Platinum-group element distribution in base-metal sulfides of the Merensky Reef from the eastern and western Bushveld Complex, South Africa

Base-metal sulfides in magmatic Ni-Cu-PGE deposits are important carriers of platinum-group elements (PGE). The distribution and concentrations of PGE in pentlandite, pyrrhotite, chalcopyrite, and pyrite were determined in samples from the mineralized portion of four Merensky Reef intersections from the eastern and western Bushveld Complex. Electron microprobe analysis was used for major elements, and in situ laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) for trace elements (PGE, Ag, and Au). Whole rock trace element analyses were performed on representative samples to obtain mineralogical balances. In Merensky Reef samples from the western Bushveld, both Pt and Pd are mainly concentrated in the upper chromitite stringer and its immediate vicinity. Samples from the eastern Bushveld reveal more complex distribution patterns. In situ LA-ICP-MS analyses of PGE in sulfides reveal that pentlandite carries distinctly elevated PGE contents, whereas pyrrhotite and chalcopyrite only contain very low PGE concentrations. Pentlandite is the principal host of Pd and Rh in the ores. Palladium and Rh concentrations in pentlandite reach up to 700 and 130 ppm, respectively, in the samples from the eastern Bushveld, and up to 1,750 ppm Pd and up to 1,000 ppm Rh in samples from the western Bushveld. Only traces of Pt are present in the base-metal sulfides (BMS). Pyrrhotite contains significant though generally low amounts of Ru, Os, and Ir, but hardly any Pd or Rh. Chalcopyrite contains most of the Ag but carries only extremely low PGE concentrations. Mass balance calculations performed on the Merensky Reef samples reveal that in general, pentlandite in the feldspathic pyroxenite and the pegmatoidal feldspathic pyroxenite hosts up to 100 % of the Pd and Rh and smaller amounts (10–40 %) of the Os, Ir, and Ru. Chalcopyrite and pyrrhotite usually contain less than 10 % of the whole rock PGE. The remaining PGE concentrations, and especially most of the Pt (up to 100 %), are present in the form of discrete platinum-group minerals such as cooperite/braggite, sperrylite, moncheite, and isoferroplatinum. Distribution patterns of whole rock Cu, Ni, and S versus whole rock Pd and Pt show commonly distinct offsets. The general sequence of “offset patterns” of PGE and BMS maxima, in the order from bottom to top, is Pd in pentlandite?→?Pd in whole rock?→?(Cu, Ni, and S). The relationship is not that straightforward in general; some of the reef sequences studied only partially show similar trends or are more complex. In general, however, the highest Pd concentrations in pentlandite appear to be related to the earliest, volumetrically rather small sulfide liquids at the base of the Merensky Reef sequence. A possible explanation for the offset patterns may be Rayleigh fractionation.     

Noble Metal Enrichment Processes in the Merensky Reef, Bushveld Complex

We have analysed sulphides, silicates, and chromites of theMerensky Reef for platinum-group elements (PGEs), Re and Auusing laser ablation-inductively coupled plasma mass spectrometryand synthetic pyrrhotite standards annealed with known quantitiesof noble metals. Os, Ir and Ru reside in solid solution in pyrrhotiteand pentlandite, Rh and part of the Reef’s Pd in pentlandite,whereas Pt, Au, Re and some Pd form discrete phases. Olivineand chromite, often suspected to carry Os, Ir and Ru, are PGEfree. All phases analysed contain noble metals as discrete micro-inclusionswith diameters typically <100 nm. Inclusions in sulphidescommonly have the element combinations Os–Ir–Ptand Pt–Pd–Au. Inclusions in olivine and chromiteare dominated by Pt ± Au–Pd. Few inclusion spectracan be related to discrete noble metal phases, and few inclusionshave formed by sub-solidus exsolution. Rather, some PGE inclusions,notably those in olivine and chromite, are early-magmatic nuggetstrapped when their host phases crystallized. We suggest thatthe silicate melt layer that preceded the Merensky Reef wasPGE oversaturated at early cumulus times. Experiments combinedwith available sulphide–silicate partition coefficientssuggest that a silicate melt in equilibrium with a sulphidemelt containing the PGE spectrum of the Merensky ore would indeedbe oversaturated with respect to the least soluble noble metals.Sulphide melt apparently played little role in enriching thenoble metals in the Merensky Reef; rather, its role was to immobilizea pre-existing in situ stratiform PGE anomaly in the liquid-stratifiedmagma chamber. KEY WORDS: Bushveld Complex; Merensky Reef; laser-ablation ICP-MS; platinum-group mineralization     

