Platinum-group Element Geochemistry Research Articles

Metallogenic model of the Jinchang Au-Ni deposit in the Ailaoshan belt, SW China, determined on the basis of pyrite trace element contents, in-situ sulfur isotope composition and PGE geochemistry

The Ailaoshan metallogenic belt in southwestern China contains numerous shear zone-related Au deposits with Au reserves greater than 200 tonnes. However, the source of ore-forming fluids and metals is controversial, hampering the construction of genetic models. In this study, we selected the Jinchang Au-Ni deposit in the northern segment of the Ailaoshan belt for detailed investigation of pyrite chemistry and in-situ sulfur isotope compositions using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The petrographic and pyrite chemistry analyses revealed four types of hydrothermal pyrite. Py1 pyrite is euhedral to subhedral and has in-situ sulfur isotope (δ34S) values of −5.30 to 6.26‰ (median: −2.93‰) and low concentrations of Au, Ni, As, Sb, Cu, Zn, Pb, and Ag. Py1 is interpreted to have formed during the early hydrothermal stage. Py2 pyrite is subhedral to anhedral and porous with variable size. Although Py2 and Py3 show different textural relationships, we conclude that both of them formed during the intermediate hydrothermal stage as evidenced by similar sulfur isotope compositions and trace element contents, and common intergrowth textures. Py2 and Py3 pyrite have in-situ δ34S values ranging from −11.6 to 1.29‰ (median: −4.45‰) and relatively elevated concentrations of Au, Ni, As, Sb, Cu, Zn, Pb, and Ag. In Py2 and Py3 pyrite, Ni concentrations correlate with Co concentration, whereas Au exhibits moderate positive correlations with Ni, Co, and As, indicating that Au, Ni and other metals were predominantly sourced from the Jinchang ultramafic rocks. Py4 pyrite is euhedral in shape and has relatively low in-situ δ34S values of −23.5 to −4.34‰ (median: −8.33‰). The metal concentrations in Py4 pyrite are lower than those in Py2 and Py3 pyrite. In general, the metal concentrations in the different pyrite populations display systematic changes, with low levels in Py1, higher levels in Py2 andPy3, and low levels again in Py4.The average total platinum-group element (PGE) concentration of the Jinchang Ni-bearing ultramafic rocks is 26.3 ppb, similar to the average value of the primitive mantle of 22.0 ppb. The Au-Ni ores from the Jinchang deposit have an average Pd/Pt ratio of 5.98, similar to that of hydrothermal Ni ores but higher than that of typical magmatic Ni ores. In contrast, the Jinchang ultramafic rocks have low Pd/Pt ratios between 0.57 and 1.13, suggesting that the PGEs in the Jinchang intrusion are of magmatic origin. Similarly, the Rh/Ir ratios of Au-Ni ores are consistent with those of hydrothermal Ni ores but differ from those of magmatic Ni ores.The pyrite chemistry, in-situ sulfur isotope compositions, and PGE geochemistry suggest that the ore-forming fluids and metals associated with the Jinchang Au-Ni deposit were dominantly derived from the Jinchang ultramafic intrusion. Mesozoic felsic magmatism or Cenozoic regional strike-slip activity may have triggered migration of the ore-forming fluids, leaching of metals from the Jinchang intrusion and precipitation of these metals at the boundary between the intrusions and carbonaceous rocks.

Geochemistry of Platinum Group Elements of the Late Permian Kaixinling Coal from North Qiangtang Basin, Tibetan Plateau: Implications for Modes of Occurrence and Origins

The Kaixinling coal is located in the eastern part of the North Qiangtang Basin, which were the important coal resources in Tibetan Plateau. A total of thirty coal samples were collected from the Kaixinling area to determine the concentrations, distribution patterns, occurrences and origins of platinum group elements (PGEs) in the Permian coal. The total contents of PGEs are low ranging from 0.56 to 1.89 ng/g with a weighed mean value of 1.21 ng/g. The contents in Os exhibit considerably positive anomaly compare to the Upper Continental Crust and the ordinary Chinese coal. The individual PGEs in coal samples from the Kaixinling area exhibit various modes of occurrence. Pd and Pt are mainly concentrated in clay minerals and P-bearing minerals. Ir is probably present in clay minerals and partly controlled by other Fe-bearing and P-bearing minerals. Os is associated with organic matter and partly related to calcite. Three possible origins of PGEs were identified in coal seams in the Kaixinling area. Pd, Pt and Ir are mainly terrigenous inputs. Rh and Ru are derived from mixed sources (seawater and terrigenous supply), while Os is mainly derived from seawater.

Platinum group element geochemistry and whole‐rock systematics of the Vempalle sills, Cuddapah Basin, India: Implications on sulphur saturation history, mantle processes, and tectonic setting

The intracratonic Cuddapah Basin of southern peninsular India has multiple phases of magmatism exposed as mafic intrusives and extrusives in the Vempalle and Tadpatri formations. We report platinum group element geochemistry along with whole‐rock systematics of the mafic sills from the Vempalle Formation to understand their sulphur saturation history, source characteristics, and tectonic setting. These sills are medium‐ to fine‐grained dolerites with plagioclase and pyroxenes as essential minerals exhibiting sub‐ophitic to intergranular texture. Geochemically, they are characterized by moderate MgO (6.3–8.5 wt.%), Ni (55–105 ppm), Cr (20–130 ppm), and ∑PGE (22–61 ppb) contents and exhibit transitional to calc‐alkaline in nature. Primitive mantle‐ and chondrite‐normalized trace and rare earth element patterns display relative enrichment of LILE–LREE over HFSE, suggesting plume‐related intraplate magmatism with contributions from subcontinental lithospheric mantle (SCLM), lithosphere–asthenosphere interaction, crustal contamination, and fractional crystallization. Their REE relationship indicates the generation of parent magma from a heterogeneous source marked by 10–25% polybaric partial melting within spinel and garnet lherzolite domain. Platinum group elements (PGE) geochemistry reveals their sulphur‐undersaturated nature, and sulphide fractionation played a key role in the distribution of PGEs, which is evidenced by their enriched character, moderate degrees of partial melting, and crustal contamination. Further, the negative platinum anomalies in these sills indicate its removal during fractional crystallization, and the enrichment of Pd over Pt endorses the decoupling nature of these elements prior to their emplacement. Diagnostic trace element signatures and their relationship corroborate a riftogenic intraplate tectonic regime for the emplacement of the Vempalle sills through an ocean–continent transition zone.

