Hydrometallurgy 2003 – Fifth International Conference in Honor of Professor Ian Ritchie –

Volume 1: Leaching and Solution Purification

Edited by C.A. Young, A.M. Alfantazi, C.G. Anderson, D.B. Dreisinger, B. Harris and A. James
TMS (The Minerals, Metals & Materials Society), 2003
EFFECT OF CARBONACEOUS COATINGS ON PREG-ROBBING OF
CHALCOPYRITE

H. Tan, D. Feng* and J.S.J. van Deventer

Department of Chemical Engineering, The university of Melbourne, Melbourne, Parkville, Vic.
3010, Australia. E-mail: dfeng@unimelb.edu.au

Abstract

“Preg-robbing” is the active adsorption of gold from cyanide solution by the ore components.
The role of carbonaceous coatings on chalcopyrite surfaces in the preg-robbing of chalcopyrite
has been investigated by using pure chalcopyrite and a copper concentrate. Activated carbon
and graphite were chosen as representative carbonaceous contaminants. It was found that the
carbonaceous coatings enhanced the preg-robbing of chalcopyrite. Activated carbon coating
increased gold adsorption onto chalcopyrite to a lager extent, in comparison with graphite
coating. In the preg-robbing of the copper concentrate, gold adsorption was increased to larger
extent at finer particle sizes and at higher contents of activated carbon or graphite. The preg-
robbing of chalcopyrite was reduced or eliminated, depending on the concentrations of free
cyanide. However, the gold adsorption on the carbon and graphite coated chalcopyrite could not
be avoided even at higher cyanide concentrations, and this adsorption was solely attributed to
the carbonaceous coatings. Zeta potential studies indicated that the carbonaceous coatings
reduced the negativity of the chalcopyrite surface charge. As shown by SEM analysis, gold not
only accumulated at the edges and defect sites, but was also spotted on the smooth surfaces of
chalcopyrite with carbon or graphite present. XPS results revealed that gold was strongly
reduced on chalcopyrite surfaces, with the sulfide ions of the chalcopyrite being oxidized to
elemental sulfur. Diagnostic elution indicated three mechanisms contributing to gold take-up by
chalcopyrite, i.e. gold reduction, physical adsorption and chemical adsorption.

Introduction

In gold- recovery plants, cyanide is universally used because of its relatively low cost and great
effectiveness for gold dissolution. A major problem in the recovery of gold via the cyanidation
process is preg-robbing, resulting in severe gold losses to tailings. The preg-robbing
components may be the carbonaceous matters, such as wood chips, organic carbon and
elemental carbon [1-3]. The aurocyanide complex may also be removed from solution by
mineral themselves such as clay minerals [2, 4], quartz [5-6] and sulfides [5, 7, 8]. This removal
of gold may occur via the physical adsorption process or by reduction of the gold cyanide
complex at the mineral surface [9].

Most work on preg-robbing is to identify and characterize preg-robbers by chemical methods

[3, 10, 11] and optical microscopy and microprobe analysis [12]. Native carbon was found to be
the most important preg-robber acting as a similar manner to activated carbon [11]. Apart from
carbonaceous matters, the other source of preg-robbing is the minerals of the ore. Urban et al.
[9] conducted one of the earliest studies investigating the adsorption of gold cyanide onto the
surfaces of minerals, on the Witwatersrand Reefs. Heavy metal minerals were the found to be
strongly preg-robbing. Quach et al. [7] reported that chalcopyrite was not preg-robbing unless
there was a carbonaceous component in the chalcopyrite. It was proposed that aurocyanide was
reduced at the pyrrhotite surface, with the sulfide ions of the pyrrhotite being oxidized to
elemental sulfur [7]. Hausen and Bucknam [2] showed that chalcopyrite would only adsorb
gold at high concentrations. Mössbauer spectroscopy indicated that gold cyanide was reduced at
35
the surfaces of chalcopyrite and arsenopyrite, with the metallic gold accumulating at defect
sites on the surface of the minerals [5, 12]. More recently, pyrite and chalcopyrite were shown
to be very strongly preg-robbing by Rees and Van Deventer [13]. A mechanism was proposed
where the gold was reduced at the chalcopyrite surface, along with the oxidation of chalcopyrite
to form copper-cyanide complexes in solution.

