Accepted Manuscript

Synergetic effect of pyrite on strengthening bornite bioleaching by

Leptospirillum ferriphilum

Xingxing Wang, Rui Liao, Hongbo Zhao, Maoxing Hong, Xiaotao

Huang, Hong Peng, Wen Wen, Wenqing Qin, Guanzhou Qiu,
Caoming Huang, Jun Wang

PII: S0304-386X(16)30706-X
DOI: doi:10.1016/j.hydromet.2017.12.003
Reference: HYDROM 4707
To appear in: Hydrometallurgy
Received date: 6 October 2016
Revised date: 23 November 2017
Accepted date: 2 December 2017

Please cite this article as: Xingxing Wang, Rui Liao, Hongbo Zhao, Maoxing Hong,
Xiaotao Huang, Hong Peng, Wen Wen, Wenqing Qin, Guanzhou Qiu, Caoming Huang,
Jun Wang , Synergetic effect of pyrite on strengthening bornite bioleaching by
Leptospirillum ferriphilum. The address for the corresponding author was captured as
affiliation for all authors. Please check if appropriate. Hydrom(2017), doi:10.1016/
j.hydromet.2017.12.003

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 ACCEPTED MANUSCRIPT

Synergetic effect of pyrite on strengthening bornite bioleaching by Leptospirillum ferriphilum

1,2 1,2 1,2 1,2
Xingxing Wang , Rui Liao , Hongbo Zhao , Maoxing Hong ,

Xiaotao Huang1,2 , Hong Peng3 , Wen Wen4 , Wenqing Qin1,2 , Guanzhou Qiu1,2 , Caoming Huang1,2,5 ,

Jun Wang1,2*
1
School of Minerals Processing & Bioengineering, Central South University, Changsha 410083, Hunan, China

2
Key Lab of Biohydrometallurgy of Ministry of Education, Changsha 410083, Hunan, China

3
School of Chemical Engineering, The University of Queensland, Brisbane, Queensland 4072, Australia

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4
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China

5
China Nonferrous Metal Mining (Group) Co., Ltd , Beijing, 100029, China

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Abstract: Bioleaching experiments and electrochemical measurements were

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conducted to investigate the effect of pyrite on bornite bioleaching by Leptospirillum
ferriphilum. Bioleaching experiments results showed that the addition of pyrite
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increased the redox potential to 360 mV vs. an Ag/AgCl electrode in the initial period
of bioleaching process. The presence of pyrite significantly increased the copper
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extraction efficiency to 95.9% while the extraction value was only 19% without pyrite
addition after 20 days. Furthermore, the addition of pyrite also decreased the
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consumption of acid during bioleaching of bornite. Especially, the total acid

consumption was only 0.002 mmol at a pyrite to bornite ratio of 5:1 while the value
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was 2.842 mmol without pyrite addition. The results of electrochemical experiments
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identified that a galvanic effect existed between bornite and pyrite, and bornite was
more prone to oxidation sand reduction. Tafel plot and galvanic corrosion tests
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indicated that the addition of pyrite accelerated the dissolution of bornite. Furthermore,
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the dissolution of bornite with pyrite additon was not inhibited by the formation of
element sulfur and jarosite that may lead to passivation of chalcopyrite bioleaching.
Based on all the observations, a mechanism model on how pyrite accelerated bornite
dissolution is proposed.

*
Corresponding author. Address: School of Minerals Processing & Bioengineering, Central South University,
Changsha 410083, Hunan, China
Tel: +86-731-88876557; E-mail: wjwq2000@126.com (Jun Wang)

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Keywords: Pyrite; Bornite; Galvanic effect; Bioleaching; Leptospirillum ferriphilum

1 Introduction

Presently, the grades of copper ores are falling continuously as the higher grade
resources are extensively exploited and progressively depleted (Norgate and
Jahanshahi, 2010; Tilton and Lagos, 2007). As the grades of copper ores deteriorate,

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the energy and greenhouse gas emissions associated with the production of copper by
pyrometallurgical and hydrometallurgical methods increase significantly, resulting in

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high costs (Donati and Sand, 2007; Norgate and Jahanshahi, 2010). Bioleaching, as a
simple, lower cost and eco-friendly technology has been widely used in leaching low

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grade copper and complex ores (Brierley and Brierley, 2001; Debaraj et al., 2005;
Rawlings and Johnson, 2007), but most studies focused on chalcopyrite and few
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reports about bornite bioleaching have been published (Bevilaqua et al., 2003;

FelĂcio et al., 2007; Wang et al., 2008). Bornite is an important source of copper
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(Bevilaqua et al., 2003; Ferraz et al., 2011), following chalcopyrite and chalcocite in
economic importance (Pesic and Olson, 1983), so the development of bornite
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processing can bring huge economic benefits. Bornite always occurs with other metal
sulfides in native deposit (Buckley et al., 1984; Mathur et al., 2005; Pesic and Olson,
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1983), so it is a prospective and valuable topic to study their interaction during

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metallurgy and mineral processing.