High-temperature carbonate minerals in the Stillwater Complex, Montana, USA

High-temperature carbonate minerals have been observed in association with sulfide minerals below the platiniferous Johns-Manville (J-M) reef of the Stillwater Complex in a stratigraphic section that has been previously shown to be characterized by unusually Cl-rich apatite. The carbonate assemblage consists of dolomite with exsolved calcite in contact with sulfide minerals: chalcopyrite and pyrrhotite in the Peridotite Zone; and pyrrhotite with pentlandite, pyrite and chalcopyrite in Gabbronorite Zone I of the Lower Banded Series. A reaction rim surrounds the carbonate–sulfide assemblages, showing an alteration of the host orthopyroxene to a more calcium-enriched, Fe-depleted pyroxene. The calcite–dolomite geothermometer yields a minimum formation temperature as high as 950 °C for the unmixed assemblages. Iron and manganese concentrations exceed the range seen in carbonatite and mantle xenolith carbonates and are distinctly different from the nearly pure end-member carbonates associated with greenschist-grade (and lower) assemblages (e.g., carbonate veins in serpentinite) that occur locally throughout the complex. The association of high-temperature carbonates with sulfides beneath the J-M reef supports the hydromagmatic theory which involves a late-stage chloride–carbonate fluid percolating upwards, dissolving PGE and sulfides and redepositing them at a higher stratigraphic level. Characterization of the processes which form strategically important metal deposits, such as the J-M reef of the Stillwater Complex and the analogous Merensky reef of the Bushveld Complex in South Africa, could potentially lead to better exploration models and, more broadly, a deeper understanding of the cooling and compositional evolution of large bodies of ultramafic and mafic magma and of carbonatites, on both a local and a regional scale.     

Modeling the Merensky Reef,Bushveld Complex,Republic of South Africa

The Merensky pegmatoid (normal reef) in the western Bushveld Complex is commonly characterized as a pyroxene-rich pegmatoidal unit with a base that is enriched in chromite and platinum-group element-bearing sulfides overlying a leuconorite footwall. Models for its formation have ranged from those that view it as entirely a magmatic cumulate succession to those that have suggested that it is a zone of volatile-induced remelting. The consequences of the latter interpretation are investigated using the numerical modeling program IRIDIUM, which links diffusive and advective mass and heat transport with a phase equilibration routine based on the MELTS program. The initial system consists of a simple stratigraphic succession of a partially molten leuconorite overlain by a partially molten pyroxenite, both initially at 1,190°C and 2 kbar. 2 wt% of a volatile fluid composed of 75 mol% H₂O, 20 mol% CO₂ and 5 mol% H₂S is then added to the lower 20 cm of the pyroxenite. The system is then allowed to evolve under conditions of chemical diffusion in the liquid. The addition of the volatile components results in a modest increase in the amount of melt in the pyroxenite. However, chemical diffusion across the leuconorite–pyroxenite boundary leads to more extensive melting at and below the boundary with preferential loss of opx from the underlying leuconorite, preferential re-precipitation of sulfide and chromite and concentration of the PGE at this boundary. These results mimic actual mineral and compositional profiles across the Merensky pegmatoid and illustrate that long-term diffusion process can effectively produce mineralogical and compositional layering not present in the original assemblage.     

Sulfide-associated mineral assemblages in the Bushveld Complex, South Africa: platinum-group element enrichment by vapor refining by chloride–carbonate fluids

The petrology of base metal sulfides and associated accessory minerals in rocks away from economically significant ore zones such as the Merensky Reef of the Bushveld Complex has previously received only scant attention, yet this information is critical in the evaluation of models for the formation of Bushveld-type platinum-group element (PGE) deposits. Trace sulfide minerals, primarily pyrite, pyrrhotite, pentlandite, and chalcopyrite are generally less than 100 microns in size, and occur as disseminated interstitial individual grains, as polyphase assemblages, and less commonly as inclusions in pyroxene, plagioclase, and olivine. Pyrite after pyrrhotite is commonly associated with low temperature greenschist alteration haloes around sulfide grains. Pyrrhotite hosted by Cr- and Ti-poor magnetite (Fe₃O₄) occurs in several samples from the Marginal to Lower Critical Zones below the platiniferous Merensky Reef. These grains occur with calcite that is in textural equilibrium with the igneous silicate minerals, occur with Cl-rich apatite, and are interpreted as resulting from high temperature sulfur loss during degassing of interstitial liquid. A quantitative model demonstrates how many of the first-order features of the Bushveld ore metal distribution could have developed by vapor refining of the crystal pile by chloride–carbonate-rich fluids during which sulfur and sulfide are continuously recycled, with sulfur moving from the interior of the crystal pile to the top during vapor degassing.     

The distribution of platinum group elements (PGE) and other chalcophile elements among sulfides from the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada, and the origin of palladium in pentlandite