In summary, previous work is mainly focused on the preg–robbing behaviors of carbonaceous

matters and ore constituents, separately. However, in practice carbonaceous matters co-exist
with minerals in gold ores. Carbonaceous matters could contaminate mineral surfaces
especially in the case of fine grinding. It is impossible to isolate carbonaceous matters from the
rest of ore constituents with regard to preg-robbing problems. The effect of carbonaceous
contaminant layers on preg-robbing behavior of minerals has been neglected in the literature. It
is expected that carbon could preferentially coat on sulfide surfaces over other hydrophilic
gangue mineral surfaces. It is the purpose of this work to examine the effect of contaminant
carbonaceous matters on the preg-robbing behavior of chalcopyrite, a very common sulfide
associated with gold ores. Activated carbon and graphite were chosen as the two typical
carbonaceous sources, as found in carbonaceous gold ores. The mechanisms of gold adsorption
on chalcopyrite were studied through diagnostic elution with cyanide, Zeta potential
determination, microanalysis with SEM/EDX and X-ray Photoelectron Spectroscopy (XPS).

Experimental Work

Materials

Gold free chalcopyrite samples were obtained from Geological Specimen Supplies, Sydney,
Australia. The chalcopyrite mineral samples were crushed in a roll crusher, milled in a ring
mill, sieved to a particle size of –45 µm and stored in air-tight plastic bags in a fridge to avoid
further oxidation. For comparison, washed fine sand was milled to –45 µm. The chalcopyrite
samples contained about 98% of chalcopyrite and trace amounts of quartz, carbonates and
sphalerite. A copper concentrate, with a particle size of 80% passing 75 µm, was supplied by a
Newcrest gold mine. A rotary splitter was used to obtain representative samples. Quantitative
XRD analysis indicated that the copper concentrate contained 46.7% chalcopyrite, 24.3%
pyrite, 16.5% dolomite, 5.9% quartz, 5.6% albite and 0.8% arsenopyrite. According to the
chemical analysis, the copper concentrate contained 225 mg/Kg Au, 440 mg/Kg Zn, 1.5%
carbon, 0.18% organic carbon, 29% S and 25% Fe.

Activated carbon powder (-106 µm, Darco KB) and graphite powder (-54 µm) were purchased
from Aldrich and were subjected to further grinding to a particle size of –10 µm in a ring mill.
The chalcopyrite mineral samples were dry mixed with desired amounts of carbon or graphite
powder and tenderly ground in a motor pestle for 30 min to make carbon or graphite coat on
chalcopyrite surfaces. The resultant chalcopyrite samples contaminated with carbon or graphite
were stored for the experimental use. For comparison, the chalcopyrite samples without the
addition of carbon or graphite were also tenderly ground for 30 min. The copper concentrate
samples were ground together with desired amounts of carbon or graphite in a ceramic ball mill
for various periods of time. Similarly, the copper concentrate samples were ground for the same
periods of time to maintain the same particle sizes. Synthetic gold solutions were prepared with
reagent grade KAu(CN)2 (Johnson Matthey). All the other chemicals were A.R. grade.

Preg-robbing tests and analytical techniques

Adsorption experiments performed in reactors using a magnetic stirrer. 2 g of the chalcopyrite

36
samples was added to 200 ml of synthesized gold solutions. For the copper concentrate, 5 g of
the ore samples was added to 400 ml of gold solutions. The stirring speed was maintained at
300 min-1. The reactors were sealed during adsorption, in an attempt to isolate slurries from air.
High purity nitrogen was also occasionally sparged into the slurries to drive off dissolved
oxygen. All the experiments were conducted at a room temperature of about 20°C. The solution
pH was controlled constantly during adsorption by adding potassium hydroxide. A platinum
electrode (M21Pt, Radiometer) was used to measure the mixed potential with a double-junction
reference electrode (Ag/AgCl, saturated KCl, Orion). Samples were taken at certain intervals
during adsorption. The samples were centrifuged and filtered for the subsequent ICP
determination. Duplicate tests were conducted with only average results reported. The standard
deviation was within 1%.

Solution analysis was performed using a Perkin-Elmer ICP-OES for the determination of
elemental concentrations. A Phillips XL30 SEM coupled with an Oxford energy dispersive
spectrometer was employed for topological studies of the chalcopyrite particles after
adsorption. Zeta potential was measured with 0.01 M NaCl electrolyte in a Colloidal Dynamics
(Model Acoustosizer II), in an attempt to determine the effect of carbon or graphite layers on
the surface charges of the chalcopyrite particles. XPS was performed on a nano probe (Fisons
Instruments) at about 10-9 torr (using monochromatic the Al Kα X-ray at 1486.6 eV). In order
to improve the sensitivity of the loaded gold to XPS and SEM/EDX measurements, the gold
concentration in solution for adsorption was increased to 1000 mg/L Au and 3 g of samples was
used. The chalcopyrite samples were immersed in carbon tetrachloride for 2 hours to remove
elemental sulfur from the chalcopyrite surfaces prior to adsorption. The adsorption took place at
a constant pH of 11. After a 24 h adsorption, the samples were filtered and rinsed with
deionized water for three times and were dried under a vacuum overnight for the subsequent
XPS and SEM/EDX studies.

