Mnera1.v Engincermng, Vol. 13, No. 1, pp.

l-18, 2000
0 1999 Elsevier Science Ltd
All rights reserved
0892--6875(99)00145-4 0892-6875/00/$ - see front matter

AN EVALUATION OF PRETREATMENTS TO INCREASE GOLD RECOVERY

FROM A REFRACTORY ORE CONTAINING
ARSENOPYRITE AND PYRRHOTITE

M. N. LEHMANN, S. OLEARY?, and J. G. DUNN@

A. J. Parker Cooperative Research Center for Hydrometalhngy. E-mail: JEFFDUNN@prodigy.net

5 School of Applied Chemistry, Curtin University of Technology, Perth, Western Australia
7 Mineral and Processing Laboratories of the Department of Energy, Waterford, Western Australia
(Received 5 July 1999; accepted 10 September 1999)

ABSTRACT

The effect of three ore pretreatments on gold recoveries from an ore in which the gold existed in
solid solution in an arsenopyrite matrix, as well as being encapsulated in a pyrrhotite phase, was
examined. The three pretreatments evaluated included fine grinding, pyrolysis-roast (Pyrox), and
an oxidative pressure acid leach (PAL). It was found that untreated ores did not yield high gold
recoveries even when a fine grind (~45~) was employed, while oxidative treatments led to a
signtjicant improvement of recoveries. The Pyrox pretreatment was found to decompose the sulfide
matrix of the ore to a greater extent than a 3 hour PAL treatmemt. However, the PAL process
produced a slightly better gold recovery of 79% compared to the Pyrox recovery of 75%, and both
of these were greater than the 55-60% recoveries achieved with the untreated ore. Furthermore, the
depletion of dissolved oxygen levels observed during cyanide leaching were signtj?cantly reduced by
the two oxidative treatments, compared to the untreated ores. PAL was found to benefit over the
Pyrox pretreatment by afording a solid product, which eflectively locked the arsenic component
of the mineral from being recovered in solution. The PAL process required more lime for
neutralization of acid produced from the decomposition reaction. 0 1999 Elsevier Science Ltd. All
rights reserved.

Keywords
Gold ores; sulfide ores: roasting; grinding; pressure leaching

INTRODUCTION

Gold deposits can be broadly classed into two categories, primary and secondary. The primary deposits are
sulfides, mainly pyrite and arsenopyrite, and more rarely other gold bearing sulfides such as pyrrhotite.
Direct cyanide leaching of the secondary deposits give good gold recoveries in excess of 95%, but direct
leaching of the primary deposits give poor recoveries of 5-70%, depending on the mineralogical
composition of the deposit and the form of the gold in the host. The difficult-to-treat concentrates are
described as refractory. There are a number of reasons why ores are refractory. It has been demonstrated
that gold can occur in sulfide matrices in a range of sizes, from so-called invisible or solid solution gold
(Cabri et al., 1989), to particles of 50-100 pm. Although the matrix offers some protection to the
particulate gold against contact with cyanide, dissolved oxygen and leaching reagents, fine grinding

* Presently employed with AMIRA gold project, Murdoch University, Murdoch, Australia
** Present address: Dept. of Chemistry, University of Toledo, Ohio, USA
2 M.N.Lehmannetal.

followed by cyanide leaching can sometimes produce acceptable recoveries (Espiell et al., 1986). However,
gold in solid solution can only be effectively recovered if the matrix is altered by some chemical or
biological pretreatment.

Furthermore, sulfides (including arsenopyrite) will oxidatively decompose during cyanide leaching, and
utilise reagents normally required for the dissolution of gold. For example, if arsenopyrite is leached
directly in aerated cyanide solutions containing lime, arsenites may be formed according to the reaction in
Eq. 1 (Nagy et al., 1966). This reaction consumes oxygen as well as lime (Eq. l), and contributes to
reduced gold recoveries.

4FeAsS + 4Ca(OH)* + 1102 (s) + 4FeS04 (aq)+ 4CaHAs03 (Q + HZ0 (1)

Any pyrite or pyrrhotite in the ore would also be expected to consume substantial quantities of both
cyanide and oxygen (Eqs. 2-4).

