Spatial Association Between Platinum Minerals and Magmatic Sulfides Imaged with the Maia Mapper and Implications for the Origin of the Chromite-Sulfide-PGE Association

ABSTRACT The spatial association between Pt minerals, magmatic sulfides, and chromite has been investigated using microbeam X-ray fluorescence (XRF) element mapping and the Maia Mapper. This lab-based instrument combines the Maia parallel energy dispersive (ESD) detector array technology with a focused X-ray beam generated from a liquid metal source. It proves to be a powerful technique for imaging Pt distribution at low-ppm levels on minimally prepared cut rock surfaces over areas of tens to hundreds of square centimeters, an ideal scale for investigating these relationships. Images of a selection of samples from the Bushveld Complex and from the Norilsk-Talnakh ore deposits (Siberia) show strikingly close association of Pt hotspots, equated with the presence of Pt-rich mineral grains, with magmatic sulfide blebs in all cases, except for a taxitic low-S ore sample from Norilsk. In all of the Bushveld samples, at least 75% of Pt hotspots (by number) occur at or within a few hundred microns of the outer edges of sulfide blebs. In samples from the leader seams of the UG2 chromitite, sulfides and platinum hotspots are also very closely associated with the chromite seams and are almost completely absent from the intervening pyroxenite. In the Merensky Reef, the area ratio of Pt hotspots to sulfides is markedly higher in the chromite stringers than in the silicate-dominated lithologies over a few centimeters either side. We take these observations as confirmation that sulfide liquid is indeed the prime collector for Pt and, by inference, for the other platinum group elements (PGEs) in all these settings. We further propose a mechanism for the sulfide-PGE-chromite association in terms of in situ heterogeneous nucleation of all these phases coupled with transient sulfide saturation during chromite growth and subsequent sulfide loss by partial re-dissolution. In the case of the amygdular Norilsk taxite, the textural relationship and high PGE/S ratio is explained by extensive loss of S to an escaping aqueous vapor phase.

UPGRADING OF MAGMATIC SULFIDES, REVISITED

There has been vigorous debate for several decades about whether the extreme enrichments of platinum group elements (PGEs) in some magmatic sulfide deposits could have resulted from simple equilibration of sulfide liquid with silicate melt. Key examples include the Ni-Cu-Pd mineralization in the Norilsk mining camp, the UG2 and Merensky reef Pt-Pd deposits in the Bushveld Complex, the Pd-rich J-M reef of the Stillwater Complex, and the Skaergaard Pd-Au mineralization. It was argued historically that the observed PGE tenors in these latter deposits are too high to be consistent with simple equilibration of sulfide and silicate melt. A commonly cited mechanism for increasing PGE tenor in magmatic sulfide is the upgrading of initially low tenor sulfide by allowing a small volume of sulfide to react with successive batches of fresh, previously undepleted silicate magma. Here we review several previous models for sulfide upgrading in light of recent changes in accepted values of the partition coefficients governing PGE exchange between sulfide and silicate, and we critically examine the physical scenarios implicit in each previous model. We show that, although sulfide upgrading may occur in natural settings such as fractional melting of the mantle, during the formation of sulfide accumulations from magmas it is unlikely to have effects that can be distinguished from simple one-stage batch equilibration. Even the most PGE-rich deposits currently known have compositions that can easily be accounted for by the simple one-stage batch process, with the possible exception of the Skaergaard Pd mineralization. It is generally not possible to use the measured composition of accumulations of magmatic sulfide to infer that sulfide upgrading has or has not occurred.

