Hydrometallurgy 101 (2010) 2834

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Two-stage bacterialchemical oxidation of refractory gold-bearing

suldic concentrates
Natal'ya V. Fomchenko , Maxim I. Muravyov 1, Tamara F. Kondrat'eva 1
Winogradsky Institute of Microbiology, Russian Academy of Sciences, Prospekt 60-let Oktyabrya, 7/2, 117312, Moscow, Russia

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

Article history: The chemical oxidation of the arsenopyrite and pyrite gold-bearing concentrates with the microbially-
Received 9 July 2009 produced Fe3+ solution was investigated. During the chemical stage, the most easily oxidized suldic
Received in revised form 10 September 2009 elements were shown to be removed from the concentrates. After chemical leaching of the arsenopyrite
Accepted 18 November 2009
concentrate, the oxidation levels for suldic iron and arsenic were 64.3% and 31.1%, respectively; for the
Available online 3 December 2009
pyrite concentrate, the oxidation levels of suldic iron and sulfur were 21.2 and 25.8%, respectively.
Biooxidation of the arsenopyrite and pyrite gold-bearing concentrates has been carried out in the onestage
Keywords:
Biooxidation
(control) and two-stage (experimental) variants in reactors in feed batch mode. An activity of biooxidation
Gold recovery of sulphidic concentrates without preliminary oxidation by Fe3+ solution (one-stage process) during the
Sulde concentrates control experiments and after preliminary oxidation of Fe3+ solution (two-stage process) in experimental
Ferric leaching variants was studied. At 4 days residence time, the oxidation level for suldic arsenic from the arsenopyrite
Two-stage technology concentrate was 38.4% in the control process and 92.8% in the experimental one; gold recovery by
cyanidation was 67.76% and 92.95%, respectively. At 8 days residence time, the results of the control process
were lower, than of experimental process after 4 days of oxidation: the oxidation level of suldic arsenic was
59.7%; gold recovery was 82.38%. In the control variant, the time of biooxidation of the pyrite concentrate
was 36 days; in the experimental variant, it was 5 days. The oxidation levels for suldic iron and sulfur were
40.3 and 55.7%, respectively; gold recovery by cyanidation was 76.9%. The results obtained demonstrate that
two-stage bacterialchemical processes are promising for intensication of the biohydrometallurgical
processing of refractory suldic concentrates containing not only nonferrous metals, but noble metals as
well.
2009 Elsevier B.V. All rights reserved.

1. Introduction The BRISA technology was proposed for copper recovery from suldes
(Carranza et al., 1997). The BRISA technology is based two-stage
Intensication of biological oxidation of suldic minerals is essential treatment of copper concentrates including () chemical leaching at
for development of hydrometallurgy. To achieve this goal, both search elevated temperature according to reaction (1) and (b) regeneration of
for new promising microbial communities (Yahya and Johnson, 2002), the oxidizer by a bacterial culture (Acidithiobacillus ferrooxidans) according
and development of new technological approaches are required. to reaction (2). The technology has been tested on the concentrates of
One of approaches to intensied leaching of non-ferrous metals secondary copper suldes (covellite and chalcocite) (Palencia et al., 2002),
involves oxidation of suldic minerals (MS) by Fe3+ ions under acidic as well as for chalcopyrite (Romero et al., 2003). After 810 h, over 90%
conditions with iron reduction to Fe2+ according to reaction (1). Micro- copper recovery was achieved.
organisms carry out Fe2+ oxidation to Fe3+ according to reaction (2) in a The Rio Tinto Research and Technology development company has
separate stage. carried out trials on leaching of copper ores in Australia (Smalley and
Davis, 2000). The plant for high-temperature (85 ) leaching at
3 2 0 2 atmospheric pressure with ferric iron sulfate (at 20 g/L Fe3+) was
S 2Fe M S 2Fe 1
developed for the ores containing mostly chalcocite (73.4%) and bornite
2 3 (15.6%). Copper content in the ore varied from 5.9 to 7.4%, the average
4Fe 4H 2 4Fe 2H2 O 2 pulp density was maintained at 30%. The plant produced about 40 kg of
cathode copper per day. After 24 h, 93% of copper was recovered, with
86% leached during the rst 6 h. The leaching solution was regenerated in
Corresponding author. Tel.: +7 499 135 04 21.
a specialized block; the mixed bacterial culture used for the purpose was
E-mail address: natalya.fomchenko@gmail.com (N.V. Fomchenko). adapted to acidic conditions and high levels of copper (up to 10 g/L) and
1
Tel.: +7 499 135 04 21. iron ions (up to 20 g/L). The rate of iron oxidation was 0.55 g Fe2+/L h.

0304-386X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2009.11.009
 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834
This technology, however, did not involve the capacity of bacteria
used to oxidize, apart from iron (reaction (2)), also elemental sulfur
according to the following reaction:
0
2S 32 2H2 O 2H2 SO4 3 2.1. Suldic concentrates
Consumption of sulfuric acid was therefore high, 40 kg per ton of
processed ore.