&%+I cs) + CN- + nFeSe, + SCN- (aq) (2)

4FeS,,, + 302 +6H20 + 4Fe(OHb ($)+ 4S,,, (3)

4FeS,,, + 902 + 10&O + 4Fe(OH),(,) + 4SO,2-,,, + 8H+,,,, (4)

The solution to these problems is the implementation of an oxidative pretreatment which will completely
break down the sulfide matrix and release the gold from solid solution (Demopoulos and Papangelakis,
1989; Dry and Coetzee, 1986; Dunn et al., 1989; Kontopoulos and Stefanakis, 1990; Linge, 1992; Udupa et
al., 1990; Weir and Berezowsky, 1986; Weir et al., 1996). A prior concentration step such as flotation
would also be required to minimise the amount of material treated, and thus make the added treatment cost
effective (Swash, 1988).

The aim of this investigation was to undertake a comparative evaluation of pretreatments on the recoveries
obtained after cyanide leaching of a well characterised natural ore body, where the majority of the gold is
located as invisible gold in an arsenopyrite matrix. The pretreatments that were evaluated included fine
grinding the ore, a two stage pyrolysis/oxidative roast treatment (Pyrox) (Avraamides et al., 1991; Dry and
Coetzee, 1986; Dunn, 1997; Dunn and Chamberlain, 1997; Dunn et al., 1989; Dunn et al., 1995b; Ferreira
et al., 1989; Graham et al., 1992), and an acidic oxidative pressure acid leach (PAL) (Berezowsky and
Weir, 1983; Dziurdzak et al., 1989; Papangelakis and Demopoulis, 1990a; Papangelakis and Demopoulis,
1990b; Robinson and Williams, 1992; Thomas, 1991; Weir and Berezowsky, 1986; Weir et al., 1996)

EXPERIMENTAL

Samples

Core samples of a gold ore were assessed for overall general mineralogy using powder X-ray diffraction
(XRD). Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were employed to
assess the native gold and/or telluride content, and solid solution gold in arsenopyrite and other sulfides.

The ore samples were made from a riffle split blend of five crushed core samples which were mixed to
yield a sample with a theoretical gold head grade of 7.5 ppm. The blended sample was milled to the three
size fractions of <45 urn, ~75 pm, and cl25 urn. The <75 urn fraction was divided into three quantities,
two of which were oxidised prior to cyanide leaching. During storage the ground samples were sealed in air
proof plastic bags and refrigerated.
 Evaluation of pretreatments to increase gold recovery from refractory ore 3

Oxidative pretreatments

The pyrolysis/roasting (Pyrox) pretreatment was carried out by heating about 5Og of ~75 umore under
nitrogen in a furnace at 700C for a period of 30 minutes, followed by heating in air at the same
temperature for 3 hours.

The acid pressure leach process was carried out as follows. 400g of the ore (~75 pm) was combined with
2.0 L of H2SO4 (10 g/L) to yield a mixture having a pulp density of 16.7%. The mix was placed in a 3.2
litre capacity autoclave and agitated at 400 rpm. The vessel was sealed and the head space purged with
about 300 kPa nitrogen, leaving a residual 25 kPa of nitrogen gas overpressure. The sample temperature
was then ramped to 180C. On reaching the target temperature, 1500 kPa of oxygen gas was introduced to
give a total vessel pressure of 2600 kPa. At this point the reaction timer was started. The experiment was
conducted over three hours and intermediate samples were taken at 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 hours
(testing for iron and sulfur in solution/solid phase and free acid in solution). The solutions were analysed
for acidity (ie. free H2S04), iron by atomic absorption spectroscopy (AAS) and total sulfur (AAS). At the
end of the experiment the system was quickly cooled to 30C. The residual slurry was removed from the
autoclave and washed. This involved 12 stages of a counter-current decantation, using approximately 240 L
of tap water. The residue was then filtered and dried.

