Platinum-group Element Geochemistry Research Articles

Geochemistry of platinum group elements in the ocean

Geochemistry of platinum group elements in the ocean

Cu-Au-Platinum Group Element Mineralization in the Mbesa Prospect, Southern Tanzania: Unconventional Magmatic Sulfides

Abstract High-grade Cu mineralization was recently discovered in the Mbesa prospect in southern Tanzania, but its origin is poorly constrained. Herein, we present new major element, trace element, rare earth element (REE), and platinum group element (PGE) geochemistry and petrographic data to constrain the origin of the mineralization. The sulfide mineralization is dominated by chalcopyrite and bornite and characterized by high Cu/Ni over 100 in the massive and disseminated ores. The mineralization lacks pyrrhotite and pentlandite, which are found commonly in magmatic Ni-Cu-PGE sulfide deposits. Platinum group minerals present are michenerite (PdBiTe) and sudburyite (PdSb). PGE concentrations expressed as Pd + Pt + Au are up to 1.31 and 1.04 ppm in the massive and disseminated ores, respectively. The δ34S of chalcopyrite separates range from –3.9 to –0.6‰, bornite separates vary from –1.8 to 1.1‰, and bornite-chalcopyrite mixtures yield –1.3 and 0.6‰, mostly consistent with a magmatic sulfur origin. The sulfides are hosted by coarse-grained plagioclase amphibolite and hornblende gneiss with recrystallization textures suggestive of metamorphism. Both rocks are characterized by enrichment in large ion lithophile elements (LILEs), with negative anomalies of Zr and Nb, consistent with crustal contamination of magmas derived from partial melting of subcontinental lithospheric mantle (SCLM). An SCLM origin is further suggested by the close association of Cu sulfides with carbonates and apatite. It is suggested that the sulfides crystallized from the fractionated Cu-rich sulfide melt enriched in intermediate solid solution (iss) at shallow crustal levels. Sulfide were likely mobilized as droplets attached to CO2 vapor phase as expressed by close association between carbonates and apatite with the Cu-rich sulfides. Nickel-rich sulfides may remain undiscovered at deeper portions around the Mbesa prospect.

Major, trace and platinum-group element geochemistry of Mesoarchean komatiites from the Banasandra greenstone belt, Western Dharwar Craton (southern India): implications for multi-stage plume magmatism in generating compositionally diverse komatiites

ABSTRACT The early Archean Al-undepleted komatiites (AUK) from two locations (Kunikenahalli, Kodihalli) of the Banasandra greenstone belt in the Western Dharwar Craton are studied for understanding their petrogenesis. The field distribution, mineralogy and geochemistry indicate their cogenetic nature. The samples are mainly cumulates (MgO: 37–45 wt%), now completely serpentinized, while the spinifex zone is obscure. Using geochemical modelling, the MgO content of the primary undifferentiated magma is estimated to be nearly 25 wt%. The depleted LREE values from this study, and the positive εNd values from previous studies suggest that the komatiites are derived from a depleted mantle source. Trace-element and PGE geochemistry eliminate the possibility of crustal contamination and sulphide-saturation in these komatiites after emplacement. Modelling results estimated in this study suggest ~45% melting of a deeper mantle (~6 GPa) to generate the komatiites. Fractionation of olivine (Fo94) from the parental melt and their accumulation formed the mesocumulates in Kodihalli, and the more fractionated orthocumulates in Kunikenahalli. The compositional spectrum from AUK through Al-depleted (ADK) to Al-enriched (AEK) varieties in the Banasandra greenstone belt reported in this study and others, are proposed to be a product of melting of a single mantle plume at different depths.

Platinum-Group Element Geochemistry of Igneous Rocks in the Chongjiang Cu–Mo–Au Deposit, Southern Tibet: Implications for the Formation of Post-Collisional Porphyry Cu Deposits