We proposed a new variant of two-stage bacterial leaching of
copper-zinc concentrate containing 15.25% zinc as sphalerite and 1.5%
copper as chalcopyrite (Fomchenko et al., 2006; Fomchenko and
Biryukov, 2009).
The leaching was carried out in a continuous mode. At the rst
stage, the solid phase was chemically leached with the ferric iron
solution ( 10 g/L) at 70 and pulp density of 33%. The suspension
was then transferred to the sludge thickener where the solid phase
was separated into the coarse and ne fractions. The former was
returned for chemical leaching, while the latter was used in the
second stage of oxidation by a mesophilic or thermophilic microbial
association. In this technological setup, reaction (1) was carried out in
a chemical reactor, while reactions (2) and (3) occurred in a bio-
reactor. Both chemical oxidation (at the rst stage) and microbiolog-
ical oxidation (at the second stage) occurred therefore under the
optimal conditions. The process involved continuous liquid recircu-
lation between the rst and second stages. After 24 h of leaching, 91.5
and 77.3% recovery levels were achieved for zinc and copper, respec-
tively. The traditional one-stage process on the same raw material
took 120 h.
For a two-stage process, a moderately thermophilic microbial
association may be used. We have previously proposed a two-stage
bacterialchemical technology for leaching copper from copper
concentrates involving moderately thermophilic chemolithotrophic
microorganisms (Fomchenko et al., 2007). Leaching of the rich copper
concentrate containing 27.0% copper, mainly as covellite and
chalcocite, 91% of copper was dissolved after 20 h. The residue
obtained after the chemical stage contained 7.7% copper, while copper
content in the residue of the second stage (from the bioreactor) was
only 2.1%. These results demonstrated that the concentrate obtained
after chemical leaching was efciently leached at the following, bio-
logical stage.
Thus, the separation of the chemical and biological stages resulted
in signicantly intensied leaching of nonferrous metal from suldic
raw material. However, two-stage bacterialchemical oxidation has
not been used for gold recovery from suldic raw materials.
Presently, biotechnologies for gold recovery from suldic refrac-
tory ores attract much attention (Brierley, 2007). Biotechnologies may
be applied even to high-arsenic gold-bearing concentrates. High levels
of oxidation and recovery of suldic minerals is achieved; the
subsequent sorption cyanidation results in recovery of up to 98% of
ne-dispersed gold, much higher than the levels of recovery by direct
cyanidation or pyrometallurgical mode (Abbruzzese et al., 1994).
BIOX (Dew et al., 1997) is the most widespread technology for
biological oxidation in the reactors of arsenopyrite-pyrite gold-
bearing concentrates. Intensication of the processes of biological
oxidation of suldic concentrates is an important issue, since the
average duration of the oxidation process under industrial conditions
is 4 to 6 days (Rawlings et al., 2003).
There were attempts to replace biooxidation of refractory
sulphidic gold-bearing concentrates with chemical oxidation by
ozone and Fe3+ solution in sulfuric medium (Li et al., 2009). Despite
good results on gold extraction by cyanidation (96.5%), the given way
is very complicated and expensive.
The goal of the present work was to investigate the processes of
chemical oxidation of arsenopyrite and pyrite concentrates and
biological oxidation with and without preliminary oxidation by Fe3+
29
ions, as well as to develop the approaches to intensication of
biooxidation technologies and enhanced gold recovery.
2. Materials and methods
Two types of gold-bearing suldic concentrates were used in the
present work. The rst one was the industrial arsenopyrite otation
concentrate obtained from the ore of the Olympiadinskoe deposit
(Russia). The 80% class neness was 0.044 mm, the total content of iron
sulde (pyrrhotite) and arsenic sulde (arsenopyrite) was up to 75%.
Quartz and carbonate were the major nonmetallic minerals. The second
type was the pyrite concentrate obtained under laboratory conditions
from the ore of the Samolazovskoe deposit (Russia). The content of iron
sulde (pyrite) was about 30%; gold content was 22.77 g/t. The chemical
composition of the concentrates is presented in Table 1. Only main
elements are presented as compounds of the concentrates.
2.2. Microbial cultures
The microbial association predominant in the process of biological
oxidation in the industrial bioreactors of the Polyus Gold factory was
used for biooxidation experiments and for generation of ferric iron for
subsequent chemical leaching experiments. The association included
strains of various Sulfobacillus species, bacteria of the genus Leptos-
pirillum, and archaeal strains of Ferroplasma acidiphilum (Sovmen
et al., 2008).