Cyanide leaching

A day before cyanide leaching, pretreated and untreated ore samples (50g) were transferred to 2 litre
capacity plastic bottles fitted with screw cap lids. Each lid was perforated with a hole to allow air to enter.
Deionised water (150 ml) was added to the solids, and the pH of the solution was adjusted to 10.5 by the
addition of calcium hydroxide (lime). Additionally a sample of iron(II1) oxide obtained from Sigma
chemicals (50g) was treated in a similar manner as a control for the experiment. The bottles were placed on
a bottle roller and rotated at 60 rpm for 24 hours. Prior to actual leaching, and if needed, the pH of the
prepared pulps was readjusted to 10.5. Leaching commenced after the addition of 50 mL of 6000 ppm
sodium cyanide solution, which afforded a 20% w/v pulp with an initial cyanide concentration of 1500
ppm. The bottles were immediately placed on a bottle roller and rotated at 60 rpm for a period of 64 hours.
During this time the pH of the solution was monitored intermittently with a Hanna HI1230 pH electrode
and, where needed, maintained at a pH of 10.5 with the addition of lime. The mass of lime added to the
solutions was recorded. The cyanide concentration of the pulp was monitored with an Ionode I/CN/Hg ion
selective electrode connected to a TPS digital pH meter referenced to a Philips Rl 1 glass silver/saturated
silver electrode, and readjusted to maintain the cyanide concentration at 1500 ppm. The oxygen
concentration of the pulps was monitored utilising an Activon Model 40 1 oxygen meter.

Sampling of the dissolved species present in the leach liquor was carried out by intermittently removing the
plastic bottles from the roller and allowing the solids to settle, after which a sample of the supematant (3
ml) was removed with an auto pipette, filtered, and its weight recorded. The solution was then acidified
with the addition of 2M HCl (10 ml) and oxidised with 20% v/v hydrogen peroxide (5 ml). The solution
volume was reduced on a hotplate and made up to 25 ml in a volumetric flask.

Leached gold, iron and sulfur were determined by ICP-OES (optical emission spectroscopy). The head
grade of gold, arsenic, iron and sulfur in the solids before and after both pretreatments and cyanide leaching
was determined by fire assay (Au) and ICP-OES (As, Fe & S) on an aqua-regia digest. Additionally, a
sample of filtered liquor obtained after leaching the untreated ore sample (~75 urn), was analysed by ion
chromatography in order to determine the ions present in solution.
4 M. N. Lehmann et al.

RESULTS AND DISCUSSION

Mineralogy

The sample was first checked for graphite, which in fine-grained form is responsible for preg-robbing.
Optical microscopy of the untreated ore samples showed no sign of carbonaceous material, which is
normally detectable by its anisotropic interaction to polarised light. It seems certain, therefore, that preg-
robbing is not a cause of refractory behaviour in the ore.

XRD analysis of the cl25 pm size fractions revealed that quartz was the most significant phase present in
each of the five core samples. The next most abundant phases were clinochlore
(Mg,Fe,A1)6(Si,A1)4010(OH)8);chlorite (Mg,Fe)S(Al,Si)S010(OH)8;and muscovite (KA12(Si3Al)0,0(OH.F)2.
Quantities of hexagonal pyrrhotite (FeS), and arsenopyrite (FeAsS), were also found. These were less
abundant than any of the silicate materials. Pyrite and galena, as well as gold, were not detected at the 1%
detection level of the technique.

An extensive particle to particle analysis of the ~125 urn ground ore samples, utilising SEM and EPMA,
revealed that the ore contained significant quantities of both arsenopyrite and pyrrhotite. The maximum
possible pyrrhotite contents were calculated to be 11% and 10% respectively. The trace results using the
electron microprobe were derived from 6 minute counts at a current of 450 nA. Pyrite was also found to be
present, as was the occasional grain of chalcopyrite (CuFe&) and galena (PbS), and an iron arsenide,
possibly FeAs*. The gangue minerals were largely undifferentiated by brightness in the SEM, and were
characterised by their qualitative energy-dispersive x-ray spectra. The major minerals found included
quartz, a potassium aluminium silicate with varying amounts of iron, an iron aluminium silicate, and an
iron manganese calcium aluminium silicate. Additionally grains of titanium were found mainly present as
sphene, with very occasional grains of ilmenite. Siderite was the only carbonate definitely identified, but in
general carbonates were elusive.