Platinum-Group Element Geochemistry of the Escondida Igneous Suites, Northern Chile: Implications for Ore Formation

Platinum-group element (PGE) geochemistry may be used to constrain the timing of sulfide saturation in magmas, which influences the Cu and Au fertility of evolving magmatic systems. We report new geochronological and geochemical data, with emphasis on PGE geochemistry, for a suite of regional porphyritic hornblende–diorite intrusions and ore-bearing porphyries from the super-giant Escondida and smaller Zaldivar Cu deposits of Northern Chile. The regional dioritic intrusions have zircon U–Pb ages between 39·6 to 37·1 Ma, which overlap with the ages of the ore-bearing Escondida and Zaldivar porphyries (38·1 to 35·0 Ma). Whole-rock major and trace element, and Sr–Nd–Pb and zircon O–Hf isotope geochemistry indicate that the regional diorites and ore-bearing porphyries are co-magmatic and originated from the same mantle-derived magma by fractional crystallization, with minor contamination by Paleozoic crust (∼10%). The low concentrations of PGE in the regional diorites show that they reached sulfide saturation before the MgO content of the melt fell to 4·7 wt %, the MgO content of the most primitive sample analysed. The fraction of sulfide melt which separated from the melts that formed the regional diorites is estimated to be ∼0·12 wt %; this resulted in the partitioning of highly chalcophile elements (Au and PGE) into a sulfide phase that was retained in cumulus rocks at depth. However, the fraction of sulfide melt was too low to have a significant effect on the Cu content of the fractionating melt. As a consequence, when the evolving melt eventually reached volatile saturation, it contained enough Cu (40 ± 10 ppm) to form a super-giant Cu deposit. In contrast, Au was largely stripped from the melt by sulfide precipitation, with the result that the mineralization at Escondida is Cu dominant, with only minor Au. The Zaldivar deposit, on the other hand, contains even less Au, which is attributed to a longer fractionation interval between sulfide and volatile saturation. This study provides evidence to support previously proposed models which suggest that the timing of sulfide saturation, the amount of sulfide melt produced, the water content and oxidation state of the melt, and the magma volume are critical factors in determining the potential to form a porphyry Cu deposit. Plots of Pd/MgO against Y can be used as empirical indicators of magma fertility for porphyry mineralization, and to discriminate between Cu–Au and Cu-dominated systems, but cannot predict the size of the deposit. The super-giant status of the Escondida deposit is attributed to it being underlain by a large batholith with a calculated minimum mass of 10 12 tonnes (∼400 km 3 ).

Platinum-group element geochemistry of boninite-derived Mesoarchean chromitites and ultramafic-mafic cumulate rocks from the Sukinda Massif (Orissa, India)

The Mesoarchean Sukinda Massif in the Singhbhum craton is the largest chromite ore deposit in India that contains ≈95% of Indian Cr resources. The Sukinda Massif consists of an elongated layered ultramafic unit (≈25 km × 400 m) that occurs within the 3.5 Ga supracrustal sequences of the Tomka-Daitari-Mahagiri greenstone belt in eastern India. The ultramafic unit comprises serpentinized dunite, orthopyroxenite and chromitite. There are six chromitite seams which are present within the serpentinized dunite. All ultramafic rocks are extensively weathered and capped by laterites (≈30 m thick). In the southwestern part of the Sukinda Massif, in the Katpal area, chromitite seams and the host ultramafic rocks are fragmented, forming breccias cemented by the gabbroic to granodioritic rocks. Whole-rock major, trace and platinum-group elements (PGE) geochemistry indicates that the ultramafic unit and the gabbro, including the cementing matrix materials of the breccias, are cogenetic. The ultramafic rocks formed by fractional crystallization of a parental boninitic or high-Mg siliceous magma. The cementing gabbroic rocks formed from an evolved boninitic magma generated from fractionated boninite or high-Mg siliceous basalt. The positive correlation between MgO and Ni, and MgO and Cr is due to fractionation of early cumulus like olivine and chromite from the high-Mg parental magma. The correlation between Zr and Cu suggests that the parental boninitic magma was S-undersaturated. However, the matrix gabbro shows a flatter trend with increasing Zr and Cu, indicating sulfide saturation occurred later in the evolved boninitic magma. In Sukinda, the concentrations of PGE in the massive chromitites (≈176–875 ppb) from the main ultramafic unit and in chromitite fragments (≈61–279 ppb) from the breccias are higher than in serpentinite (≈19–71 ppb), orthopyroxenite (≈14–19 ppb) and gabbro (≈3–11 ppb). Three samples of the massive chromitites from the main ultramafic unit have significant PGE concentrations (PGEtotal ≈ 651–875 ppb) with IPGE (Ir, Os, Ru) ≈ 528–634 ppb, much higher than PPGE (Pd, Pt, Rh) ≈ 93–332 ppb. Detailed PGE mineralogical studies of these samples revealed presence of IPGE-bearing platinum-group minerals (PGM) dominated by Os-Ir-Ru alloys (containing minor Pt) enclosed in chromite grains. Other PGMs are laurite present as composite grain within chromite plus irarsite which are associated with cracks in chromite grains and a small sperrylite grain attached to an Os-Ir-Ru alloy. All the As-bearing PGM are associated with cracks in the chromite suggesting introduction of As during alteration of primary PGM to PGM-arsenides. The positive correlation between IPGE (Os, Ir, Ru) and MgO or Cr indicates they are fractionated during the early stage of magmatic differentiation from a S-undersaturated boninitic magma.The low Ir of the silicate rocks indicate prior removal of Ir-bearing alloys from the parental boninitic magma which would account for the occurrence of Os-Ir-Ru alloys in massive chromitites. The results suggest that Os-Ir-Ru alloys from the Sukinda chromitites crystallized at relatively high temperature and low fS2 condition within a S-undersaturated boninitic magma ascending from the upper mantle where they entrapped by the growing chromite crystals. Overall, the initial PGE analysis from the Sukinda breccias, presented herein, indicate similarities with the Nuasahi breccias in the Singhbhum craton, and highlight the potential for mineralization in this area.