2.3. Generation of the ferric iron
Ferrous iron biooxidation was carried out in 5.0-L vessel with 4 L of
the liquid at temperature of 39 C and aeration 4 min 1. Liquid
contained 9 K medium (Silverman and Lundgren, 1959) supplemen-
ted with 0.02% (w/v) of yeast extract and 10% (v/v) inoculum. The
initial pH of the medium was adjusted to 1.5 with 98.5% H2SO4. The pH
and concentration of ferrous and ferric iron were monitored twice a
day. The pH values were maintained in the range from 1.5 to 1.8 with
addition of sulfuric acid (98.5%) when necessary. FeSO47H2O was
added in liquid when ferrous iron was oxidized. The nal Fe3+
concentration was 2030 g/L. This liquid was used for lixiviation
during chemical leaching experiments.
2.4. Chemical leaching experiments
Before chemical oxidation or biooxidation the concentrates were
treated with diluted sulfuric acid in 2-L reactor (440 rpm) during 20 h
and dried overnight at 60 C. The pH of the pulp was monitored
continuously and 98.5% H2SO4 was added when necessary to maintain
its values in the range from 1.5 to 1.6. The pulp density was 17% (w/v).
This operation was used to remove carbonates from the concentrates.
Chemical leaching was carried out in a 2.0-L reactor containing 1 L
of the pulp. The stirring speed was 440 rpm. The temperature was
maintained by means of heat exchangers connected to a thermostat.
Experiments were carried out at 50, 65 and 80 C.
Table 1
Analytical data for the concentrates.
Element Arsenopyrite concentrate Pyrite concentrate
Fe (wt.%) 27.0 15.06
As (wt.%) 8.21
Sb (wt.%) 5.59
Ss (wt.%) 20.32 14.89
S0 (wt.%) n.d. 0.25
Au (g/t) 108 22.77
n.d.not detected.
30 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834
The leaching was carried out cyclically. In each cycle, the
concentrate was loaded to 20% (w/v) of the solid phase (acid treated
concentrate) and mixed with the Fe3+-containing solution. The liquor
was heated to the desired temperature. The initial pH of the liquor
was adjusted to 1.2 with 98.5% sulfuric acid. Reduction of Fe3+ to Fe2+
occurred; ion concentration and pH values were measured at 5-min
intervals. Sulfuric acid (98.5%) was added when necessary to maintain
pH values in the range from 1.15 to 1.35. The leaching was stopped
when the Fe3+ concentration was 35 g/L; the suspension was
centrifuged and supplemented with a new portion of the solution
for the next leaching cycle. The data obtained were used to calculate
the average rate of changes of the iron ions concentrations in the
liquid phase. The biooxidation was carried out after preliminary
treatment of the concentrates with acid or after acid treatment with
the subsequent chemical leaching with Fe3+ ion.
2.5. Biooxidation experiments
Biooxidation was carried out in 2.0-L reactors containing 1 L of the
pulp. The salt solution of the 9 K medium not containing Fe2+ was
used as the liquid phase. The medium was supplemented with yeast
extract (0.02% w/v). The pulp density was maintained at 17% (w/v), by
addition of the fresh pulp in the place of material taken from the
reactor. The set up consisted of two reactors connected in series for
biooxidation experiments of arsenopyrite concentrate. Time of stay of
a pulp in two reactors 8 days. One reactor was used for experiments
on biooxidation of the chemically leached pyrite concentrate. Pulp
residence time was 5 days. Replacement of the pulp was carried out
twice a day. Acid treated pyrite concentrate biooxidation experiment
(control) was carried out under batch conditions during 36 days.
Experiments were carried out at 39 C and aeration of 4 min 1. The
stirring speed was 440 rpm. The pH of the pulp was monitored
continuously and 10 N H2SO4 was added when necessary to maintain
its values in the range from 1.45 to 1.9. Samples (10 mL) were
removed twice a day to determine ferric and ferrous iron and arsenic
concentration.
2.6. Analytical methods
Enumeration of microorganisms was carried out by direct count
under an Amplival (Carl Zeiss, Germany) phase-contrast microscope.
The values of and Eh were measured with a -150 pH
meter-millivoltmeter (Belarus). The concentrations of Fe3+ and Fe2+
ions in the liquid phase were determined by complexometric titration
(Reznikov et al., 1970).
The rates of Fe2+ accumulation and of Fe3+ decrease () in the
pulp in the course of chemical leaching may be determined from the
following equation:
Cini Ci
= 4
i
where Cini is the concentration of Fe2+ or Fe3+ in the initial leaching
solution, g/L; Ci is the concentration of Fe2+ or Fe3+ in the leaching
solution after the time i, g/L; i is the time of chemical leaching, h.
The overall concentration of As3+ and As5+ ions in the liquid phase
was determined by iodometric titration (Surovskaya et al., 1957). The
content of suldic elements and elemental sulfur was determined by
the phase method (Ostroumov and Ivanov-Emin, 1945). Gold content
in the solid phase was determined by the assay method. The degree of
gold recovery was determined by sorption cyanidation of the residue.
Sorption cyanidation was carried out at the following conditions:
pulp density 30% (w/v), pH 10.210.5 (adjusted with NaOH), cyanide
(NaCN) concentration 1.0 g/L (70% of time), air supply 25 L/h, content
of sorbent (carbon Norit 3515) 8% (w/v), and 20 C. The experiments
were run for 48 h. Adsorption level of gold on sorbent was 99100%.
