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Contact author:
Mr. James K. Afidenyo
Mining Engineering Department, Queens University,
Kingston, Ontario, Canada K7L 3N6
Tel: (613)767 7659
Fax: (613) 533 6590
Email:james.afidenyo@mine.queensu.ca
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INTRODUCTION
Gold ores and concentrates are classified as refractory when a significant
portiona sizable portion of the gold content cannot be extracted effectively by
conventional cyanidation, even after fine grinding. The refractory behavior of ores
is generally attributed to two main factors: the presence of carbonaceous matter
and the occurrence of sulfides, tellurides and cyanicides [Boyle, 1979; Guay,
1981]. When the refractoriness is due to the presence of sulfides and
carbonaceous matter, the ore or concentrate can be referred to as double
refractory [Nyavor and Egiebor, 1992].
The most important classes of carbonaceous matter are organic carbon
(hydrocarbons, humic acids and other organic substances) and graphitic or
amorphous elemental carbon [Radtke and Scheiner, 1970; Osseo-Asare et al.,
1984; Hausen and Bucknam, 1985; Stenebraten et al. 1999, 2000; Rees and Van
Deventer, 2000]. However, graphitic carbon is the main carbonaceous matter in
double refractory gold ores and poses serious recovery concerns during
leaching. The carbonaceous matter tend to adsorb gold from leach solutions, a
phenomenon known as preg-robbing and the sulfide minerals which may
occlude gold also limits the access of leaching reagents and thereby reducing
recovery.
The use of fungi in the field of mineral processing has not been studied much
until recent times. Some recent research into the use of fungi include leaching
and precipitation of nickel and iron from laterites (Alibhai et al 1993),
solubilisation of manganese from ores (Baglin et al, 1992), leaching of lateritic
nickel ores (Bosecker ,Bosecker, 1985; Sukla et al, 1993), and mineral leaching
of non sulfide nickelferrous ores (Agatzini and Tzeferis, 1994). The fungal
strains used in all above investigation were Aspergillus sp and Penicilliun sp.
Results of the studies on nickel oxide ores (Bosecker, 1985; Tzeferis et al 1991)
have shown the amenability of this mineral to leaching by fungal strains. The
efficiency of leaching depended on the type of ore and the kind and
concentration of organic metabolite produced by the fungi (Bosecker, 1985;
Alibhai, et al 1993)
In this study, sulfide sulfur and carbon degrading abilities of a white rot fungus
was investigated for double refractory gold ore and concentrate with the aim of
improving gold extraction.
Both a single stage and two-step microbial pretreatment processes were used to
oxidize the sulfides and to passivate/oxidize carbonaceous matter in a double
refractory gold ore. During the single stage process, the ore was contacted with
the fungus culture (biotic) for 3 weeks at 30 oC and pH range, 9.5 -10.5 during
which carbonaceous matter passivation and sulfide oxidation occur
simultaneously. For the two steptwo-step process, the first step is abiotic and it
involves the use of the culture medium adjusted to an alkaline pH range of 9.5
10.5 for oxidation of the sulfides minerals; followed by fungal contact (biotic) at
30oC to further oxidize the sulfides and passivate the carbonaceous matter. The
single stage process conditions resulted in higher recovery. Results indicate that
sulfides were oxidized and carbonaceous matter was partially degraded and
passivated at the same time; as preg-robbing activities dropped significantly gold
extraction in the subsequent cyanidation step increased.
EXPERIMENTAL
Ore Characterization
Ore samples were sourced from plants which process double refractory gold ore.