Gold was only observed in large particles which had avoided fine crushing, and was consistent with a
native gold content of about 5 & 10 ppm. Despite a long search, gold or tellurides were not observed.
Arsenopyrite particles were analysed for trace gold, with the result that some arsenopyrite contained up to
250 ppm of gold, but most contained only a few ppm. The distribution was too irregular to allow
quantification for the limited number of analyses conducted, but is a characteristic observation for solid
solution gold in arsenopyrite. Measurements on several particles of pyrrhotite indicated that some of the
gold present was most likely encapsulated in this phase, and had a gold content of up to 5 & 10 ppm.

PAL pretreatment

The conditions for pressure oxidation were selected on the basis of prior studies on ores having similar
sulfide matrices. Pressure oxidation was carried out for a period of 3 hours at 180 C with an oxygen
overpressure of 1500 kPa. Table 1 shows the mass transfer of sulfur and iron from the solid sulfide matrix
to solution as the reaction occurs. Figure 1 shows that over a three-hour period, a 75% decomposition of the
sulfide was achieved. Just over two thirds of this maximum breakdown occurred in the first half hour, and
then the rate slowed considerably. If this second slower rate was maintained, it would take about a further 3
hours to decompose the sample completely.

Figure 2 shows that the oxidation produces free acid. This is favourable in terms of increasing the rate of
sulfide matrix breakdown. However, an effective residue wash is required to limit the amount of lime
required for neutralisation to the pH value needed for cyanide leaching.
 Evaluation of pretreatments to increase gold recovery from refractory ore 5

TABLE 1 Solution and solid breakdown occurring during oxidative pressure acid leach

Time Free Acid Solid Solution % Sulfide

@ours) G/L Fe % S% Fe % s % Decomposition
0 10 16.2 8.79 0.00 0.33 0
0.5 19.6 10.7 3.82 2.22 1.03 40
1 23.0 11.1 5.38 1.80 1.27 55
1.5 25.7 10.3 3.36 1.67 1.35 62
2 26.9 10.0 4.15 1.65 1.40 66
2.5 27.3 10.6 2.33 1.62 1.45 72
3 27.8 10.3 1.48 1.62 1.46 75

aaL.......,....., ....> ,.,

. . , . a..
0 0.5 1 1.5 2 2.5 3 3.5

Fig. 1 Total sulfide matrix breakdown as calculated from sulfur leached into solution.

Total Free Acid

Time (hours)

Fig.2 Acid concentrations measured during oxidative pressure acid leach.

6 M. N. Lehmann et al.

Pyrox pretreatment

Figure 3 shows the thermogram of a small sample (24 mg) of the <75 urn ore sample obtained during
pyrolysis.

24 - '\
: \
'1

\;\
\
235
'\
g
:: \

\
g 23.
\
i
\!
:\
_
225

22 ~'~'~"~ I"""""'!
0 100 200 300 400 500 600 700 800 900 1000
Temperature (Celcius)

Fig.3 Mass loss of an untreated ore sample (175 pm) during pyrolysis (Heating rate, 20C/min, N2
atmosphere).

Decomposition, as monitored by weight loss, commenced at 500 C, and a maximum weight loss is
reached at temperatures greater than 720 C. This supports the assumption that a maximum breakdown of
the sulfide matrix would be expected under the conditions employed in the Pyrox pretreatment. The
chemical analysis results shown in Table 2 indicate that significant quantities of both arsenic (ca. 96%) and
sulfur (ca. 96%) were lost from the ore after the Pyrox treatment.

TABLE 2 Elemental compositions before and after Pyrox treatment

Arsenic (kg/t) Sulfur (kg/t) Gold (g/t)

Before Pyrox 49 74 6.61
After Pyrox 2 3 7.82

These results suggest that the Pyrox pretreatment affords a greater decomposition of the sulfide matrix
compared to the three hour oxidative pressure acid leach. The rise in the gold concentration after treatment
is expected on the basis that the samples undergo weight-loss after the Pyrox treatment, while gold is
conserved in the sample.

Gold recoveries by cyanide leaching

Table 3 shows the gold recoveries achieved for the untreated ores for a range of size fractions, as well as
those pretreated by Pyrox and PAL.