Concentrations of platinum group elements (PGE), Ag, As, Au, Bi, Cd, Co, Mo, Pb, Re, Sb, Se, Sn, Te, and Zn, have been determined in base metal sulfide (BMS) minerals from the western branch (402 Trough orebodies) of the Creighton Ni–Cu–PGE sulfide deposit, Sudbury, Canada. The sulfide assemblage is dominated by pyrrhotite, with minor pentlandite, chalcopyrite, and pyrite, and they represent monosulfide solid solution (MSS) cumulates. The aim of this study was to establish the distribution of the PGE among the BMS and platinum group minerals (PGM) in order to understand better the petrogenesis of the deposit. Mass balance calculations show that the BMS host all of the Co and Se, a significant proportion (40–90%) of Os, Pd, Ru, Cd, Sn, and Zn, but very little (<35%) of the Ag, Au, Bi, Ir, Mo, Pb, Pt, Rh, Re, Sb, and Te. Osmium and Ru are concentrated in equal proportions in pyrrhotite, pentlandite, and pyrite. Cobalt and Pd (∼1 ppm) are concentrated in pentlandite. Silver, Cd, Sn, Zn, and in rare cases Au and Te, are concentrated in chalcopyrite. Selenium is present in equal proportions in all three BMS. Iridium, Rh, and Pt are present in euhedrally zoned PGE sulfarsenides, which comprise irarsite (IrAsS), hollingworthite (RhAsS), PGE-Ni-rich cobaltite (CoAsS), and subordinate sperrylite (PtAs₂), all of which are hosted predominantly in pyrrhotite and pentlandite. Silver, Au, Bi, Mo, Pb, Re, Sb, and Te are found predominantly in discrete accessory minerals such as electrum (Au–Ag alloy), hessite (Ag₂Te), michenerite (PdBiTe), and rhenium sulfides. The enrichment of Os, Ru, Ni, and Co in pyrrhotite, pentlandite, and pyrite and Ag, Au, Cd, Sn, Te, and Zn in chalcopyrite can be explained by fractional crystallization of MSS from a sulfide liquid followed by exsolution of the sulfides. The early crystallization of the PGE sulfarsenides from the sulfide melt depleted the MSS in Ir and Rh. The bulk of Pd in pentlandite cannot be explained by sulfide fractionation alone because Pd should have partitioned into the residual Cu-rich liquid and be in chalcopyrite or in PGM around chalcopyrite. The variation of Pd among different pentlandite textures provides evidence that Pd diffuses into pentlandite during its exsolution from MSS. The source of Pd was from the small quantity of Pd that partitioned originally into the MSS and a larger quantity of Pd in the nearby Cu-rich portion (intermediate solid solution and/or Pd-bearing PGM). The source of Pd became depleted during the diffusion process, thus later-forming pentlandite (rims of coarse-granular, veinlets, and exsolution flames) contains less Pd than early-forming pentlandite (cores of coarse-granular).     

The Merensky Cyclic Unit and its impact on footwall cumulates below Normal and Regional Pothole reef types in the Western Bushveld Complex

The Merensky Reef of the Bushveld Complex occurs in its highest stratigraphic position as a heterogeneous, pegmatitic, feldspathic melanorite bounded by two narrow chromitite stringers at the base of the Merensky Cyclic Unit (MCU). In the Swartklip Facies of the Rustenburg Layered Suite, the occurrence of widespread thermal and mechanical erosion termed “potholing” has led to the subdivision of the Merensky Reef into Normal Reef and Regional Pothole Reef sub-facies. The transition between the two sub-facies occurs where the MCU transgresses the lower chromitite stringer of the Normal Merensky Reef and cuts down into the underlying cumulate lithologies. In the Regional Pothole Reef at the Northam Platinum Mine, several economic reef types are identified, where the Merensky Reef becomes conformable to cumulate layering, in particular, to the footwall marker (NP2 reef type) and the upper pseudoReef (P2 reef type). The Normal Merensky Reef, as well as the P2 and NP2 Reefs, contains economic platinum group element (PGE) grades and includes the lower portion of the MCU melanorite and the Merensky Chromitite. Whole rock geochemistry indicates that this package is compositionally identical in Normal, P2, and NP2 Reefs, suggesting that the base of the MCU is a relatively homogeneous drape over both Normal and Regional Pothole Reef regions. However, the lower sections of the three Reefs are variables depending on the depth of transgression of the MCU. In the Normal and P2 reef types, transgression by the MCU was arrested within harzburgites, melanorites, and norites, resulting in coarse, pegmatitic textures in the immediate footwall units. For the NP2 Reef, transgression by the MCU was arrested within leucocratic rocks and resulted in the formation of troctolites below the Merensky Chromitite. These troctolites are characterised by a coupled relationship between olivine and sulphides and by changes in major element chemistry and PGE contents relative to equivalent units in the footwall of the Normal Reef. Along with micro-textural relationships, these features suggest that troctolization of leucocratic cumulates in the NP2 Reef beneath the Merensky chromitite was a result of a reactive infiltration of a chromite-saturated melt and an immiscible sulphide liquid from the overlying MCU, rather than a significant fluid flux from below. In all reef types, the concentration of S defines symmetrical peaks centred on the Merensky Chromitite (and chromitites from pre-existing cyclic units in Normal and P2 Reefs), whereas PGE concentrations define asymmetrical peaks with higher PGE contents in reconstituted footwall rocks relative to the MCU melanorite. This signature is attributable to a magmatic model of PGE collection followed by deposition towards the base of the MCU and within reconstituted footwall rocks. The continuity of the asymmetrical magmatic PGE signature between the Normal Reef and Regional Pothole Reef sub-facies indicates that PGE mineralization inherent to the Merensky magma occurred as a drape over a variably eroded and subsequent texturally and geochemically reworked or reconstituted footwall.     

