Hydrometallurgy 196 (2020) 105419

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Bioprocessing of oxidized platinum group element (PGE) ores as pre- T

treatment for efficient chemical extraction of PGE
⁎,1
Sabrina Hedricha, , Dennis Kraemerb, Malte Jungec, Herwig Marblerd, Michael Baub,
Axel Schippersa
a
Geomicrobiology unit, Federal Institute for Geosciences and Natural Resources (BGR), Stilleweg 2, 30655 Hannover, Germany
b
Department of Physics and Earth Sciences, Jacobs University Bremen, Campus Ring 1, 28759 Bremen, Germany
c
Institute of Earth and Environmental Sciences, University Freiburg, Albertstr. 23b, 79104 Freiburg, Germany
d
German Mineral Resources Agency (DERA) within BGR, Wilhelmstr. 25-30, 13593 Berlin, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: Platinum-group elements (PGE) are relevant for many high technology applications, prompting the search for
Oxidized PGE ore potential alternative resources and environmentally friendly processing technologies. The largest deposit of PGE
Platinum worldwide is the Bushveld Complex in South Africa. The pristine sulfide-bearing ore is mined using conventional
Bioleaching metallurgical methods, while the near-surface oxidized PGE ore is currently stockpiled. Economic extraction of
Chemical leaching
PGE from these stockpiles using conventional technologies is not feasible to date. Hence, biohydrometallurgical
Mineral liberation
approaches to recover valuable transition metals and liberate platinum-group minerals for subsequent chemical
PGE extraction have been considered. The four stockpile samples taken from a heap of oxidized PGE ores from
the Platreef formation showed a similar mineralogical composition with > 90 wt% silicates and minor amounts
of Fe-(oxy)/hydroxides, both associated with Ni, Mn and Cu. Platinum-group minerals were present as sperrylite
(PtAs2), cooperite (PtS low Pd), native platinum and Pd‑bismuthotellurides and mostly associated with silicates.
Stirred tank bioleaching under various conditions was proven to be most feasible for an oxidative process at
moderately-high temperatures using a consortium of iron- and sulfur-oxidizing acidophiles dominated by
Acidithiobacillus caldus and Sulfobacillus thermosulfidooxidans. Bioleaching achieved up to 86% total metal re-
covery (including Co, Cu, Mn and Ni) and led to a liberation of platinum-group minerals. The bioleach residues
were subsequently chemically leached by a HNO3/NaCl and a cyanide leach, allowing for the enhanced ex-
traction of up to 89% Pt and 96% Pd after bioleaching. Chemical and mineralogical analysis validated the
potential of oxidative bioleaching as a promising processing option for a pre-treatment of oxidized PGE ore,
allowing separate and efficient recovery of valuable base metals and enhancing the subsequent chemical PGE
extraction.

1. Introduction
Platinum-group elements (PGE: Ru, Rh, Pd, Os, Ir and Pt) are pre-
sent in extremely low concentrations (0.000022–0.00052 ppm; Rudnick
and Gao, 2003) in the upper continental crust. In ore deposits, con-
centrations occur in the range of 1 to 15 ppm. The majority of PGE is
mined from the Bushveld Complex in South Africa. Here, the most
important geological PGE sources are the Merensky Reef, the Platreef
and the UG-2 chromitite (e.g. Oberthür et al., 2016). The pristine sul-
fide-bearing ore mined in the Bushveld Complex and elsewhere is
treated following conventional metallurgical practice that includes
milling, froth flotation, matte smelting and chemical leaching, and
recoveries for Pt of more than 85% are commonly reached (Rule, 1998).
However, the near-surface oxidized PGE ores from the Bushveld Com-
plex in South Africa have a high potential for future mining and pro-
cessing. The near-surface deposits contain a high tonnage of low-grade
ores that occur at maximum depths of about 15 to 50 m. Hence, a
potential low-cost open-pit mining makes exploitation of these ores
economically attractive. Resource estimates in the Bushveld Complex
are in the range of 337 million tons of oxidized ores, of which two
thirds occur in the Platreef ore body. The oxidized ores in the Bushveld
Complex contain 819 t of on average 2.4 ppm of the four elements (4E)
Pt, Pd, Rh and Au together (Buchholz and Foya, 2015). Platinum-group
elements are polymodally distributed within the oxidized reef-type and

⁎
Corresponding author.
E-mail address: sabrina.hedrich@bio.tu-freiberg.de (S. Hedrich).
1
Present address: Institute of Biosciences, TU Bergakademie Freiberg, Leipziger Straße 29, 09599 Freiberg, Germany.

https://doi.org/10.1016/j.hydromet.2020.105419
Received 9 April 2020; Received in revised form 29 June 2020; Accepted 9 July 2020
Available online 12 July 2020
0304-386X/ © 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
S. Hedrich, et al.
chromitite ores, which is challenging for the recovery of PGE from these
near-surface ores. In oxidized ores, the PGE are mainly hosted in Pt-Pd-
oxides and -hydroxides as well as in Fe- and Mn-oxides and -hydroxides
and are intercalated in and sorbed on clay minerals (Junge et al., 2019).