Figure 4 shows the leaching profile of gold during the period of cyanidation.
 Evaluation of pretreatments to increase gold recovery from refractory ore

TABLE 3 Gold recoveries of pretreated and untreated ores obtained from cyanidation

100

7 T T 75pm PAL 1

60
-----__-.._ ----__._- ___

45 pm Untreated
_______~ .-.-- .--------_-_- _.___
75 blrn Untreated
-2
5 ____ _.~___ _~__~
~_~
i? 6o 125 pm Untreate

$
8
2
s
s 40

20

0
10 20 30 40 50 60 70
Time (hours)

Fig.4 The leaching profile of gold from pretreated and untreated ores during cyanidation.

It can be concluded that gold recoveries are significantly improved with a pretreatment. The solution
analysis of the gold indicated that after a period of 10 hours 79% and 75% of the gold was found to be
leached from both the PAL and Pyrox pretreated ores respectively, as compared to 60%, 57%, and 55% of
the untreated ores, listed in increasing particle size. The fact that recoveries from a range of particle sizes
are not only low but similar (55-60%) suggests that fine grinding alone would not significantly improve
recoveries, and is consistent with the gold being trapped in a solid solution form.

In batch leaching the rate of leaching is described by Eq. 5 (Nicol, 1988);

8 M. N. Lehmann et al.

4Aul
-- = kl{[Au]-[Au]e}2 (5)
dt

Equation 5 can be integrated to give Eq. 6, which describes the concentration of undissolved gold as a
function of time;

1 1
=kl.t + (6)
[Au]- [Au1e [Au1o - [Au1e

where [Au] is the concentration of gold in the ore at any time t, [Au]~ and [Au]~ are the initial and
equilibrium gold concentrations in the solid respectively, while k, is the leaching rate constant. From Eq. 6,
the rate constant for the cyanidation of the ~45 urn untreated ore can be obtained by plotting the data of
Table 4 as shown in Figure 5.

TABLE 4 Data for the determination of leaching rate constant kl for the ~45 pm untreated ore

*For the above calculations [AulBt 61hrs.= [Au]~ = 2.25 g/t

Time (hours)

Fig.5 Plot of l/( [Au] - [Au]~ ) vs time for the determination of the leaching rate constant k, for the first
18.5 hours of cyanidation of the ~45 urn untreated ore.
 Evaluation of pretreatments to increase gold recovery from refractory ore 9

Table 5 lists the leaching rate constants obtained from the initial stages of leaching, utilising the
equilibrium concentrations of the gold at the completion of the leach time.

TABLE 5 Leaching rate constants (k,) for treated and untreated ores obtained during the initial
stages of cyanidation

Ore Blend Leaching rate R2

constant (tg-h-l)
Untreated ore ~45 pm 0.10 0.98
Untreated ore ~75 pm 0.28 0.96
Untreated ore ~125 urn 0.21 0.97
Pyrox treated ore ~75 pm 0.53 0.90
PAL treated ore <75 urn 0.32 0.96

It is apparent that over extended time the PAL treatment yields slightly higher gold recoveries than the
Pyrox treatment. These are reflected in the final recoveries of 85% and 75% for the PAL and Pyrox
pretreatments respectively, as determined by fire assay. However, as displayed by Table 5, gold is leached
out of the Pyrox treated ore more quickly compared to the PAL ore, as indicated by the greater leaching
rate constant of the former. Figure 4 shows that the Pyrox treated ore exhibits a slight reduction of the gold
in solution at extended leach times, which may be due to the reprecipitation of gold. The leaching rate
constants for the untreated ores are significantly less than the treated ores. The <45 pm ore was found to
have a leaching rate constant less than for the <75 and ~125 pm ores, and although unexpected might be
accounted for by the small particles forming a thicker impervious iron oxide coating during milling.

Since sulfur in the cyanide leach liquor originates from the sulfide component of the ore, a measure of its
concentration gives an indication of the leach rate of the sulfide matrix component in untreated ores. In
treated ores it gives evidence as to the level of completion of the oxidative pretreatment. The importance of
the amount of sulfur in an ore that can undergo dissolution is dependent on the nature of the sulfur species
that will be dissolved. In general, sulfur species other than sulfate can react with cyanide in a variety of
ways and act as cyanicides. For example, cyanide readily reacts non-oxidatively with elemental sulfur to
form thiocyanate (Eq. 7) as do a range of sulfoxy ions such as thiosulfate (Eq. 8) and tetrathionate ions (Eq.
9). Under oxidative conditions sulfide ions released from non-oxidative mineral sulfide dissolution can be
oxidised to thiosulphate ions (Eq. lo), to then form thiocyanate ions via Eq. 8.