Platinum-group element distribution in base-metal sulfides of the UG2 chromitite,Bushveld Complex,South Africa—a reconnaissance study

Two drill cores of the UG2 chromitite from the eastern and western Bushveld Complex were studied by whole-rock analysis, ore microscopy, SEM/Mineral Liberation Analysis (MLA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis. The top and base of the UG2 main seam have the highest bulk-rock Pd and Pt concentrations. Sulfides mostly occur as aggregates of pentlandite, chalcopyrite, and rare pyrrhotite and pyrite or as individual grains associated mostly with chromite grains. In situ LA-ICP-MS analyses reveal that pentlandite carries distinctly elevated platinum-group element (PGE) contents. In contrast, pyrrhotite and chalcopyrite contain very low PGE concentrations. Pentlandite shows average maximum values of 350–1,000 ppm Pd, 200 ppm Rh, 130–175 ppm Ru, 20 ppm Os, and 150 ppm Ir, and is the principal host of Pd and Rh in the studied ores of the UG2. Mass balance calculations were conducted for samples representing the UG2 main seam of the drill core DT46, eastern Bushveld. Pentlandite consistently hosts elevated contents of the whole-rock Pd (up to 55 %) and Rh (up to 46 %), and erratic contents of Os (up to 50 %), Ir (2 to 17 %), and Ru (1–39 %). Platinum-group mineral (PGM) investigations support these mass balance results; most of the PGM are Pt-dominant such as braggite/cooperite and Pt-Fe alloys or laurite (carrying elevated concentrations of Os and Ir). Palladium and Rh-bearing PGM are rare. Both PGE concentrations and their distribution in base-metal sulfides (BMS) in the UG2 largely resemble that of the Merensky Reef, as most of the Pd and Rh are incorporated in pentlandite, whereas pyrrhotite, chalcopyrite, and pyrite are almost devoid of PGE.     

Element mapping the Merensky Reef of the Bushveld Complex

The Merensky Reef hosts one of the largest PGE resources globally.It has been exploited for nearly 100 years, yet its origin remains unresolved.In the present study, we characterised eight samples of the reef at four localities in the western Bushveld Complex using micro-X-ray fluorescence and field emission scanning electron microscopy.Our results indicate that the Merensky Reef formed through a range of diverse processes.Textures exhibited by chromite grains at the base of the reef are consistent with supercooling and in situ growth.The local thickening of the Merensky chromitite layers within troughs in the floor rocks is most readily explained by granular flow.Annealing and deformation textures in pyroxenes of the Merensky pegmatoid bear testament to recrystallisation and deformation.The footwall rocks to the reef contain disseminations of PGE rich sulphides as well as olivine grains with peritectic reaction rims along their upper margins suggesting reactive downward flow of silicate and sulphide melts.Olivine-hosted melt inclusions containing Cl-rich apatite, sodic plagioclase, and phlogopite suggest the presence of highly evolved, volatile-rich melts.Pervasive reverse zonation of cumulus plagioclase in the footwall of the reef indicates dissolution or partial melting of plagioclase, possibly triggered by flux of heat, acidic fluids, or hydrous melt.Together, these data suggest that the reef formed through a combination of magmatic, hydrodynamic and hydromagmatic processes.     

Distribution of platinum-group elements in magmatic and altered ores in the Jinchuan intrusion, China: an example of selenium remobilization by postmagmatic fluids

The division of platinum-group elements (PGE) between those hosted in platinum-group minerals (PGM) versus those in solid solution in base metal sulfides (BMS) has been determined for ores from the PGE-bearing Ni-Cu-rich Jinchuan intrusion in northwest China. All the BMS are devoid of Pt and Ir, and magmatic BMS are also barren of Rh. These PGE may have been scavenged by arsenic to form PGM during magmatic crystallization of the BMS. Pd, Os, and Ru are recorded in BMS and Pd is predominantly in solid solution in pentlandite. Unlike the fresh magmatic ores, in altered or serpentinized ores, Pd-PGM are present. Froodite is hosted in magnetite, formed during alteration of BMS, accompanied by sulfur loss and liberation of Pd. Michenerite ([Pd,Pt]BiTe), sperrylite (PtAs₂), and Au-bearing PGM are located in altered silicates. Irarsite (IrAsS) occurs mainly enclosed in BMS. Padmaite (PdBiSe), identified at the junctions of magnetite and BMS, was the last PGM to form and locally partially replaces earlier non-Se-bearing PGM. We propose that padmaite formed under oxidizing conditions during late local remobilization of Se from the BMS. Se-bearing PGM are rare and our review shows they are frequently associated with carbonate, suggesting that Pd and Se can be mobilized great distances in low pH oxidizing fluids and may be precipitated on contact with carbonate. S/Se ratios are used by researchers of magmatic Ni-Cu-PGE ores to determine sulfur loss, assuming Se is immobile and representative of magmatic sulfur content. This study shows that Se as well as S is potentially mobile and this should be considered in the use of S/Se ratios.     