The ore was milled to 95% with particle size less than 75 um. Sulfide sulfur and
carbonaceous matter in the ore sample were determined using the combustion
and volumetric method. A Leco titrator, SC-444DR was employed for the
analysis. The conventional fire assay method was used to determine the grade of
gold. The main sulfide minerals present is pyrite. The grade of the main
components in the ores is indicated in TABLE 1:
Component Grade
Whole OreWhole Ore Flotation Concentrate
Total Sulfide sulfur (%) 3.80 8.95
Total Carbon (%) 0.63 6.84
Carbonate (%) 0.038 1.56
Elemental carbon (%) 0.592 5.28
Gold (g/t) 2.33 65.75
The fungal strain used for the studies was Coriolus versicolor (ATTC 20869)
which was maintained at 4 oC on plates containing Kirk's medium, 1.5% agar and
3% malt extract. Several agaragar plugs of the actively growing fungus were
used to inoculate 500 ml of Kirk's medium in 1000 ml Erlenmeyer flasks. The
medium contained 10 g/l glucose, 1.2 g/l ammonium tartrate, 0.05 g/l MnSO 4 .
7H2O, 0.01 g/l CaCl2 .2H2O, 1 mg/l thiamin, 1 ml/l of trace minerals (Kirk et al.
1978). The medium was also supplemented 2.92 g/l 2, 2-dimethylsuccinate. The
trace mineral solution contained 30 g/l MnSO 4. 7H2O, 10 g/l NaCl, 5g/l
MnSO4.H2O, 1 g/l CoSO4, 1 g/l FeSO4 .7H2O, 1 g/l ZnSO4 .7H2O, 0.82 g/l CaCl2,
0.1g/l CuSO4 .5H2O, 0.1 g/l NaMoO4. 2H2O, 0.1 g/l H3BO3 and 1 g/l EDTA.
Shake-flask cultures were grown at 30 oC with continuous agitation (180 rpm) for
10 14 days.
A series of single stage preliminary tests (biotic) during which the whole ore was
contacted with the fungal culture were conducted to investigate the amenability to
fungal sulfide sulfur and carbon degradation. The first batch of test was
conducted at the natural pH (unadjusted) of the fungal-medium ore system at
pulp density of 10% for 2 weeks. Further investigations at various adjusted pH
values of 3.5, 4.5, 7.0 and 10.0 were conducted. Other process variables
investigated were pulp density, retention time and temperature at the established
optimum pH of 10.0.
Control tests (abiotic) to investigate the effect of the culture medium on the ore at
the established conditions were also studied. The fungus Coriolus versicolor is
reported to thrive optimally at temperatures of 28 to 30 oC.
For the single stage process, the sulfide ore was contacted with the fungal
medium in 2000 liters Erlenmeyer flasks for 2 weeks at 20% pulp density and
temperatures of 30oC at alkaline conditions. The flask was agitated continuously
on an orbital shaker at 180 rpm. The initial pH of 4.5 to 5.0 was adjusted to
between 9.5 and 10.5 and maintained daily with 10 M sodium hydroxide solution.
The oxidized product of the biotic leaching was filtered and solids washed
several times with water to get rid of the alkali, dried and subjected to gold
extraction by cyanidation. Duplicate experiments were run and the difference in
values was within 1-2%.
For the two steptwo-step process, the ore was first contacted with the culture
medium (abiotic) in 2000 liters Erlenmeyer flasks for 2 weeks at a pulp density of
20% and temperatures of 45oC at alkaline conditions. The product of the abiotic
leaching was filtered and repulped to 20% solids with the fungal culture in
Erlenmeyer flasks and agitated continuously on an orbital shaker at 180 rpm for a
further 7 days. Daily monitored pH for the second step was between 5 and 6. At
the end of the biotic contact time, the ore samples were filtered, washed and
dried.
Samples of bioleach filtrate for both pretreatment processes were taken for gold
analysis by atomic absorption spectrometer
Preg-robbing and cyanidation tests were used to evaluate the gold extraction
properties of products obtained from the microbial pretreatment processes. All
pretreated samples were washed with water and dried before evaluation.
Biooxidation of sulfides
Biooxidation of refractory gold ore sulfides using the fungal pretreatment is novel.