Some researchers (Cruz et al., 2005; Mehta and Murr, 1983; Payant et al., 2012)
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have concluded that galvanic interactions between different sulfide ores could change
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their dissolution behavior. When two sulfide ores coexist in a leaching system, the

mineral with higher rest potential is protected from oxidation as the cathode, while the
mineral with lower rest potential is the anode, and the oxidation of the latter is
accelerated (Azizi et al., 2011; Teague et al., 1999).
Based on these galvanic interactions, many researchers paid regard to strengthen
other sulfide minerals leaching by adding pyrite (Chandraprabha and Natarajan, 2006;

Dutrizac et al., 1971; Mehta and Murr, 1982; Ruiz et al., 2014; Zhao et al., 2015b).
Berry et al. (1978) investigated the galvanic interaction between chalcopyrite and
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pyrite during bacterial leaching of low-grade waste rock. They reported that the
leaching of chalcopyrite was accelerated in contact with pyrite, and this effect was
enchaned in the presence of bacteria. Mehta and Murr (1982) studied the effect of

galvanic interactions between chalcopyrite, pyrite and sphalerite on bioleaching in

acidic medium in detail, they found that the reaction rate of metal dissolution
increased dramatically to more than ten times of the bioleaching rate for a single
metal sulfide. Dixon et al. (2008) developed a novel technology (GalvanoxT M) for the

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galvanically-assisted atmospheric leaching of primary copper concentrates. The key

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of the GalvanoxT M process was the presence of ground pyrite in the leaching reactor at
a level of two to four times the mass of chalcopyrite. The galvanic effect between

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pyrite and chalcopyrite ensureed rapid and complete dissolution of chalcopyrite,
thereby they found that copper recoveries of 98% or greater can be achieved at 80 ℃
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under atmospheric conditions in 4 hours of residence time. Nazari et al. (2011) found

that pyrite samples from different sources had a different catalytic effect on the
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process. Some pyrite samples increased the dissoulution rate significantly, while
others were less efficient. In our previously studies (Zhao et al., 2016; Zhao et al.,
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2015b), we found that the presence of pyrite could change the redox potential and
maintain it over an appropriate range, combined with the galvanic effect, the
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dissolution of chalcopyrite was accelerated.

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The relationship between bornite and chalcopyrite has been investigated in

previously work (Zhao et al., 2015b; Zhao et al., 2013), a synergistic effect during
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bioleaching was found. Chalcopyrite accelerated the dissolution of bornite, and

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bornite also accelerated the dissolution of chalcopyrite. This synergistic effect might

be attributed to the galvanic effect between chalcopyrite and bornite, and to the
formation of appropriate solution potential range for chalcopyrite bioleaching by the
addition of bornite. Dutrizac et al. (1971) conducted an experiment to elucidate the
effect of pyrite, chalcopyrite and digenite on the bornite dissolution rate. Sintered
discs of synthetic bornite prepared with pyrite, chalcopyrite or digenite were leached

in acidified ferric sulfate solution, and results revealed that the presence of pyrite
increased the dissolution rate at 15 ℃, while the presence of chalcopyrite or digenite
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caused only small changes in the dissolution rate. At 70 ℃, the dissolution rate was
essentially independent of the presence of pyrite or digenite in amounts up to 25%,
while the addition of chalcopyrite decreased the rate slightly. It is worthwhile to

mention that pyrite had different effect on bornite dissolution rate in acidified ferric
sulfate solution at different temperature.
Since pyrite is detrimental for pyrometallurgical copper recovery it must be

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separated from copper bearing sulfides (Ahmadi et al., 2012). In traditional
hydrometallurgical processes, the dissolution of pyrite is highly acid-producing,

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therefore, during the treatment of a concentrate with a high pyrite content, it is
necessary to add a neutralizing agent to maintain the right pH of solution (Rawlings

