Compositions and Ni-Cu-Platinum Group Element Tenors of Nova-Bollinger Ores with Implications for the Origin of Pt Anomalies in Platinum Group Element-Poor Massive Sulfides

The Nova-Bollinger Ni-Cu-platinum group element (PGE) deposit in the Fraser zone of the Albany-Fraser orogen consists of two main orebodies, Nova and Bollinger, hosted by the same tube-shaped intrusion but having distinctly different Ni tenors of around 6.5 and 4.8 wt %, respectively. Nova is also higher in Pd, but Cu and Pt tenors are similar. Both deposits have very low PGE tenors, with average Pd concentrations of 110 ppb in massive sulfide at Bollinger and 136 ppb at Nova. The Nova and Bollinger orebodies show relatively little internal differentiation overall on deposit scale but show strong differentiation into chalcopyrite-rich and chalcopyrite-poor regions at a meter scale. This differentiation is more prevalent at Nova, where massive sulfide-filled vein arrays are more extensively developed, and in massive ores, particularly veins, than in net-textured ores. Net-textured and disseminated ores have on average Ni and Cu grades and tenors similar to those of massive, semimassive, and breccia ores in the same orebody but a smaller range of variation, largely due to a more limited extent of sulfide liquid fractionation and higher average concentrations of Pt and Pd than adjacent massive ores. Unusually for differentiated magmatic sulfides, there is no systematic positive correlation between Pt, Pd, and Cu. A partial explanation for the lack of a Pd-Cu correlation is that Pd was partitioned into peritectic pentlandite in the middle stages of sulfide liquid solidification. This explanation is not applicable to Pt, as Pt characteristically forms its own phases rather than residing in base metal sulfides. PGE tenors are very low in both orebodies, very similar to those observed in other Ni-Cu-Co sulfide ores in orogenic settings, notably the Savannah and Savannah North orebodies. This depletion is attributed to sulfide retention in the mantle source of the parent magmas rather than to previous fractional extraction of sulfide liquid in staging chambers or feeder networks. The higher Ni and Pd tenors at Nova are attributed to reworking and upgrading of precursor sulfide liquid originally deposited upstream at the Bollinger site. Replicate analyses of multiple jaw-crusher splits returned highly variable Pt and Au assays but much smaller relative errors in the other PGEs. The poor Pt and Au reproducibilities are attributed to nugget effects, explicable by much of the Pt and Au in the samples being present in sparse Pt- and Au-rich grains. This is principally true for Pt in massive rather than disseminated ores, accounting for a strong contrast in the distribution of Pt/Pd ratios between the two ore types. Numerical simulation suggests that Pt is predominantly resident in Pt-rich platinum group minerals with grain diameters of 100 μm or more and that at the low (<100 ppb) concentrations in these ores, this results in most assays significantly underreporting Pt. This is likely to be true in other low-PGE ores, such that apparent negative Pt anomalies in massive ores may in such cases be attributable to sampling artifacts.

Origin of the Pd-Rich Pentlandite in the Massive Sulfide Ores of the Talnakh Deposit, Norilsk Region, Russia

Pd-rich pentlandite (PdPn) along with ore-forming pentlandite (Pn) occurs in the cubanite and chalcopyrite massive sulfide ores in the EM-7 well of the Southern-2 ore body of the Talnakh deposit. PdPn forms groups of small grains and comprises marginal areas in large crystals of Pn. The palladium content in PdPn reaches up to 11.26 wt.%. EDS elemental mapping and a contour map of palladium concentrations indicate distinct variations in the palladium content within and between individual grains. Palladium distribution in the large grains is uneven and non-zoned. PdPn was formed as the result of a superimposed process, which is not associated with either the sulfide liquid crystallization or the subsolidus transformations of sulfides. Deming regression calculations demonstrated the isomorphic substitution character of Ni by 0.71 Pd and 0.30 Fe (apfu), leading to PdPn occurrence. The replacement of Ni by Fe may also indicate a change in sulfur fugacity, compared to that taking place during the crystallization of the primary Pn. The transformation of Pn into PdPn could have occurred under the influence of a Pd-bearing fluid, which separated from the crystallizing body of the massive sulfide ores.