The motivation for this research into the microbial pretreatment of a double
refractory gold ore stems from the abilities of a versatile fungus Trametes
versicolor whose strains, Polyporius and Coriolus versicolor are known to
degrade coal by the generation of a regime of mixed oxidative enzymes including
manganese peroxidase and lignin peroxidase (Kirk and Farrel,
1987).Managanese peroxidase and lignin peroxidase have been known to
produce strong oxidants for the oxidation of coal and other carbon bearing matter
in wood. Peroxidases require H2O2 to complete their catalytic cycle degrading
activities. Extracellular H2O2-generating enzymes are secreted simultaneously
with lignin modifying enzymes. Hydrogen peroxide has also been reported to
have the ability to deactivate active sites on carbonaceous matter [Nyavor and
Egiebor, 1992].
In this study, the two-step process achieved a sulfide oxidation 76.3% for the
2 week abiotic step compared with 54.1% for 2 weeks biotic treatment at 30 oC.
Sulfide oxidation may be enhanced by the presence of hydroxyl ions in solution
and the increase in sulfide oxidation during the 45 oC abiotic step may be due to
improved kinetics. Generally, sulfide oxidation for the abiotic test was higher than
the biotic step as indicated in the FIG 1. This may be due to build up of
metabolites on the sulfide surfaces during the biotic process. Analysis of the
filtrate after both biotic and abiotic steps at alkaline conditions revealed that some
gold had been leached into solution. The gold dissolution can be attributed to
formation of thiosulfate due to the alkaline conditions as indicated by equation 1
for arsenopyrite oxidation.
6FeAsS +1302 +22 NaOH = 6Fe (OH) 3 +2Na3AsO3S +4Na3AsO4 +2Na2S2O3 +2H2O (1)
FIG 1: Sulfide sulfur oxidation for abiotic and biotic process at alkaline conditions
and pulp density 10% solids at 30oC
In this investigation, no clear trend was observed for carbon degradation for both
the abiotic and biotic steps as data was rather erratic. However, preg-robbing
trends were clearly defined at the pHs investigated. There was no appreciable
change in carbonaceous matter content after the fungal-medium contact with ore
but preg-robbing activity reduced drastically showing that there was passivation
of carbonaceous matter. Preg-robbing activity dropped considerably by 82.5%
after the abiotic process and 98-99% reduction was achieved after fungal
contact. The culture medium itself had some carbon passivating abilities which is
worth investigating. Passivation in the presence of fungus may be attributed to
enzymatic secretions by the fungus.
Sulfide sulfur oxidation was studied at various pulp densities between 5% and
50% solids for the biotic process at alkaline condition and 30 oC for 2 weeks. The
changes in sulfide oxidation with increasing pulp density were not very significant
as all were in the range 48% to 44% as density increased from 5% to 50%. This
indicates that pulp density is not a major a variable in the biotreatment of sulfides
using Coriolus versicolor.
Carbon degradation trends were not well defined and was characterised by
fluctuations. Sorption of gold was remarkably low at 0.7% at 5% solids. It was
equally low for all pulp densities used and even after pretreatment at 50% solids
pregrobbing was 6.5%. Increasing preg-robbing with percent solids might be due
to high attrition rate and thereby hindering the passivating effect of the fungal
metabolites. It was observed that preg-robbing values did not correlate with
undegraded carbonaceous matter.
Effect of pH
The effect of pH was investigated for unadjusted (natural), 3.5, 4.5 and 10.5 for
both abiotic and biotic process for 2 weeks at a temperature of 30 oC. Sulfide
oxidation for both processes followed the same trend but values for the abiotic
were slightly higher than the biotic. The alkaline pH gave the overall best sulfide
degradation followed by the unadjusted (averaged 4.3), 4.5 and 3.5 in that order.
The lower sulfur sulfide oxidation by the culture alone may be due to coating of
sulfide mineral surfaces by the metabolites produced by the fungus. The higher
oxidation at the alkaline conditions may be attributed to the presence of hydroxyl
ions in solution.
Carbon degradation was erratic but generally values were higher than the
original ore due to introduction organic carbon by the fungi biomass and culture
medium. However, preg-robbing trends were clear. GenerallyGenerally, preg-
robbing data for the biotic were better than the abiotic as shown in FIG 2. This
indicates that there is microbial involvement in the carbon passivation process.