Precious and base metal geochemistry and mineralogy of the Grasvally Norite–Pyroxenite–Anorthosite (GNPA) member,northern Bushveld Complex,South Africa: implications for a multistage emplacement

The Grasvally Norite–Pyroxenite–Anorthosite (GNPA) member within the northern limb of the Bushveld Complex is a mineralized, layered package of mafic cumulates developed to the south of the town of Mokopane, at a similar stratigraphic position to the Platreef. The concentration of platinum-group elements (PGE) in base metal sulfides (BMS) has been determined by laser ablation inductively coupled plasma–mass spectrometry. These data, coupled with whole-rock PGE concentrations and a detailed account of the platinum-group mineralogy (PGM), provide an insight into the distribution of PGE and chalcophile elements within the GNPA member, during both primary magmatic and secondary hydrothermal alteration processes. Within the most unaltered sulfides (containing pyrrhotite, pentlandite, and chalcopyrite only), the majority of IPGE, Rh, and some Pd occur in solid solution within pyrrhotite and pentlandite, with an associated Pt–As and Pd–Bi–Te dominated PGM assemblage. These observations in conjunction with the presence of good correlations between all bulk PGE and base metals throughout the GNPA member indicate the presence and subsequent fractionation of a single PGE-rich sulfide liquid, which has not been significantly altered. In places, the primary sulfides have been replaced to varying degrees by a low-temperature assemblage of pyrite, millerite, and chalcopyrite. These sulfides are associated with a PGM assemblage characterized by the presence of Pd antimonides and Pd arsenides, which are indicative of hydrothermal assemblages. The presence of appreciable quantities of IPGE, Pd and Rh within pyrite, and, to a lesser, extent millerite suggests these phases directly inherited PGE contents from the pyrrhotite and pentlandite that they replaced. The replacement of both the sulfides and PGM occurred in situ, thus preserving the originally strong spatial association between PGM and BMS, but altering the mineralogy. Precious metal geochemistry indicates that fluid redistribution of PGE is minimal with only Pd, Au, and Cu being partially remobilized and decoupled from BMS. This is also indicated by the lower concentrations of Pd evident in both pyrite and millerite compared with the pentlandite being replaced. The observations that the GNPA member was mineralized prior to intrusion of the Main Zone and that there was no local footwall control over the development of sulfide mineralization are inconsistent with genetic models involving the in situ development of a sulfide liquid through either depletion of an overlying magma column or in situ contamination of crustal S. We therefore believe that our observations are more compatible with a multistage emplacement model, where preformed PGE-rich sulfides were emplaced into the GNPA member. Such a model explains the development and distribution of a single sulfide liquid throughout the entire 400–800 m thick succession. It is therefore envisaged that the GNPA member formed in a similar manner to its nearest analogue the Platreef. Notable differences however in PGE tenors indicate that the ore-forming process may have differed slightly within the staging chambers that supplied the Platreef and GNPA member.     

Platinum-Group Elements in Sulphide Minerals, Platinum-Group Minerals, and Whole-Rocks of the Merensky Reef (Bushveld Complex, South Africa): Implications for the Formation of the Reef

The concentrations of platinum-group elements (PGE), Co, Re,Au and Ag have been determined in the base-metal sulphide (BMS)of a section of the Merensky Reef. In addition we performeddetailed image analysis of the platinum-group minerals (PGM).The aims of the study were to establish: (1) whether the BMSare the principal host of these elements; (2) whether individualelements preferentially partition into a specific BMS; (3) whetherthe concentration of the elements varies with stratigraphy orlithology; (4) what is the proportion of PGE hosted by PGM;(5) whether the PGM and the PGE found in BMS could account forthe complete PGE budget of the whole-rocks. In all lithologies,most of the PGE (65 up to 85%) are hosted by PGM (essentiallyPt–Fe alloy, Pt–Pd sulphide, Pt–Pd bismuthotelluride).Lesser amounts of PGE occur in solid solution within the BMS.In most cases, the PGM occur at the contact between the BMSand silicates or oxides, or are included within the BMS. Pentlanditeis the principal BMS host of all of the PGE, except Pt, andcontains up to 600 ppm combined PGE. It is preferentially enrichedin Pd, Rh and Co. Pyrrhotite contains, Rh, Os, Ir and Ru, butexcludes both Pt and Pd. Chalcopyrite contains very little ofthe PGE, but does concentrate Ag and Cd. Platinum and Au donot partition into any of the BMS. Instead, they occur in theform of PGM and electrum. In the chromitite layers the whole-rockconcentrations of all the PGE except Pd are enriched by a factorof five relative to S, Ni, Cu and Au. This enrichment couldbe attributed to BMS in these layers being richer in PGE thanthe BMS in the silicate layers. However, the PGE content inthe BMS varies only slightly as a function of the stratigraphy.The BMS in the chromitites contain twice as much PGE as theBMS in the silicate rocks, but this is not sufficient to explainthe strong enrichment of PGE in the chromitites. In the lightof our results, we propose that the collection of the PGE occurredin two steps in the chromitites: some PGM formed before sulphidesaturation during chromitite layer formation. The remainingPGE were collected by an immiscible sulphide liquid that percolateddownward until it encountered the chromitite layers. In thesilicate rocks, PGE were collected by only the sulphide liquid. KEY WORDS: Merensky Reef; Rustenburg Platinum Mine; sulphide; platinum-group elements; image analysis; laser ablation ICP-MS     

Pyrite tracks assimilation of crustal sulfur in Pyrenean peridotites

Cobalt-bearing pyrite (0.5?C2.0?wt.% Co) is abnormally abundant (up to 35?vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular (??blocky??) pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (>10⁵), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO₂-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T?=?300?C550°C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.     