Chalcophile element fertility and the formation of porphyry Cu \xb1 Au deposits

Chalcophile element fertility, the chalcophile metal abundance in the source magma, is likely to be a critical factor for the formation of porphyry Cu ± Au deposits. In this study, we provide evidence to support this hypothesis by comparing the platinum group element (PGE) geochemistry of barren and ore-bearing Cu ± Au granitic suites. We report the PGE contents of three barren volcanic and subvolcanic suites from Argentina and Japan and two Cu ± Au bearing suites from Indonesia and Chile. These results are compared with those from previous studies of a porphyry Cu-only subvolcanic suite from Chile and three porphyry Cu-Au-bearing suites from Australia and the USA. The barren suites are depleted in PGE abundances by the time of fluid exsolution (< 0.1 ppb Pd and Pd/Pt < ~ 3), which is attributed to early sulfide saturation in a mid to lower crustal magma chamber. In contrast, the Cu ± Au ore-bearing suites contain at least an order of magnitude higher PGE contents than the barren ones at fluid saturation (up to ~ 10 ppb Pd and Pd/Pt of 0.1–40). They are characterized by late sulfide saturation, which allows both chalcophile elements and sulfur to concentrate by fractional crystallization before volatile saturation. We suggest that plots of Pd/MgO against Pd/Pt for igneous suites can be used to estimate chalcophile element fertility and distinguish between barren, porphyry Cu, and porphyry Cu-Au granitoid systems. The positive correlation of these chalcophile element fertility indicators and ore grades suggests that metal contents in magmas play an important role in controlling ore grade, particularly Au, in porphyry Cu ± Au deposits.

Platinum-group elements, zircon Hf-O isotopes, and mineralogical constraints on magmatic evolution of the Pulang porphyry Cu-Au system, SW China

A new model of porphyry Cu system, which involves pre-enrichment of Cu through sulfide accumulation near the mantle-crust boundary, has been recently proposed to account for variations of Cu endowment in different magmatic arcs. To test this model and explore the possible controlling factors of porphyry Cu metallogeny, we studied the mineralogy and platinum-group elements (PGE) geochemistry of the giant Pulang porphyry Cu-Au system in the Sanjiang Region, SW China. The Late Triassic Pulang intrusive complex comprises five phase of porphyrtic stocks and dikes (ca. 217–212 Ma), which intruded a slightly older (ca. 230–218 Ma) volcanic-sedimentary sequence of the Tumugou Formation. Both the intrusive complex and the related volcanic wall rocks have similar PGE concentrations, Pd/Pt ratios and primitive mantle-normalized PGE patterns, indicating that no discernible sulfide cumulates were lost or gained during magmatic differentiation. The variation in PGE concentrations between different types of rocks at Pulang is probably ascribed to magma mixing between mafic and felsic end-members.Two types of amphibole, i.e., high-Al (Al2O3 = 9.4–11.8 wt%) and low-Al (5.9–7.3 wt%) types, have been identified in the Pulang complex. It is estimated that the magma equilibrated with the high-Al amphibole may have contained up to 6.2 wt% H2O, and was formed under 334–538 MPa (ca. 11–18 km deep eqv.) with oxygen fugacity (fO2) between NNO + 0.2 and NNO + 1.5. In contrast, the magma that equilibrated with the low-Al amphibole was likely formed at a much shallower depth (89–202 MPa, ca. 3–7 km eqv.), and was more oxidized (NNO + 1.0–NNO + 1.7) with a low H2O content (4.2–4.9 wt%). High fO2 would increase sulfur solubility in the magma, thus prohibiting early removal of metals via sulfide precipitation. In addition, the higher H2O content may have enhanced volatile exsolution from the evolving magmas at Pulang. We suggest that oxygen fugacity and H2O content of the magma are two critical factors that controlled the Pulang porphyry Cu-Au metallogeny.