Arsenotučekite, Ni18Sb3AsS16, a new mineral from the Tsangli chromitites, Othrys ophiolite, Greece

Arsenotučekite, Ni18Sb3AsS16, is a new mineral discovered in the abandoned chromium mine of Tsangli, located in the eastern portion of the Othrys ophiolite complex, central Greece. Tsangli is one of the largest chromite deposit at which chromite was mined since 1870. The Tsangli chromitite occurs as lenticular and irregular bodies. The studied chromitites are hosted in a strongly serpentinized mantle peridotite. Arsenotučekite forms anhedral to subhedral grains that vary in size between 5 μm up to 100 μm, and occurs as single phase grains or is associated with pentlandite, breithauptite, gersdorffite and chlorite. It is brittle and has a metallic luster. In plane-polarized light, it is creamy-yellow, the bireflectance is barely perceptible and the pleochroism is weak. In crossed polarized reflected light, the anisotropic rotation tints vary from pale blue to brown. Internal reflections were not observed. Reflectance values of arsenotučekite in air (Ro, Re′ in %) are: 41.8–46.4 at 470 nm, 47.2–50.6 at 546 nm, 49.4–52.3 at 589 nm, and 51.3–53.2 at 650 nm. The empirical formula of arsenotučekite, based on 38 atoms per formula unit, and according to the structural results, is (Ni16.19Co1.01Fe0.83)Σ18.03Sb3(As0.67Sb0.32)Σ0.99S15.98. The mass density is 6.477 g·cm−3. The simplified chemical formula is (Ni,Co,Fe)18Sb3(As,Sb)S16. The mineral is tetragonal and belongs to space group I4/mmm, with a = 9.7856(3) Å, c = 10.7582(6) Å, V = 1030.2(6) Å3 and Z = 2. The structure is layered (stacking along the c-axis) and is dominated by three different Ni-coordination polyhedral, one octahedral and two cubic. The arsenotučekite structure can be considered as a superstructure of tučekite resulting from the ordering of Sb and As. The name of the new mineral species indicates the As-dominant of tučekite. Arsenotučekite occurs as rims partly replacing pentlandite and irregularly developed grains. Furthermore, it is locally associated with chlorite. These observations suggest that it was likely precipitated at relatively low temperatures during: 1) the late hydrothermal stages of the ore-forming process by reaction of Sb- and As-bearing solutions with magmatic sulfides such as pentlandite, or 2) during the serpentinization of the host peridotite. The mineral and its name have been approved by the Commission of New Minerals, Nomenclature, and Classification of the International Mineralogical Association (number 2019–135).

Early sulfide saturation is not detrimental to porphyry Cu-Au formation

Ore-forming magmas are commonly considered to have been unusually metal rich. Because Cu and Au are strongly chalcophile, early sulfide saturation has been regarded as detrimental to porphyry Cu-Au mineralization. Here we demonstrate, based on amphibole-rich cumulate xenoliths and amphibole megacrysts from the Tongling porphyry(-skarn) Cu-Au mining district in southeastern China, that this view is not necessarily correct. Age data combined with petrological and geochemical evidence suggest that the mineralizing magmas at Tongling underwent significant fractional crystallization of amphibole, clinopyroxene, and magmatic sulfides in the middle to lower crust. The fact that the silicate melts nevertheless were able to produce substantial porphyry(-skarn) Cu-Au deposits implies that the formation of metal-rich cumulates at depth was not detrimental to their fertility. On the contrary, the common association of porphyry Cu (Au, Mo) deposits with high-Sr/Y magmas suggests that amphibole fractionation at depth even promotes the mineralization potential, despite the likely loss of metals.

Magmatic sulfides in high-potassium calc-alkaline to shoshonitic and alkaline rocks