S + CN- + SCN- (7)

S2032- + CN- + SCN- + S032- (8)

S4062- + CN- + 2SCN- + 2S032- (9)

S*- + O2 +H20 + S20s2- + 20H- (10)

Although gold can form stable complexes with thiocyanate, at the pH employed for cyanidation, gold does
not complex with thiocyanate to any appreciable extent (Marsden and House, 1992).

Table 6 presents the quantity of sulfur dissolved for the pretreated and untreated ores, while Figure 6 shows
the rate of sulfur dissolution into the cyanide liquor.
IO M. N. Lehmann et al.

TABLE 6 Dissolved sulfur levels of pretreated and untreated ores obtained from cyanidatiou

00~~~~~~~~~~~~~
0 10 20 30 40 50 60 70
Time (hours)

Fig.6 The extent of sulfur dissolution from pretreated and untreated ores during cyanidation.

Each material (untreated and treated) was conditioned in deionised water for 24 hours, and the pH of the
solution adjusted to 10.5 prior to the addition of cyanide solution. In the first 24 hours of cyanide leaching,
all but the Pyrox treated ore show increases in the concentration of sulfur in the leach liquor. The Pyrox
sulfur level in solution was relatively high to start with, indicating that water soluble sulfur compounds
were present in the roasted product. This may have been entrained S02, or compounds such as calcium
sulfate formed during the roasting step. The sulfur level was relatively constant over the leach period.
Furthermore, Table 6 shows that almost all the sulfur in the matrix is leached. Both solution and residue
analysis showed that the ~75 pm leached a greater amount of sulfur than the ~45 pm or the cl25 pm. This
anomalous observation may be due to the fact that the ore is comprised of a variety of minerals, each with
differing reactivities. Consequently, at certain particle sizes the dissolution of certain fractions of the ore
may be favoured over others. For example pyrrhotite readily oxidises in air to form protective coatings
(Pratt, et al.,) which may either be thicker or more uniform at certain particle sizes. However, the overall
 Evaluation of pretreatments to increase gold recovery from refractory ore 11

ncrease in dissolved sulfur levels indicates that the sulfidic components of the ore are oxidising under the
conditions of cyanide leaching.

Figure 7 shows the dissolved oxygen (DO) levels during cyanide leaching. During the initial stages, both
treated and untreated ores showed a significant decrease in the levels of DO. The most extreme decreases
were experienced by the ~45 and ~75 urn untreated ores, and these results are consistent with the sulfide
minerals consuming oxygen during oxidation (Dunn et al., 1995a).

Table 7 shows the relative concentrations of soluble ions found after leaching the ~75 urn ore for the
duration of the test under normal bottle roll conditions, and additionally when oxygen gas is sparged
through the solution, instead of air, to promote further oxidation.

1, 75 pm Pyrox
2. 75 pm PAL
3. 125 pm Untreated
4. Control
5. 75 pm Untreated
6. 45 pm Untreated

._ _^ ^^
cl 10 20 30 40 50 BU IO

Time (hours)

Fig.7 Dissolved oxygen levels during cyanidation of pretreated and untreated ores.

TABLE 7 Concentration of major ions found in solution after cyanidation of the minus 75 pm
untreated ore for a period of 64 hours
12 M. N. Lehmann et al.

The major soluble product of mineral sulfide oxidation during cyanidation is the thiocyanate ion. As
expected, the yield of this product rises with increasing oxidation of the mineral. In contrast, the dissolution
of product ions which are cyanicides, such as copper and nickel, are inhibited when the oxidation potential
of the solution is increased and is due to the oxidation of these ions to insoluble hydroxy carbonates such as
malachite (Eq. 11). A reduction in the concentration of these ions would be expected if the CIP plant is
sparged with oxygen gas rather than air (Muir et al., 1988). This is a positive outcome, as complexes of
copper and nickel are known to catalyse the oxidation of cyanide.