Abstract The timing and extent of sulfide saturation have been suggested as controlling factors in the formation of economically significant porphyry Cu deposits in subduction zone settings. However, details on the sulfide saturation history in post-collisional porphyry systems remain ambiguous. Accordingly, we have characterized the whole-rock geochemistry, including platinum-group elements (PGE), of igneous intrusions in the post-collisional Chongjiang porphyry Cu–Mo–Au deposit (southern Tibet) and utilize this data in conjunction with zircon U–Pb geochronological results and sulfide chemistry to assess the timing of sulfide saturation, the nature and amount of magmatic sulfide produced. The Chongjiang intrusions (monzogranite, biotite monzogranite porphyry, granodiorite, dacite porphyry, and quartz diorite porphyry) and mafic microgranular enclaves (MMEs) have zircon U–Pb ages of 14.2 to 12.8 Ma. Covariations in whole-rock major and trace elements among the Chongjiang intrusions and MMEs, together with similarities in their Sr–Nd and zircon Hf isotope compositions, indicate that they are co-magmatic and crystallized from a juvenile lower crustal melt that mixed with mafic melt derived from the lithospheric mantle; this hybrid melt subsequently evolved via fractional crystallization. Trace-element ratios in zircon and temperature − ∆FMQ estimates of the different intrusions suggest that they all crystallized from oxidized (average ∆FMQ = 1.9–2.6) and water-rich magmas. Palladium contents and Pd/Pt ratios in the Chongjiang igneous intrusions increase with decreasing MgO up to 3.9 wt % MgO, after which they abruptly decrease. The initial increase in Pd/Pt ratios likely results from the fractionation of a Pt-rich mineral (e.g. Pt–Fe alloy). The decrease in Pd contents and Pd/Pt ratios at 3.9 wt % MgO likely results from sulfide saturation during magma evolution, but prior to volatile exsolution, which occurred at approximately 1.4 to 2.4 wt % MgO. The presence of magmatic sulfide inclusions in amphibole and magnetite in samples with 3.9 wt % MgO, and the geochemical compositions of sulfide inclusions suggest that they represented trapped sulfide liquid and intermediate solid solution. Results of Monte Carlo simulations demonstrate that 0.003 to 0.009 wt % magmatic sulfide is required to have fractionated from the magma to explain the decrease in Pd contents at 3.9 wt % MgO. Highly chalcophile elements, such as Pd, will be sequestered by the magmatic sulfide that saturates at depth, decreasing their concentrations in the residual silicate melt, whereas concentrations of the less chalcophile elements, such as Cu, Mo, and even Au, will not be as significantly affected. Consequently, sufficient concentrations of Cu–Mo–Au will remain in the residual melt and, upon reaching volatile saturation, can be transported by the vapor phase to form porphyry Cu–Mo–Au deposits. In the case of the Chongjiang deposit, sulfide saturation was likely triggered by the high pressures and/or depletion of FeO caused by the thick (~70 km) crust beneath the Gangdese belt. This contribution presents evidence of sulfide saturation in post-collisional magmatic systems, and demonstrates that the amount of magmatic sulfide produced is a critical factor in controlling the formation of post-collisional porphyry Cu deposits.

Contrasting platinum-group element geochemistry of post-collisional porphyry Cu ± Au ore-bearing and barren suites in the central and southeastern Urumieh-Dokhtar magmatic arc, Iran

Contrasting platinum-group element geochemistry of post-collisional porphyry Cu ± Au ore-bearing and barren suites in the central and southeastern Urumieh-Dokhtar magmatic arc, Iran

Origin of Silicate Spherules and Geochemistry of Re and Platinum-Group Elements Within Microfossil-Bearing Archean Chert from the 3.4 Ga Strelley Pool Formation, Western Australia.

Silicate spherules have been identified from the ca. 3.4 Ga-old Strelley Pool Formation (SPF) in the Pilbara Craton, Western Australia. Their origins and geochemical characteristics, including the Re and platinum-group elements of their host clastic layer and the overlying and underlying microfossil-bearing finely laminated carbonaceous cherts, were examined. The spherules have various morphologies (completely spherical to angular), sizes (∼20 to >500 μm), textures (layered, non-layered, and fibrous), mineralogy (various proportions of microcrystalline quartz, sericite, anatase and Fe-oxides), and chemistry (enriched in Ni and/or Cr), commonly with thin anatase-rich walls. Their host clastic layer is characterized by rip-up clasts, suggesting a suddenly occurring high-energy depositional environment, such as tsunamis. Although various origins other than asteroid impact were considered, none could unequivocally explain the features of the spherules. In contrast, non-layered spherical spherules that occur as individual framework grains or collectively comprise angular-shaped rock fragments appear to be more consistent with the asteroid impact origin. The calculated Re-Os age of the cherts (3331 ± 220 Ma) was consistent with the established age of the SPF (3426-3350 Ma), suggesting that the Re-Os system was not significantly disturbed by later metamorphic and weathering events.