The ores are hosted in intensely weathered and serpentinized pyrox-
enite rocks. Reports on metallurgical tests conducted on oxidized ore
material suffer from very low Pt recoveries of considerably less than
30% (Oberthür et al., 2013; Kraemer et al., 2017).
One of the main issues faced with processing of near-surface oxi-
dized PGE ores is the very heterogeneous and polymodal PGE dis-
tribution, including dispersion of PGE in secondary silicates and in iron-
and manganese oxides/hydroxides. Concentrate dilution during froth
flotation due to the occurrence of naturally floating gangue (NFG;
Becker et al., 2009; Bulatovic, 2003) and lack of base metal sulfide
association (Becker et al., 2014) further aggravate the metallurgical
processing of oxidized ores. Concentrate dilution during froth flotation
is mainly caused by the presence of talc-coated pyroxene grains, which
causes a different flotation behavior in comparison to pristine ores,
where pyroxene grains are not coated by weathering products (Becker
et al., 2009). Prendergast (1988) reported processing trials of oxidized
PGE ores from the Great Dyke, Zimbabwe, by means of gravity con-
centration and flotation and the reported recoveries were far below
50%. Oberthür et al. (2013) stated that metallurgical test work on
oxidized ores from the Ngezi mine in Zimbabwe achieved Pt and Pd
recoveries of only 15–30%.
The Mogalakwena Mine, situated near the town of Mokopane in the
Limpopo province, South Africa, and operated by Anglo American
Platinum Ltd., is the largest open-pit PGE mine in the world to-date, by
reserves and production. Significant portions of the near-surface oxi-
dized ores are already excavated, crushed, analyzed and classified and
stockpiled according to 4E grades. Processing of these stockpiles is not
feasible at the moment due to the lack of adequate processing tech-
nologies that enable the economic extraction of PGE.
Since metal recovery from these PGE ores using conventional
technologies is usually low or in the case of stockpiles not economic,
biohydrometallurgical approaches to recover valuable transition metals
and to extract PGE have been considered. These include bioleaching
using acid-producing and redox-active microorganisms as well as the
application of complexing compounds produced by microorganisms to
recover PGE (Schippers et al., 2014; Brandl, 2008; Kraemer et al.,
2015a). Bioleaching refers to the extraction of metals from ores and
solid residues by microorganisms transferring the metals into their so-
luble form. Microorganisms contribute to metal bioleaching either
through acid production (inorganic or organic) or indirectly by pro-
viding ferric iron as a leaching agent (Schippers et al., 2014; Glombitza
and Reichel, 2014) to dissolve the mineral structure. Bioleaching is
industrially applied to recover e.g., copper, cobalt, nickel and zinc from
sulfidic minerals. Refractory gold ores, in contrast, are processed via
biooxidation, which is a bioleaching process where the sulfidic host
mineral is dissolved but the target metal remains in the residue for
further chemical extraction. To date, industrial-scale biooxidation has
only been applied for gold-containing sulfidic ores (Brierley, 2016),
while biooxidation of sulfidic low-grade platinum ore concentrates has
been shown in lab scale (e.g. Yopps and Baglin, 1991; Mwase et al.,
2014). Yopps and Baglin (1991) successfully demonstrated bioleaching
of sulfide minerals, including pentlandite, from a PGE ore flotation
concentrate by Acidithiobacillus ferrooxidans in stirred tank bioreactors.
The thereby liberated PGE were further subjected to chemical extrac-
tion. Laboratory-scale bioleaching of low-grade ore flotation con-
centrate and coarse ore with thermophilic, iron- and sulfur-oxidizing
acidophiles in packed bed columns was successfully applied to recover
base metals, and PGE in a following cyanide leaching step (Mwase
et al., 2012; Mwase et al., 2014). While these studies focused on bio-
leaching of mainly sulfidic PGE ore, oxidized PGE ore hosting re-
markable amounts of precious metals, has not been the target of bio-
leaching yet. Recent developments have, however, brought about an
2
Hydrometallurgy 196 (2020) 105419
approach (reductive bioleaching) which also allows for the processing
of oxidized iron ores using microorganisms that are capable of ferric
iron reduction (Hallberg et al., 2011). Reductive bioleaching dissolves
the host mineral structure by microbially catalyzed iron reduction and
valuable metals are released. The process has been observed under
anaerobic conditions catalyzed by facultative iron reducing acidophiles
(Hallberg et al., 2011) as well as at ultra-low pH in aerobic cultures of
sulfur-oxidizing Acidithiobacillus thiooxidans (Marrero et al., 2015).
Reductive bioleaching has successfully been applied in laboratory-scale
for limonitic ores (Hallberg et al., 2011; Johnson et al., 2013;
Ñancucheo et al., 2014; Johnson and du Plessis, 2015; Marrero et al.,
2015) and could also be a promising approach for the bioprocessing of
oxidized PGE ore by attacking the ferric iron and manganese minerals.