A laser ablation ICP-MS study of platinum-group and chalcophile elements in base metal sulfide minerals of the Jinchuan Ni–Cu sulfide deposit,NW China

The paper presents concentrations of the platinum-group and chalcophile elements in the base metal sulfides (BMS) from the Jinchuan Ni–Cu sulfide deposit determined by laser ablation-inductively coupled plasma-mass spectrometry. Mass balance calculations reveal that pentlandite hosts a large proportion of Co, Ni and Pd (> 65%), and that pentlandite and pyrrhotite accommodate significant proportions of Re, Os, Ru, Rh, and Ag (~ 35–90%), whereas chalcopyrite contains a small amount of Ag (~ 10%) but negligible platinum-group elements. Iridium and Pt are not concentrated in the BMS and mostly occur in As-rich platinum-group minerals. The enrichments of Co, Ni, Re, Os, Ru, and Rh in pentlandite and pyrrhotite, and Cu in chalcopyrite are consistent with the fractionation of sulfide liquid and exsolution of pentlandite and pyrrhotite from the mono-sulfide solid solution (MSS). The Ir-bearing minerals exsolved from the MSS, depleting pentlandite and pyrrhotite in Ir, whereas sperrylite exsolved from the residual sulfide liquid on cooling. Diffusion of Pd from residual sulfide liquid into pentlandite during its exsolution from the MSS and crystallization of Pt-bearing minerals in the residual sulfide liquid resulted in the enrichment of Pd in pentlandite and decoupling between Pd and Pt in the Jinchuan net-textured and massive ores.     

Sulfide and platinum mineralization in the Merensky Reef: evidence from hydrous silicates and fluid inclusions

The base metal sulfides of the Merensky Reef are associated with hydrous silicates and intense deuteric hydrous alteration of cumulus and postcumulus silicates. Biotite and phlogopite crystallized in the vicinity of sulfides from a volatile-enriched highly fractionated intercumulus melt. Amphibole, chlorite, and talc are later alteration phases of cumulus pyroxene and intercumulus plagioclase. Biotite is often accompanied by zircon, rutile, and quartz. Accessory quartz hosts a complex suite of H₂O-NaCl-(CaCl₂)-CO₂-CH₄ fluid inclusions which have thus far not been described from the Merensky Reef. The earliest fluid inclusion compositions are NaCl-(H₂O) with less than 10 vol.% water; CO₂ coexisting with a halite daughter crystal and brine; and polyphase inclusions with up to six daughter and accidental phases and high contents of divalent cations. The maximum trapping temperature is around 730° C at 4 to 5 kb pressure. Later inclusion generations are H₂O-NaCl, CO₂-H₂O, and pure CO₂ and CH₄. The presence of Cl-rich fluids during the intercumulus stage of the crystallizing Merensky Reef is directly related to the mode of sulfide precipitation. Prior to sulfide unmixing in a hydrous magma sulfur is likely to be present as H₂S. Sulfur saturation causes reaction of H₂S with oxides of the silicate melt to form a sulfide melt plus water. During reaction the magma is enriched in water until a separate fluid unmixes. It carries all compounds with high fluid/melt partition coefficients, as well as metals capable of forming OH- and Cl-complexes. Precious metals are assumed to have fractionated into the Cl-rich fluid as Cl-complexes rather than being dissolved in the sulfide melt. During the cooling evolution of the fluid the precious elements precipitate around the periphery of sulfide melt droplets. The model proposed explains the distribution pattern of platinum-group minerals in the Merensky Reef better than any orthomagmatic mineralization concept offered so far.     

Platinum-group Elements and Microstructures of Normal Merensky Reef from Impala Platinum Mines, Bushveld Complex