Results and Discussion

Effect of carbon or graphite coating on preg-robbing of chalcopyrite

The effect of carbon or graphite coating on the preg-robbing of chalcopyrite was investigated in
free cyanide deficient systems. Figure 1 shows the preg-robbing of chalcopyrite and quartz in
the presence of 1% carbon or graphite. No gold adsorption was observed on quartz in the
absence of carbon or graphite. The gold adsorptions on quartz with 1% free carbon or graphite
were the same as those on the quartz being coated with 1% carbon or graphite, respectively. As
a matter of fact, only carbon and graphite acted as gold sorbents in the carbon and graphite
coated quartz systems. Clearly, graphite had a very limited gold adsorption capacity. In
contrast, activated carbon adsorbed a significant amount of gold (Figure 1). The gold
adsorptions on chalcopyrite almost reached equilibria after 8 h contact with gold solutions in
the absence and presence of carbon or graphite (Figure 1). It is noteworthy that the carbon or
graphite coated quartz became preg-robbing despite the fact that quartz did not adsorb gold on
its own. Therefore, it could be important to separate carbonaceous matters from bulk ores prior
to fine grinding.

Figure 1 shows that chalcopyrite was very strong preg-robbing, in accordance with previous
studies [5, 13]. Gold adsorptions were slightly higher for the carbon or graphite coated
chalcopyrite samples than the corresponding chalcopyrite samples with free carbon or graphite
(Figure 1). Thus, in the carbon or graphite coated chalcopyrite systems carbon and graphite not
only acted as gold sorbents on their own, but also enhanced the adsorption of gold on
chalcopyrite. The activated carbon coating enhanced the adsorption of gold to a larger extent,
compared to the graphite coating.
37
 1.8

Gold adsorption, mg Au/2 g

1.5

1.2
CP CP+C CP+G
0.9
CP(C) CP (G) qz(C)
0.6
qz(G)

0.3

0.0
0 5 10 15 20 25
Time, h

Figure 1: Effect of carbon or graphite contaminant on preg-robbing of chalcopyrite. Condition:

22.3 ppm Au, pH 11.0, 1% carbon or graphite, no free CN-. CP – chalcopyrite; qz – quartz; C –
carbon; G – graphite; (C) or (G) - carbon or graphite coating; + C or + G – free carbon or
graphite.

Gold adsorption on chalcopyrite could be based on the three mechanisms. One possibility is the
physical adsorption, in which the gold cyanide radicals are attracted because of their negative
charge to a positively charged surface. The second possibility is that the gold cyanide radicals
react with the chalcopyrite surface to form gold sulfide complexes, which remain chemisorbed
on chalcopyrite [14]. Finally, the gold cyanide could be reduced at the chalcopyrite surface, as
proposed in a number of previous studies on sulfide preg-robbing [5, 7, 13]. Gold is reduced to
elemental gold, with the sulfide ions of chalcopyrite being oxidized to elemental sulfur.

-2
Zeta potential, mV

-4

-6
CP
-8
CP(5%C)
-10 CP(5%G)

-12
1 3 5 7 9 11 13
pH

Figure 2: Effect of carbon or graphite coating on Zeta potential of chalcopyrite. (5%C) – 5%

carbon coating; (5%G) – 5% graphite coating.

Figure 2 shows the Zeta potentials of the chalcopyrite coated with 5% carbon or graphite. From
pH 2 to 12, the chalcopyrite surface was negatively charged and the negativity decreased at
lower pH levels (Figure 2). It indicates that the physical adsorption might take a minor part in
chalcopyrite preg-robbing, especially at a higher pH. Previous studies [15] have shown that the
addition of calcium ions can generally increase the zeta-potentials of sulfides and hence reverse
38
the negative surface charge in alkaline solutions. It can be expected that chalcopyrite surface
can become positively charged by the presence of a small amount of calcium ions in the Stern
double layer. In adsorption tests, trace amounts of calcium ions could be introduced through the
dissolution of calcium bearing minerals, and distilled water. Thus, gold cyanide complex could
physically attach onto the chalcopyrite via electrostatic forces. Clearly the presence of carbon
or graphite coatings decreased the negativity of the chalcopyrite surface charges (Figure 2). The
chalcopyrite surface still remained negatively charged, even in the presence of 5% carbon or
graphite coating, however, it is expected that the carbon or graphite coatings intended to
increase the physical adsorption of gold on chalcopyrite via reddening the chalcopyrite surface
more positively charged (Figure 2).