3. Results and discussion
3.1. Chemical leaching of the arsenopyrite concentrate
Increasing of the pH values and Fe3+ reduction were observed
during the chemical leaching. The pH increased in the rst 15 min of the
process, then this parameter became stable. The processes of oxidation
(leaching) of the arsenopyrite concentrate containing mostly pyrrhotite
and arsenopyrite by ferric iron ions may be described by the following
reactions:
0
FeS Fe2 SO4 3 3FeSO4 S 5
0
2FeAsS 5Fe2 SO4 3 6H2 O 12FeSO4 2H3 AsO3 2S 3H2 SO4
6
It is possible the direct solubilization of the pyrrhotite by the
reaction:
2
Fe1x S 2H 1xFe H2 S 7
The rate of chemical leaching increases signicantly at elevated
temperatures (7080 ) (Palencia et al., 2002). However, the higher
the temperature and pH of the pulp, the higher the precipitation rate for
the ferric iron ions (the major oxidizer of suldic minerals) resulting in
jarosite formation (Dutrizac, 1983) according to the equation:
3Fe2 SO4 3 12H2 O M2 SO4 2MFe3 SO4 2 OH6  6H2 SO4 8
where M = K+, Na+, NH+ 4 , H3O
+
The above reactions can be used to estimate the efciency of
chemical leaching. The changes in Fe2+ and Fe3+ concentrations
should characterize the rate of oxidation of the concentrate by ferric
iron ions.
The effect of temperature on the average rates of Fe2+ accumula-
tion and Fe3+ consumption during the rst 30 min of chemical
leaching of the arsenopyrite concentrate is presented on Fig. 1. The
average rates of ferrous iron accumulation and ferric iron consumption
in the course of chemical leaching were shown to increase signicantly
with the temperature increase from 50 to 65 and then to 80 . The
average rate of Fe2+ accumulation was 13.4, 25.0, and 42.08 g L 1 h 1
at 50, 65, and 80 , respectively. The average rate of Fe3+
consumption at 50, 65, and 80 was 10.1, 18.0, and 29.9 g L 1 h 1,
respectively.
The rate of Fe2+ accumulation depending on the duration of
chemical leaching at different temperatures is presented on Fig. 2.
During the rst minutes of the process, the difference was the most
Fig. 1. The average rates of Fe2+ accumulation (1) and Fe3+ consumption (2) depending
on the temperature during the rst 30 min of the chemical leaching of the arsenopyrite
concentrate.
 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834
Fig. 2. The rate of Fe2+ accumulation depending on the oxidation duration in chemical
leaching of the arsenopyrite concentrate at 80 (1), 65 (2) and 50 (3).
pronounced; subsequently, the oxidation rates steadily decreased and
became almost equal after 150 min. Analysis of the graph demon-
strated that most of the suldes were oxidized early in the process. A
short-term process which requires minimal power input for temper-
ature maintenance may therefore be the most efcient.
Our previous work also demonstrated the effect of temperature on
the rate of chemical leaching, especially in the beginning of the
process (Fomchenko et al., 2009). The highest rate of changes in the
concentrations of iron ions was observed at the highest leaching
temperature, i.e. at 80 . The process of chemical leaching of the
pyrite concentrate at this temperature was therefore investigated.
3.2. Chemical leaching of the pyrite concentrate
The process of oxidation of the pyrite concentrate is described by
the following reactions:
0
FeS2 Fe2 SO4 3 3FeSO4 2S
FeS2 7Fe2 SO4 3 8H2 O 15FeSO4 8H2 SO4 10
The rates of Fe3+ reduction (1) and Fe2+ accumulation (2) depending
on the duration of chemical leaching of the pyrite concentrate at 80
are presented on Fig. 3.
The data presented demonstrate that at the beginning of chemical
leaching of the pyrite concentrate, both the rate of Fe3+ reduction and the
rate of Fe2+ accumulation were signicantly lower than the values
observed for the arsenopyrite concentrate. For example, the rate of ferrous
iron accumulation at 80 for pyrite concentrate was 35 g L 1 h 1,
almost equal to the rate of Fe2+ accumulation for the arsenopyrite
concentrate at 50 . At 80 , the differences were most pronounced in
the rst 60 min of oxidation; during this period, the rate decreased from
Fig. 3. The rates of Fe3+ reduction (1) and Fe2+ accumulation (2) depending on the
duration of chemical leaching of the pyrite concentrate at 80 .
31
94.1 to 16.8 g L 1 h 1 in the case of the arsenopyrite concentrate
and from 35.3 to 5.3 g L 1 h 1 in the case of the pyrite concentrate (Figs. 1
and 3). However, 150 min after the onset of the process the difference in
rates decreased signicantly.