We investigate the occurrence and chemistry of magmatic sulfides and their chalcophile metal cargo behaviour during the evolution of compositionally different magmas from diverse geodynamic settings both in mineralised and barren systems. The investigated areas are the following: (a) the Miocene Konya magmatic province (hosting the Doğanbey Cu–Mo porphyry and Inlice Au epithermal deposits, representing post-subduction) and (b) the Miocene Usak basin (Elmadag, Itecektepe, and Beydagi volcanoes, the latter associated with the Kişladağ Au porphyry in western Turkey, representing post-subduction). For comparison we also investigate (c) the barren intraplate Plio-Quaternary Kula volcanic field west of Usak. Finally, we discuss and compare all the above areas with the already studied (d) Quaternary Ecuadorian volcanic arc (host to the Miocene Llurimagua Cu–Mo and Cascabel Cu–Au porphyry deposits, representing subduction). The volcanism of the newly studied areas ranges from basalts to andesites–dacites and from high-K calc-alkaline to shoshonitic series. Multiphase magmatic sulfides occur in different amounts in rocks of all investigated areas, and, based on textural and compositional differences, they can be classified into different types according to their crystallisation at different stages of magma evolution (early versus late saturation). Our results suggest that independently of the magma composition, geodynamic setting, and association with an ore deposit, sulfide saturation occurred in all investigated magmatic systems. Those systems present similar initial metal contents of the magmas. However, not all studied areas present all sulfide types, and the sulfide composition depends on the nature of the host mineral. A decrease in the sulfide Ni∕Cu (a proxy for the monosulfide solid solution (mss) to intermediate solid solution (iss) ratio) is noted with magmatic evolution. At an early stage, Ni-richer, Cu-poorer sulfides are hosted by early crystallising minerals, e.g. olivine–pyroxene, whereas, at a later stage, Cu-rich sulfides are hosted by magnetite. The most common sulfide type in the early saturation stage is composed of a Cu-poor, Ni-rich (pyrrhotite mss) phase and one to two Cu-rich (cubanite, chalcopyrite iss) phases, making up ∼84 and ∼16 area % of the sulfide, respectively. Sulfides resulting from the late stage, consisting of Cu-rich phases (chalcopyrite, bornite, digenite iss), are hosted exclusively by magnetite and are found only in evolved rocks (andesites and dacites) of magmatic provinces associated with porphyry Cu (Konya and Ecuador) and porphyry Au (Beydagi) deposits.

Origin and Evolution of Magmas in the Porphyry Au-mineralized Javorie Volcano (Central Slovakia): Evidence from Thermobarometry, Melt Inclusions and Sulfide Inclusions

The effect of magmatic sulfide precipitation on the potential of magmatic systems to produce porphyry-type ore deposits is still a matter of debate. In particular, we need to know whether magmatic sulfide precipitation has an impact on the Cu and Au content of the exsolving magmatic volatile phases and, by this way, on the Cu/Au ratio of porphyry deposits. The Javorie volcano is a perfect place to explore these questions. First, it hosts several Au-only porphyry-type mineralized occurrences which have among the lowest Cu/Au ratios reported in the literature. Secondly, the geology of the Javorie volcano and the timing of porphyry Au mineralization are well established. The evolution of the Javorie magmatic system was reconstructed by detailed petrographic studies and laser ablation inductively coupled plasma mass spectrometry analysis of minerals, melt inclusions and sulfide inclusions. The Javorie volcano was formed during the post-subduction magmatic activity affecting the Western Carpathians. It is a typical stratovolcano, composed dominantly of basaltic andesites and andesites which were intruded by several small stocks of dacitic to dioritic composition. According to our thermobarometric data, the volcano was fed by a transcrustal magmatic system in which two levels of magma chambers could be identified. Part of the magma evolved in the lower crust as suggested by the occurrence of magmatic garnet antecrysts in some of the studied rocks. The occurrence of magmatic sulfide inclusions in garnet indicates that sulfide saturation was reached in this lower crustal magma chamber. Most of the rocks crystallized in an upper crustal magma chamber (∼2 ± 1 kbar) that was fed by a basaltic to basaltic andesite magmas. A large variation in temperatures, ranging between 820°C and 1025°C, recorded by the extrusive and intrusive rocks suggest either that the upper crustal magma chamber was thermally zoned, or that the temperature of the whole magma chamber varied dramatically during its lifetime. Magmatic sulfide inclusions are present in all minerals and rocks of the upper crustal magma chamber, independent of their timing relative to porphyry Au mineralization (pre-, syn-, post-ore). These observations suggest that the magmatic system was sulfide saturated during its entire evolution. With very few exceptions, the precipitating sulfides were composed of monosulfide solid solution containing 0·2–9·2 wt % Cu and 0·05–11 ppm Au. The presence of these magmatic sulfides, together with results of a numerical model, suggest that the primitive magma feeding the upper crustal magma chamber contained less than 2·75 wt % H2O and that only a minor part of the magmatic sulfides was fractionated out of the system. Finally, the Cu/Au ratios measured in the magmatic sulfide inclusions and the ones predicted for the exsolved aqueous fluids are 10 to 100 times higher than the Cu/Au ratios of the porphyry deposits. Therefore, the extremely low Cu/Au ratios of the porphyry deposits must have been acquired during the hydrothermal stage.