Formation of the Neoproterozoic ophiolites in southern China: New constraints from trace element and PGE geochemistry and Os isotopes

The South Anhui ophiolite (SAO) and the Northeast Jiangxi ophiolite (NJO) are the only two known Precambrian ophiolite suites within the eastern segment of the Jiangnan Orogen, South China. These ophiolites may provide significant insights into the convergence history of the South China Block during the Rodinia supercontinent cycle. SHRIMP zircon U–Pb dating indicates that the SAO formed at 831 ± 5 Ma whereas the NJO formed at ca. 1000 Ma. Modal mineral assemblages and the preservation of relict primary mineral assemblages indicate that serpentinized peridotites from both ophiolites were mainly harzburgite in protolith. Relict olivine and orthopyroxene fragments within both ophiolite suites yield similarly high Mg# values. The serpentinized peridotite samples yield U-shaped rare earth element patterns and contain high-Cr# spinel, both of which are indicative of supra-subduction zone ophiolites. However, serpentinized peridotites within the SAO contain olivine and clinopyroxene with slightly higher Mg# values, and have lower platinum-group element (PGE) and trace element concentrations than peridotites from the NJO. The SAO peridotites are also depleted in Ir, Pt, and Pd, in contrast to the flat and chondrite-like PGE patterns of the NJO peridotites. These observations indicate that compared with the NJO, SAO peridotites were subjected to a greater degree of melt extraction prior to emplacement.Furthermore, gabbro and basalt from the SAO have N-MORB- or arc-like geochemical characteristics that reflect the incorporation of crustal materials into the mantle source, suggesting that this ophiolite formed in a continental marginal back-arc basin setting. In comparison, the less pronounced depletions in trace elements and PGEs, as well as the restricted 187Os/188Os isotopic compositions of NJO serpentinized peridotites, suggest that they formed in a fore-arc setting. The contrasting geochemical characteristics of the two ophiolite suites indicate that they were generated during distinct stages of convergence along the southeastern margin of the Yangtze Block. Our results show that ophiolite suites produced within a single orogenic cycle could preserve diverse geochemical characteristics, and may provide insights into the initiation and cessation of continental amalgamation.

A review of platinum group element (PGE) geochemistry and a study of the changes of PGE contents in the topsoil of Berlin, Germany, between 1992 and 2013

The data represent the first available data set on platinum group element (PGE) levels in Berlin topsoil. In 2013, over 100 topsoil samples (0–20cm) were collected in the inner city of Berlin. The PGEs in topsoil samples were analysed by ICP-MS after a trace-matrix separation. The results were compared to analyses of PGEs in Berlin topsoil collected at the same sample sites in 1992.The data show an increased accumulation of PGE concentrations in Berlin topsoil during this two-decade interval as a result of gradual increase in the use of vehicles with catalytic converters. A comparison of PGE median concentrations show an increase by a factor of 1.5 for Pt, 3.0 for Pd, 4.3 for Rh, and 3.1 for Au, over the 20-year period. The single element distribution maps of PGEs from 2013 confirm a clear correlation with traffic density. The PGE ratios (Pt/Pd, Pt/Rh, Pd/Rh) were consistent with known catalytic converter compositions, and indicate catalytic exhausts as the main source of these elements. A comparison of the maps of measured raw PGE data with the clr-transformed maps reveals identical distribution patterns (including PGE anomalies). Principal component analysis (PCA) results obtained from the classical statistical approach (standardised) are quite similar to those from PCA carried out using the compositional data analysis (CoDA) approach. Grouping of the PGEs, based on hierarchical cluster analysis, provides a complementary treatment and confirms the PCA results, indicating that the PGE concentrations in Berlin topsoil from 2013 are mainly caused by vehicle emissions.

Genesis of the Huangshannan high-Ni tenor magmatic sulfide deposit in the Eastern Tianshan, northwest China: Constraints from PGE geochemistry and Os–S isotopes

The Huangshannan magmatic Ni-Cu sulfide deposit is one of a group of Permian magmatic Ni-Cu deposits located in the southern Central Asian Orogenic belt in the Eastern Tianshan, northwest China. It is characterized by elevated Ni tenor (concentrations in recalculated 100% sulfide) in sulfide within ultramafic rocks (9–19wt%), with values much higher than other deposits in the region. Sulfides of the Huangshannan deposit are composed of pentlandite, chalcopyrite, and pyrrhotite and the host rock is relatively fresh, indicating that the high-Ni tenor is a primary magmatic feature rather than formed by alteration processes. It is shown that sulfides with high-Ni tenor can be generated by sulfide-olivine equilibrium at an oxygen fugacity of QFM +0.5, for magmas containing 450ppm Ni and 20% olivine. Ores with >10wt% sulfur have relatively low PGE and Ni tenors compared to other ores, R factor (mass ratio of silicate to sulfide liquid) modeling of Ni indicates that they formed at moderate R values (150–600). Based on this constraint on R values, ores with <10wt% sulfides in the Huangshannan deposit can be segregated from a similar parental magma with 0.05ppb Os, 0.023ppb Ir, and 0.5ppb Pd at R values between 600 and 3000. This, coupled with the supra-cotectic proportions of sulfide liquid to cumulus silicates in the Huangshannan ores imply mechanical transport and deposition of sulfide liquid in a magma pathway or conduit, in which sulfides must have interacted with large volumes of silicate magma. Platinum and Pd depletion relative to other platinum group elements (PGEs) are observed in fresh and sulfide-rich samples (S>4.5wt%). As sulfide-rich samples are also depleted in Cu, and as interstitial sulfides in those samples are physically interconnected at a scale of several cms, the low Pt and Pd anomalies are attributed to solid Pt and Pd phases crystallization and retention with the monosulfide solid solution (MSS) and Cu-rich sulfide liquid percolation during MSS fractionation. This finding indicates that Pt anomalies in sulfide-rich rocks from magmatic Ni-Cu deposits in the Eastern Tianshan are the result of sulfide fractionation rather than a hydrothermal effect. 187Os/188Os(278Ma) values of the lherzolite samples vary from 0.27 to 0.37 and γOs(278Ma) values vary from 110 to 189, indicating significant magma interaction with crustal sulfides, rich in radiogenic Os. Well constrained γOs values and δ34S values (−0.4 to 0.8‰) indicate that crustal contamination occurred at depth before the arrival of the magma in the Huangshannan chamber. Regionally, deposits with high-Ni tenor have not been reported other than the Huangshannan deposit; however, many intrusions with high-Ni contents in olivine are present in NW China, such as the Erhongwa, Poyi and Poshi intrusions. Those intrusions are capable of forming high-Ni tenor sulfides due to olivine-sulfide-silicate equilibrium and relative high-Ni content in parent magma, making them attractive exploration targets.