Genesis of sulfide vein mineralization at the Sakatti Ni-Cu-PGE deposit, Finland

ABSTRACT The Sakatti Ni-Cu-platinum-group element deposit is situated in northern Finland and comprises massive, disseminated, and vein sulfide mineralization. A stockwork is formed by chalcopyrite-rich sulfide veins, which contain exceptionally high platinum-group elements and Au grades. The mineralogy and geochemistry of this stockwork zone ore is documented in this investigation. The results are used to develop the first robust genetic concept and its relationship to massive and disseminated mineralization of the Sakatti deposit. This model is similar to that proposed for many Cu-rich magmatic sulfide ores, most importantly the Cu-rich footwall veins described from the Sudbury Complex in Canada and the Cu-rich ore at Noril'sk-Talnakh in Russia. Detailed petrographic studies using a sample suite from exploration drill core intersecting vein-style mineralization revealed a classic magmatic sulfide assemblage of chalcopyrite ± pyrrhotite, pentlandite, and pyrite. More than 1000 platinum-group mineral grains belonging almost exclusively to the moncheite (PtTe2) – merenskyite (PdTe2) – melonite (NiTe2) solid solution series were identified in the studied samples. Notably, almost two thirds of the platinum-group element-bearing minerals consist of melonite. Some of the platinum-group minerals contain inclusions of Ag-rich gold (AgAu2) and muthmannite (AuAgTe2). Most of the platinum-group minerals occur as inclusions in chalcopyrite, although a few grains are located at base-metal sulfide grain boundaries and in fractures in base-metal sulfides. The whole-rock compositions of the stockwork veins are Cu-rich and are interpreted to represent a fractionated Cu-rich sulfide liquid enriched in Pt, Pd, Au, Ag, As, Bi, Pb, Se, Te, Zn, which separated from a monosulfide solid solution (mss). An intermediate solid solution (iss) solidified from the Cu-rich sulfide liquid, recrystallizing chalcopyrite at <550 °C. Simultaneously, small volumes of intercumulus residual melt contained mainly the precious metals, Bi, and Te due to their incompatibility in iss. Solitary and composite platinum-group minerals as well as Au-minerals crystallized first from the residual melt (<600 °C), followed by a succession of various Bi-, Ag-, and Pb-tellurides (∼540 °C), and finally sphalerite and galena. Melonite crystallized as mostly large, solitary grains exsolved directly from Ni-bearing intermediate solid solution (∼600 °C), shortly after the formation of moncheite and merenskyite from the residual melt. Finally, remobilization of the platinum-group minerals occurred at temperatures of <300 °C, as suggested by the presence of minor amounts of Cl-bearing minerals and ragged grain shapes.

Breaking of Henry’s law for sulfide liquid–basaltic melt partitioning of Pt and Pd

Platinum group elements are invaluable tracers for planetary accretion and differentiation and the formation of PGE sulfide deposits. Previous laboratory determinations of the sulfide liquid–basaltic melt partition coefficients of PGE ($${D}_{PGE}^{SL/SM}$$ D P G E S L / S M ) yielded values of 102–109, and values of >105 have been accepted by the geochemical and cosmochemical society. Here we perform measurements of $${D}_{Pt,\,Pd}^{SL/SM}$$ D P t , P d S L / S M at 1 GPa and 1,400 °C, and find that $${D}_{Pt,\,Pd}^{SL/SM}$$ D P t , P d S L / S M increase respectively from 3,500 to 3.5 × 105 and 1,800 to 7 × 105, as the Pt and Pd concentration in the sulfide liquid increases from 60 to 21,000 ppm and 26 to 7,000 ppm, respectively, implying non-Henrian behavior of the Pt and Pd partitioning. The use of $${D}_{Pt,\,Pd}^{SL/SM}$$ D P t , P d S L / S M values of 2,000–6,000 well explains the Pt and Pd systematics of Earth’s mantle peridotites and mid-ocean ridge basalts. Our findings suggest that the behavior of PGE needs to be reevaluated when using them to trace planetary magmatic processes.

Origin of Fe-Ni-Cu (Co) sulfide and Fe-Ti oxide minerals in the c. 1.77 Ga dolerite dyke, Singhbhum Craton (eastern India)