Mineralogy and geochemistry of platinum-group elements in the zoned mafic-ultramafic intrusions of the Uralian Platinum belt, Russia

Three styles of platinum-group element mineralization occur within the Ural-Alaskan type complexes of the Uralian Platinum belt: chromite-platinum, noble metal, and noble metal-copper ones. They are associated with dunite and chromitite (chromite-platinum), pyroxenite (noble metal) and gabbro (noble metal-copper). Three common platinum group element distribution patterns are observed for dunite and chromitite: (1) M-shaped (defined by positive Ir and Pt anomalies); (2) with positive Ir-Rh(Pt) anomalies; and (3) W-shaped with positive Os and Pt, or Os and Rh anomalies. In contrast, pyroxenite and gabbro are enriched in Pd and Au. The PGM assemblages correlate to the PGE + Au distribution patterns as exemplified by the predominance of Ir-rich Pt-Fe alloys within dunite and chromitite. The noble metal assemblages of pyroxenite and gabbro comprise tellurides, arsenides, and various Pd minerals, as well as native gold and Au-Ag alloy. An indicative Pd/Ir ratio in a succession dunite-chromitite-gabbro increases from 0.04 to 148 with a maximum value of ~5000 in massive sulfide ore of the Volkovsky that is attributable to the contrasting magma compositions defining chromite vs sulfide controls over PGE concentration.

Mineralogy and PGE geochemistry of chromitites and peridotites of the sapat complex in the indus suture zone, northern Pakistan: implications for magmatic processes in the supra-subduction zone

ABSTRACT The Sapat Complex in Northern Pakistan contains remnants of the northern Neo-Tethys Ocean, presently exposed along the Indus Suture Zone. The mantle peridotites of the Sapat Complex include harzburgites, dunites, and subordinate lherzolites. Harzburgites are the dominant peridotite variety over dunites. The dunites are hosted by harzburgites and occur exclusively as ‘envelopes’ surrounding chromitite pods. The podiform chromitites show disseminated, banded, and massive textures. Chromitites exhibit variable Cr# [Cr/(Cr + Al)] and Mg# [Mg/(Mg + Fe2+)], which range from 0.76 to 0.77, and from 0.64 to 0.66, respectively, while TiO2 contents are <0.2 wt.%. These features perhaps reflect crystallization of the chromian spinel from a boninitic magma. Similarly, chromian spinel in peridotites manifest a wide range of Cr# and Mg#, from 0.49 to 0.83 and 0.41 to 0.57, respectively, and are characterized by very low TiO2 values, averaging at 0.1 wt.%. Chromian spinel of chromitites and peridotites of the Sapat Complex have also very low Fe3+# (<0.01), which indicate their crystallization under low oxygen fugacities. The platinum group elements (PGE) distributions show high (Os + Ir + Ru)/(Rh + Pt + Pd), very low Pd/Ir values, and are defined by a prominently fractionated chondritic normalized PGE pattern, hence, this deposit is a typical example of an ophiolitic chromitite. The studied peridotites are highly depleted in PGE compared to chondritic values. The PdN/IrN values, averaging to 1.5 in dunites are unfractionated, while PGE spidergrams of harzburgites and lherzolites depict minor positive slopes, a minor positive Ru anomaly, and have average PdN/IrN values of 2.3 and 2.4, respectively. Furthermore, the harzburgites, dunites, and lherzolites display generally flat chondritic and primitive mantle normalized PGE patterns, and therefore, are nearly identical to highly depleted mantle peridotites. The mineralogical and PGE geochemical imprints of Sapat Complex chromitites and peridotites establish a strong affinity to supra-subduction zone ophiolites. Moreover, calculated parental melts of the chromitites and various geochemical discrimination diagrams elucidate that the chromitites were derived from boninitic magma produced by melting of depleted mantle peridotites in an oceanic arc, characterized by low oxygen fugacity, similar to a supra-subduction zone tectonic setting. This research highlights the use of mineralogy and geochemical compositions of chromitites and peridotites to reveal deep magmatic processes in a supra-subduction zone environment.