Platinum-group element geochemistry used to determine Cu and Au fertility in the Northparkes igneous suites, New South Wales, Australia

Recent studies have shown that platinum-group elements (PGE) can be used to constrain the timing of sulfide saturation in evolving felsic systems. In this study, we report trace-element, PGE, Re and Au data for the barren and ore-associated suites of intermediate to felsic rocks from the Northparkes Cu-Au porphyry region, emphasizing the timing of sulfide saturation and its influence on the tenor of the associated hydrothermal mineralization. Two barren suites, the Goonumbla and Wombin Volcanics and associate intrusive rocks, are found in the region. Geochemical modelling shows that the barren suites are dominated by plagioclase-pyroxene fractionation, whereas the ore-associated Northparkes Cu-Au porphyry suite is characterized by plagioclase-amphibole fractionation, which requires the ore-bearing suite to have crystallized from a wetter magma than barren suites. The concentrations of PGE, Re and Au in the barren suites decrease continuously during fractional crystallization. This is attributed to early sulfide saturation with the fraction of immiscible sulfide precipitation required to produce the observed trend, being 0.13 and 0.16wt.% for the Goonumbla and Wombin suites, respectively. The calculated partition coefficients for Au and Pd required to model the observed change in these elements with MgO are well below published values, indicating that R, the mass ratio of silicate to sulfide melt, played a significant role in controlling the rate of decline of these elements with fractionation. Palladium in the ore-associated suite, in contrast, first increases with fractionation then decreases abruptly at 1.2wt.% MgO. The sharp decrease is attributed to the onset of sulfide precipitation. Platinum on the other hand shows a moderate decrease, starting from the highest MgO sample analysed, but then decreasing strongly from 1.2wt.% MgO. The initial Pt decrease is attributed to precipitation of a platinum-group mineral (PGM), probably a Pt-Fe alloy, and the sharp decrease of both Pt and Pd at 1.2wt.% MgO to sulfide saturation. We suggest that the Goonumbla and Wombin suites are barren because early sulfide saturation locked most of the Cu and Au in a sulfide phase in the cumulus pile of a deep parental magma chamber, well before volatile saturation, so that when the magma reached volatile saturation, it did not have access to the Cu and Au. This contrasts with the relatively late sulfide saturation in the ore-associated suite, which was followed shortly afterwards by volatile saturation. Rayleigh fractionation concentrated incompatible Cu and Au by at least a factor of five before volatile saturation. The short crystallization interval between immiscible sulfide and volatile saturation allowed some Au and Cu to be stripped from the evolving magma. Gold, with its higher partition coefficient into immiscible sulfide melts, was more affected than Cu. The result is a Cu-Au deposit. Our study also suggests that Rayleigh fractionation is as at least as important as the initial concentration of chalcophile elements in the parent magma in determining the fertility of felsic magma suites.

Platinum-group element geochemistry of the layered intrusions in the Emeishan large igneous province, SW China: Implications for the principal controls on magmatic sulfide immiscibility

It is widely accepted that the incorporation of external sulfur via crustal contamination is an important trigger for sulfide immiscibility that generates Ni-Cu-(PGE) sulfide mineralization, yet other controlling factors for sulfide immiscibility may also be present. The late Permian Panzhihua, Baima, Hongge, Xinjie and Taihe layered intrusions in the Emeishan Large Igneous Province (ELIP, SW China), are well-endowed with Fe-Ti oxide deposits, whereas their sulfide mineralization is mainly sub-economic. For example, the lower part of the Xinjie intrusion hosts a few thin PGE-rich ore layers, yet other ELIP layered intrusions do not contain any Ni-Cu sulfide mineralization and are PGE-depleted (0.01–1 ppb). Compared with the PGE-undepleted Emeishan high-Ti basalts that are genetically related to the intrusions, the extent of PGE depletion and elevated Cu/Pd ratios (up to 3.2×106) of the Panzhihua, Baima, Taihe and Hongge intrusions suggest PGE-depletion in their parental magmas due to early-stage sulfide removal. Sr-Nd isotopic compositions of the Panzhihua, Baima and Taihe intrusions suggest crustal contamination was insignificant and sulfide saturation produced mainly by crustal sulfur input was unlikely. MELTS modeling shows that extensive fractionation of chromite, olivine and clinopyroxene in deep-seated magma chambers may have induced early-stage sulfide saturation of the primary magmas. The relatively high sulfide contents in the Fe-Ti oxide layers at Panzhihua, Baima, Hongge and Taihe indicate a close relationship between the second-stage sulfide immiscibility and extensive Fe-Ti oxide crystallization. Positive correlations between sulfur and total Fe2O3, V and TiO2 suggest that Fe-Ti oxide (magnetite and ilmenite) crystallization may have triggered the second-stage sulfide saturation via sharply lowering the Fe concentration and oxygen fugacity of the magmas. Moderate degree of crustal contamination for the Xinjie Fe-Ti oxide-barren rocks may have induced sulfide saturation and accumulation at the lower part of the intrusion. Our calculations indicate that the Xinjie PGE-rich rocks have high R-factors (1000–10000), which are ascribed to PGE-upgrading of the sulfides via reaction with new replenishments of PGE-undepleted magmas. A few Panzhihua, Baima and Taihe samples that contain higher PGE concentrations suggest that the early-stage sulfide droplets at depths were entrained in later magma pulses delivered to shallower magma chambers. The very high R-factors determined by mass balance calculation, implies a good potential for discovering more PGE mineralization in the deep-seated intrusions of the magma plumbing system.