Chalcopyrite is considered to be semi-conductive. Thus, chemical adsorption and reduction of

gold are readily to occur via electrochemical reactions. The chemical reaction could involve
electron transfer within the sulfur of the chalcopyrite, resulting in the formation of polysulfides,
which were reactive with gold [14]. The reduction of gold cyanide on chalcopyrite could result
from the electron transfer from the sulfur of the chalcopyrite to the gold cyanide radicals. Gold
cyanide could physically adsorb on chalcopyrite first. Then, electrons could transfer from the
anodic site, the sulfur, to the cathodic site, the aurous ion, via the conduction band of the
chalcopyrite, due to its semiconducting properties. The highly conductive coatings of carbon or
graphite on chalcopyrite would enhance the conductivity of the chalcopyrite surfaces and hence
the electron-transfer in the electrochemical reactions occurring in the gold adsorption. In the
presence of carbon or graphite coatings, gold cyanide was first attracted to the coated
chalcopyrite surfaces by carbon or graphite and was subjected to further reduction at the
chalcopyrite surfaces. Carbon had a much higher ability to attract the gold cyanide radicals to
the chalcopyrite surfaces than graphite, and more gold cyanide could be reduced at the
chalcopyrite surfaces. On the other hand, carbon could enhance the conductivity of the
chalcopyrite surfaces to a larger extent than graphite, which was indirectly indicated by the
higher slurry conductivities in the carbon coated chalcopyrite systems than the corresponding
graphite coated chalcopyrite systems during the measurements of Zeta potentials. As a result,
the carbon coating had a larger effect than the graphite coating in enhancing the chemical
adsorption of gold as well as the reduction of gold at the chalcopyrite surfaces.

The pHiep (iso-electric point) of quartz was found to be around 5, and its surface was negatively
charged at pH over 5. As a result, no physical adsorption of gold on quartz could occur at pH
11.0 in the adsorption tests. On the other hand, quartz was inert without surface conductivity.
Gold was unlikely chemisorbed or reduced at quartz surfaces, involving electrochemical
reactions. As a consequence no gold adsorption on quartz was observed in the adsorption tests,
as shown in Figure 1. The carbon or graphite coatings could render the quartz surfaces
conductive. However, the lack of electron donors made the chemical adsorption and the
reduction of gold at the quartz surfaces impossible. Therefore, the carbon and graphite coatings
could not only enhance the adsorption of gold on quartz, but adsorbed gold on their own.

Effect of pH on preg-robbing

Slurry pH has been shown to be a significant factor affecting the preg-robbing of sulfides in
previous studies [16]. It was claimed that preg-robbing was inhibited at a higher pH for the
treatment of sulfide gold ores. Figure 3 shows the preg-robbing of chalcopyrite was extremely
sensitive to pH. The gold adsorption on chalcopyrite was fairly high at lower pH levels, and
decreased with an increase in the slurry pH. A minimum gold adsorption was achieved with
increasing pH up to around 11.0. With a further increase in the pH level up to 12.5, the gold
adsorption on chalcopyrite significantly increased again. The chalcopyrite contaminated with
graphite or carbon had similar pH dependence for gold adsorption. Similarly, the carbon and
39
graphite coatings still enhanced the adsorption of gold on chalcopyrite at different pH levels. In
comparison with the graphite coatings, the carbon coatings enhanced gold adsorption on
chalcopyrite to a larger extent.

6.0

Gold adsorption, mg Au/2 g

CP
5.0 CP+C
CP+G
4.0 CP(C)
CP(G)
3.0

2.0

1.0

0.0
3 5 7 9 11 13
pH

Figure 3: Effect of pH on preg-robbing of chalcopyrite contaminated with carbon or graphite.

Condition: 22.3 ppm Au, 1% carbon or graphite, no free CN-.

At lower pH levels, the chalcopyrite surfaces were less negatively charged in the absence or
presence of carbon or graphite (Figure 2). Thus, the physical adsorption of gold on chalcopyrite
was likely higher. Chalcopyrite dissolved in acidic solutions to release iron into solutions and to
render its surface rich in sulfur, which was indicated by the disproportionate increase in the Fe,
Cu and S concentrations in solutions. The fresh and sulfur rich surfaces due to dissolution could
enhance gold adsorption on chalcopyrite via chemical adsorption or gold reduction on
chalcopyrite. On the other hand, the gold cyanide could not be stable at lower pH levels, as the
mixed potentials were about 400-430 mV at pH 4, compared to about 300-350 mV at pH 11.
Carbon and graphite had higher adsorptions of gold at lower pH levels, due to lesser
competition between the gold cyanide radicals and the hydroxide radicals. Therefore, gold
adsorptions increased when pH was lowered in all the systems. At higher pH levels, the gold
adsorptions decreased, due to the competition between the hydroxide radicals and the gold
cyanide radicals for adsorption on chalcopyrite. However, the gold adsorption sharply increased
when pH was increased up to 12.5. At pH 12.5, the mixed potential sharply decreased to 120-
180 mV, compared to 300-350 mV at pH 11. This indicates that reductive potentials dominated
the adsorption system at high pH levels, which was beneficial for gold reduction at the
chalcopyrite surfaces. Gold reduction was expected to be the predominant mechanism for gold
adsorption at such a high pH level, while physical adsorption could be negligible.