Major, trace and platinum-group element geochemistry of harzburgites and chromitites from Fuchuan, China, and its geological significance

Abstract The Fuchuan ophiolite, one of the oldest ophiolites in southern China, is located in the northeasternmost segment of the Jiangnan Orogen. It mainly consists of harzburgites, with minor dunites, pyroxenites and gabbro veins. To investigate the origin of the Fuchuan ophiolite and its related chromite ore deposit, bulk-rock major and minor element and platinum-group element (PGE) studies have been carried out. Major and trace element analyses show dual features of mid-ocean ridge basalt (MORB) and supra-subducted zone (SSZ) peridotites and high degrees of partial melting. The chondrite-normalized rare earth element (REE) patterns of the Fuchuan harzburgites are “U” shaped, reflecting the influence of light REE-enriched subducted melts or fluids. The Fuchuan chromitites originate from MORB-like melts and are enriched in IPGE and depleted in PPGE, which are basically consistent with high-Al chromitites worldwide, and the low PGE concentrations of chromitites reflect a lack of sulfur saturation of the parental melts during an early stage of their crystallization. Combining with the tectonic setting of the Jiangnan Orogen, we suggest that the Fuchuan peridotites and chromitites are believed to be formed in a back-arc spreading ridge between the Yangtze and Cathaysia blocks during 860–820 Ma.

Role of magma differentiation depth in controlling the Au grade of giant porphyry deposits

Porphyry deposits are the world's most important source of Cu and a major source of Au. It has been recognized that low Au grades generally characterize porphyry deposits in thick continental arcs, like the Andes, where the magmas are likely to differentiate at depth. In contrast, Au-rich porphyries are mainly found in thin island arcs, for example, those of the southwest Pacific, or associated with short extensional periods in continental arcs, where the magmas are likely to experience relatively shallow differentiation. However, the key factors that control this difference remain debated. This study shows that the Au grade of giant porphyry deposits and La/Yb ratios of the ore-associated suites are negatively correlated (r=∼0.7, p=10−7). We attribute the negative correlation to be mainly due to varying sulfide saturation histories, modulated by the depth of magma differentiation.Magmas differentiating in deep crustal reservoirs are likely to reach sulfide saturation early due to high pressure and early depletion of FeO (calc-alkaline trend). Early sulfide saturation causes most Au to be held in cumulus sulfides, making it unavailable to enter ore-forming fluid released in the upper crust, resulting in Au-poor porphyry systems. In contrast, magmas evolving in shallow reservoirs are likely to experience late sulfide saturation because of the high sulfur solubility induced by low pressure and the high FeO content of the melts (tholeiitic trend). Late sulfide saturation enhances the potential of a magmatic system to form Au-rich porphyry deposits due to the high Au content of the magma at voluminous fluid saturation and efficient Au transfer from melt to the ore-forming fluids via sulfide-fluid interaction. The link between average magma differentiation depth and Au content is supported by platinum-group element geochemistry of the porphyry ore-forming suites, which shows that the magmas differentiating at shallower depths (lower La/Yb) reach sulfide saturation later and therefore have higher Au concentrations than those that differentiate at deeper levels (higher La/Yb). Numerical models for ore-associated magmas with different sulfide saturation histories indicate that variations in the Au grades of giant porphyry deposits can be explained by the variations in the timing of sulfide saturation. Based on the results, we propose that Au concentration in the magma, modulated by average magma differentiation depth and sulfide saturation history, is one of the critical factors controlling the Au grade of giant porphyry Cu deposits.

Platinum-group element geochemistry of the Panjal Traps: constraints on mantle melting and implications for mineral exploration

Abstract Forty-two volcanic rocks of the Panjal Traps were analysed for platinum-group elements (PGEs) to investigate the magma genesis, high-temperature behaviour and exploration potential of these elements. The PGE data exhibit substantial variability and show no systematic relation to their low- or high-Ti affinity. Instead, the basalts can be subdivided into a PGE-undepleted group (group 1) that has ΣPGE &gt;10 ppb and Cu/Pd &lt;30 000, and a PGE-depleted group, which consists of a subgroup showing limited (group 2A) or substantial depletion in Ir-series PGEs relative to Ni (group 2B). The group 1 samples indicate an S-undersaturated history, whereas the group 2 samples might have different origins in terms of S-saturation. Fractionation of a tiny amount of sulfide melts (0.075–0.1%) from a representative group 1 sample accounts for the chalcophile element patterns observed in the group 2B samples. The relatively high Cu/Pd, unfractionated Ni/Ir and low PGE abundances observed in the group 2A samples cannot be explained by equilibration of an immiscible sulfide melt alone, and probably require decomposition of residual sulfides into sulfide melt and a monosulfide solid solution in the mantle restite. Our results question the notion that the coexistence of PGE-undepleted and -depleted magmas is prospective in the exploration of magmatic Ni–Cu–(PGE) sulfide mineralization.