Subsequent extraction of the PGE from the residues can be achieved
by either biological-based or chemical approaches. Siderophores are
capable of mobilizing Pt and Pd (and other polyvalent metals) at high
pH from oxidized PGE ores, which were preconditioned with hydro-
chloric acid for the removal of base metals (Kraemer et al., 2015a,
2015b). Several publications also suggest that direct mobilization of
PGE from various ores by organic-acid producing bacteria or fungi (e.g.
Brandl, 2008) is possible, this has, however, not been investigated for
PGE ores yet. Conventional chemical methods for PGE recovery there-
fore comprise cyanidation, acid or bromide leaching (reviewed in
Sefako et al., 2017).
This study aims to apply and assess a range of bioleaching ap-
proaches as a pretreatment option for oxidized PGE ores to recover
valuable transition metals and enhance the recovery of PGE in a second
chemical extraction step using HNO3/NaCl as a modified leach of the
“Saturated Saline Nitric” (SSN) leach, which targets lixiviation of pre-
cious metals like Au, Pt and Pd (Lashley, 1994).
2. Experimental
2.1. Ore samples
The near-surface oxidized PGE ores of approximately 30 m thickness
are removed as overburden and stockpiled in order to obtain access to
the underlying pristine Platreef ores. Four samples of oxidized PGE ore
were collected from various sites of a stockpile within the Mogalakwena
Mine in the northern Bushveld Complex, South Africa. The samples
were crushed and sieved to achieve different size fractions (< 63 μm,
63–200 μm, 200–315 μm, > 315 μm) for bioleaching experiments.
2.2. Bioleaching
2.2.1. Bioleaching consortia
Various acidophilic, iron- and sulfur-oxidizing microorganisms were
applied for bioleaching experiments. Basal salt medium supplemented
with trace elements was used in all experiments (Wakeman et al.,
2008). A consortium containing a mixture of the pure type strains
Acidithiobacillus (At.) thiooxidansT, At. ferroxidansT and Leptospirillum
(L.) ferrooxidansT was grown in medium with 1% sulfur and 20 mM
ferrous iron at pH 2.0 and 30 °C. Sulfobacillus (Sb.) thermo-
sulfidooxidansT and At. ferrooxidansT were maintained together on 1%
sulfur at pH 2.0 and 35 °C. A mixed culture of moderate thermophiles
containing the pure type strains Sb. thermosulfidooxidansT, Sb. acid-
ophilusT, Sb. benefaciensT, At. caldusT, L. ferriphilumT and a strain of
Acidiplasma (Ap.) cupricumulans was grown in medium with 1% sulfur
and 20 mM ferrous iron at 42 °C (Hedrich et al., 2018). A mixed culture
of Sulfolobus spp. and Metallosphaera spp. was maintained in medium
with 1% pyrite at 65 °C.
2.2.2. Bioleaching setup
Bioleaching experiments in stirred tank reactors were carried out
under aerobic and anaerobic conditions. 2-L-Bioreactors (Electrolab,
UK) with 1.5 L working volume were operated with 10% (w/v) pulp
S. Hedrich, et al.
Table 1
Elements of interest for the leaching process of the four bulk samples of PGE ore.
Sample Au Pt Pd Pt/Pd
ppm
102 0.22 1.07 0.89 1.20
103 0.18 1.07 1.05 1.02
104 0.25 1.55 1.20 1.29
105 0.17 0.85 0.58 1.46
density in basal salt medium pH 1.8 for 10 to 14 days. As the total sulfur
content of the oxidized samples was ≤0.02%, 1% sulfur was added to
the bioreactors as substrate for the microorganisms. Mixed cultures
were adapted to 5% solids in shake flasks as inoculum for the bior-
eactors. The following parameters were varied in the bioreactors: (i)
temperature (sample 102, < 63 μm; 30 °C, 42 °C, 65 °C), (ii) ore sample
(Table 1; < 63 μm, 42 °C), (iii) particle size (sample 103; < 63 μm,
63–200 μm, 200–315 μm, > 315 μm) and (iv) microbial community
composition (sample 102, < 63 μm) (see 2.2.1). For aerobic experi-
ments, bioreactors were sparged with filter-sterilized air. Anaerobic
experiments using At. ferrooxidans and Sb. thermosulfidooxidans were
initiated by allowing microbial growth in basal salt medium pH 2.5
with 1% sulfur under aeration with air until pH reached 1.8, when
aeration was switched to nitrogen and ore was added. For all experi-
ments the pH of the slurry was adjusted to 1.8 after ore addition by
automated dosing of 2 M sulfuric acid.
Abiotic control experiments were conducted under sterile condi-
tions with automated pH adjustment according to pH values de-
termined in corresponding bioleaching experiments upfront.