2Cu(CN),-,,,, + ; O2 + 9H20 + Cu(OH)&uC03 (s) + 3CO,-(,,, + 4NH,+ (aq) (11)

The concentration of the ferro- and ferricyanide complexes in solution are also noticeably less significant
than the concentration of thiocyanate ions. If iron hydroxide/oxides are initially formed from oxidative
pathways, then the kinetics of subsequent dissolution in solutions containing cyanide ions (Eq. 12) must be
slow. This would explain the absence of a large amount of the former, even though many reports have
postulated on the thermodynamic stability of these iron cyanide complexes (Osseo-Asare et al., 1984;
Wang and Forssberg, 1990).

Fe(OH)3 cs)+ 6CN- caq)+ Fe(CN)b3- caq)+ 3OH. caq) (12)

Figures 8 and 9 show the cumulative cyanide additions made to the untreated and treated ores, respectively,
in order to maintain the cyanide concentration at 1500 ppm. In the initial 8 hours of leach there was little
difference in the amount of cyanide consumed by any of the samples. After this time differentiation in
cyanide consumption became evident. Notably, the Pyrox treated ore consumed significant quantities of
cyanide with respect to the PAL and the untreated ores, and may be related to the elevated levels of
dissolved iron that were observed in the leach, as shown in Figure 10. Interestingly, during the initial stages
of cyanide leaching of the Pyrox treated sample, iron is readily solubilised and reprecipitated. Such
behaviour is not observed with the PAL or untreated ores.

0.4""""'."'."""',""'.".""
0 10 20 30 40 50 60 7(
Time (hours)

Fig.8 Cyanide consumed during the cyanidation of untreated ores to maintain the cyanide concentration at
1500 ppm (kg of NaCN / tonne ore).
 Evaluation of pretreatments to increase gold recovery from refractory ore

0 10 20 50 60 70
Tilt! (houf$

Fig.9 Cyanide consumed during the cyanidation of treated ores to maintain the cyanide concentration at
1500 ppm (kg of NaCN / tonne ore). .

The dissolution of arsenic from the untreated ores is most likely due to the formation of soluble arsenates
arising from reactions similar to Eq. 13, and also may arise from resolubilisation of arsenites formed from
the reaction described by Eq. 1.

FeAsS (sj+ 702 + 2H20 -_) 4HAs02 (aqj+ 4Fe+caqj+ 4SOa2- (aqj (13)

Ferrous ions produced from oxidation of iron sulfides may be further oxidised with oxygen to yield ferric
ions (Eq. 14) (Hiskey and Schlitt, 1981). The ferric ions produced can combine with arsenate to form ferric
arsenate, which precipitates as crystalline scorodite (Eq. 15). Furthermore, it is this reaction which is
thought to contribute largely to the free acid produced during pressure oxidation of FeAsS as shown in
Figure 2 (Bailey and Peters, 1976; Papangelakis and Demopoulis, 199Oa).

4Fe2+(,,)
+ o2 + 4H,,,, + 4Fe3+(,) + 2H20 (14)

Fe3+(,,)
+ H&Q caq) + 2H20 + FeAs04.2HzO cs)+ 3H,,, (15)

Consequently, the observation that the iron concentration for the PAL ore initially starts low and remains
comparatively low throughout the leach, is most likely a result of it being bound in scorodite. This also
explains why the PAL treated ore had the highest head grade of iron (Table 8), and that throughout the
leach little iron was dissolved (Figure 10). Table 9 shows the low arsenic recoveries obtained fi-om cyanide
leaching of the PAL treated ores as compared to those untreated, even though the initial head grades are the
same. This further confirms that after PAL, the arsenic is locked into the scorodite matrix, which is
desirable as it is nonreactive. Although the stability of this complex has been questioned, provided that the
molar ratio of ironzsenic is four, the ferric arsenate is stable enough for landfill disposal (Haines, 1986).
The Pyrox treated ore is also observed to yield a low arsenic recovery, which is not unexpected given the
low residual arsenic levels remaining after the pyrolysis reaction.
14 M. N. Lehmann et al.

TABLE 8 Dissolved iron levels of pretreated and untreated ores obtained from cyanidation

50

40

45 pm Untreated
f-
30
h
/1 75 pm PAL

20

IO
125 pm Untreatf
f

1
30 40 50 60 70

Time (hours)

Fig. 10 The extent of iron dissolution from pretreated and untreated ores during cyanidation.