Chemical leaching of the pyrite concentrate exhibited certain
peculiarities. The rates of Fe2+ accumulation and Fe3+ reduction were
almost the same during the rst 30 min of the process; in the case of
the arsenopyrite concentrate, the difference was signicant. Subse-
quently, these rates became closer.
Chemical analysis of the residue obtained after chemical leaching
of the concentrates are presented in Table 2. Duration of chemical
leaching was 120 and 420 min for the arsenopyrite and pyrite concen-
trate, respectively.
These data demonstrate that the concentrates under study differed
signicantly in the oxidation level of suldic iron (which was present
in all oxidized concentrates). For example, the level of iron oxidation
in the arsenopyrite concentrate was 64.3%, while in the pyrite one it
was only 21.2%. This difference may be due to the fact that the major
suldic minerals of the rst concentrate, pyrrhotite and arsenopyrite,
have an electrode potential of 0.45 and 0.5 V, respectively. In the
second concentrate, the electrode potential of pyrite is higher (0.55
0.6 V). The electrode potential (a potential jump at the mineral
electrolyte boundary) may act as a criterion of the oxidability of
suldic minerals under both chemical and biological oxidation. The
values of the electrode potentials depend on the electrochemical
properties of the minerals and are proportional to the work function
for the electrons escaping from the sulde crystal structure (Nester-
ovich, 1988).
Thus, the most easily oxidizable components of the suldic
concentrates under study can be removed at the stage of chemical
leaching with a Fe3+ solution. This degree of oxidation is, however,
insufcient for gold recovery. The biooxidation stage was therefore
used after the chemical stage.
9 3.3. Effect of chemical leaching of the concentrates on their subsequent
biooxidation
3.3.1. Effect of chemical leaching of the arsenopyrite concentrate on its
subsequent biooxidation
To study the effect of chemical leaching of gold-bearing concen-
trates on their subsequent biooxidation, oxidation of the original
concentrate (control) and the chemically leached one (experiment)
was compared under a feed-batch mode. Biooxidation was carried out
sequentially in two reactors. The original concentrate was introduced
into the rst reactor, and the oxidized concentrate was removed from
the second reactor.
The total leaching time was determined from the following
equation:
V1 V
T= + 2 = t1 + t2 11
where T is the total duration of biooxidation, days; V1 and V2 are the
volumes of pulp in the rst and second reactor, respectively, L; v is the
Table 2
Content in the residue and oxidation level for the major sulde elements after chemical
leaching of the arsenopyrite and pyrite concentrates at 80 duration 120 and 420 min
respectively.
Arsenopyrite concentrate Pyrite concentrate
Content Oxidation level Content Oxidation level
(wt.%) (wt.%) (wt.%) (wt.%)
Fes 10.01 64.3 11.97 21.2
Ass 5.93 31.1
Ss n.d. n.d. 11.14 25.8
n.d.not detected.
32 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834

ow rate of the pulp transferred from one reactor into another, L/day;
t1 and t2 are the duration of oxidation in the rst and second reactor,
respectively, days.
The pulp volume in our experiments was 1 L, the volume of the
pulp transferred from one reactor into another was 0.25 L/day, the
time of biooxidation was 4 days in the rst reactor and 8 days in the
second one (after the process onset in the rst reactor). Thus, t1 was
4 days, t2 was also 4 days, and T was 8 days.
Key parameters of biooxidation of control and experimental
samples of the concentrate are presented in Table 3.
Essential differences in the fate of compounds of the liquid phase
in control and experimental processes were revealed. The difference
in arsenic concentration in the rst reactor, and also the difference of
the quantity of sulfuric acid necessary for the maintenance during
the biooxidation have been registered.
It is known that during bacterial oxidation of Fe2+ ions in sulfuric
acid containing medium the consumption of hydrogen ions (reac-
tion (2)) leads to increasing of the medium pH. The data presented in
Table 3 indicate that during biooxidation of the chemically leached
concentrate considerably smaller increase of pH values was observed.
That was an evidence of active bacteria oxidation of sulfur according
to reaction (3). During biooxidation of the control concentrate the
activity of oxidation of sulfur and reduced sulfur containing com-
pounds increased only in the second reactor, as it may be seen from
the diminishing of the expense of sulfuric acid. In the rst reactor for
maintenance of pH in a required range during biooxidation of the
chemically leached concentrate 7.6 times less concentrated sulfuric
acid was required than during biooxidation of a control concentrate.
Thus preliminary chemically leaching of a concentrate signicantly
simplies the control of pH during the process of biooxidation. In the
second reactor addition of acid was not required during biooxidation
of the chemically leached concentrate. This indicates that process of
sulfur and its reduced compounds oxidation to sulphatesions by
microbial association predominated over consumption of hydrogen
ions by reaction (2).
Concentration of total iron in a liquid phase of pulp during
biooxidation of control concentrate both in the rst and in the second
reactor was signicantly higher than during biooxidation of the
chemically leached concentrate. It may be explained by the fact that
main quantity of iron (64.3%) from experimental concentrate was
leached during chemical stage. Besides, ion Fe3+ possibly sedimented
as a result of following reactions (8) and (12).