Regular sampling involved determination of pH, redox potential,
dissolved metals, light microscopy and microbial community mon-
itoring (section 2.4.2). Bulk samples and leaching residues were ana-
lyzed as described in the section 2.4.1.
2.3. Chemical extraction of PGE from bioleach residues
Following bioleaching of the ore samples, the residues were sub-
jected to chemical extraction of PGE using HNO3/NaCl. The HNO3/
NaCl leach is a modified leach of the Saturated Saline Nitric (SSN)
leach, which targets lixiviation of precious metals like Au, Pt and Pd.
The leach was first published by the American Society for Applied
Technology (Lashley, 1994) and was tested within this study with dif-
ferent parameters such as acid admixture (acid to brine ratio), pulp
density and leaching time with the aim to determine the optimal
parameters for extraction of Pt and Pd from oxidized PGE ores. The
experiments were conducted at room temperature on the crushed ore
without prior treatment with microorganisms (untreated PGE ores). The
optimized leach was then used on the bioleach residues. The lixivants
were prepared from concentrated nitric acid (Merck Suprapur®) and
analytical grade sodium chloride with ultrapure deionized water. All
reagents were tested for Pt and Pd contamination by blank tests with
mass spectrometry. The reagents were prepared immediately before the
leaching experiments in properly sized acid-cleaned low density poly-
ethylene (LDPE) bottles. The ideal amount of nitric acid relative to
saturated sodium chloride solution was determined (acid admixture).
For this, concentrated (68%) nitric acid was mixed to the saturated
sodium chloride solution in different ratios (5:1, 7:1, 10:1, 15:1, 20:1
and 50:1). A pulp density test was conducted to optimize the ratio of
oxidized PGE ore to lixivant. The initial ratio of 1:10 (1 g ore on 10 mL
leaching solution) was changed to 2:10, 3:10, 4:10 and 5:10 and each
experiment was performed for 24 h. The pulp density experiments were
combined with the admixture experiments in order to identify the most
efficient parameters for solubilization of Pt and Pd from the oxidized
PGE ores. Time-series experiments at room temperature were con-
ducted after optimization of acid admixture and pulp density to de-
termine the optimal reaction time with the oxidized PGE ore. Samples
Hydrometallurgy 196 (2020) 105419
Mn Fe Ni Co Cu Zn S
%
0.16 8.12 0.21 0.02 0.24 0.01 0.02
0.18 8.57 0.25 0.02 0.27 0.01 0.03
0.19 9.26 0.23 0.02 0.22 0.01 < 0.01
0.13 5.02 0.13 0.01 0.01 0.01 < 0.01
were taken after 3 h, 24 h, 48 h, 72 h and 1 week. The bioleach residues
were treated with the optimized HNO3/NaCl leach parameters at either
40 °C, 60 °C or 80 °C to determine the temperature effect. Samples were
taken after 2 h, 4 h, 6 h, 8 h, 24 h and 36 h. The experiments were
conducted in an end-over-end shaker and the bottles were shaken for a
designated amount of time with 20 rpm. Samples were taken with an
acid-cleaned syringe and a 0.2 μm membrane filter from the well
shaken dispersion.
For validation of the HNO3/NaCl leach method, cyanide leaching
was also performed on the samples. Therefore 125 g/L solids were
treated with 0.1% KCN at pH 11 for 8 h at ambient temperature under
aeration. Chemical leaching was carried out in triplicate for the bio-
leach residues and the original ore samples. From the leaching assays,
samples were taken at regular intervals for Pt and Pd analysis via ICP-
MS.
2.4. Analytical methods
2.4.1. Geochemical and mineralogical analysis of the oxidized ore samples
Two aliquots (A and B) of each of the four homogenized heap
samples were sent to Activation Laboratories Ltd. (Actlabs), Canada, for
bulk chemical analysis of major and trace elements, including Au, Pt
and Pd grades. The complete geochemical dataset is provided in Table
S1. Gold, Pt and Pd were determined by fire assay followed by in-
ductively coupled plasma - mass spectrometry (ICP-MS) analysis
(Actlabs Code 1C-Research), whilst other major and trace elements
were determined with four-acid (HCl, HNO3, HClO4, HF) near-total
dissolution followed by inductively coupled plasma – optical emission
spectrometry (ICP-OES) and - MS analysis (Code Ultratrace 6). For
further characterization, homogenized and split samples were also
analyzed for their mineralogical composition using mineral liberation
analysis at Actlabs. Samples were embedded in epoxy resin for the
preparation of polished sections. These polished sections were then
analyzed using the FEI MLA 650F field-emission scanning electron
microscope. The X-ray model analysis (XMOD) method was used for the
modal mineralogy and the sparse phase liberation (SPL) method for
precious metals (Au, Ag, PGE). The conditions for the field emission gun
were an acceleration voltage of 25 kV with a working distance of
13 mm. X-ray diffraction (XRD) analysis was done at BGR, Hannover.
The results are provided in appendix Table S2.