Reply to the comment on Zafar et al., 2020: “Petrogenesis, platinum-group element geochemistry and geodynamic evolution of Cretaceous Chilas gabbros, Kohistan island arc, NE Pakistan” by Hussain et al., 2021

Reply to the comment on Zafar et al., 2020: “Petrogenesis, platinum-group element geochemistry and geodynamic evolution of Cretaceous Chilas gabbros, Kohistan island arc, NE Pakistan” by Hussain et al., 2021

Geochemistry of platinum-group elements in the podiform chromitites and associated peridotites of the Nain ophiolites, Central Iran: Implications for geotectonic setting

Geochemistry of platinum-group elements in the podiform chromitites and associated peridotites of the Nain ophiolites, Central Iran: Implications for geotectonic setting

Platinum mineralization and geochemistry of the Matysken zoned Ural-Alaskan type complex and related placer (Far East Russia)

Ural-Alaskan type complexes are the sources for unique placer platinum deposits and contain platinum-group minerals (PGM) within lodes. Such complexes occur along modern and ancient convergent tectonic margins and are comprised of dunite, wehrlite, clinopyroxenite and gabbro, which gradually interchange towards the marginal parts of the complex. In-situ PGM are largely restricted to chromitites, which are comprised of small veinlets and schlieren of chromian spinel in the dunite unit. PGM mineralization in chromitites can be extremely rich; however, their distribution is very sporadic, without any apparent regularity. Moreover, the role of accessory chromian spinel and post-magmatic overprinting of platinum group element (PGE) concentrations is poorly defined. Detailed studies of PGM assemblages, including those in chromitites, serpentine veinlets in dunites, and wehrlites, combined with PGE geochemistry could provide insights into the distribution and processes responsible for PGE accumulation.The Matysken complex in the Koryak Highlands (Far East Russia) is comprised of dunite, wehrlite, clinopyroxenite and gabbro units, and has a classic zoned structure, rendering it an excellent example of an Ural-Alaskan type complex, ideal for this case study. This locality contains mm-scale isoferroplatinum (Pt3Fe) nuggets that cement chromitites and occur as µm-scale euhedral inclusions in chromian spinel. Placer PGM assemblages in the nearby Matysken River consist of exactly the same assemblages of minerals that are found in dunites and chromitites but with larger compositional scatter, reflecting a complex history of alluvium accumulation, which was sourced from different eroded parts of the complex. Detailed textural investigations discovered a diverse array of hydrous silicate–related mineralization, including euhedral isoferroplatinum grains in chlorite matrix, isoferroplatinum–amphibole intergrowths, and a wide range of PGE, Fe and Cu alloys, sulfarsenides and antimonides, which formed in serpentine veinlets together with awaruite (Ni3Fe) and base metal sulfides. This provides further evidence that isoferroplatinum, which is widely accepted to be a magmatic mineral, may form under a wide range of conditions, including during serpentinization.Dunites have fractioned primitive mantle-normalized PGE patterns, typical of Ural-Alaskan type complexes, with strong enrichments in Pt and depletions in Ir, Ru and Pd. PGE, with an exception of Pd, are quite uniformly distributed in dunite containing accessory chromian spinel, with good correlations between PGE and Cr. This correlation, together with data from previous studies, allowed us to calculate the concentration of Pt in accessory chromian spinel (probably hosted as minute PGM inclusions), which is of the same grade as for chromitites (ppm levels). This suggests that the formation of chromitites does not concentrate PGE over Cr, but only assembles them into larger aggregates, causing the observed unevenness in the PGM distribution.

Geochemistry of Platinum-Group Elements (PGE) in Cerro Matoso and Planeta Rica Ni-Laterite deposits, Northern Colombia