Effect of free cyanide on preg-robbing of chalcopyrite

The gold adsorptions reduced significantly even at a low free cyanide concentration of 50
mg/L, as shown in Figure 4. Above this concentration, the gold adsorptions decreased gradually
and then leveled off with a further increase in the cyanide concentration. At an initial cyanide
concentration of about 400 mg/L, the preg-robbing of chalcopyrite was completely eliminated,
with almost no gold adsorbing on chalcopyrite (Figure 4). Likewise, at an initial cyanide
concentration of about 400 mg/L a slight gold adsorption was observed on the graphite-
contaminated chalcopyrite. However, the gold adsorptions still remained at high levels on the
carbon-contaminated chalcopyrite even at an initial cyanide concentration of 400 mg/L (Figure
4). The gold adsorptions on the carbon-contaminated chalcopyrite were only attributed to the
40
activated carbon, as the gold adsorption on chalcopyrite was inhibited at high cyanide
concentrations. At lower cyanide concentrations, chalcopyrite adsorbed gold and the carbon or
graphite coatings still enhanced the adsorption of gold on chalcopyrite. Compared with the gold
cyanide species, the cyanide species is much smaller in size. The cyanide species could
compete with gold cyanide to physically adsorb on chalcopyrite. In comparison with the
polysulfide species, the cyanide species has stronger complexing ability for gold. As a result,
the chemical adsorption of gold on chalcopyrite could also be eliminated in the presence of free
cyanide. Metallic gold on chalcopyrite surfaces, due to the reduction of gold cyanide, could be
readily soluble in cyanide. Therefore, the adsorption of gold on chalcopyrite could be inhibited
in the presence of free cyanide. However, gold still adsorbed onto activated carbon or graphite
in the presence of free cyanide.

1.0
Gold adsorption, mg Au/2g

50 ppm

0.8 400 ppm

0.6

0.4

0.2

0.0
CP CP + C CP +G CP (C) CP (G)
Samples

Figure 4: Preg-robbing of chalcopyrite in the presence of free cyanide. Condition: 22.3 ppm Au,
pH of 11.0.

Preg-robbing behavior of the chalcopyrite concentrate

Figure 5 shows the effect of carbon or graphite content on the adsorption of gold on the copper
concentrate. The gold adsorptions increased with an increase in the content of carbon and
graphite. The carbon and graphite coatings not only acted as gold sorbents on their own, but
also enhanced the adsorption of gold on the ore particles, as shown in Figure 5. It is expected
that only a part of carbon or graphite could be coated on the copper concentrate and that the
coverage with the carbon or graphite coatings on the ore particles could be higher at a higher
carbon or graphite content. A higher coverage of coatings could further enhance the adsorption
of gold on the copper concentrate via chemical adsorption or gold reduction.

The gold adsorptions increased to lesser extents in the graphite-contaminated systems than in
the corresponding carbon-contaminated systems. The copper concentrate contained 0.18%
organic carbon and 1.5% carbon, which could be highly preg-robbing. In addition, the copper
concentrate contained 24.3% pyrite. Pyrite has a lower conductivity than chalcopyrite. As a
result, pyrite could have a lower ability to adsorb gold in the absence of carbonaceous coatings,
due to the limited chemical adsorption and gold reduction via electrochemical reaction.
Obviously, the carbonaceous coatings could enhance the conductivity of pyrite, and hence
increase the adsorption of gold on pyrite. The overall gold adsorption on the copper concentrate
was thus increased with the presence of the carbon or graphite coatings. It is expected that
carbonaceous matters in the concentrate could also coat on the minerals during fine grinding.
The coverage of the mineral surfaces in the copper concentrate with the carbon or graphite
41
coatings could be higher when a larger amount of carbon or graphite was ground with the ore.
A higher coverage of the minerals surfaces especially chalcopyrite and pyrite surfaces with the
carbon or graphite coatings could thus further enhance the adsorption of gold on the minerals in
the copper concentrate. The other gangue minerals such as quartz or dolomite could be non
preg-robbing on their own. However, when coated with carbonaceous matters in fine grinding
these gangue minerals could become preg-robbing.

Gold adsorption, mg Au/5g 3.5 0.5% coating

1% coating
3.0

2.5

2.0

1.5

1.0
CC CC + C CC(C) CC +G CC (G)
Samples

Figure 5: Effect of carbon or graphite content onto gold adsorption of the copper concentrate.
Condition: particle size 85% passing -75 µm, 26.2 ppm Au, pH 11.0, no free CN-. CC – copper
concentrate.