TABLE 9 Dissolved arsenic levels of pretreated and untreated ores obtained from cyanidation
 Evaluation of pretreatments to increase gold recovery from refractory ore 15

The PAL treated ore showed a continual increase in the amount of sulfur released into the leach liquor.
However, the percentage of sulfur recovered in the tail was much higher than for the Pyrox treated ore but
lower than for the untreated ores. The oxygen consumption during cyanidation was also comparatively low
for the PAL treated ore, but the consumption of lime over the leach period was high with respect to the
untreated ores but lower than the Pyrox treated ore. It would be expected that any sulfide present in the ore
would be oxidised in the PAL process to a soluble sulfate species. It is curious that much of the residual
sulfur in the head material was retained after cyanidation, and yet a relatively high cyanide consumption
was recorded, compared to the untreated ores. One possibility is that the consumption of cyanide is due to
either an insoluble polysultide species, or elemental sulfur retained in the PAL product. This is in
agreement with the observation of Dunn et al. (1996) who postulated that a major product of oxidation
must be elemental sulfur, in order to stoichiometrically balance the oxidation of arsenopyrite in aqueous
solutions. It would be expected that if it was merely a sulfur layer that the rate of dissolution would be quite
rapid. However, this is not the case, and hence the sulfur must also be integrated into either the iron oxide
or scorodite product layers. Figure 11 shows that the PAL treated ore also had the highest consumption of
lime during the leach, which is consistent with an iron oxide product layer undergoing reactions similar to
those described by Eqs. 16 and 17. Furthermore, an initially large lime addition might have been required to
neutralise any residual acid in the PAL product, in a reaction described by Eq. 18.

FeO,,, + Hz0 -_) FeOOH,,, + H+ + 1em (16)

FeO(,, + OH- + FeOOHe, + 1e- (17)

30H-,,,, + H3As04 (aq)+ As0d3- (aq)+ 3H20 (18)

Time (hours)

Fig. 11 Lime consumed during the cyanidation of ores to maintain the slurry pH at a value of 10.5 (kg
Ca(OH)2 / tonne ore).

The solubilisation and reprecipitation of iron for the Pyrox treated ore in Figure 10 is also observed in the
control material hematite and can be thought of as being due to a combination of hydration and dehydration
reactions which might follow a pathway as described by Eq. 19.

Fez03 cs)+ 3H20 --+ 2Fe(OH)3 (sacurated sown.) + 2FeOOH cs) + 2&O (19)
16 M. N. Lehmann et al.

CONCLUSION

This study has shown that in order to obtain appreciable gold recoveries from a gold ore, where the gold is
located as invisible gold in a sulfide matrix composed mainly of arsenopyrite and pyrrhotite, an oxidative
pretreatment is required prior to cyanide leaching. Fine grinding (~45 pm) of this ore type did not lead to a
significant improvement in the gold recovery. A cyanide leach of untreated ores yielded soluble arsenic
ions. As a consequence, if this treatment was to be adopted, the liquor from the leach would require further
treatment to remove these ions. The oxygen consumption of the PAL and Pyrox treated ores was
significantly lower during leaching than for the untreated ores, while the leaching rates of the ores was
significantly increased with pretreatment.

Of the oxidative pretreatments examined, the PAL treatment yielded a gold recovery of 79% after 10 hours
which is slightly better than the 75% achieved after the Pyrox process, and appreciably better than the
55-60% recovered without treatment. The Pyrox treated ore was observed to have the faster leach rate and
decomposed the sulfide matrix of the ore to a greater extent than the PAL treatment. PAL, however,
afforded a solid product which effectively locked the arsenic component of the mineral from being
recovered in solution. As a consequence, lime consumption during cyanide leaching was significantly
higher for the PAL treated ores than for Pyrox or untreated ores.

The choice of which oxidative pretreatment to employ commercially will have to be balanced by the fact
that soluble arsenic will be evolved during leaching of the Pyrox treated ore. While this is not a problem
with the PAL treated ores, substantially more lime will be needed in order to leach the latter.

ACKNOWLEDGMENTS

The authors wish to thank Dr J. Graham for conducting the mineralogical assessment of the ore used in this
study. This research has been supported by the Australian Governments Cooperative Research Centres
Program, through the A J Parker CRC for Hydrometallugry.

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