2.4.2. Chemical and microbial analysis of bioleaching samples
Regular offline pH (BlueLine 18 pH electrode, Schott, Germany) and
redox potential vs. Ag/AgCl reference (PCE Instruments) measurements
were performed directly in the bioreactor pulp. Ferrous and ferric iron
concentrations were measured in 0.45 μm-filtered samples using the
Ferrozine assay (Lovley and Phillips, 1987). Dissolved metals were
regularly determined in filtered, acidified samples using inductively
coupled plasma mass spectrometry (ICP-MS) for PGE and ICP-OES
(Varian SpectrAA-300) for transition metals. At the end of the experi-
ment, the residue was harvested, washed with acidified water and dried
before performing digestion with nitric acid, following analysis of the
metals by ICP-OES. Light microscopy was carried out using a phase-
contrast microscope (Leica DM3000) at 400× magnification. The mi-
crobial community structure and abundance were monitored in slurry
samples after DNA extraction by terminal restriction fragment length
3
S. Hedrich, et al.
Fig. 1. Total metal recovery from PGE ore 102, particle size < 63 μm, during
bioleaching in stirred tank bioreactors at 10% pulp density under various
conditions. Bars represent total metal recovery as mean recovery of Co, Cu and
Ni. ▲ refers to final pH.
polymorphism (T-RFLP) and quantitative real-time PCR (qPCR) as de-
scribed previously (Hedrich et al., 2016) and with primers for Ap. cu-
pricumulans according to Tupikina et al. (2013).
2.4.3. Geochemical analysis of the chemical leaching solutions
The leachates of the HNO3/NaCl leaching experiments were ana-
lyzed for Pt and Pd with a Perkin Elmer Nexion 350x low resolution
quadrupole ICP-MS at the Geochemistry Laboratory of Jacobs
University Bremen. For quality control, the certified reference material
SARM-7, a sulfidic PGE ore, was measured together with the leachates.
Internal standardization was achieved by addition of 2 ppb of each Ru,
Re and Bi to each sample in order to compensate for severe sample
matrix effects due to the high salt load of the leachates.
3. Results and discussion
3.1. Resource characterization
The PGE ores showed a very similar mineralogical composition and
were composed of > 90 wt% silicates, predominantly clay minerals like
vermiculite, kaolinite or talc in combination with residual pyroxenes in
the form of enstatite and augite. Additionally, traces of feldspar, ser-
pentine minerals and amphibole were detected (Appendix Table S2).
The presence of alteration minerals (serpentine minerals like chrysotile
and clay minerals like talc and kaolinite) indicate an overall high de-
gree of weathering. Minor amounts of Fe-(oxy)/hydroxides were pre-
sent. The silicates and the Fe-(oxy)/hydroxides were associated with Ni,
Mn and Cu. The complete geochemical dataset of the bulk PGE ores is
provided in Appendix Table S1.
The Pt/Pd ratio of the untreated oxidized ore samples varied from
1.02 to 1.46 ppm (Table 1). For the untreated ore samples including
different grain sizes, Mineral Liberation Analysis (MLA) showed simi-
larities in the abundance of sulfides, platinum-group minerals (PGM),
and secondary minerals. Platinum-group minerals were present as
sperrylite (PtAs2), cooperite (PtS low Pd), native platinum and Pd‑bis-
muthotellurides, and electrum was common as well. In the untreated
stockpile PGE ores, PGM and electrum did not have a complete free
surface. Electrum and PGM were mostly associated with Fe-(oxy)/hy-
droxides, silicates (amphibole), clay minerals and other PGM (Fig. S4a-
b). Relict sulfide minerals were rare in the untreated ore samples and
were dominated by chalcopyrite (CuFeS2) and pentlandite ((Fe,Ni)9S8).
4
Hydrometallurgy 196 (2020) 105419
No major differences in the modal mineralogy in respect to the sulfide
content within the grain size fractions was detected. Secondary Fe-
(oxy)/hydroxides were abundant (varying from 2.9 to 7.7%). The lar-
gest amount of Fe-(oxy)/hydroxides occurred within the smallest grain
size fraction (< 63 μm). Further minerals as a result of alteration and
oxidation were chlorite, illite, smectite and clay minerals. The abun-
dance of clay minerals, illite and smectite, was highest within the
smallest grain size fraction (< 63 μm). Chlorite minerals, which could
be a result of hydrothermal alteration, were equally abundant in all
grain size fractions.
Locmelis et al. (2010) indicated that Pt/Pd ratios change with the
degree of weathering of reef-type PGE ores and a comparison of the Pt/
Pd ratios of oxidized relative to pristine ores enables a rough estimation
of the oxidation state. The reason for this is that Pd shows a higher
mobility than Pt during surface weathering, especially in presence of
organic acids (Oppermann et al., 2017), and hence Pd is preferably
removed from the residual ore, whereas Pt remains in place due to its
relative immobility. While all PGE ores investigated here were enriched
in Pt over Pd, as expected for oxidized ores, samples 102 and 103 had
the lowest Pt/Pd ratios of 1.2 and 1.02, respectively (Table 1). Sample
104 had a ratio of 1.29 and 105 had the highest Pt/Pd ratio of 1.46. In
comparison, pristine Platreef ores had Pt/Pd ratios in the range of, for
example, 0.49 to 1.01 (Junge et al., 2019). According to this oxidation
proxy, samples 102 and 103 were the most pristine, whilst the other
samples were the most oxidized samples.