Dolerite dyke swarms are widespread within the Singhbhum Craton (eastern India) that emplaced from the Neoarchean to Paleoproterozoic era just after the stabilization of crust before c. 3 Ga. These dyke swarms are oriented in NE - SW to NNE - SSW, NW - SE to WNW - ESE, E - W, and N - S directions. The WNW - ESE trending c. 1.77 Ga Pipilia dyke swarm is sampled from the Satkosia area of the Orissa state. The dyke shows a noticeable disparity in terms of the modal proportion and grain size of pyroxenes, plagioclase, Fe-Ti-oxide minerals and texture across the trend. At places the primary silicates are altered to secondary hydrated mineral assemblages of amphibole, chlorite and sericite. Primary silicates are clinopyroxene (augite: Mg# = 65.7 - 82.6; En37-48Fs11-17Wo36-41), orthopyroxene (clinoenstatite: Mg# = 68.5 − 78; En63-70Fs20-29Wo4-5), plagioclase (An11-39Ab44-82Or1-7) and Fe-Ti oxides are titanomagnetite (FeO = 34.38 − 39.50 wt%, Fe2O3 = 48.26 − 56.21 wt%, TiO2 = 5.05 − 9.60 wt%) and ilmenite (FeO = 40.75 − 43.79 wt%, Fe2O3 = 3.54 − 10.03 wt%, TiO2 = 47.82 − 50.87 wt%). Application of two-pyroxene thermometry yields an equilibration temperature range of 1065oC to 978oC, and coexisting titanomagnetite-ilmenite pairs reveal 731.39oC to 573.37oC at the oxygen fugacity (fO2) condition NNO+0.3 to FMQ-1.03. The dyke contains disseminated sulfides at the interstices of Fe-Ti-oxides, and silicates. Major sulfide minerals are pyrite, chalcopyrite, and vaesite; Pyrite-vaesite assemblages occur in association with secondary silicate minerals. Pyrite grains contain variable concentration of Co = 0.01 − 5.70 wt% and Ni = 0.02 − 1.95 wt%. Coexisting vaesite contains Co = 2.42 − 10.44 wt%, Ni = 26.40 − 47.88 wt%, and Fe = 7.32 − 26.55 wt%. Texture, sulfide-silicate assemblage, and presence of low metal/S sulfides such as the pyrite-vaesite assemblage indicate primary Fe-Ni- sulfides (pyrrhotite-pentlandite) that segregated from immiscible sulfide liquid at high temperature is modified by late magmatic/hydrothermal fluid activities. Numerous sulfide-bearing deposits hosted in ultramafic-mafic intrusions of Paleoproterozoic age have been recorded globally and the occurrence of Fe-Ni-sulfides in the c. 1.77 Ga Pipilia dyke swarm in the Singhbhum Craton enhances the exploration potential of this craton in eastern India.Supplementary material at https://doi.org/10.6084/m9.figshare.c.5643989

Nova-Bollinger Ni-Cu Sulfide Ore Deposits, Fraser Zone, Western Australia: Petrogenesis of the Host Intrusions

The Nova-Bollinger Ni-Cu sulfide ore deposit is the first economic Ni-Cu-Co sulfide deposit to have been discovered in the Albany-Fraser orogen in Western Australia. The host rocks are mafic-ultramafic intrusive cumulates subdivided into two connected intrusions, designated Upper and Lower. The Upper Intrusion is bowl-shaped and modally layered with alternating peridotite and norite mesocumulate layers, with a Basal Series of dominantly orthocumulate mafic lithologies. The Lower Intrusion is a much thinner, semiconformable chonolith (flattened tube-shaped intrusion) consisting of mostly unlayered mafic to ultramafic orthocumulates. The Lower Intrusion hosts all the high-grade mineralization and most of the disseminated ores. A distinctive plagioclase-bearing lherzolite containing both orthopyroxene and olivine as cumulus phases is a characteristic of the Lower Intrusion and the Basal Series of the Upper. The intrusions differ slightly in olivine and spinel chemistry, the differences being largely attributable to the more orthocumulate character of the Lower Intrusion. Sector zoning in Cr content of pyroxenes is observed in the Lower Intrusion and in the lower marginal zone of the Upper and is attributed to crystallization under supercooled conditions. Symplectite pyroxene-spinel-amphibole coronas at olivine-plagioclase contacts are ubiquitous and are attributed to near-solidus peritectic reaction between olivine, plagioclase, and liquid during and after high-pressure emplacement, consistent with high Al contents in igneous pyroxenes and estimates of the peak regional metamorphism. Original cumulus olivines had compositions around Fo86 and were variably Ni depleted, interpreted as the result of preintrusion equilibration with sulfide liquid. The Upper and Lower Intrusion rocks represent cumulates from a similar parental magma, a high-Al tholeiite with MgO between 10 and 12%, low TiO2 (0.5–0.6%), and high Al2O3 (14–17%). Modeling using alphaMELTS indicates a primary water content of around 2 wt %. The cumulates of both intrusions were derived via multiple magma pulses of liquid-olivine-sulfide slurries with variable amounts of orthopyroxene, emplaced into the deep crust at pressures of around 0.7 GPa during the peak of regional metamorphism. The intrusions developed initially as a bifurcating sill, the lower arm developing into the ore-bearing Lower Intrusion chonolith and the upper arm inflating into the cyclically layered Upper Intrusion.

Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite Xenoliths from East Antarctica

Sulfides in upper mantle lherzolite xenoliths from Cretaceous alkaline-ultramafic rocks in the Jetty Peninsula (East Antarctica) were studied for their major and trace-element compositions using SEM and LA-ICP-MS applied in situ. Modal abundance of sulfides is the lowest in Cpx-poor lherzolites ≤ Spl-Grt lherzolites << Cpx-rich lherzolites. Most sulfides are either interstitial (i-type) or inclusions in rock-forming minerals (e-type) with minor sulfide phases mostly present in metasomatic veinlets and carbonate-silicate interstitial patches (m-type). The main sulfide assemblage is pentlandite + chalcopyrite ± pyrrhotite; minor sulfides are polydymite, millerite, violarite, siegenite, and monosulfide solution (mss). Sulfide assemblages in the xenolith matrix are a product of the subsolidus re-equilibration of primary mss at temperatures below ≤300 °C. Platinum group elements (PGE) abundances suggest that most e-type sulfides are the residues of melting processes and that the i-type sulfides are crystallization products of sulfide-bearing fluids/liquids. The m-type sulfides might have resulted from low-temperature metasomatism by percolating sulfide-carbonate-silicate fluids/melts. The PGE in sulfide record processes are related to partial melting in mantle and intramantle melt migration. Most other trace elements initially partitioned into interstitial sulfide liquid and later metasomatically re-enriched residual sulfides overprinting their primary signatures. The extent of element partitioning into sulfide liquids depends on P, T, fO2, and host peridotite composition.

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.

Iron Isotope Compositions of Coexisting Sulfide and Silicate Minerals in Sudbury-Type Ores from the Jinchuan Ni-Cu Sulfide Deposit: A Perspective on Possible Core-Mantle Iron Isotope Fractionation

Many studies have shown that the average iron (Fe) isotope compositions of mantle-derived rocks, mantle peridotite and model mantle are close to those of chondrites. Therefore, it is considered that chondrite values represent the bulk Earth Fe isotope composition. However, this is a brave assumption because nearly 90% of Fe of the Earth is in the core, where its Fe isotope composition is unknown, but it is required to construct bulk Earth Fe isotope composition. We approach the problem by assuming that the Earth’s core separation can be approximated in terms of the Sudbury-type Ni-Cu sulfide mineralization, where sulfide-saturated mafic magmas segregate into immiscible sulfide liquid and silicate liquid. Their density/buoyancy controlled stratification and solidification produced net-textured ores above massive ores and below disseminated ores. The coexisting sulfide minerals (pyrrhotite (Po) > pentlandite (Pn) > chalcopyrite (Cp)) and silicate minerals (olivine (Ol) > orthopyroxene (Opx) > clinopyroxene (Cpx)) are expected to hold messages on Fe isotope fractionation between the two liquids before their solidification. We studied the net-textured ores of the Sudbury-type Jinchuan Ni-Cu sulfide deposit. The sulfide minerals show varying δ56Fe values (−1.37–−0.74‰ (Po) < 0.09–0.56‰ (Cp) < 0.53–1.05‰ (Pn)), but silicate minerals (Ol, Opx, and Cpx) have δ56Fe values close to chondrites (δ56Fe = −0.01 ± 0.01‰). The heavy δ56Fe value (0.52–0.60‰) of serpentines may reflect Fe isotopes exchange with the coexisting pyrrhotite with light δ56Fe. We obtained an equilibrium fractionation factor of Δ56Fesilicate-sulfide ≈ 0.51‰ between reconstructed silicate liquid (δ56Fe ≈ 0.21‰) and sulfide liquid (δ56Fe ≈ −0.30‰), or Δ56Fesilicate-sulfide ≈ 0.36‰ between the weighted mean bulk-silicate minerals (δ56Fe[0.70ol,0.25opx,0.05cpx] = 0.06‰) with weighted mean bulk-sulfide minerals (δ56Fe ≈ −0.30‰). Our study indicates that significant Fe isotope fractionation does take place between silicate and sulfide liquids during the Sudbury-type sulfide mineralization. We hypothesize that significant iron isotope fractionation must have taken place during core–mantle segregation, and the bulk Earth may have lighter Fe isotope composition than chondrites although Fe isotope analysis on experimental sulfide-silicate liquids produced under the varying mantle depth conditions is needed to test our results. We advocate the importance of further research on the subject. Given the close Fe-Ni association in the magmatic mineralization and the majority of the Earth’s Ni is also in the core, we infer that Ni isotope fractionation must also have taken place during the core separation that needs attention.