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and Johnson, 2007), otherwise, low pH corrodes the dressing equipment. Though
excessive acid is harmful in the traditional hydrometallurgical processes , the H+ and
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Fe2+ ions generated during dissolution of pyrite are essential for the growth of

extremely acidophilic iron-oxidizing bacteria during bioleaching (Brierley and

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Brierley, 2013; Coram and Rawlings, 2002; Gao et al., 2007; Nurmi et al., 2009),
indicating that the addition of pyrite would be beneficial for mixed sulfides
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bioleaching.
The moderately thermophilic Leptospirillum ferriphilum (L. ferriphilum) is an
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iron-oxidizing bacterium (Debaraj et al., 2005). It can tolerate a pH of lower than 1

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and a temperature of 45 ℃, and it has become one of the most important bioleaching
bacteria (Gao et al., 2007; Nurmi et al., 2009; Penev and Karamanev, 2010).
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Therefore, L. ferriphilum was chosen in this study, and bioleaching experiments and
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electrochemical measurements were conducted to investigate the effect of pyrite on

bornite bioleaching.

2 Materials and methods

2.1 Minerals
Bornite samples were obtained from Meizhou, Guangdong Province, China, and

pyrite samples were obtained from Daye, Hubei Province, China. Chemical analysis
showed that the bornite sample contained (w/w) 61.8% Cu, 9.7% Fe, 21.2% S and the
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pyrite sample contained 43.6% Fe, 43.5% S. Synchrotron-XRD results indicated that
bornite and pyrite were the main mineralogical components, ore samples used in the
study were of high purity. All samples were milled to a particle size of 200 mesh

(-0.074 mm) for experiments.

a b
P P-Pyrite B
P B-Bornite
Intensity (Counts)

Intensity (Counts)

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P P
P P B
B

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B B B B BB B
P B B B B B
PPP BB B B B B B
P PP P
P

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4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40


2-Theta/ 2-Theta/
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Fig. 1 Synchrotron X-ray powder diffraction analysis of the chosen mineral samples: (a)
Pyrite; (b) Bornite
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2.2 Microorganisms and culture media

L. ferriphilum used in this work was provided by the Key Lab of

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Bio-hydrometallurgy of Ministry of Education, Central South University. The bacteria

were cultured in a medium containing (NH4 )2 SO4 (3.00 g/L), KCl (0.10 g/L), K2 HPO 4
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(0.50 g/L), MgSO 4 ·7H2 O (0.50 g/L), Ca(NO 3 )2 (0.01 g/L) at the temperature of 45 ℃
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and pH of 1.7. The energy source was FeSO 4 ·7H2 O (44.70 g/L). Planktonic cells were

collected from bacteria solution in logarithmic phase by centrifugation (Beckman

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Coulter, lnc. Avanti j-E) at 104 rpm and 4 ℃ for 20 min, then bacteria adhered on
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centrifuge bottle wall were rinsed with 10 mL sterilized distilled water, then the
bacteria were collected for bioleaching experiments.

2.3 Bioleaching experiments

Bioleaching experiments were conducted in 250 mL flasks containing 100 mL
sterilized basal medium. 2 mL of a bacteria culture as well as pyrite and bornite at
different mass ratios were added to each flask, which were then incubated at 45 ℃ and
170 rpm on a rotary shaker. The initial cell concentration was higher than 1.0×107
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cells/mL. Evaporation loss was compensated periodically by adding distilled water,

and the pH was adjusted to 1.70 ± 0.03 with sulfuric acid on the first day. During the
bioleaching process, the variation of pH value, redox potential, and the concentrations

of ferric, ferrous and copper were measured.

2.4 Electrochemical measurements

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The Carbon Paste Electroactive Electrodes (CPEE) were fabricated by mixing 0.7
g minerals (-0.038 mm), 0.2 g graphite and 0.1 g solid paraffin. The mixture was

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heated and transferred rapidly into a tablet model for tableting under the pressure of
500 kg/cm2 , and then removed for air drying. Massive bornite and pyrite electrode for

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galvanic corrosion tests were cut from high-purity bulk ores. The electrodes were
polished using silicon carbide paper to obtain smooth surface before electrochemical
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measurements. Working surface of each electrode used in this study was 1 cm2 . Tafel

tests, cyclic voltammetry and potentiostatic test were conducted with a conventional
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three-electrode cell. CPEE was used as working electrode, and a graphite rod as the
counter electrode and Ag/AgCl (3 M KCl) electrode as reference electrode. During
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the galvanic corrosion tests, bornite electrode was connected to the working electrode,
and the pyrite electrode was connected to instrument ground. The potentiostat here
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effectively functioned as a zero-resistance ammeter (ZRA) (Santos et al., 2015). The