Platinum-group elements (PGE) are included among the so-called critical metals, and are essential metals for the technological industry. However, there are very few deposits in the world from which these metals can be extracted. The present work investigates three Ni-laterite profiles (hydrous Mg silicate type) formed over the ultramafic rocks of Cerro Matoso and Planeta Rica in Colombia. The main goal is to determine their PGE concentration and distribution, as well as to identify the carrier phases of these noble metals. The highest PGE contents in Cerro Matoso and Planeta Rica are concentrated in the limonite horizon (141–272 ppb), showing a strong decrease towards the saprolite and the underlying serpentinized peridotite (parent rock; &lt; 50 ppb). The highest concentrations correspond to Pt&gt;Ru&gt;Pd and the lowest to Rh&lt;Os&lt;Ir. Such distribution indicates that PGE are mobilized in different proportions by the laterization processes. The high affinity between PGE and Fe favors the formation of PGE-Fe mineral alloys such as the Pt-Ir-Fe-Ni minerals hosted by Fe-oxyhydroxide found in the limonite–saprolite transition zone in Planeta Rica. In addition, in the same zone, nanoparticles of Pt (&lt; 1 µm) were found within framboidal pyrite. Both types of platinum group minerals (PGM) are secondary in origin. In the case of Pt-Ir-Fe-Ni alloys, this interpretation is supported by their morphology and chemical composition, which is comparable with PGE-Fe-Ni alloys found in laterites of Dominican Republic. In the case of Pt nanoparticle, textural relations suggest the neoformation of PGM adhered to the porous edges of altered pyrite. Cerro Matoso and Planeta Rica should be considered as unconventional PGE deposits, if adequate recovery processes can be applied for their recovery as by-products during Ni (+Co) production.

A machine learning approach for regional geochemical data: Platinum-group element geochemistry vs geodynamic settings of the North Atlantic Igneous Province

Whilst traditional approaches to geochemistry provide valuable insights into magmatic processes such as melting and element fractionation, by considering entire regional data sets on an objective basis using machine learning algorithms (MLAs), we can highlight new facets within the broader data structure and significantly enhance previous geochemical interpretations. The platinum-group element (PGE) budget of lavas in the North Atlantic Igneous Province (NAIP) has been shown to vary systematically according to age, geographic location and geodynamic environment. Given the large multi-element geochemical data set available for the region, MLAs were employed to explore the magmatic controls on these shifting concentrations. The key advantage of using machine learning in analysis is its ability to cluster samples across multi-dimensional (i.e., multi-element) space. The NAIP data set is manipulated using Principal Component Analysis (PCA) and t-Distributed Stochastic Neighbour Embedding (t-SNE) techniques to increase separability in the data alongside clustering using the k-means MLA. The new multi-element classification is compared to the original geographic classification to assess the performance of both approaches. The workflow provides a means for creating an objective high-dimensional investigation on a geochemical data set and particularly enhances the identification of metallogenic anomalies across the region. The techniques used highlight three distinct multi-element end-members which successfully capture the variability of the majority of elements included as input variables. These end-members are seen to fluctuate in prominence throughout the NAIP, which we propose reflects the changing geodynamic environment and melting source. Crucially, the variability of Pt and Pd are not reflected in MLA-based clustering trends, suggesting that they vary independently through controls not readily demonstrated by the NAIP major or trace element data structure (i.e., other proxies for magmatic differentiation). This data science approach thus highlights that PGE (here signalled by Pt/Pd ratio) may be used to identify otherwise localised or cryptic geochemical inputs from the subcontinental lithospheric mantle (SCLM) during the ascent of plume-derived magma, and thereby impact upon the resulting metallogenic basket.

Petrogenesis, platinum-group element geochemistry and geodynamic evolution of the Cretaceous Chilas gabbros, Kohistan island arc, NE Pakistan