Fe2 SO4 3 2H3 AsO4 2FeAsO4 3H2 SO4 12
Decrease in concentration of total iron in the second reactor where
concentration of arsenic in medium was higher comparing to the rst
apparatus was also an evident that reactions (8) and (12) took place
in control process. Data on total concentration of arsenic ions in a
liquid phase indicated that during biooxidation of chemically leached
concentrate in the second reactor arsenic transition to non soluble
state and its sedimentation were observed. This phenomenon may
Table 3
Biooxidation parameters for one-stage and two-stage processes of arsenopyrite
concentrate.
Reactor no. One-stage process Two-stage process
1 2 1 2
pH 1.801.90 1.701.80 1.601.85 1.451.55
Eh 643661 685698 670684 753766
Concentration in liquid Fe3+ 4.78 6.74 5.95 7.0
phase, g/L Fe2+ 6.13 3.08 0.5 0 One-stage (control)
As 1.85 4.2 4.2 3.8
H2SO4 consumption, kg/tday 52.0 4.5 6.8 0 Two-stage
Number of cells, 107/mL 11.5 4.4 1.6 4.5
play a positive role at biooxidation process reducing toxic for bacteria
arsenic ions from a liquid phase to insoluble sediment.
During the biooxidation of the chemically leached concentrate
more than 92% of Fe2+ ions have been oxidised to Fe3+ already in the
rst reactor, and in the second reactor all iron ions were trivalent.
During the biooxidation of the control concentrate in the rst reactor
only up to 44% of Fe2+ ions and in the second about 69% of Fe2+ ions
have been oxidized. It may be explained by the actively proceeding
processes of chemical leaching of iron in reactions (5) and (6).
The number of Sulfobacillus cells in the rst reactor during
biooxidation of control concentrate was 11.5107 cells/ml and more
than in 7 times exceeds cells number during biooxidation of chemi-
cally leached concentrate. Probably it may be explained by signi-
cantly lower arsenic concentration in the solution. In the second
reactor cells number was similar both during biooxidation of the
control and chemically leached concentrates. The microscopy revealed
the presence of archaeon F. acidiphilum besides of Sulfobacillus.
The results of analyses of the residues (solid phase) obtained after
biooxidation of the arsenopyrite concentrate are presented in Table 4.
The calculated oxidation levels for the major suldic elements
provided an indication of the efciency of biooxidation in the reactors.
The data of Table 4 demonstrate intense oxidation in both reactors
in the case of one-stage biooxidation of the arsenopyrite concentrate
(control). Thus, the oxidation level for iron in the rst reactor was
60.4%; it increased to 71.1% in the second reactor. This nding
conrms an earlier suggestion that pyrrhotite was almost completely
oxidized in the rst reactor, while the oxidation of arsenopyrite and
other suldic minerals, including pyrite, continued in the second
reactor. In the rst reactor, 38.4% of arsenic was oxidized; only 21.3%
of arsenic was additionally oxidized in the second reactor. At 8 days
residence time, the oxidation level for arsenopyrite, the major gold-
bearing mineral, was 59.7%, a relatively low value.
In the case of biooxidation of the concentrate after chemical
leaching in the two-stage mode (experiment), high oxidation levels
for iron and arsenic were already achieved in the rst reactor. Thus,
the oxidation level was 79.3% for iron and 92.8% for arsenic. In the
second reactor, the oxidation levels for iron and arsenic increased only
by 9.9% and 4.4%, respectively. This is an indication of complete
oxidation of pyrrhotite and almost complete oxidation of arsenopyrite
in the rst reactor (4 days residence time); the next 4 days residence
time in the second reactor, oxidation of residue arsenopyrite and
pyrite occurred. Comparative analysis demonstrates that the oxida-
tion levels for the major suldic elements are signicantly higher in
the two-stage process (4 days residence time) than in the one-stage
process (8 days residence time). For example, at 4 days residence time
(in the rst reactor) in the two-stage process, the oxidation level of
arsenic was 33.1% higher than the level achieved in the one-stage
process at 8 days residence time (in the second reactor).
The residue yields for one-stage (8 days residence time in the
second reactor) and two-stage (4 days residence time in the rst
reactor) biooxidation were similar.
The data on sorption cyanidation of gold from the residues
(Table 5) provide information for conclusive judgment on the
biooxidation efciency. Our previous investigations of cyanidation of
Table 4
Analysis of the solid phase after biooxidation of the arsenopyrite concentrate in a one-
and two-stage process.