3.2. Bioleaching
Bioleaching of host minerals of the oxidized PGE ore was applied in
stirred tank bioreactors under various conditions comparing the effect
of (i) temperature, (ii) ore sample, (iii) particle size and (iv) microbial
community. All experiments were supplemented with 1% elemental
sulfur as the total sulfur concentration (Table 1) of the samples was too
low to support microbial growth. Bioleaching experiments without
additional sulfur showed similar metal recovery as abiotic control ex-
periments (Fig. 1, Table S1).
Bioleaching efficiency was reported as total metal recovery calcu-
lated as mean value of the recovery of copper, cobalt and nickel as the
most relevant metals.
Oxidative bioleaching using the grain size fraction < 63 μm of
sample 102 at various temperatures resulted in the highest total metal
recovery (86%) at 42 °C at the end of the bioleaching process at pH 1.1
using a microbial consortium consisting dominantly of At. caldus (85%)
and a minor abundance of Sb. thermosulfidooxidans (9%) and Ap. cu-
pricumulans (6%). In contrast, experiments with thermophilic archaea
at 65 °C and a mesophilic consortium at 30 °C achieved almost 10% less
total metal recovery at a higher final pH (1.4 and 1.2, respectively,
Fig. 1). Active bioleaching at 42 °C accounted for about 6 days after
which no further significant increase in metal recovery was achieved
(Fig. S1a). The decrease of pH during the course of the experiment in
Fig. S1b are proof of active sulfur-oxidizing microorganisms in the
bioreactor as well as iron-oxidizers as indicated by an increase of the
redox potential. The respective microbial community structure is shown
in Fig. S2. The moderately thermophilic consortium used in this study
has also proven to be favorable in other bioleaching studies (Hedrich
et al., 2018).
Oxidative bioleaching at 30 °C, 42° and 65 °C with the respective
microbial communities did not affect the abundance of the secondary
Fe-(oxy)/hydroxides as they remained in a similar range than in the
untreated ore. The presence of chloritic clay and chlorite decreased
during the oxidative bioleaching, indicating a possible proton or ferric
iron attack. The occurrence of PbO as well as a relative increase of silica
oxide was slightly increased during the bioleaching. The final products
after bioleaching showed that PGM and electrum had a largely com-
pletely free surface, and remained intergrown with other PGM or were
associated with phases as a result of the bioleaching methodology (Fig.
S. Hedrich, et al. Hydrometallurgy 196 (2020) 105419

Fig. 2. Comparison of (a) total metal and (b) Fe recovery from PGE ore 102 (particle size < 63 μm, 10% pulp density) in stirred tank bioreactors under optimum
oxidative and reductive bioleaching (solid bars) conditions relative to abiotic control experiments (hatched bars).

Fig. 3. Results of bioleaching in stirred tank bioreactors at 10% pulp density and 42 °C of (a) the four oxidized PGE ores (particle size < 63 μm) and (b) PGE ore 103
at various particle sizes.

S4c-f). In particular sperrylite, cooperite (PtS low Pd), and
Pd‑bismuthotellurides were usually completely liberated, which is of
great benefit for subsequent chemical PGE extraction.
Abiotic control experiments with pH control showed, however,
significantly less metal leaching compared to biological setups. Proton
concentration therefore is not a single key factor for leaching but rather
a complex interaction between microorganisms operating in biofilms
close to the mineral surface, redox potential, other (metal) ions and
protons (Vera et al., 2013).
Reductive bioleaching under aerobic (30°C) and anaerobic (35°C)
conditions, targeting mainly ferric iron minerals, achieved no higher
metal recovery compared to oxidative methods (Figs. 1 and 2), sug-
gesting recalcitrance of the ferric iron-containing minerals present in
the ore to biological iron reduction (Fig. 2b). Also a combined approach
of 10 days oxidative bioleaching at 42 °C followed by 7 days anaerobic,
reductive bioleaching using Sb. thermosulfidooxidans did not result in
enhanced iron and overall metal extraction (Table S3), indicating a
predominant effect of microbially produced sulfuric acid on the mi-
nerals rather than iron reduction. According to the mineralogical
composition of the ores, most of the iron seemed to be associated with
silicates, which were hardly attacked during the applied bioleaching
approaches. These findings are supported by the mineralogy of the
samples which is dominated by silicates. These cannot be attacked and
dissolved by ferric iron as in the case of sulfide minerals. So far, only
attack by inorganic and organic acids which in the latter case may also
be metal-complexing agents have been identified as bioleaching agents
for silicates (Bosecker, 1993; Brandl et al., 2008; Glombitza and
Reichel, 2014). In previous studies, reductive bioleaching mainly at-
tacked oxide iron minerals such as goethite (Hallberg et al., 2011;
Ñancucheo et al., 2014; Marrero et al., 2015).