The Merensky Reef of the Bushveld Complex contains one of theworld’s largest concentrations of platinum-group elements(PGE). We have investigated ‘normal’ reef, its footwalland its hanging wall at Impala Platinum Mines. The Reef is 46cm thick and consists from bottom to top of leuconorite, anorthosite,chromitite and a very coarse-grained melanorite. The footwallis leuconorite and the hanging wall is melanorite. The onlyhydrous mineral present is biotite, which amounts to 1%, orless, of the rock. All of the rocks contain 0·1–5%interstitial sulphides (pyrrhotite, pentlandite and chalcopyrite),with the Reef rocks containing the most sulphides (1–5%).Lithophile inter-element ratios suggest that the magma fromwhich the rocks formed was a mixture of the two parental magmasof the Bushveld Complex (a high-Mg basaltic andesite and a tholeiiticbasalt). The Reef rocks have low incompatible element contentsindicating that they contain 10% or less melt fraction. Nickel,Cu, Se, Ag, Au and the PGE show good correlations with S inthe silicate rocks, suggesting control of the abundance of thesemetals by sulphides. The concentration of the chalcophile elementsand PGE in the silicate rocks may be modelled by assuming thatthe rocks contain sulphide liquid formed in equilibrium withthe evolving silicate magma. It is, however, difficult to modelthe Os, Ir, Ru, Rh and Pt concentrations in the chromititesby sulphide liquid collection alone, as the rocks contain 3–4times more Os, Ir, Ru, Rh and Pt than the sulphide-collectionmodel would predict. Two possible solutions to this are: (1)platinum-group minerals (PGM) crystallize from the sulphideliquid in the chromitites; (2) PGM crystallize directly fromthe silicate magma. To model the concentrations of Os, Ir, Ru,Rh and Pt in the chromitites it is necessary to postulate thatin addition to the 1% sulphides in the chromitites there isa small quantity (0·005%) of cumulus PGM (laurite, cooperiteand malanite) present. Sulphide liquids do crystallize PGM atlow f_S2. Possibly the sulphide liquid that was trapped betweenthe chromite grains lost some Fe and S by reaction with thechromite and this provoked the crystallization of PGM from thesulphide liquid. Alternatively, the PGM could have crystallizeddirectly from the silicate magma when it became saturated inchromite. A weakness of this model is that at present the exactmechanism of how and why the magma becomes saturated in PGMand chromite synchronously is not understood. A third modelfor the concentration of PGE in the Reef is that the PGE arecollected from the underlying cumulus pile by Cl-rich hydrousfluids and concentrated in the Reef at a reaction front. Althoughthere is ample evidence of compaction and intercumulus meltmigration in the Impala rocks, we do not think that the PGEwere introduced into the Reef from below, because the rocksunderlying the Reef are not depleted in PGE, whereas those overlyingthe Reef are depleted. This distribution pattern is inconsistentwith a model that requires introduction of PGE by intercumulusfluid percolation from below. KEY WORDS: Merensky Reef; platinum-group elements; chalcophile elements; microstructures     

Loypishnyun Low-Sulfide Pt–Pd Deposit of the Monchetundra Basic Massif,Kola Peninsula,Russia

The geology of the basal-structural Loypishnyun low-sulfide Pt–Pd deposit is characterized, including its mineral composition and the peculiarities of its PGE and chalcophile-element distribution in ore. The deposit is situated in the northeastern part of the Monchetundra basic massif and is localized in its lower norite–orthopyroxenite zone, intensely injected with late gabbroic rocks. Two ore zones are distinguished within the deposit. Ore zone 1 has been traced by drilling for about 1.5 km at a thickness from 10–15 to 120 m and incorporates from two to nine separate lenticular–sheetlike orebodies 0.5–25 m in thickness. Ore zone 2 has been traced for 550 m and is represented by one orebody 5–35 m thick. The internal structure of the orebodies is characterized by alternation of low-grade (Pt + Pd = 0.5–0.9 gpt), ordinary (Pt + Pd = 1.0–1.9 gpt), and high-grade (Pt + Pd > 2 gpt) interlayers of various thickness. The ores are spatially and genetically related to sulfide mineralization (pentlandite–chalcopyrite–pyrrhotite) in an amount of 1–5 vol %. The PGE distribution in ores normalized to primitive mantle is characterized by fractionation of easily fusible platinoids with a positive Pd anomaly. The spectra of chalcophile elements normalized to primitive mantle are notable for elevated Te, Bi, As, and Se contents with respect to Sn, Hg, and Pb, which reflects the significant contribution of Te, Bi, and As in the formation of platinum group minerals (PGM), whereas Se, which is devoid of proper mineral phases, most likely is an admixture in the composition of sulfides. The S/Se value in ore of the Loypishnyun deposit varies from 31 to 814. The platinum group elements (PGE) in ore are represented by 45 noble metal minerals. Ore zone 1 is characterized by lateral mineral zoning, which is expressed as replacement of a bismuthotelluride–sulfide PGM assemblage by an assemblage of copper–PGE compounds and alloys. In ore zone 2, a mineral assemblage of tellurides, copper–PGE compounds and alloys predominates, with native gold, silver, and palladium, as well as sulfides and bismuthotellurides, playing a subordinate role. The formation of PGM ore proceeded under variable sulfur fugacity conditions, beginning with the late magmatic stage at temperatures of 900–700°C and ending with hydrothermal transformation at a temperature of <500°C.     