Processes Reactor Time of Residue Content, Oxidation
no. biooxidation, yield, wt.% level, wt.%
days wt.%
Fes Ass Fes Ass
1 4 90.0 11.83 5.58 60.4 38.4
2 8 68.1 11.46 4.85 71.1 59.7
1 4 71.8 7.75 0.82 79.3 92.8
(experiment) 2 8 56.0 5.19 0.41 89.2 97.2
 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834 33

Table 5 Table 7
Gold recovery by cyanidation after biooxidation of the arsenopyrite concentrate. Results of gold recovery by cyanidation from the pyrite concentrate.

Processes Reactor no. Time of Au recovery,
biooxidation, wt.%
days
One-stage process 1 4 67.76
(control) 2 8 82.38
Two-stage process 1 4 92.95
(experiment) 2 8 94.06
Original concentrate 0 57.0
sulphidic gold-bearing concentrates carrying out after a stage of
short-term (about 2 h) chemical leaching have shown that gold
extraction, as a rule, is low and exceeds extraction of gold from initial
concentrate not more than 10%. Therefore for investigated arseno-
piritic concentrate this parameter was not dened.
The data suggest that after two-stage biooxidation of the
concentrate, an almost maximal degree of gold recovery (92.95%)
was achieved in the rst reactor. Biooxidation of the concentrate in a
one-stage process resulted in 67.76% gold recovery. Cyanidation of the
original concentrate yielded 57% gold recovery. Cyanidation of the
residue from the second reactor resulted in a signicant increase for
the one-stage process (from 67.76 to 82.38%) and in an insignicant
increase for the two-stage process (from 92.95 to 94.06%).
Biooxidation of the concentrate in the one-stage process for 8 days
residence time (in the second reactor) resulted in 82.38% gold
recovery, 10.57% less than for its biooxidation in the two-stage
process for 4 days residence time (in the rst reactor).
Thus, the possibility was demonstrated to intensify the process of
biooxidation of the arsenopyrite concentrate by carrying it up in two
sequential stages. The rst stage (2 h) is chemical leaching of the
concentrate with the Fe3+ produced by the bacteria involved in the
process; during the second stage. The second stage is biological
oxidation of the chemical leaching concentrate. This setup resulted in a
twofold decreased duration of biooxidation; gold recovery by
cyanidation was 25% higher than in the case of one-stage biooxidation
for 4 days.
3.3.2. Effect of chemical leaching of the pyrite concentrate on subsequent
biooxidation
Biooxidation of the pyrite concentrate was initially also studied in
the traditional one-stage process. Prior to the onset of biooxidation,
14-day adaptation of the microbial culture was required. The process
of biooxidation took 36 days.
The analysis of a liquid phase in control process of pyrite
concentrate biooxidation has shown the accumulation of Fe3+ ions
up to 2.6 g/L at almost total absence of Fe2+ ions in the solution. pH
and Eh values at the beginning of the process were 1.81 and 744 mV
respectively, at the end of the process 1.38 and 788 mV respectively.
Cells number in the inoculated pulp was 2.5107 cells/mL, at the end of
process it was (0.91.0)108 cells/mL.
Biooxidation of the pyrite concentrate after chemical leaching was
carried out in one reactor.
Residue Au Au recovery, wt.% Residue Au content
content after after cyanidation, g/t
cyanidation, g/t
Original 6.0 21.0
27.4 After one-stage biooxidation 73.1 6.9
14.1 After two-stage biooxidation 76.9 6.3
6.7
5.7
46.0
The analysis of the liquid phase during the experimental process of
pyrite concentrate biooxidation has shown the accumulation of Fe3+
ions to 3.4 g/L and almost total absence of Fe2+ ions in the solution. pH
and Eh values during the beginning of the process were 1.83 and
735 mV respectively, at the end of the process 1.31 and 795 mV
respectively. Cells number in inoculated pulp was 6.6 106 cells/mL, in
the feed-batch mode (1.21.5) 108 cells/mL.
Results of the analysis of the residue obtained after one- and two-
stage biooxidation are presented in Table 6. The content of suldic
iron and suldic sulfur in the residue after one-stage biooxidation was
10.09% and 7.63%, respectively. These data demonstrate that bioox-
idation of the pyrite concentrate for 5 days according to the two-stage
technology resulted in 84% yield of the residue; its content of suldic
iron was 1.4 times lower than in the original concentrate, and the
content of suldic sulfur (SS) was 1.9 times lower. These results
revealed that the content of suldic sulfur and iron in the residue was
almost the same as after 36 days of biooxidation in the control
process.
Analysis of the results demonstrates that the traditional one-stage
biooxidation process was not promising for this kind of raw materials.
The introduction of stage of chemical oxidation enabled more efcient
microbial oxidation of the pyrite material.
The results on cyanidation of the original pyrite concentrate and
after one- and two-stage biooxidation are presented in Table 7.
These data demonstrate that after two-stage biooxidation of the
pyrite concentrate for 5 days gold recovery by cyanidation (76.9%)
was higher than from one-stage biooxidation for 36 days (73.1%).
After a stage of chemical leaching of pyrite concentrate gold
extraction was only 21.7%.