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galvanic current and potential were measured by the ZRA tests at any desirable time
interval.
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The electrolyte used in the experiments consisted of the following components:

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(NH4 )2 SO 4 (3.00 g/L), KCl (0.10 g/L), K2 HPO 4 (0.50 g/L), MgSO 4 ·7H2 O (0.50 g/L),

Ca(NO 3 )2 (0.01 g/L), and the pH of the solution was adjusted to 1.70 by sulfuric acid.
Nitrogen gas was sparged for 15 minutes before and during the electrochemical
measurements to remove dissolved oxygen from the electrolyte. Electrochemical
measurements were performed with a Princeton Model 283 potentiostat (EG&G of
Princeton Applied Research) coupled to a personal computer. Cyclic voltammetry

(CV) tests were conducted at a sweep rate of 20 mV/s. Tafel tests were performed at a
sweep rate of 2 mV/s, and potentiostatic test were performed for 240 s. All potentials
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in this paper are versus to an Ag/AgCl electrode (3 M KCl).

2.5 Analyses methods

The pH and ORP values in the leaching solutions were measured with a pH meter
(PHSJ-4A) and a Pt electrode in reference to an Ag/AgCl electrode (3 M KCl)
(BPP-922). The copper and iron concentration were analyzed by inductively coupled

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plasma-atomic emission spectrometer (ICP-AES) (America Baird Co. PS-6). In the
end of experiment, solids were filtered from leach solution, then the residues were

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washed with acidified distilled water (pH=1.7) and dried at a vacuum drying oven at
ambient temperature for mineralogical components analysis. The mineralogical

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components of bornite, pyrite and leaching residues were analyzed by
synchrotron-XRD at beamline BL14B1 of the Shanghai Synchrotron Radiation
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Facility (SSRF) with a wavelength of 0.6887 Å.

All chemicals used in this study were of analytical grade.

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3 Results and discussion

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3.1 Bioleaching experiments

5.0
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4.5
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4.0
m(pyrite),m(bornite);Unit:g
1,0 0,1
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3.5
1,1 3,1
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3.0 5,1 abiotic 3,1

pH

2.5

2.0

1.5

1.0

0.5
0 2 4 6 8 10 12 14 16 18 20 22 24
Time (d)
Fig. 2 Variations of solution pH during bioleaching
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Fig. 2 shows the variations of solution pH during bioleaching of bornite and

mixed sulfides. The solution pH of single bornite substantially increased from 1.7 to
4.6 in the first 11 days, after that pH maintained at approximate 4.6. Conversely, the

solution pH of single pyrite decreased continuously. Trends of pH suggested that the

dissolution of bornite was an acid consuming process, while the dissolution of pyrite
was an acid producing process. Reactions for the dissolution of bornite and pyrite

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were as follows (Bevilaqua et al., 2010; Descostes et al., 2004):
4Cu5 FeS4 + 37O2 + 20H + → 20Cu2+ + 4Fe3+ + 16SO42− + 10H2 O (5)

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FeS2 + 7/2O2 + H2 O → Fe2+ + 2SO42− + 2H + (6)
FeS2 + 14Fe3+ + 8H2 O → 15Fe2+ + 16H + + 2SO42− (7)

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The solution pH of mixed sulfides increased in the first day and was higher than
that of single bornite, indicating that the early leaching process was dominated by
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bornite, and the addition of pyrite accelerated the dissolution of bornite. The solution

pH of mixed sulfides continuously decreased in the later leaching process, and

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maintained between the solution pH of single bornite and pyrite. The solution pH for
abiotic experiments at a pyrite to bornite ratio of 3:1 was lower than that for 1:1 and
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0:1, which suggests that the interaction between bornite and pyrite could also
obviously reduce solution pH in the absence of bacteria. However, the effect of pyrite
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on solution pH reduction was more significant in the presence of bacteria. This is

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supported by the comparison of solution pH for abiotic and bioleaching experiment at

a pyrite to bornite ratio of 3:1 after leaching for 12 days.
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AC

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3 2.842
Total acid consumption (mmol)
2

1.111
1
0.459
0.018 0.002
0

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1,0 0,1 1,1 3,1 5,1 abiotic 3,1
-1 m(pyrite),m(bornite);Unit:g

