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Literature review on platinum-group minerals
Platinum-group element mineralogy
Introduction
The distribution of PGEs (platinum-group elements) in an ore is directly related to the type of ore, which in turn, dictates the mineralogical constitution. PGE ores can be divided into the following main classes (Stribrny et al., 2000):
• Alluvial ores: These ores contain almost no sulphide and are composed of individual particles of rock and liberated minerals: an example is the Colombian deposit.
• Layered intrusions (e.g. Bushveld, Stillwater, Great Dyke)
• Magmatic nickel sulphide deposits (e.g. Noril’sk-Talnakh, Sudbury)
The layered intrusion ores contain by the far the world’s largest reserves of PGE. The mineralization and occurrence of the PGEs are of utmost importance considering the very low concentrations of these elements in the ores (1-15 g/t). PGE deposits can be divided into two categories: discrete platinum-group minerals (PGMs), and those hosted as “impurities” within other minerals. The latter category also includes the so-called “invisible” portion of the precious-metal distribution (Oberthür et al., 2002a). The reason for the “invisibility” is not always known but can be twofold in nature: PGEs are present in submicroscopic particles or they occur as a dilute solid-solution. The understanding of the PGE associations is of utmost importance in order to construct mineralogical balances.
Hosted platinum-group elements
The PGE distribution between and content of the base-metal sulphides, sulpharsenides, oxides, and silicates are largely speculative, without substantial experimental evidence. However, the invention of the electron microprobe has led to an explosion in the number of discrete PGM species being identified. It has also contributed to the understanding of the PGE distributions within other minerals as indicated by the results of the studies given below.
PGEs hosted in sulphides
There is little doubt at this stage that sulphides are a major repository of PGEs and these minerals can contain PGEs in variable amounts up to a few percent (by mass).
Pentlandite (Fe,Ni)9S8.
The best known carrier of PGEs is pentlandite (which can contain up to 12.1 wt% Pd). Pentlandite from Stillwater contains between 8.6-12.1 % Pd (Cabri, 1992). Reported maximum levels of Pd in pentlandite in (ppmw) (ppmw refers to parts per million by weight) are: J-M reef (46000), Platreef (20000), Lac des Iles (6500), Medvezhy Creek (2540), Great Dyke (1990), Penikat (1800) and Merensky reef (1164) (Cabri, 1992). Strirny et al. (2000) reported Pd and Rh partioning up to 2236 and 259 ppmw, respectively, in pentlandite from the Hartley Mine in the Great Dyke. In addition to this Prendergast (1990) reported a maximum of around 0.2 wt% Pd in pentlandite and that these low Pd concentrations could not account for the “missing Pd”. “Missing” PGMs were also reported by Oberthür et al. (1998) from the Hartley Mine in the Great Dyke.
Lidsay et al. (1988) reported that the Pt content of the pentlandite from the Merensky reef is usually less than 36 ppmw and has a mean content of around 10-13 ppmw. Pentlandite from the Hartley Mine in the Great Dyke has a mean content of around 8.5 ppmw Pt. In contrast to this Prendergast (1988a) reported no association of Pt with pentlandite from samples taken at Mimosa Mine in the Great Dyke. The maximum reported solubilities of Pd, Rh and Ru in pentlandite are 12.5%, 12.4% and 12.9%, respectively, but no Pt could be detected at the analytical sensitivity value of 0.05%(Makovicky, 1986). This clearly indicates that pentlandite is mainly a Pd carrier and that high pentlandite recoveries are essential to optimise the Pd recoveries.
Pyrrhotite (Fe1-xS)
Pyrrhotite can accommodate considerable quantities of PGE in solid solution at elevated temperatures, up to 11% Pd, 1.3 % Ru, 10.5% Rh and 2.2 %Pt, but upon cooling most of these PGM are expelled. A higher Fe content in the pyrrhotite is also detrimental to the solubility limit of PGMs in the mineral. Cabri (1988) reported a maximum of 47 ppmw Pd in pyrrhotite from the J-M reef. The contents of the rest of the PGEs in pyrrhotite from the most important PGE deposits are usually lower than 20 ppmw. The detection limit of many of the PGMs is of the order of 10 ppmw. These results indicate that pyrrhotite contains PGEs very close to the detection limit; indeed Oberthür et al. (1997) reported that pyrrhotite usually contains PGEs at concentrations close to or lower than the detection limit. Another important aspect is the occurrence of pentlandite as flame-shaped exsolutions in pyrrhotite (typical in ore from Mimosa Mine, Great Dyke). Hence the flotation characteristics of pyrrhotite will impact on the recovery of the PGEs, largely due to the occurrence of pentlandite within pyrrhotite.
Pyrite (FeS2)
Pyrite does not accommodate appreciable quantities of PGM as shown by the experimental work performed by Makovicky (1986). However, Strirny et al. (2000) reported that pyrite from the Hartley Mine in the Great Dyke can contain on average about 36 ppmw Pt (range from 0.4 to 244; mean of 35.5 ppmw).