Kohistan, an intra-oceanic arc, formed due to the India-Asia collision-related tectonics. The arc is comprised of mafic-ultramafic and crustal lithologies. Chilas Complex, one of the major mafic-ultramafic body that lies at the base of the Kohistan arc, is dominantly composed of massive gabbronorites with local ultramafic-mafic intrusive bodies. The ultramafic rocks were considered as the products of fractional crystallization whereas gabbronorites were reported to have formed at the root zone of the magma chamber either from melts or due to fractional crystallization, based on major and trace element data. To understand the petrogenesis and origin of the Chilas gabbros, we conducted platinum group elements (PGEs) geochemistry combined with whole-rock major and trace element compositions. Geochemical data of the Chilas gabbros show tholeiite series, likely derived from a depleted lithospheric mantle source via peridotite melts. Presence of hornblende and relatively higher Al/Ti ratios of clinopyroxene in the Chilas gabbros suggest hydrous magma, ascribed to mantle wedge metasomatism by slab-derived fluids. Poor correlations between MgO vs. Ni, Cr, and V, Ni vs. Cr, Dy/Yb vs. SiO2, Sr/Y vs. Eu/Eu* and relatively low TiO2 indicate a minimal role of fractional crystallization. Low contents of LOI (0–3.24 wt%), Ce/Ce* (0.92–1.01), and positive relation of La, Ta, and Hf with Zr strongly support the insignificant impact of hydrothermal alteration. Enrichment of PGEs, such as Pt (0.63–13.75 ppb), Pd (0.43–13.87 ppb), and lower Pd/Ir ratios (0.76–40.04) suggest low degree partial melting of the parent magma. Higher Pd, Pd/Ir ratios compared to Pt and Pt/Pd, combined with enrichment of PPGE over IPGE, suggest the participation of slab-dehydrated fluids and mantle metasomatism however Cu/Ir vs. Ni/Pd, V-Pd/Ir and La-Pd/Ir ratios point towards olivine fractionation in the magma. Lower Cu/Pd ratios, relationships of Ru and Pt against Cr, and Os diminution corroborate S-undersaturation in parental magma. The PGEs contents and Pd/Pt ratios attest depleted mantle source for their production. In view of Cu/Zr and Cu/Pd ratios, it is substantiated that the sulphide segregation cannot be a promising reason for PGEs depletion. Therefore, we infer PGEs depletions in parental magma are due to PGEs-depleted mantle source, though sulfide retention in mantle source cannot be eliminated. The geochemical fingerprints in tectonic diagrams and negative anomalies of Nb and Zr in the studied samples provide credible facts that favour arc magmatism. Based on major and trace element data and PGEs values, we consider that the Chilas gabbros were formed from a lithospheric mantle that was metasomatized by fluids generated at the mantle wedge and derived from mafic melts in an arc setting. Geochemical data and their plotting on various tectonic discrimination diagrams indicate Chilas Complex as a remnant of the Neo-Tethyan oceanic arc system.

Platinum-group element geochemistry of the volcanic rocks associated with the Jaguar and Bentley Cu–Zn volcanogenic massive sulfide (VMS) deposits, Western Australia: implications for the role of chalcophile element fertility on VMS mineralization

We report whole-rock major, trace, and platinum-group element (PGE) geochemistry of volcanic rocks from the Teutonic Bore complex that hosts the Jaguar and Bentley Cu–Zn volcanogenic massive sulfide (VMS) deposits. This study aims to understand their sulfide saturation history and chalcophile element evolution during differentiation of the Jaguar and Bentley magmas, and investigate the role of chalcophile element fertility on the formation of VMS deposits. The fractionated primitive mantle–normalized trace element patterns, with negative Nb and Ti anomalies of basalts, andesites, dacites, and rhyolites from Jaguar and Bentley, are similar to each other. The trace elements and PGE show continuous variations when plotted against fractionation indices such as Yb, which can be explained by a two-stage fractional crystallization model: stage 1 Rayleigh fractionation of plagioclase + clinopyroxene + Cr-spinel, and stage 2 the fractional of plagioclase + clinopyroxene + magnetite + 0.1 wt% sulfide liquid. Dolerites, which postdate the mineralization, differ from the other rock types and require a different magma source. Andesite and basalt are the most PGE-enriched lithologies in Jaguar and Bentley. The PGE behave incompatibly in the early stage of magma differentiation at < 4 ppm Yb, whereas they abruptly decrease at > 4 ppm Yb, indicating sulfide saturation at this point. When Pd/MgO and Pd/Pt are used as chalcophile element fertility indicators, the andesite before sulfide saturation (< 4 ppm Yb) is as fertile as the magmas associated with porphyry Cu-only deposits. In contrast, the andesite after sulfide saturation and other lithologies are characterized by markedly depleted fertility similar to those of barren suites. This suggests that sulfide-undersaturated andesite, and probably basalt, may have been a significant source for Cu in the Jaguar and Bentley Cu–Zn VMS deposits. However, the Au fertility of the Jaguar and Bentley andesite must have been low and not enough to form Au-rich VMS deposits because their Pd/MgO and Pd/Pt values are 5–10 times lower than those of andesite and dacite from the modern Au-rich seafloor massive sulfide deposits. This can be explained if ore formation occurred shortly after sulfide saturation. If the amount of sulfide melt to precipitate was small, Au, with its high partition coefficient into immiscible sulfide melts, would have been largely stripped from the silicate melt, whereas Cu, with its lower partition coefficient, would be little affected. Our study shows that chalcophile element fertility may play an important role in the formation of VMS deposits, especially in controlling the Au contents of the ore, if the magmatic-hydrothermal component is the dominant source for metals in VMS systems.