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-2

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-3
-2.991
-4
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Fig. 3 Total acid consumption during bioleaching
Fig. 3 shows the total acid consumption during bioleaching process. The result of
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single sulfide was consistent with the previous conclusion, that the dissolution of

bornite was an acid consuming process, while the dissolution of pyrite was an acid
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producing process. The results of mixed sulfides indicated that the addition of pyrite
reduced the total acid consumption during bioleaching process of bornite, and the
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total acid consumption decreased with the increase of the ratio of pyrite to bornite.
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The total acid consumption was almost zero at a pyrite to bornite ratio of 5:1,

suggesting that the acid consumption and the acid production could be balanced
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during bioleaching. The total acid consumption for abiotic experiments was 0.459
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mmol at a pyrite to bornite ratio of 3:1, while that was 0.018 mmol for bioleaching
experiments. The results demonstrated that bacteria played an important role in
reducing total acid consumption.

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100

90 m(pyrite),m(bornite);Unit:g
0,1
80
1,1
3,1
Copper extraction (%) 70
5,1
60 abiotic 3,1
50

40

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30

20

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10

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0
0 2 4 6 8 10 12 14 16 18 20 22
Time (d)
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Fig. 4 Variation of copper extraction during bioleaching
Fig. 4 shows the variations of copper extraction during bioleaching of bornite and

mixed sulfides. Copper extraction of single bornite always remained low below 19%
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during bioleaching, because L. ferriphilum cannot survive at the unfavorable pH.

Copper extraction at a pyrite to bornite ratio of 3:1 and 5:1 steadily increased to 93.6%
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and 95.9%, respectively, while copper extraction of 1:1 pyrite-to-bornite stayed at low
rates. The result indicated that pyrite was beneficial for the dissolution of bornite, and
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the copper extraction of mixed ore increased as the amount of added pyrite increased.
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In the first 6 days, there was no obvious difference between the copper extraction for
abiotic and bioleaching experiments at a pyrite to bornite ratio of 3:1, while the latter
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was also steadily increasing and the former increased slowly after that. The result
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revealed that the presence of bacteria could induce a higher copper extraction rate

during mixed minerals bioleaching, and the enhancement was more obvious in the
late stage.
Synchrotron X-ray powder diffraction analysis (Fig. 5) showed that the peaks of
bornite undergone massive changes while that of pyrite remained unchanged. The
main intermediate for bornite dissolution was mooihoekite (Cu9 Fe9 S16 , PDF#27-0165)

on the 1st day, which converted to isocubanite (CuFe2 S3 , PDF#27-0165) on the 5th day.
Large amounts of element sulfur (S, PDF#85-0799) and jarosite (KFe3 (SO 4 )2 (OH)6 ,
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PDF#76-0629) were formed on the 9th day. All peaks of pyrite were always observed
during the experiment. The results suggested that bornite was preferentially dissolved
and the peaks of pyrite remained unchanged during the bioleaching of mixed sulfides

in the first 9 days. Combined with the variations of copper extraction during
bioleaching, we found that the formation of element sulfur and jarosite did not inhibit
the further dissolution of bornite, which was different from the conclusion of

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chalcopyrite bioleaching (Sandström et al., 2005; Wang et al., 2016).

J J J
J J

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S J
J J
J J
S J

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S J
J S
9 day I
Intensity (Counts)

I
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I
I
5 day
M
M
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M M M
1 day
P P P P P
P P P P P P P P P P

pyrite
B
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B
B B B B
B B B
B B B
B B B
borntie
T
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4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
2-Theta/
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Fig. 5 Synchrotron X-ray powder diffraction analysis of leaching residues for bioleaching
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experiments at a pyrite to bornite ratio of 3:1 (B-Bornite, Cu5 FeS4 , I-Isocubanite, CuFe2 S3 ,
J-Jarosite, KFe3 (SO4 )2 (OH)6 , M-Mooihoekite, Cu9 Fe9 S16 , P-Pyrite, FeS2 , S-Element Sulfur, S)

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700
m(pyrite),m(bornite);Unit:g
650
1,0
600 0,1
1,1
550 3,1
5,1
500
ORP
abiotic 3,1
450

400

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350

300

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250
0 2 4 6 8 10 12 14 16 18 20 22

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Time (d)

Fig. 6 Variations of redox potential during bioleaching

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2.5
a
m(pyrite),m(bornite);Unit:g
Concentration of ferrous ions (g/L)