Chalcophile and platinum-group element (PGE) concentrations in the sulfide minerals from the McCreedy East deposit,Sudbury, Canada,and the origin of PGE in pyrite

Magmatic sulfide deposits consist of pyrrhotite, pentlandite, chalcopyrite (± pyrite), and platinum-group minerals (PGM). Understanding the distribution of the chalcophile and platinum-group element (PGE) concentrations among the base metal sulfide phases and PGM is important both for the petrogenetic models of the ores and for the efficient extraction of the PGE. Typically, pyrrhotite and pentlandite host much of the PGE, except Pt which forms Pt minerals. Chalcopyrite does not host PGE and the role of pyrite has not been closely investigated. The Ni–Cu–PGE ores from the South Range of Sudbury are unusual in that sulfarsenide PGM, rather than pyrrhotite and pentlandite, are the main carrier of PGE, probably as the result of arsenic contribution to the sulfide liquid by the As-bearing metasedimentary footwall rocks. In comparison, the North Range deposits of Sudbury, such as the McCreedy East deposit, have As-poor granites in the footwall, and the ores commonly contain pyrite. Our results show that in the pyrrhotite-rich ores of the McCreedy East deposit Os, Ir, Ru, Rh (IPGE), and Re are concentrated in pyrrhotite, pentlandite, and surprisingly in pyrite. This indicates that sulfarsenides, which are not present in the ores, were not important in concentrating PGE in the North Range of Sudbury. Palladium is present in pentlandite and, together with Pt, form PGM such as (PtPd)(TeBi)₂. Platinum is also found in pyrite. Two generations of pyrite are present. One pyrite is primary and locally exsolved from monosulfide solid solution (MSS) in small amounts (<2 wt.%) together with pyrrhotite and pentlandite. This pyrite is unexpectedly enriched in IPGE, As (± Pt) and the concentrations of these elements are oscillatory zoned. The other pyrite is secondary and formed by alteration of the MSS cumulates by late magmatic/hydrothermal fluids. This pyrite is unzoned and has inherited the low concentrations of IPGE and Re from the pyrrhotite and pentlandite that it has replaced.     

Platinoids in the Kaalamo Differentiated Massif in the Northern Ladoga Region,Karelia, Russia

The Kaalamo massif is located in the Northern Ladoga region, Karelia, on the extension of the Kotalahti Belt of Ni-bearing ultramafic intrusions in Finland. The massif, 1.89 Ga in age, is differentiated from pyroxenite to diorite. Nickel–copper sulfide mineralization with platinoids is related to the pyroxenite phase. The ore consists of two mineral types: (i) pentlandite–chalcopyrite–pyrrhotite and (ii) chalcopyrite, both enriched in PGE. Pd and Pt bismuthotellurides, as well as Pd and Pt tellurobismuthides, are represented by the following mineral species: kotulskite, sobolevskite, merenskyite, michenerite, moncheite, keithconnite, telluropalladinite; Pt and Pd sulfides comprise vysotskite, cooperite, braggite, palladium pentlandite, and some other rare phases. High-palladium minerals are contained in pentlandite–chalcopyrite–pyrrhotite ore. Native gold intergrown with kotulskite commonly contains microinclusions (1–3 μm) of Pd stannides: paolovite and atokite. Ore with 20–60% copper sulfides (0.2–6.0% Cu) contains 5.1–6.6 gpt PGE and up to 0.13–2.3 gpt Au. Pd minerals, arsenides and sulfoarsenides of Pt, Rh, Ir, Os, and Ru are identified as well. These are sperrylite, ruthenium platarsite, hollingworthite, and irarsite; silvery gold and paolovite have also been noted. All these minerals have been revealed in the massif for the first time. The paper also presents data on the compositions of 25 PGE minerals (PGM) from Kaalamo ores.     

Platinum-group elements, S, Se and Cu in highly depleted abyssal peridotites from the Mid-Atlantic Ocean Ridge (ODP Hole 1274A): Influence of hydrothermal and magmatic processes

Highly depleted harzburgites and dunites were recovered from ODP Hole 1274A, near the intersection between the Mid-Atlantic Ocean Ridge and the 15°20′N Fracture Zone. In addition to high degrees of partial melting, these peridotites underwent multiple episodes of melt–rock reaction and intense serpentinization and seawater alteration close to the seafloor. Low concentrations of Se, Cu and platinum-group elements (PGE) in harzburgites drilled at around 35–85 m below seafloor are consistent with the consumption of mantle sulfides after high degrees (>15–20 %) of partial melting and redistribution of chalcophile and siderophile elements into PGE-rich residual microphases. Higher concentrations of Cu, Se, Ru, Rh and Pd in harzburgites from the uppermost and lowest cores testify to late reaction with a sulfide melt. Dunites were formed by percolation of silica- and sulfur-undersaturated melts into low-Se harzburgites. Platinum-group and chalcophile elements were not mobilized during dunite formation and mostly preserve the signature of precursor harzburgites, except for higher Ru and lower Pt contents caused by precipitation and removal of platinum-group minerals. During serpentinization at low temperature (<250 °C) and reducing conditions, mantle sulfides experienced desulfurization to S-poor sulfides (mainly heazlewoodite) and awaruite. Contrary to Se and Cu, sulfur does not record the magmatic evolution of peridotites but was mostly added in hydrothermal sulfides and sulfate from seawater. Platinum-group elements were unaffected by post-magmatic low-temperature processes, except Pt and Pd that may have been slightly remobilized during oxidative seawater alteration.