3.6
Gold adsorption, mg Au/5g

85% passing 75 mirons

90% passing 75 microns
3.2
2.8

2.4
2.0

1.6

1.2
CC CC + C CC(C) CC +G CC (G)
Samples

Figure 6: Effect of fine grinding on preg-robbing of the copper concentrate. Condition: 1%

carbon or graphite, 26.2 ppm Au, pH 11.0, no free CN-.

The copper concentrate was subjected to further fine grinding for two different periods. 1%
carbon or graphite was ground with the copper concentrate. For comparison, the copper
concentrate was ground in the absence of carbon or graphite, and 1% carbon or graphite was
added after grinding. The effect of particle size on gold adsorption on the copper concentrate is
shown in Figure 6. Gold adsorptions increased when the particle size was reduced from 85% to
90% passing –75 µm. The carbon or graphite coatings enhanced the adsorption of gold on the
copper concentrate with different sizes, and the enhancement appeared to be more prominent at
42
the smaller particle size (Figure 6). Previous studies indicated that gold cyanide mainly
adsorbed on the chalcopyrite surfaces at edges and defect sites via adsorption and gold
reduction [5,13]. The defect sites and edges of particles had higher free energy than the smooth
surfaces, resulting from the particle reduction processes. Finer particles could have higher ratios
of defects. Fine grinding could cause a larger extent of carbon or graphite smearing on the
mineral particles, as carbon or graphite could be more easily coated on the fine particle surfaces
due to larger surface areas. It is expected that more carbon or graphite could be coated on
mineral particles with an increase in the period of grinding, which could enhance the adsorption
of gold on the minerals especially chalcopyrite and pyrite.

Sulfide gold ores are generally considered to be refractory, due to their inability to respond to
conventional leaching with high cyanide consumption, high oxygen consumption and preg-
robbing. Pre-treatment to unlock the gold in these ores is generally required to achieve
satisfactory gold recoveries. One of the significant methods is physical pre-treatment, which
involves finer grinding (100% < 38 µm) or ultra fine grinding (1-20 µm). It is possible that the
action of fine grinding could intensify the smearing effect of carbon or graphite onto the larger
surface areas, which could aggravate the preg-robbing problem. Therefore, processing
strategies could be devised to separate carbonaceous matters from bulk ores, or to treat smaller
volumes of carbonaceous matters concentrated concentrates and the bulk ores separately, in an
attempt to minimize the effect of carbon or graphite smearing on mineral particles.

Diagnostic elution of gold from the preg-robbed chalcopyrite

In order to understand the gold adsorption mechanisms, a diagnostic elution process was
conducted in 4 steps to strip gold from the gold loaded chalcopyrite. 5 g of samples were
separated from slurries by filtration after 24 h contact with the gold cyanide solutions initially
containing 30 mg/L Au at a pH of 11. The solids were rinsed with 100 ml distilled water at pH
11. 100 ml of 50 mg/L CN- was added to the solids, and then stirred for 30 min, finally
separated from the liquid. 100 ml of 100 mg/L CN- was used to repeat the previous step. Finally
the resultant solids were leached in a stirred container with 1000 mg/L CN- solutions for 20 h,
and afterwards separated from the solutions by filtration. All the filtrates were collected and
analyzed for gold, and the remained solids were also subjected for gold determination.

About 2.1% gold, likely due to mechanical entrapment, was rinsed out by distilled water from
the preg-robbed chalcopyrite samples. Around 8.1%, 4.7% and 85.1% of gold were stripped
from the preg-robbed chalcopyrite in the elution with 50, 100 and 1000 mg/L CN- solution,
respectively. The gold recovery from the 50 mg/L CN- elution could mainly be due to physical
adsorption, which was readily reversible in the presence of free cyanide. The 100 mg/L CN-
elution could mainly recover the gold of chemical adsorption. Finally, the metallic gold due to
reduction at the chalcopyrite surfaces was leached in 1000 mg/L CN- solution. Therefore, the
reduction of gold at the chalcopyrite surfaces was the dominant mechanism for gold adsorption
on chalcopyrite, followed by physical and chemical adsorptions. The elution process recovered
all the gold adsorbed on chalcopyrite. This demonstrated that the preg-robbing could be
eliminated in the chalcopyrite at a raised cyanide concentration, in accordance with the
previous preg-robbing tests. The elution process only recovered about 67% and 80% for the
gold loaded chalcopyrite in the presence of the 1% carbon or graphite coating, compared to
71% and 83% for the gold loaded chalcopyrite with 1% free carbon or graphite respectively.
The chalcopyrite with the carbonaceous coatings had a lower elution recovery, indicating that
the carbonaceous coatings made it more difficult to elute gold from chalcopyrite.