No significant variance in total metal recovery (81–94%) was ob-
served between the various Platreef stockpile samples under oxidative
bioleaching at 42 °C (particle size < 63 μm, Fig. 3a), which was cor-
roborated by the similar mineralogy of the ores. The mineralogical
modification after bioleaching was therefore similar for all untreated
samples with the particle size of < 63 μm irrespective of the original
material due to the similarity in the primary mineralogy.
Experiments on the influence of particle size on the bioleaching
behavior clearly showed that metal recovery was most efficient at the
smallest particle size (< 63 μm, Fig. 3b) as also reported for other ores
before (e.g. Nemati et al., 2000). The mineralogical change for the
different particle sizes was also negligible (sample 103). No large

5
S. Hedrich, et al. Hydrometallurgy 196 (2020) 105419

Fig. 4. Pt and Pd recoveries in % vs. acid admixture for HNO3/NaCl experiments with different pulp densities.

6
S. Hedrich, et al.
Fig. 5. Pt and Pd recoveries versus time for the HNO3/NaCl experiments on bulk PGE ores 103 and 104. Note different scales.
Fig. 6. Pt (grey bars) and Pd (black bars) recovery via HNO3/NaCl leaching at 80 °C from residues of sample 102 < 63 μm after bioleaching under various
conditions.
variation was observed between the mineral composition of the un-
treated ore and the samples treated by bioleaching of the respective
grain size (< 63 μm, 63–200 μm, 200–315 μm, > 315 μm). The overall
sulfide content was very low in both treated and untreated ore samples.
Hydrosilicate clays with sulfur formed due to the addition of sulfur for
bioleaching. Secondary Fe-(oxy)/hydroxides were still present after the
bioleaching procedure. The relative amount of quartz increased after
bioleaching, likely due to the dissolution of other mineral phases.
PGEs were not leached in any of the bioleaching approaches and
therefore remained in the residue for subsequent chemical extraction.
Similar data for oxidative bioleaching from sulfidic PGE ore were
reported by Mwase et al. (2014) during column leaching over 304 days
with Metallosphaera hakonensis. The overall extraction of base metals
was, however, lower in their experiments compared to our stirred tank
reactor bioleaching experiments at lower temperatures. Stirred tank
reactor experiments on a PGE-bearing flotation concentrate using
Acidithiobacillus ferrooxidans resulted in 94% sulfide oxidation after
7
Hydrometallurgy 196 (2020) 105419
35 days with high recovery of nickel but less copper extraction, most
likely due to a different mineralogy of the samples.
3.3. Optimization of chemical PGE extraction method from untreated PGE
ores
The bioleaching experiments showed that an almost complete ex-
traction of base metals from oxidized PGE ores is feasible, whilst the
PGE largely remained in the bioleach residue. For subsequent chemical
extraction of the precious metals from the bioleach residues an alter-
native method to conventional cyanidation was investigated. The
HNO3/NaCl leach was initially tested and optimized on the bulk oxi-
dized PGE ore and then on the bioleach residue to compare Pt and Pd
mobilization with and without prior bioleaching.
The results of the combined pulp density and acid admixture ex-
periments on untreated PGE ore with an experimental time of 24 h are
shown in Fig. 4. The amount of nitric acid added to the saturated
S. Hedrich, et al.
Fig. 7. Comparison of Pt and Pd recovery by cyanidation and HNO3/NaCl treatment from untreated ore 102 < 63 μm and bioleached ore at 42 °C.
sodium chloride solution greatly affected the extraction of Pt and Pd
from the oxidized PGE ores. In almost all cases, less nitric acid during
leaching also led to significantly lower Pt and Pd recoveries. Regardless
of the pulp density, the 5:1 to 10:1 admixture experiments showed the
highest recoveries for Pt and Pd of 22–57% and 23–51%, respectively
(Fig. 4; Table S4). The highest recoveries for Pt and Pd were achieved
with a pulp density of 100 to 300 g/L. Among the samples, the highest
recoveries were achieved with a 5:1 brine acid ratio for samples 103
and 104 with almost 57% and 36% mobilized Pt at 200 g/L pulp density
and 41% and 48% mobilized Pd at 100 g/L pulp density, respectively
(see Table S4). In general, the experiments with various nitric acid
admixtures showed that brine:acid ratios between 5:1 and 10:1 are the
most efficient ratios for solubilizing Pt and Pd. Overall, the net differ-
ences in recoveries between 5:1, 7:1 and 10:1 were consistently small,
despite some variation between individual samples. With regard to the
optimum leaching time, the time-series experiments conducted with
200 g/L pulp density and 7:1 acid admixture indicated that even after
one week, the system did not reach steady-state and recoveries in-
creased slightly further, but at an overall lower rate (Fig. 5; Table S5).