Metallogeny of the Chrome Ores of the Xerolivado-Skoumtsa Mine, Vourinos Ophiolite, Greece: Implications on the genesis of IPGE-bearing high-Cr chromitites within a heterogeneously depleted mantle section

Chrome ore deposits comprise less than 1% of the volume of a pervasively serpentinized dunite body (∼3.5km3) that constitutes the Xerolivado-Skoumtsa Mine of the Vourinos Ophiolite in northwestern Greece. Ores have been examined to aid determination of their geological mode of occurrence, their mineralogy and mineral chemistry (Cr-spinel and olivine), and platinum-group element (PGE) geochemistry. The ore bodies are highly deformed and of the schlieren type, where Cr-spinel-rich and serpentine (after olivine)-rich layers (1–20cm thick) alternate. The Cr-spinel displays a limited range in Cr# [100×Cr/(Cr+Al)] atomic ratio (77–85) and TiO2 content (0.05–0.22wt%). The Mg# [100×Mg/(Mg+Fe2+)] of Cr-spinel shows a wider variation (52–74) indicating that subsolidus (MgSp-Fe2+Ol) re-equilibration occurred. Remnant fresh olivine in the serpentine-rich layers is typical forsterite [Fo#: 100×Mg/(Mg+Fe2+)=93–95]. The Cr-rich chromitite ores have total PGE and Au abundances that range between 74.3 and 205ppb: they show a general enrichment in Ir and Ru over PPGE (Rh, Pt and Pd) resulting mostly in a negatively-sloping C1 chondrite-normalized PGE profile with a quite strong Ru peak. Field observations indicate that the schlieren banding of the deformed ore bodies is a tectonometamorphic feature acquired within ductile deformation of the ophiolitic slab. Geochemical calculations demonstrate that the parental melts of the Xerolivado-Skoumtsa high-Cr chromitites were boninitic. Their high Ru content and variation in Cr#Sp values indicate a polygenetic origin from geochemically similar, but spatially distinct melt inputs. These melts originated within a hydrated mantle wedge beneath a forearc basin within an evolving lithospheric slab. We emphasize that the PGE budget of the Xerolivado-Skoumtsa chromitites was not inherited from interactions of the migrating melts with their parental harzburgites, but it is an intrinsic feature of the deep-seated and heterogeneously depleted mantle source of these magmas.

Petrogenesis of Cenozoic basalts in central-eastern China: Constraints from Re–Os and PGE geochemistry

We present Re–Os and PGE (platinum group elements), together with major–, trace–element and Sr–Nd isotope data, to further constrain the petrogenesis for the Cenozoic basalts in central-eastern China. The basalts include low-Ca alkali, high-Ca alkali and tholeiitic varieties. Most low-Ca alkali basalts have unradiogenic 187Os/188Os (mostly <0.14), flat chondrite-normalized PGE patterns and depleted Sr–Nd isotopic compositions, indicating that they probably originated from a depleted mantle source with insignificant shallow-level crustal contamination. Minor high-Ca alkali/tholeiitic basalts have low PGE concentrations, particularly Os (down to 0.0056ppb), and highly suprachondritic initial 187Os/188Os ratios (up to >0.4), indicating involvements of sulfide/PGE-alloy segregation–AFC (assimilation–fractionation–contamination) processes. Most tholeiites and high-Ca alkali basalts have relatively high Os concentrations, highly variable and suprachondritic Os isotopic compositions, high Pd/Ir ratios and enriched Sr–Nd isotopic compositions. Modeling results reveal that the Os isotopic variations in these basalts cannot be ascribed to crustal contamination during ascent but mainly reflect source characteristics. Combined with their low CaO, low Mg#, high FC3MS values (FeOT/CaO–3×MgO/SiO2, all in wt.%), and high Fe/Mn signatures, a large portion of pyroxenite is inferred as an enriched component in the mantle sources to account for their highly suprachondritic Os isotopic compositions. The formation of the pyroxenites was probably due to the subducted sediment-bearing Pacific oceanic crust or the recycled lower continental crust resulted from the collision between the Yangtze and North China blocks.

Platinum-group element geochemistry of mafic rocks from the Dongchuan area, southwestern China

Mafic intrusions and dykes are well preserved in the Yinmin and Lanniping districts, located within the western margin of the Yangtze Block, SW China. Although these mafic rocks from the two areas formed during different periods, they share similar ranges of PGE concentration. Most of the Yinmin gabbroic dykes contain relatively high PGE concentrations (PGEs = 13.9–87.0 ppb) and low S contents (0.003 %–0.020 %), higher than the maximum PGE concentrations of mafic magmas melting from the mantle. Two exceptional Yinmin samples are characterized by relatively low PGE (PGEs = 0.31–0.37 ppb) and high S (0.114 %–0.257 %) contents. In contrast, most samples from the Lanniping gabbroic intrusion have low PGE concentrations (PGEs = 0.12–1.02 ppb) and high S contents (0.130 %–0.360 %), except that the three samples exhibit relatively high PGE (PGEs = 16.3–34.8 ppb) and low S concentrations (0.014 %–0.070 %). All the Yinmin and Lanniping samples are characterized by the enrichment of PPGE relative to IPGE in the primitive-mantle normalized diagrams, and the high-PGE samples exhibit obvious Ru anomalies. This study suggests that during the ascent of the parental magma, removal of Os–Ir–Ru alloys and/or chromite/spinel leads to high Pd/Ir ratios and Ru anomalies for the Yinmin high-PGE samples and relatively lower Pd/Ir ratios and Ru anomalies for the Lanniping low-PGE samples. We propose that the magmas parental to the Yinmin gabbroic dykes are initially S-unsaturated, and subsequently, minor evolved magma reached sulfur saturation and led to sulfide segregation. Although the Lanniping parental magmas are originally not saturated in S, the high Cu/Pd ratios (3.8 × 104 to 3.2 × 106) for most of the Lanniping samples indicate the S-saturated state and sulfide segregation. A calculation shows that the PGE-poor magmas might have experienced 0.01 %–0.1 % sulfide segregation in the magma chamber. Therefore, our study provides a possible opportunity to discover PGE-enriched sulfide mineralization somewhere near or within the Lanniping mafic intrusion.