2.0 1,0 0,1

1,1 3,1
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5,1 abiotic 3,1

1.5

1.0
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0.5
T

0.0
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-0.5
0 2 4 6 8 10 12 14 16 18 20 22
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Time (d)
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b 5.0
m(pyrite),m(bornite);Unit:g
4.0 1,0
0,1

TFe concentration (g/L)

1,1
3.0
3,1
5,1
2.0 abiotic 3,1

1.0

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0.0

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-1.0
0 2 4 6 8 10 12 14 16 18 20 22
Time (d)

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Fig. 7 Variations of the concentration of (a) ferrous ions and (b) total iron (TFe) during
bioleaching
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Fig. 6 shows variations of redox potential during bioleaching. Many authors
(Hiroyoshi et al., 2008; Lotfalian et al., 2015) pointed out that the redox potential of
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the leaching solution was primarily determined by the Nernst equation:

RT [Fe3+ ]
E = E0 + ln
F [Fe2+ ]
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Fig. 7 indicates that the addition of pyrite increased the concentration of Fe 2+, and
then Fe2+ was oxidant to Fe3+ with dissolved oxygen by L. ferriphilum, so the addition
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of pyrite obviously increased solution redox potential. The conclusion is also true in
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abiotic experiments, as can be seen from the result for abiotic experiments at a pyrite

to bornite ratio of 3:1.

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Compared with the redox potential of single bornite, the addition of pyrite
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obviously increased solution redox potential. Combined with the variations of copper
extraction during bioleaching (Fig. 4), it could be found that when the redox potential
was up to 360 mV in the initial period of bioleaching process, copper extraction

concomitantly began to sharply increase. The results at a pyrite to bornite ratio of 3:1
and 5:1 indicated that the addition of pyrite could induce that the solution redox
potential increased to 360 mV in the initial period of bioleaching process and copper
extraction increased to 90%. Conversely, the solution redox potential was at low level
at a pyrite to bornite ratio of 0:1 and 1:1, and the copper extraction efficiencies also
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were at low level. The results for abiotic experiments at a pyrite to bornite ratio of 3:1
indicated that in the absence of bacteria, the addition of pyrite could also induce that
the solution redox potential increased to 360 mV and copper extraction increased

quickly in the initial period of leaching process. Therefore it is very important to

maintain an optimum redox potential for bornite dissolution.

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3.2 Electrochemical experiments
3.2.1 Rest potential tests

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Rest potential is an important electrochemical property of mineral, and it
determines the role of mineral in a galvanic couple (Azizi et al., 2011; Qin et al., 2015;

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Teague et al., 1999). Rest potential tests results showed that the rest potential of single
pyrite (415 mV) was higher than that of single bornite (235 mV), a pyrite to bornite
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ratio of 1:1 (291 mV) and 5:1 (368 mV) mixed sulfides. The rest potential of mixed

sulfides was higher than that of single bornite, and increased as the amount of added
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pyrite increased. In the galvanic couple of pyrite-bornite, pyrite would act as a

cathode and bornite would act as an anode, and the oxidation of bornite would be
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accelerated (Gu et al., 2004). The result was consistent with the previous conclusion
from variations of copper extraction during bioleaching (Fig. 3).
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3.2.2 Potentiostatic tests

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Potentiostatic tests were conducted to investigate the potential range in which the
oxidation and reduction reactions of pyrite and bornite occurred. The results are
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shown in Fig. 8. The reduction of pyrite occurred when potential was less than 0.3 V,
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and the oxidation of pyrite occurred when potential was more than 0.3V. It can also be

seen that reduction of bornite took place when the potential was lower than 0.2 V, and
oxidation of pyrite took place when the potential was higher than 0.2 V. Compared to
that of pyrite under the same potential, the current density of bornite was higher,
indicating that bornite was more prone to oxidation and reduction.

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3
a 2
0.8 mV
1 0.6 mV

Current density (mA/cm2)

0
-1 -0.5 mV -0.1~0.3 mV
-2
-3

Current density (mA/cm2)

0.1
-4 0.0
0.3 mV
-5 -0.1 0.2 mV
-0.8 mV

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-0.2
-6 -0.3 -0.1 mV
-7 -0.4

-8 -0.5

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0 50 100 150 200 250
Time (s)
-9
0 50 100 150 200 250

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Time (s)
15
b
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10 0.8 mV
Current density (mA/cm2)

5 0.6 mV
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0
-0.5 mV -0.1~0.2 mV
-5
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Current density (mA/cm2)