Chalcopyrite (CuFeS2)
Chalcopyrite usually contains PGE at concentrations lower than the detection limit [(Oberthür et al., 1997) and (Cabri, 1992)]. In addition to this, experimental studies also indicate the low solubility of PGMs in Cu-Fe sulphides (Lindsay et al., 1988).
PGEs hosted in oxides
The most important oxides currently under investigation are chromite (FeCr2O4) and magnetite (Fe3O4). Cabri (1981) reported the presence of Pt in magnetite, but this needs verification (Cabri, 1981), since magnetite can be associated with Pt-Fe alloys. Parry (1984) reported PGE values of typically less than 1 ppmw for mixtures of magnetite and ilmenite.
PGEs hosted in silicates
There is little information on the PGE content of silicates. Michell et al. (1987) reported values less than 5 ppb and typically of the order of 1ppb. It is postulated that the Sudbury ores contains a significant portion of minute PGMs, which occur interstitially in silicates (Sizgoric, 1984) and that the Merensky reef contains PGMs in solid solution within oxides and silicates (Kinloch, 1982; Peyerl, 1983). It remains difficult to assess whether large or small quantities of PGEs are associated with the silicates.
PGEs hosted in sulpharsenides, arsenides and tellurides
These groups of minerals can contain appreciable levels of PGE. For example cobaltite (CoAsS) contains up to 600 ppmw Pt, 2800 ppmw Pd, 25000 ppmw Rh and 2600 ppm Ir (Cabri, 1981).
Platinum-group minerals
Platinum-group element mineralogy of the Merensky Reef, UG-2 Reef and the Great Dyke of Zimbabwe
Microbeam techniques enable the investigator to analyse the PGMs quantitatively to understand better the platinum-group element (PGE) distribution between discrete PGMs. As stated earlier, the number of identified PGMs exploded after the development of the microprobe. Broadly, PGMs can be grouped into metals, intermetallic compounds and alloys especially with Sn, Fe, Pb, Hg, Cu and Ni. The remaining PGMs are formed with Bi, Te, As, Sb and S. The latter group of PGMs and compounds is of great interest and this study focused on characterising the flotation behaviour of two members of this group. Usually it is believed that the most common PGMs are the sulphides, arsenides and tellurides. The proportions and textures of these minerals vary considerably locally and regionally. Very informative surveys on PGMs and PGEs, covering all aspects of identification, composition, properties and recoveries may be found in Cabri (1981).
Table 1 and 2 list the most common Pt and Pd minerals in alphabetical order. The lists represent estimates of PGMs bearing Pt and Pd on a world basis, taking into consideration amounts produced from different deposits (Cabri, 1994). Although these lists are not intended to be highly accurate (Cabri, 1994), they do give a good account of the most common PGMs of Pt and Pd found in the world, with their ideal compositions and common substitutions in these PGMs. According to Cabri (1994) sperrylite is the most common PGM worldwide, and it can be found in every type of geological environment.
1. Background
2. Literature review on platinum-group minerals
2.1. Platinum-group element mineralogy
2.1.1. Introduction
2.1.2. Hosted platinum-group elements
2.1.2.1. PGEs hosted in sulphides
2.1.2.1.1. Pentlandite (Fe,Ni)9S8
2.1.2.1.2. Pyrrhotite (Fe1-xS)
2.1.2.1.3. Pyrite (FeS2)
2.1.2.1.4. Chalcopyrite (CuFeS2)
2.1.2.2. PGEs hosted in oxides
2.1.2.3. PGEs hosted in silicates
2.1.2.4. PGEs hosted in sulpharsenide, arsenides and tellurides
2.1.3. Platinum-group minerals
2.1.3.1. Platinum-group element mineralogy of the Merensky Reef, UG-2 Reef and the Great Dyke of Zimbabwe
2.1.3.2. Microprobe analysis of platinum-group minerals from Mimosa Mine (Great Dyke)
2.1.3.3. Platinum-group element mineralogy of the Platreef
2.1.3.4. Platinum-group element mineralogy of the oxidized MSZ of the Great Dyke Zimbabwe
2.2. Phase and phase relations of the platinum-group elements
2.3. Flotation behaviour of the platinum-group minerals
2.3.1. Platinum-group element recovery from the oxidized MSZ of the Great Dyke Zimbabwe
2.4. Chemical stability of Michenerite
2.5. Interaction of Thiols with metals
3. Research problem and objectives
4.Experimentalprocedure
4.1. X-ray diffraction and Scanning Electron Microscopy
4.2. Synthesis of selected platinum-group minerals
4.3. Electrochemical measurements
4.4. Raman spectroscopy
4.5. Contact angle measurements
4.6. Microflotation measurements
5.Resultsanddiscussion
5.1. Electrochemical and contact angle results
5.2. Characteristic peaks of Raman spectra
5.3. Flotation kinetics of Pd-Bi-Te
6.Conclusion
7. Recommendations for future research
8. References
9.Appendices
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