Late Neoarchean arc magmatism and crustal growth associated with microblock amalgamation in the North China Craton: Evidence from the Fuping Complex

The Fuping, Wutai, and Hengshan Complexes in the North China Craton preserve imprints of widespread late Neoarchean magmatism. Here, we report results from systematic petrology, mineral chemistry, whole-rock major, trace and platinum-group element geochemistry, zircon U–Pb geochronology and Hf–O isotopes from the Yangmuqiao mafic–ultramafic intrusion and coeval tonalite–trondhjemite–granodiorite (TTG) gneiss from the Fuping Complex. The mafic–ultramafic intrusion is composed of pyroxene hornblendites, hornblendites, and minor harzburgites. The salient geochemical features of the mafic–ultramafic intrusion and the Fuping TTG gneiss display subduction-related island arc signature, such as fractionated REE patterns with elevated LREE, enrichment of LILE (K, Rb, and Ba) and LREE (La and Ce), and depletion of HFSE (Nb, Ta, Zr, and Hf) and HREE. The chemistry of the clinopyroxene and chromite in the pyroxene hornblendites shows affinity with Alaskan-type mafic–ultramafic intrusions.Zircons from the pyroxene hornblendite yield weighted mean 207Pb/206Pb age of 2514±15 Ma, and those in the Fuping TTG gneiss show mean age of 2513±13Ma. Zircon Hf and O isotopic compositions are used as magma source and crustal evolution indicators. Zircon grains in the pyroxene hornblendite display positive εHf(t) values (2.6–6.7), Neoarchean TDM (2570–2723Ma), and their δ18O values vary from 3.8‰ to 7.0‰ (average 6.2‰). Zircons in the TTG gneiss show εHf(t) values in the range of −1.8 to 4.9, TDM of 2637–2888Ma, and δ18O values of 4.1‰–6.7‰ (average of 6.1‰). These results suggest that the parental magma of the late Neoarchean magmatism in the Fuping area was dominantly extracted from the depleted mantle and contaminated to different degrees by crustal components. The pyroxene hornblendites have obviously higher IPGE contents (ΣIPGE=1.69–2.39ppb) and lower Pd/Ir ratios (5.97–6.28) than those in the hornblendites (ΣIPGE=0.56–0.72ppb, Pd/Ir=6.48–15.25), suggesting different compatibility of IPGE and PPGE during the fractional crystallization. The study area is located at the western segment of the Fuping Complex and the eastern periphery of the Wutai greenstone belt. We propose that the late Neoarchean arc magmatism recorded by the Yangmuqiao mafic–ultramafic intrusion and the Fuping TTG gneiss is related to the subduction–collision process of the Ordos and the Qianhuai microblocks along the zone of ocean closure represented by the Wutai greenstone belt.

Geochemistry of platinum-group elements and mineral composition in chromitites and associated rocks from the Abdasht ultramafic complex, Kerman, Southeastern Iran

The Abdasht complex is a major ultramafic complex in south-east Iran (Esfandagheh area). It is composed mainly of dunite, harzburgite, podiform chromitites, and subordinate lherzolite and wehrlite. The podiform chromitites display massive, disseminated, banded and nodular textures. Chromian spinels in massive chromitites exhibit a uniform and restricted composition and are characterized by Cr# [=Cr/(Cr+Al)] ranging from 0.76 to 0.77, Mg# [=Mg/(Mg+Fe2+)] from 0.63 to 0.65 and TiO2<0.2wt.%. These values may reflect crystallization of the chromian spinels from boninitic magmas. Chromian spinels in peridotites exhibit a wide range of Cr# from 0.48 to 0.86, Mg# from 0.26 to 0.56 and very low TiO2 contents (averaging 0.07wt.%). The Fe3+# is very low, (<0.08wt.%) in the chromian spinel of chromitites and peridotites of the Abdasht complex which reflects crystallization under low oxygen fugacities.The distribution of platinum group elements (PGE) in Abdasht chromitites displays a high (Os+Ir+Ru)/(Rh+Pt+Pd) ratio with strongly fractionated chondrite-normalized PGE patterns typical of ophiolitic chromitites. Moreover, the Pd/Ir value, which is an indicator of PGE fractionation, is very low (<0.1) in the chromitites.The harzburgite, dunite and lherzolite samples are highly depleted in PGE contents relative to chondrites. The PdN/IrN ratios in dunites are unfractionated, averaging 0.72, whereas the harzburgites and lherzolites show slightly positive slopes PGE spidergrams, together with a small positive Ru anomaly, and their PdN/IrN ratio averages 2.4 and 2.3 respectively. Moreover, the PGE chondrite and primitive mantle normalized patterns of harzburgite, dunite and lherzolite are relatively flat which are comparable to the highly depleted mantle peridotites.The mineral chemistry data and PGE geochemistry indicate that the Abdasht chromitites and peridotites were generated from a melt with boninitic affinity under low oxygen fugacity in a supra-subduction zone setting. The composition of calculated parental melts of the Abdasht chromitites is consistent with the differentiation of arc-related magmas.