-10 0.02
0.2 mV
0.00

-15 -0.8 mV 0.1 mV

-0.02
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-0.04 -0.1 mV
-20
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-0.06
0 50 100 150 200 250
Time (s)
-25
0 50 100 150 200 250
C

Time (s)
Fig. 8 Current-time curves of (a) pyrite electrode and (b) bornite electrode at different applied
AC

potentials

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2250
2000 Pyrite
1750 Bornite
1500
Q (mC) 1250
1000
750
500

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250
0

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-250
-0.9 -0.6 -0.3 0.0 0.3 0.6 0.9

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Potential (V)

Fig. 9 Relationship between the total charge and applied potential

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Fig. 9 shows the relationship between the total charge (calculated based on the
integrals from the current-time curves of bornite and pyrite electrode) and applied
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potential, indicating that the total charge of bornite was higher than that of pyrite in

the potential range between 0.3 V to 0.9 V. Therefore, the oxidation and reduction of
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bornite took place more easily, and the result agreed quite well with the conclusion
from the current-time curves (Fig. 6).
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3.2.3 Cyclic voltammetry experiments

Cyclic voltammetry (CV) is a potential-controlled reversal technique, and it is

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very useful in obtaining information about chemical reactions at the electrode-solution

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interface. Fig. 10 shows cyclic voltammograms obtain for pyrite and bornite electrode
in 9K medium at a sweep rate of 20 mV/s. The difference between cyclic voltammetry
spectra of pyrite electrode and bornite electrode indicated that the oxidation and

reduction mechanisms of pyrite and bornite were different. The anodic and cathodic
current peaks of bornite and mixed electrode were in the similar range, indicating that
the addition of pyrite did not change the oxidation and reduction mechanisms of
bornite, but changed the current density. The reaction occurred indicated by an anodic
peak as discussed in the literature (Zhao et al., 2015a), and it was related to the
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oxidation of copper. Peak b was probably related to the oxidation of species formed in
the potential region of peak a. Peak c in the range of 600 mV to 800 mV was related
to the bornite oxidation process and the formation of covellite (Arce and González,

2002; Majuste et al., 2012). Cathodic peak d represented the reduction of covellite
formed during the oxidation (Liang et al., 2013; Zhao et al., 2015a). Peak e was
associated with the reduction of some products of covellite or bornite reduction. Peak

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f was related to the reduction of copper(I) to metallic copper (Bevilaqua et al., 2009).
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pyrite:bornite c

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20 0:1
1:0
Current density (mA/cm2)

15 1:1

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3:1
10
5:1
5 b
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a
0

-5
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e
-10 d

-15
f

-1000 -800 -600 -400 -200 0 200 400 600 800 1000
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Potential (mV)
Fig. 10 Comparison of cyclic voltammetry spectra of pyrite electrode, bornite electrode
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and mixed electrode

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3.2.4 Tafel and galvanic corrosion tests

1.0
C

a
0.8
AC

0.6

0.4
Potential (mV)

0.2

0.0

-0.2

-0.4

-0.6
-10.00 -9.50 -9.00 -8.50 -8.00 -7.50 -7.00 -6.50 -6.00
2
log(Current density) (A/cm )
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4.0
b -1.58
3.0
-1.59

Current density (μA/cm2)

2.0
-1.60

Potential (mV)
1.0
-1.61
0.0
-1.62
-1.0
-1.63
-2.0
-1.64

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-3.0
-1.65
-4.0
-1.66

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-25 0 25 50 75 100 125 150 175 200 225
Time (s)

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Fig. 11 (a) Tafel plots of bornite electrode and galvanic potential and
(b) galvanic current vs. time between pyrite and bornite
Fig. 11 shows Tafel plots of bornite electrode and galvanic potential and galvanic
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current with time between pyrite and bornite. The result calculated from Tafel plot
showed that the corrosion current density of bornite was 3.968×10-2 µA/cm2 . The
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galvanic current established between pyrite and bornite was 1.652 µA/cm2 . The

higher galvanic current indicated that the bornite corrosion was obviously accelerated
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in the presence of pyrite.