The role of early sulfide saturation in the formation of the Yulong porphyry Cu-Mo deposit: Evidence from mineralogy of sulfide melt inclusions and platinum-group element geochemistry

Sulfide melt inclusions enclosed in silicate minerals have been observed in many oxidized Cu-bearing porphyries. The origin of such sulfide melt inclusions could bear critical information of metal enrichment or depletion during magma evolution of porphyry systems. The giant Yulong porphyry Cu-Mo deposit in eastern Tibetan Plateau consists of a series of felsic intrusions, among which the mineralized Yulong intrusion emplaced at a late stage of the magmatic activity. This study reports detailed texture and composition of sulfide melt inclusions from barren and mineralized intrusions, as well as platinum-group elements of these intrusions, to evaluate potential role of early sulfide saturation in the porphyry mineralization system. These sulfide melt inclusions, occurring as globules or droplets, are preserved in zircon, amphibole and quartz grains. Most of them are composed of a major phase of pyrrhotite and minor pyrite, chalcopyrite and pentlandite. Smooth boundaries between these phases suggest the origin of fractionation from sulfide melt upon cooling. Small amounts of Cu and Ni are heterogeneously distributed in the pyrrhotite. The sulfide melt inclusions could be observed in both the pre- and syn-mineralization intrusions at Yulong, indicating that sulfide saturation had commonly occurred during magma evolution. Magnetite mineral inclusions could be observed in zircon and amphibole grains as well. The mineral assemblage of magnetite + pyrrhotite + pyrite of the mineral inclusions constrains the Yulong magmatic system to redox conditions near the magnetite-pyrite/pyrrhotite buffer and above the fayalite/ magnetite-quartz buffer (FMQ). High Eu/Eu* values (0.56–0.78) of the hosting zircons and high calculated ΔNNO values (>0.5) of the hosting amphibole indicate highly oxidized nature of the parental magma.Both pre- and syn-mineralization intrusions have low PGE contents (Pt = 0.04 to 0.17 ppb, Pd = 0.19–0.60 ppb) with compositions plotting in the Au-poor porphyry Cu fields in discriminating diagrams. Early sulfide saturation may have been reached and small amounts of sulfides have been segregated from magma. Most PGEs and Au but little Cu have been removed from the evolved magma because the partition coefficient of Cu between sulfide and silicate melt is about two orders of magnitude lower than PGE or Au. As a consequence, the evolved magma would have high Cu but very low PGE and Au, resulting in the Au-poor porphyry Cu mineralization at Yulong.

Mineralogy and geochemistry of peridotites and chromitites in the Jijal Complex ophiolite along the Main Mantle Thrust (MMT or Indus Suture Zone) North Pakistan

The Jijal Complex, one of the largest Neo-Tethyan ophiolites (ca. 150 km2) in Pakistan, occupies a deep-level section of the Cretaceous Kohistan Arc that was obducted along the Main Mantle Thrust or Indus Suture Zone. Peridotites of the Jijal Complex consist mainly of harzburgite and dunite with numerous podiform chromitites. In this paper, we present new mineral compositions, whole-rock major elements, trace elements, rare earth elements (REEs) and platinum group elements (PGEs) to evaluate the melt evolution and petrogenesis of these rocks. Chromian spinel in the chromitites is fairly uniform in composition with Cr#s ranging from 75 to 81, Mg#s from 59 to 63 and TiO2 < 0.2 wt%, which suggest crystallization from boninitic magmas. Chromian spinel in the peridotites has relatively lower Cr#s of 71–74, Mg#s of 38–48 and very low TiO2 contents (averaging 0.09 wt%). The Fe3+#s of chromian spinels both in the chromitites and peridotites are very low (maximum 0.02), reflecting crystallization under low oxygen fugacity (fO2). The harzburgites and dunites have low average CaO, Al2O3 and REE values and contain Al-poor clinopyroxene and high-Cr spinels. Mantle-normalized trace element patterns of the harzburgite, dunites and chromitites reflect high-degrees of partial melting (25%–30%). The high-Cr chromitites all show similar chondrite-normalized platinum group element patterns characterized by enrichment in Os, Ir, Ru and Rh relative to Pt and Pd. The mineral chemistry, whole-rock compositions and PGE geochemistry indicate that the chromitites in the Jijal Complex were generated from a boninitic parental magma generated under low to high fO2 in a supra-subduction zone environment. The calculated compositions of the parental melts of the Jijal chromitites are consistent with differentiation of arc-related magmas.