43
SEM/EDX studies

In Figure 7a, surface topological studies by SEM coupled with EDX showed that gold adsorbed
at defect sites on the surface of the chalcopyrite particle. The defect sites could have higher free
energy, which favored the adsorption of gold at these active sites. When chalcopyrite was
coated with 1% carbon via grinding, carbon was found to be present at the chalcopyrite surfaces
especially the fractured surfaces (Figure 7b). Gold was found to adsorb not only at the defect
sites, but also at the smooth surfaces with carbon present. This can further confirm that the
carbon coating enhanced the adsorption of gold on chalcopyrite. When chalcopyrite was ground
with 5% graphite, C was also found at the pyrite surfaces especially the fractured surfaces. Gold
was found at the smooth surfaces at low concentrations with the presence of C. In the SEM
studies, a small amount of nitrogen was found, which gave the evident of physical adsorption.
The values were higher in chalcopyrite with coating of carbon and graphite than chalcopyrite
without coating. This indicates that the carbonaceous coatings increased the preg-robbing of
chalcopyrite.

(a) (b)
Figure 7: Typical SEM images of the pre-robbed (a) chalcopyrite, (b) 1% carbon coated
chalcopyrite.

XPS studies

XPS involves irradiating a sample in high vacuum with monochromatic X-rays. This produces
electrons with kinetic energies that are determined by the atom. The kinetic energies are
dependent on the atomic type, the atomic orbital occupied by the electrons in the atom, and the
oxidation state of the atom. In XPS this kinetic energy is translated to binding energy. The X-
ray photoelectron spectra were recorded for Au 4f, C 1s and S 2p for the gold loaded
chalcopyrite samples. The spectra for gold in pure gold, gold in KAu(CN)2 powder, gold in
Au(CN)2- adsorbed on activated carbon and gold in Au(CN)2- adsorbed on graphite were
recorded as references.

Au 4f5/2 and Au 4f7/2. The energy centers for Au 4f7/2 were at 83.40, 85.53, 85.50 and 84.82 eV
for gold in metallic gold, in KAu(CN)2 powder, in Au(CN)2- adsorbed on activated carbon and
in Au(CN)2- adsorbed on graphite, respectively. The gold in the gold cyanide molecule
experienced an increase in electron population as a result of adsorption on activated carbon or
graphite, due to the formation of the graphite to gold π-donor complex, in which delocalized π-
electrons from the graphitic crystallites of activated carbon or graphite were donated to gold
[17]. Figure 8 shows the Au 4f5/2 and Au 4f7/2 peaks in the X-ray photoelectron spectra for gold
in Au(CN)2- adsorbed on chalcopyrite, on the carbon-coated chalcopyrite and on the graphite-

44
coated chalcopyrite. Even after 100 cumulative scans, the signals were still relatively weak, due
to the low concentrations of the gold loaded on the samples. For this reason, it is impossible by
deconvolution to identify all the states of gold present on the gold loaded surfaces. However,
the shift of the energy centers could demonstrate the change of electron population and hence
the change of the gold oxidation state. The peaks for Au 4f7/2 read from these XPS spectra are at
83.14, 84.94 and 84.64 eV for the gold adsorbed on chalcopyrite, chalcopyrite with a 5%
carbon coating and chalcopyrite with a 5% graphite coating, respectively.

20000

Chalcopyrite
18000
Counts

Chalcopyrite
5% carbon
16000 Chalcopyrit
e

14000
95 90 85 80
Bonding energy, eV

Figure 8: X-ray photoelectron spectra for gold in Au(CN)2- adsorbed on chalcopyrite,

chalcopyrite with activated carbon coating; and chalcopyrite with graphite coating respectively.

All the gold binding energies for gold cyanide adsorbed on chalcopyrite with or without carbon
or graphite coatings were much lower than that for gold cyanide adsorbed on carbon or graphite
(Figure 8). The gold adsorbed on chalcopyrite experienced the most significant increase in
electron population (Figure 8). This indicates that the gold adsorbed on chalcopyrite had the
largest tendency to form metallic gold. Physical adsorption of gold could only change the
binding energy slightly. The binding energies for gold (I) polysulfide complexes were found to
be 85.0 to 85.2 eV with the reference of 285 eV for C [18]. Therefore, chemical adsorption
could not change much the binding energy for gold. Only the gold reduction could reduce the
binding energy substantially. Therefore, it is expected that the gold adsorption on chalcopyrite
could be attributed to different mechanisms despite the difficulty in identifying gold species.
This is accordance with the diagnostic elution, which indicated that about 85% of the gold was
reduced on chalcopyrite and physical and chemical adsorption contributed to the rest. The
binding energy for the loaded gold increased to 84.94 eV for the 5% carbon coated
chalcopyrite, due to the increase of physical adsorption. In comparison, the gold binding energy
for the gold adsorbed on the 5% graphite-coated chalcopyrite was slightly lower. This was
caused by the lower percentage of the physical adsorption of gold on the latter, due to the much
lower adsorption capacity of gold on graphite than on carbon.