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3.3 A model of pyrite accelerated dissolution of bornite

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From thermodynamics, it is known that two phases are in equilibrium if their

electrochemical potentials are equal. The electrochemical potential of redox couples

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(electrolyte) in solution is available as Eredox (Reiss, 1985), while the electrochemical

AC

potential of the electrons in the semiconductor is available as the Fermi level EF. If
Eredox and EF are different, a charge redistribution between semiconductor and solution
is required to equilibrate the two phases (Tiginyanu et al., 2009). From the calculation

by conversion formula of Fermi level and the redox potential (Reiss, 1985), we could
find that when the redox potential is higher than a certain value, Eredox is less than the
EF of bornite. The electrolyte extracts electrons directly from the bornite resulting in
an anodic current. Combined with the experiments results, the presence of pyrite and
bacteria induced a higher redox potential (>360 mV), which promoted the dissolution
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of bornite.
Rest potential is a voltage of the bulk sulfide minerals relative to bulk electrolyte,
and it is the result of the electrification of the minerals/electrolyte interface

(Mirnezami et al., 2013). The Fermi energy of a semiconductor mineral is close to its
rest potential, and the difference in these potentials induces charge transfer between
semiconductor and solution in order to equilibrate the two phases (Estrada-de los

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Santos et al., 2016; Wei and Osseo-Asare, 1996). In the galvanic couple of
pyrite-bornite, pyrite with higher rest potential would act as a cathode and bornite

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with lower rest potential would act as an anode, and the oxidation of bornite would be
accelerated.

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A schematic is shown in Fig. 12 to explain how the pyrite accelerated the
dissolution of bornite, revealing that low pH, high ORP, oxidant and galvanic effect
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are the four important factors for the synergetic bioleaching of bornite and pyrite. The

dissolution of pyrite increased the concentration of H+ and Fe2+, and the rise of H+
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created a low pH environment, which is essential for the growth of L. ferriphilum.

Fe2+ was oxidized to Fe3+ by L. ferriphilum, and the Fe3+ and H+ are crucial leachants
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for bornite, meanwhile, resulting in optimum match of Fe2+ and Fe3+, maintaining a
high redox potential. Additionally, the galvanic effect between pyrite and bornite was
T

an essential factor for enhancing the oxidation of bornite, and the principle of electron
EP

transfer has been explained. As suggested above, an optimum environment was

formed by the addition of pyrite for accelerating the dissolution of bornite.
C
AC

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Fig. 12 Proposed model of pyrite accelerated dissolution of bornite during bioleaching
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4 Conclusions
In the present study, bioleaching experiments of single bornite, single pyrite and
mixed sulfides were conducted to investigate the effect of pyrite on bioleaching of
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bornite in the presence of L. ferriphilum, and electrochemical experiments were

conducted to provide some information to explain the effect.
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The result of bioleaching experiments showed that the solution pH of mixed

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sulfides increased in the first day and were higher than that of single bornite, but the
C

pH decreased in the follow-up experiments. Therefore, bornite preferentially

AC

dissolved, and pyrite could accelerate the process, and the strengthening effect
increased as the amount of added pyrite increased.
The total acid consumption was almost zero at a pyrite to bornite ratio of 5:1,
indicating that the acid consumption and the acid production could be balanced
without adding acid during bioleaching process, so the process of bioleaching of

mixed sulfides included pyrite and bornite has potential value. The results at a pyrite
to bornite ratio of 3:1 and 5:1 showed that the addition of pyrite increased the redox
potential to 360 mV in the initial period of the bioleaching process and copper

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extraction efficiency concomitantly began to sharply increase and eventually reached

90%. The results of electrochemical experiments indicated that the rest potential of
single pyrite was higher than that of single bornite, a galvanic effect existing between

bornite and pyrite could accelerate the dissolution of bornite but could not change the
dissolution mechanism of bornite. Tafel plot identified that the addition of pyrite
accelerated the dissolution of bornite. To sum up, a model of pyrite accelerated the

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dissolution of bornite was proposed.

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Acknowledgments
This work was supported by the National Natural Science Foundation of China

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(No. 51774332, 51704331, 51320105006, 51374248), the National Key Research and
Development Program of China (No. 2017YFA0402800), the Open Funds of SSRF
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(No. 2016-SSRF-PT-005985) and the Fundamental Research Funds for the Central

Universities of Central South University. The authors thank beamline BL14B1

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(Shanghai Synchrotron Radiation Facility) for providing the beam time and helps
during experiments. We also thank the reviewers and editors of the manuscript
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including Prof. Jochen Petersen and Prof. Versiane Leao.

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Graphical abstract
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Highlights

 Pyrite addition decreased the solution pH, and the total acid

consumption was almost zero at a pyrite to bornite ratio of 5:1

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 Pyrite addition adjusted an optimum redox potential range for

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accelerating the bornite dissolution

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 The galvanic effect of bornite with pyrite increased copper extraction

during bioleaching
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