Reduced CO2 fluid as an agent of ore-forming processes: a case study of dolomite-replacement skarns at the Yoko-Dovyren massif)

The paper presents newly obtained geochemical data on outer-contact rocks and carbonatereplacement skarns of the Yoko-Dovyren layered ultramafic-mafic intrusion in the northern Baikal area. The rocks initially contained CO2-rich fluid with a high oxygen fugacity (up to NNO + 3–4), which was generated by the partial decomposition of dolomite and by reactions between SiO2 and carbonates. The skarn blue diopside is enriched in Pt (up to 0.2 ppm) and V (300 ppm), and the wollastonite zone of the skarns contains elevated Re concentrations (up to 0.4 ppm). The REE pattern of the contact-zone quartzite is identical to the REE patterns of phlogopite-bearing lherzolites from the lower contact part of the Yoko-Dovyren massif. These geochemical features of the rocks of the intrusion may be explained by the transfer and redeposition of material by reduced H2O-CO2 fluid. According to thermodynamic calculations, a reaction between H2O-CO2 fluid and high-Mg olivine at a subsolidus temperature of T = 950оC and pressure P = 2 kbar should result in a decrease in the oxygen fugacity to QFM – 2 and, hence, generate much CO. According to the calculations, a low oxygen fugacity (close to QFM + 0.7) can also be maintained by pyrrhotite oxidation with H2O and CO2 fluid components under cumulus P-T parameters. As a result of these reactions, the fluid should enrich in Pt extracted from magmatic sulfides, and this Pt can be redeposited in rocks, including those composing the skarn zones.

Platinum-group minerals of the F and T zones, Waterberg Project, far northern Bushveld Complex: implication for the formation of the PGE mineralization

ABSTRACTThis study provides the first detailed mineralogical data on platinum-group element (PGE) mineralization of the Waterberg Project, in a previously unknown segment of the Bushveld Complex located in the Southern Marginal Zone of the Limpopo Belt. The lower ultramafic F zone is dominated by sperrylite (up to 82 area%) with minor Pt–Pd bismuthotellurides, Pd–Ni arsenides, Au–Ag alloy, Rh–Pt sulfoarsenides and rare Pt–Fe alloys. The upper more felsic-rich gabbroic T zone is dominated by Pt–Pd bismuthotellurides (up to 90 area%), Pd tellurides and Au–Ag alloy with rare sperrylite, braggite, Pd stannides and antimonides. The platinum-group minerals (PGM) of the F zone are associated mainly with magmatic base-metal sulfides (pyrrhotite, troilite, chalcopyrite and pentlandite), that have undergone alteration during significant serpentinization, accompanied by the formation of the secondary sulfide assemblage. The T zone in a leucogabbroic sequence contains relics of magmatic sulfides and is characterized by the development of the indicative chalcopyrite-millerite-pyrite assemblage, which is associated with widespread hydrothermal quartz and hydrous silicates (amphiboles, phlogopite, epidote and chlorite). The fluid-induced style of PGM remobilization, the high Au/PGE and the high proportion of native gold in the high-grade T zone ores in the magnetite-bearing leucogabbroic rocks are unique to the Bushveld Complex. The genesis of the T ores is interpreted as a result of primary PGE enrichment in the zone of interaction between the first influxes of the Upper Zone fertile melt and a resident gabbroic melt at the top of the Troctolite-Gabbronorite-Anorthosite (TGA) fractionated sequence with subsequent fluid remobilization. Whether the hydrothermal overprint facilitated the PGE sequestration in a favourable setting or dispersed the pre-existing magmatic concentrations along fluid pathways remains essentially unresolved at the current stage.