C 1s. The C 1s spectra indicated a tiny peak at 284.24 eV, apart from a dominant peak at 285
eV originating from activated carbon or graphite. This tiny peak could result from C in
Au(CN)2-, which is close to 284.4 eV in the previous study [17]. The XPS result for N 1s also
showed a very tiny peak at 400.2 eV for gold cyanide loaded chalcopyrite and chalcopyrite with
the carbon or graphite coatings. This nitrogen peak could be assigned to nitrogen in Au(CN)2-
[17]. The presence of C and N in Au(CN)2- indicated that a small amount of gold physically
adsorbed on chalcopyrite or chalcopyrite with the carbon or graphite coatings.

45
S 2p. Figure 9 shows the XPS results for sulfur on chalcopyrite or chalcopyrite with the carbon
or graphite coatings after loaded with Au(CN)2-. All the S 2p peaks were composed of at least 6
peaks that were deconvoluted to two dominant peaks at 158.7 and 162.3 eV, which could be
originated from the sulfur in chalcopyrite, and four tiny peaks at about 163.6, 164.2, 166.3 and
168.14 eV, which could be allocated as polysulfide (~ 163.01-163.6 eV), S8 (~ 164.2 eV),
thiosulfate (~ 166.45 eV) and sulfate (~168.25 eV) respectively [18].

19000

Chalcopyrite

16000 Chalcopyrite
Counts

5% carbon
Chalcopyrite
5% graphite
13000

10000
169 165 161 157 153
Bonding energy, eV

Figure 9: X-ray photoelectron spectra for activated carbon/graphite contaminated chalcopyrite

loaded with Au(CN)2- giving the S 2p peaks.

The presence of polysulfide revealed the likely formation of gold polysulfides during the
chemical adsorption at the chalcopyrite surfaces. Elemental sulfur could result from the
reduction of gold at the chalcopyrite surfaces, which gave the further evidence for reduction
adsorption of gold on the chalcopyrite.

Conclusions

• In the absence of free cyanide, chalcopyrite was strongly preg-robbing, while quartz did not
absorb gold cyanide. In the carbon or graphite coated chalcopyrite systems carbon and
graphite not only acted as gold sorbents, but also enhanced the adsorption of gold on
chalcopyrite. Carbon had a larger effect than graphite in enhancing the adsorption of gold.
• The preg-robbing of chalcopyrite was pH dependant. The gold adsorption on chalcopyrite
was higher at lower pH. A minimum gold adsorption reached at around pH 11.0 and the
gold adsorption increased again with a further increase in the solution pH up to 12.5. The
gold adsorption on chalcopyrite was reversible depending on cyanide concentration.
However, the gold adsorption on the carbon-coated chalcopyrite was still strong at higher
cyanide concentrations.
• The carbon and graphite coatings increased the adsorption of gold on the copper concentrate
as well. Fine grinding intensified the smearing of carbon or graphite on the mineral
particles, resulting in a larger extent of enhancement in the preg-robbing of the concentrate
by the carbon or graphite coatings. Likewise, the adsorption of gold was further improved at
a higher content of the activated carbon or graphite coatings.
• The diagnostic elution of the preg-robbed samples indicated that the reduction of gold at the
chalcopyrite surfaces was the dominant mechanism for gold adsorption on chalcopyrite,
followed by physical and chemical adsorptions.
• Surface topological studies by SEM/EDX showed that gold adsorbed at defect sites on the

46
 surface of the chalcopyrite particle. For the gold loaded chalcopyrite with the carbon and
graphite coatings, gold was found not only at the defect sites, but also at the smooth
surfaces with carbon present.
• XPS studies on Au 4f indicated that gold reduction was the dominant mechanisms for the
gold adsorption on chalcopyrite. Physical and chemical adsorption also contributed to the
total gold adsorption on the chalcopyrite with the carbon or graphite coatings. The XPS S
2p studies demonstrated the presence of elemental sulfur and polysulfides, which gave
further evidence for gold reduction and chemical adsorption on chalcopyrite.

Acknowledgement

The financial support from Stawell Gold Mine and the Australian Research Council is
gratefully acknowledged. Appreciation is also expressed to Dr. Johan du Plessis in the
Department of Applied Physics at RMIT for assistance with the XPS analysis.

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