grain contains arsenic (lower-right EDS spectrum). The darker gray along the right side of this grain may be quartz, with the iron and
sulfur of the EDS spectrum from the nearby pyrite. The upper-most and lower-most EDS spectra are typical of most of the pyrite coatings observed during
this study, showing increased iron and lower sulfur in comparison to pyrite, with the addition of calcium and silicon. (For interpretation of the references
in colour in this gure legend, the reader is referred to the web version of this article.)

tion is achieved with addition of 5 g/kg lime during ne

grinding (compare Tests 8 and 10).
It can be noted that the results of Tests 11 and 12 indicate that an excess of lime addition reduces sulde oxidation as well as gold extraction. Further research is
required to explain the phenomenon. The encapsulation
of the sulde particle in Tests 11 and 12 residues was
observed by X-ray energy dispersion spectroscopy.
The cyanide/CIL gold extractions from the residues
after the alkaline pre-oxidation tests are illustrated in
Fig. 12. Fig. 12 demonstrates that the alkaline oxidation
is an eective pretreatment for this refractory sulde ore.
The pH eect of pre-oxidation slurry on sulde oxidation
and gold extraction is signicant. Substantial increase in
gold extraction with the pretreatment is realized when compared to direct cyanide/CIL without pre-oxidation.
4. Reaction products after pre-oxidation and cyanidation
The reaction products of selected residues after alkaline
pre-oxidation and cyanidation from Tests 4, 10, and 12
were examined by X-ray diraction (XRD). Also, backscattered electron (BSE) images of the pyrite particles in

these residues were taken. Finally, reaction products and/

or coatings at the surface of pyrite particles were analyzed
by X-ray energy dispersion (EDS) spectroscopy.
Quantitative treatment of the XRD spectra was accomplished by Rietveld analysis and whole pattern tting methods. The Rietveld analysis rened the crystal structures
(lattice parameters, etc.) of the minerals using the powder
diraction data, beginning with close approximation from
previous results. The whole pattern tting adjusted mineral
percentages until a best t occurred between a calculated
spectrum and the chemical analysis. The results determined
by the quantitative analysis are presented in Table 5.
According to the results presented in Table 5, it is obvious
that the XRD analysis for the Twin Creek refractory gold
ore head sample agrees quite well with the chemical analysis presented in Section 3.1. The level of sulde oxidation
from Tests 4, 10, and 12 determined by the XRD analysis
in Table 5 matches roughly with the results of chemical
analysis presented in Tables 3 and 4, in which the level of
sulde oxidation from Tests 4, 10, and 12 reaches about
70.0%. It is further conrmed with these results that gold
extraction (up to 70%) by cyanidation mainly depends
on the level of pyrite oxidation (up to 70%). Table 5 also

894

J. Li et al. / Minerals Engineering 19 (2006) 883895

Fig. 17. BSE image showing two pyrite grains (light gray, upper-left and lower-right) in the Test 12 (lime 10 g/kg ore) residue sample. Cyan arrows show
EDS analysis points in coatings around pyrite. All of the coatings contain calcium and silicon, and higher Fe:S ratios than pyrite. Aluminum and
potassium of the lower-right EDS spectrum indicates muscovite/illite. (For interpretation of the references in colour in this gure legend, the reader is
referred to the web version of this article.)

shows that the residues from tests where Ca(OH)2 was used
contain 1213% calcite in addition to the quartz, muscovite/illite, pyrite, and anatase.
The pyrite particles and the reaction products at the surface of pyrite particles after the alkaline pre-oxidation and
cyanidation were examined in these three residue samples
by BSE images and EDS spectroscopy. Fig. 13 shows the
BSE micrographs of pyrite particles and the EDS spectra
of the reaction products at the surface of pyrite in the residue sample from Test 4. Figs. 14 and 15 show the results in
the residue sample from Test 10, and Figs. 16 and 17 show
the results in the residue sample from Test 12. These BSE
images and EDS spectra clearly show that iron-, silicon-,
and calcium-bearing compounds, with variable amounts
of sulfur, commonly surround the pyrite particles. Some
mineral nes were found in the product layer, such as
arsenic, aluminum, and/or potassium-bearing minerals.
Additionally, it can be noted that the EDS spectrum intensity for elemental calcium at the surface of pyrite particles
is signicantly greater for lime addition 10 g/kg ore (Figs.
16 and 17) than the calcium intensity for a lime addition
is 5 g/kg ore (Figs. 14 and 15). This result supports the
hypothesis that when lime is added in excess (10 g/kg) the