According to the results of Ubaldini et al. (2000), one-stage
biooxidation of a gold-bearing suldic ore resulted in 91% gold recovery
by cyanidation only after 30 days of the process (batch mode). Thus,
although high levels of gold recovery by cyanidation may be obtained by
traditional one-stage processes for biooxidation of gold-bearing suldic
materials, the intensity of such processes is usually very low.
3.4. Comparison of biooxidation of the pyrite and arsenopyrite concentrates
Our results demonstrate that the pyrite concentrate is much more
difcult as a gold-bearing material than the arsenopyrite one.
However, the technology of two-stage bacterialchemical oxidation
for only 5 days residence time made it possible to obtain the product
from which gold could be efciently recovered.

Table 8
Table 6 Specic rate of oxidation for sulde iron, sulfur, and arsenic in the arsenopyrite and
Analysis of the precipitate obtained by one- and two-stage biooxidation of the pyrite pyrite concentrates in the one-stage and two-stage processes.
concentrate.
Specic rate of
Processes Residue yield, Content, wt.% Oxidation oxidation, g kg1 day 1
wt.% level, wt.%
S As Fe
Fes Ss S0 Fes Ss
Arsenopyrite concentrate (4 days), two-stage process n.d. 19.0 53.6
One-stage process 87.0 10.09 7.63 1.66 41.7 55.4 Arsenopyrite concentrate (4 days), one-stage process n.d. 7.9 35.6
(control, 36 days) Pyrite concentrate (5 days), two-stage process 11.1 8.3
Two-stage process 84.0 10.71 7.85 2.18 40.3 55.7 Pyrite concentrate (36 days), one-stage process 1.5 1.2
(experiment, 5 days)
n.d.not detected.
34 N.'V. Fomchenko et al. / Hydrometallurgy 101 (2010) 2834
Specic rates of oxidation for the major suldic elements in the
arsenopyrite and pyrite concentrates under the one-stage and two-
stage processes are presented in Table 8.
The values of specic rates of oxidation for the major elements
from the arsenopyrite and pyrite concentrates indicate much higher
oxidation rates in the two-stage process compared to the one-stage
one. For example, for the pyrite concentrate, specic oxidation rates
for sulfur and iron were 7.4 and 6.9 times higher, respectively, than in
the one-stage process.
4. Conclusion
Based on our previous results (Fomchenko et al., 2009), a new
concept of two-stage bacterialchemical process is proposed for
leaching the suldic material. This concept implies sequential stages
of chemical and biological oxidation; the ferric iron solution obtained
at the biological stage is used at the stage of chemical oxidation. The
duration of chemical oxidation (leaching) should be relatively short
(not exceeding 57 h), while the biological oxidation should take
several days. Such a realization of the two-stage process involves its
better adaptation to the existing industrial one-stage technology for
biological oxidation of gold-bearing suldic concentrates.
The effect of chemical leaching (oxidation) of gold-bearing suldic
concentrates (the rst stage) on subsequent biooxidation (the second
stage) has not been previously studied. Breed et al. (1997) have
demonstrated only principal possibility of transition of arsenic from
arsenopyrite into solution during its leaching by Fe3+ ions. The lack of
the analysis of residue after leaching made impossible an estimation
of an efciency of a process. In Li et al. (2009) work the most detailed
research of process of chemical leaching (pre-oxidation) of refractory
sulphidic gold-arsenic concentrates with Fe3+ ion has been per-
formed. At these experiments oxygen and ozone were used as
additional oxidizers, experiments were carried out at temperature
from 60 to 100 . It has been found that the optimum conditions for
pre-oxidation are as following: 5% solid in pulp, temperature is 100 ,
54 ppm of ozone, 1.4 M of ferric iron, 8 h of treatment. The aim of the
treatment was the gold releasing from suldic minerals for its
subsequent extraction by cyanidation. Despite high extraction of
gold achieving by cyanidation 96.5% after pre-oxidation at the
optimum conditions, suggested process is difcult, power-intensive
and ecologically dangerous. Therefore suggested process cannot
replace biooxidation even in its traditional, one-stage variant.
Chemical leaching in our work is offered as a stage of short-term
preprocessings of energetic substratum for its subsequent biooxida-
tion at the second stage of process. It allows simple enough, cheap and
harmless way to achieve higher efciency subsequent biooxidation.
Optimal parameters of two-stage bacterialchemical processes have
been dened. Moreover, traditional one-stage processes (control)
were compared to the proposed two-stage processes (experiment) for
the gold-bearing suldic concentrates under study in this article.
These results demonstrate that two-stage bacterialchemical pro-
cesses are a promising approach for the intensication of biohydrome-
tallurgical processing of refractory suldic concentrates containing not
only nonferrous metals, but noble metals as well.
Acknowledgements
The work was supported by the grant from the Presidium of the
Russian Academy of Sciences Program 14, Scientic Bases for Efcient
Nature Management, Development of Mineral Raw Material Resources
and New Sources of Natural and Anthropogenic Raw Materials.
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