Most of the contained Pt and Pd was extracted within the first 24 h and
hence the leaching experiments on the bioleach residues were con-
ducted for 24 h only.
Temperature experiments proved increased recoveries (by more
than 15%) of Pt and Pd at 80 °C compared to lower temperatures, while
40 °C and 60 °C data showed similar recoveries of both metals (Fig. S3).
Highest leaching of the PGE was achieved after 24 h with no significant
changes after 36 h (Fig. S3). In order to keep the leaching process as
inexpensive as possible, an admixture of 10:1 was chosen in combina-
tion with a pulp density of 200 g/L at 80 °C for the subsequent chemical
leaching step on the bioleach residues as presented in chapter 3–4.
3.4. Chemical extraction of PGE from bioleach residues
The HNO3/NaCl leach was conducted as a subsequent leaching step
on the bioleach residues with optimized parameters as described in
section 3.3.
Extraction of Pt and Pd from residues bioleached under the various
conditions described in 3–2 resulted in maximum extraction of 89% Pt
and 96% Pd depending on the pretreatment conditions (Fig. 6). Re-
covery of Pt and Pd was up to 45% and 43%, respectively, higher than
8
Hydrometallurgy 196 (2020) 105419
compared to extraction from untreated ore as described in 3–3. Highest
extraction of both metals was achieved from bioleach residue of the
42 °C experiment, which also accounted for the highest base metal re-
covery during bioleaching. Pt recoveries were similar for the 65 °C and
reductive bioleaching residues, while Pt leaching from the 30 °C residue
was at least 10% lower. Pd recoveries in contrast were slightly lower in
bioleach residues treated under reductive conditions compared to 30 °C
bioleach residue, indicating a possible effect of the bioleach conditions
on the liberation of Pd minerals. Overall bioleaching facilitates the
chemical extraction of Pt and Pd from oxidized platinum ore and none
of the bioleaching methods hindered the extraction of the precious
metals in any form. As already indicated in section 3.2., bioleaching at
42 °C led to the highest recovery of base metals and caused a high
degree of liberation of PGE-containing minerals, which enabled the
highest chemical PGE extraction. Reductive bioleaching seemed not to
significantly enhance the liberation of PGM from the oxidized platinum
ore compared to oxidative leaching at moderately higher temperatures,
although mineralogical data indicated the additional attack of ferric
iron ores under reductive conditions. Further experiments were there-
fore carried out with bioleach residues from the 42 °C experiment.
Comparative experiments applying cyanidation to extract PGE from
untreated ore and bioleach residue confirmed the applicability of the
HNO3/NaCl leach. While Pt/Pd recovery from untreated ore was almost
similar for both extraction methods with up to 44% Pt and 56% Pd
recovery, significantly higher recoveries (+20%) for Pd and slightly
higher (+7%) Pt recovery were achieved by the HNO3/NaCl leach over
cyanidation from the bioleach residue (Fig. 7). HNO3/NaCl extraction
of PGE from oxidized ore following bioleaching therefore presents a
potentially economic alternative to cyanide leaching with even higher
metal recoveries than reported for similar ores in the literature before
(Yopps and Baglin, 1991; Mwase et al., 2012, 2014; Kraemer et al.,
2015a).
4. Conclusion
The presented study demonstrates the feasibility of bioleaching of
base metals from well characterized oxidized PGE ores using auto-
trophic, acidophilic microorganisms. Various processing options have
been tested to define the most efficient and economic bioleaching ap-
proach for the subsequent chemical extraction of PGE from the ore.
S. Hedrich, et al.
Chemical and mineralogical analyses proved the potential of oxidative
bioleaching using moderate thermophiles as promising processing op-
tion for oxidized PGE ores. Bioleaching of the PGE ore prior to chemical
extraction of PGE allowed for separate recovery of valuable base metals
followed by efficient chemical PGE extraction using, for example,
HNO3/NaCl leaching as an alternative to cyanidation.
Declaration of Competing Interest
The authors declare that there is no conflict of interest.
Acknowledgement
We thank Anglo American Platinum for providing access to the mine
and the sample material and especially Trust Muzondo and Zama Langa
for their help during sampling at the Mogalakwena Mine. Financial
support was provided by BGR/DERA and the German BMBF (project
“BioPGE”; FKZ 01DG17026). We thank M. Smart and S.T.L. Harrison
(CEBER, UCT, South Africa) for scientific discussions. We acknowledge
W. Schulze and Y. Meve for assistance with ore processing and bio-
leaching experiments at BGR. J. Stummeyer, M. Hilsberg and L. Grüger
are acknowledged for ICP analyses at BGR. We are grateful to S.
Tuchtfeld und F. Römer (TU Clausthal, Germany) for cyanide leaching.
G. Merschel is thanked for her help with the chemical leaching ex-
periments.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.hydromet.2020.105419.
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