lime may physically encapsulate mineral particles, causing

low levels of sulde oxidation and low gold extraction.
However, this conclusion needs to be conrmed by more
evidences in future research.
Based on the fact that gold extraction mainly depends on
the extent of suldes or pyrite oxidation, it appears that the
product layers at pyrite surface are porous under the conditions studied. However, the results from Test 6 with the
addition of lime (Ca(OH)2) show that the extent of pyrite
oxidation and gold leaching are much less than those from
Tests 4, 10 and 12. In this regard, the morphology of the
coatings on pyrite after alkaline pre-oxidation under dierent conditions needs to be studied further in future research.
5. Summary and conclusions
In this investigation, the kinetics of anodic pyrite oxidation in alkaline solutions was studied by electrochemical
measurements, including chronoamperometry and linear
sweep voltammetry. Based on these electrochemical measurements, some experiments were designed for alkaline
pre-oxidation of Twin Creek refractory gold ore in which
the major sulde mineral was pyrite. Gold extraction from

J. Li et al. / Minerals Engineering 19 (2006) 883895

the pre-oxidized auriferous pyrite ore was accomplished by

cyanidation.
From the electrochemical measurements, it was found
that the rate of anodic pyrite oxidation increased with an
increase in oxidation potential, pH, and temperature. However, when temperature was above 45 C and pH was
above 11, the pH eect from pH 11 to pH 12 was not signicant. The alkaline reagents, NaOH, NH4OH, Na2CO3,
and Ca(OH)2, had a similar eect on the oxidation rate
under the conditions studied. The reaction kinetics for pyrite oxidation were found to be under surface reaction control or under mixed control, which was supported by the
independence on stirring speed and by the relatively high
apparent activation energy of 8.20 kcal/mol (or 34.5 kJ/
mol). Purging with nitrogen reduced the oxidation kinetics
and Purging with oxygen did not aect the oxidation rate
when compared with those open to the atmosphere.
The results of alkaline pre-oxidation and gold leaching
by cyanidation suggested that the alkaline pre-oxidation
was an eective treatment for the refractory gold ore. Gold
extraction after pre-oxidation under appropriate conditions increased from 20% of direct cyanide leaching to
70.0%. Cyanide consumption decreased from 2.5 kg/t ore
for direct cyanide leaching to 1.5 kg/t ore with the pre-oxidation. It was found that gold extraction mainly dependent
on the extent of sulde oxidation under the conditions
studied though the ore had a moderate pre-robbing activity. Sulde oxidation increased with an increase in pH.
Upon comparison of the alkaline reagents used, NaOH
and Na2CO3/Ca(OH)2 were superior to Ca(OH)2 for the
sulde oxidation. Appropriate addition of lime (5 g/kg
ore) during the ne grinding improved the sulde oxidation
(up to 7080%).
Additionally, the residues at the surface of pyrite particles after alkaline pre-oxidation and cyanidation examined
with selected samples were by XRD, BSE images, and EDS
spectroscopy. It was observed that an iron-, silicon-, and
calcium-bearing compound, with variable amounts of sulfur, commonly surrounded pyrite grains. Mineral nes also
were found in the product layer including arsenic, aluminum, and/or potassium-bearing minerals. At the same
time, it was revealed that when the lime addition was
10 g/kg ore for the ultra-ne grinding the lime physically
encapsulated pyrite grains, which caused low sulde oxidation and low gold extraction.
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