Sulfide oxidation increased with retention time. About 45% sulfide oxidation was
achieved after 2 weeks and 73% after 9 weeks during the preliminary studies.
The rate however, slowed down as the retention time increased. Since a batch
culture was used, the decrease in oxidation rate can be attributed to reduction in
microbial activity due to exhaustion of growth media.
Effect of Temperature
Temperature effect on sulfide oxidation was studied at alkaline pH for both biotic
and abiotic process at room temperature (26 oC), 30 and 45oC. Sulfide oxidation
tends to increase with temperature. 76.7% sulfide oxidation was achieved for
abiotic process at 45oC as against 44.74% and 50.0% at 26 oC and 30oC
respectively. Biotic experiments achieved 42.7% and 45.8% sulfide oxidation at
room temperature and 30oC respectively. The increasing trend can be attributed
to increased kinetics. These results were pivotal in investigating the two steptwo-
step process of abiotic at 45oC followed by biotic at 30oC.
Preg-robbing activity dropped from 18.1% for the untreated ore to below 1.0% for
both the 3 weeksweeks single stage and the two steps pre-treatment process of
2 weeks abiotic at 45oC and 7days biotic at 30oC. When the single stage
pretreated whole ore was subjected to cyanidation, gold extraction after 24 hours
was 78.9% compared with 73.3% for the two-step process. The single stage pre-
treatment process thus gave better results than the two steps process. Gold
extraction for the untreated ore was however, 15% (FIG 3).
FIG 3: Gold extraction from pretreated samples. Samples 1-4 are ores while 5
and 6 are concentrates; (1) Untreated ore, (2) 14 days biotic at 30 oC, (3) 14 days
biotic at 30oC (4) 2 weeks abiotic at 45oC + 1 week biotic at 30oC, (5) untreated
concentrate, (6) 2 weeks abiotic at 45oC + 1 week biotic at 30oC. All experiments
were conducted at pH 10.0
PROCESSING PROPOSAL
Single stage:
Two-step:
The result of this study is a new technical process for recovering gold from
double refractory gold ores. This novel process is a potential for pretreating
double refractory gold ores. The fungal passivation of carbonaceous matter can
be used to complement the traditional processes like pressure oxidation and
bacterial leaching where the carbonaceous matter is not oxidized significantly.
CONCLUSIONS
It could be concluded from the above results and discussion that both the single
and theand the two steptwo-step microbial pre-treatment process for the
treatment of double refractory gold ores and concentrates led to a substantial
increase in gold extraction. The fungus, Coriolus versicolor passivated
carbonaceous matter in the double refractory gold ore while alkaline medium
enhanced sulfide sulfur oxidation significantly. The single stage process will be a
preferred choice due to its simplicity.
Further investigations into this novel pretreatment option is in progress and
results may alter the processing proposal outlined above.
ACKNOWLEDGEMENTS
Gratefully acknowledge funding of the research by National Sciences and
Engineering Research Council of Canada (NSERC), Barrick Gold Corporation
and AngloGold Ashanti (Ghana) Limited. We are also grateful to Mr Paul
Philippe-Champagne, a PhD candidate of the Biochemical Engineering Research
group, Queens University for his guidance and advice during the research
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LIST OF HEADINGS
INTRODUCTION
EXPERIMENTAL
Ore Characterization
Biooxidation of sulfides
Effect of pH
Effect of pulp density
Effects of contact time
Effects of temperature
PROCESSING PROPOSAL
CONCLUSIONS
ACKNOWLEDGEMENTS
REFERENCES
CAPTIONS
Table captions
TABLE1
Partial Chemical analysis of the ore samples used
Component Grade
Ore Concentrate
Total Sulfide sulfur (%) 3.80 8.89
Total Carbon (%) 0.63 6.84
Carbonate (%) 0.138 5.38
Elemental carbon (%) 0.592 1.28
Gold(g/t) 2.33 65.75
Figure Captions
FIG 1: Sulfide sulfur oxidation for abiotic and biotic process at alkaline conditions
and pulp density 10% solids
FIG 2: Sorption of gold by ore sample after microbial pre-treatment at different
pH values