Abundances of platinum group elements in native sulfur condensates from the Niuatahi-Motutahi submarine volcano, Tonga rear arc: Implications for PGE mineralization in porphyry deposits

Some porphyry Cu–Au deposits, which are enriched in Pd, are potentially an economic source of Pd. Magmatic volatile phases are thought to transport the platinum group elements (PGEs) from the porphyry source magma to the point of deposition. However, the compatibilities of the PGEs in magmatic volatile phases are poorly constrained. We report PGE and Re contents in native sulfur condensates and associated altered dacites from the Niuatahi-Motutahi submarine volcano, Tonga rear arc, in order to determine the compatibility of PGEs and Re in magmatic volatile phases, and their mobility during secondary hydrothermal alteration. The native sulfur we analyzed is the condensate of a magmatic volatile phase exsolved from the Niuatahi-Motutahi magma. The PGEs are moderately enriched in the sulfur condensates in comparison to the associated fresh dacite, with enrichment factors of 11–285, whereas Au, Cu and Re are strongly enriched with enrichment factors of ∼20,000, ∼5000 and ∼800 respectively. Although the PGEs are moderately compatible into magmatic volatile phases, their compatibility is significantly lower than that of Au, Cu and Re. Furthermore, the compatibility of PGEs decrease in the order: Ru>Pt>Ir>Pd. This trend is also observed in condensates and sublimates from other localities.PGE mineralization in porphyry Cu–Au deposits is characterized by substantially higher Pd/Pt (∼7–60) and Pd/Ir (∼100–10,500) than typical orthomagmatic sulfide deposits (e.g. Pd/Pt ∼0.6 and Pd/Ir ∼20 for the Bushveld). It has previously been suggested that the high mobility of Pd, relative to the other PGEs, may account for the preferential enrichment of Pd in porphyry Cu–Au deposits. However, the low compatibility of Pd in the volatile phase relative to the other PGEs, shown in this study, invalidates this explanation. We suggest that the PGE geochemistry of Pd-rich Cu–Au deposits is principally derived from the PGE characteristics of the magma from which the ore-forming fluid exsolved. Pd-rich porphyry Cu–Au deposits are associated with highly oxidized magmas. Prior to sulfide saturation Pd, Au and Cu behave as incompatible elements and concentrate in the melt with fractional crystallization, whereas Pt is depleted by early crystallization of a Pt-rich alloy and the other PGEs by the co-crystallization of the Pt-rich alloy and Cr spinel. As a consequence the Pd/Pt and Pd/Ir in the evolving melt and the magmatic volatile phases that exsolve from that melt, increase with increased fractionation. The high Pd content and high Pd/Pt (∼7–60) of Cu–Au porphyry ores therefore require the parent magma to have undergone extensive sulfide-undersaturated fractional crystallization prior to volatile exsolution.Our study also showed that the altered dacites contain PGE abundances that are similar to those of fresh dacites although Pt and Rh are slightly enriched in the altered dacites, which indicates low mobility of PGEs during secondary hydrothermal alteration.

Major, trace and platinum group element (PGE) geochemistry of Archean Iron Ore Group and Proterozoic Malangtoli metavolcanic rocks of Singhbhum Craton, Eastern India: Inferences on mantle melting and sulphur saturation history

The geological and metallogenic history of the Singhbhum Craton of eastern India is marked by several episodes of volcanism, plutonism, sedimentation and mineralization spanning from Paleoarchean to Mesoproterozoic in a dynamic tectonic milieu. Distinct signatures of this Archean-Proterozoic geodynamic process are preserved in discrete crustal provinces that constitute the Singhbhum Craton. Here we report new major, trace and PGE geochemical data from the ~3.4Ga Iron Ore Group (IOG) volcanic rocks of the Jamda-Koira basin, a part of the BIF-bearing volcano-sedimentary sequences of the Noamundi-Jamda-Koira iron ore basin in the western part of Singhbhum Granite (SBG), and ~2.25Ga metavolcanic rocks of Malangtoli. The IOG and Malangtoli volcanic rocks are porphyritic basalts and despite belonging to different ages, they exhibit similar mineralogical composition marked by clinopyroxene, plagioclase (present as both phenocryst and groundmass), opaques and volcanic glass (restricted to groundmass). The igneous mineralogy of these rocks has been overprinted by greenschist to lower amphibolite grade of metamorphism. The Malangtoli samples show low and high MgO compositional varieties. Immobile trace element compositions classify the IOG samples as andesite having a calc-alkaline composition, whereas the Malangtoli rocks correspond to basalt and andesite displaying a tholeiitic to calc-alkaline trend. The IOG basalts show low to moderate PGE contents marked by 26.23–68.35ppb of ΣPGE, whereas the Malangtoli basalts display a moderate to high concentration of PGE (ΣPGE=43.01–190.43ppb). The studied samples have relatively enriched ΣPPGE ranging from 24.1–63.3ppb (IOG) and 34–227.3ppb (Malangtoli) against 2.2–4.1ppb and 1.9–8.9ppb ΣIPGE contents respectively. PPGE/IPGE ratios for IOG and Malangtoli samples range from 7.7–17.6 and 4.8–59.9. HFSE, REE and PGE compositions suggest a low degree (<1 to 1%) of partial melting in the garnet lherzolite domain for the generation of IOG volcanic rocks. The parental magma of the Malangtoli basalts were generated by lower to higher degrees (3–<10%) of mantle melting at depths corresponding to spinel to garnet lherzolite regime. Trace element (Zr/Nb, Th/Ta, Th/Nb, Ni/Cu) and PGE (Pd/Ir, Pd/Pt, Cu/Pd, Ni/Pd, Cu/Ir) ratios corroborate a sulphide saturated and PGE depleted character of IOG volcanic rocks that underwent crustal assimilation. In contrast, the high MgO Malangtoli basalts exhibit sulphide undersaturated, PGE undepleted nature devoid of crustal contamination whereas the low MgO Malangtoli basalts are sulphide saturated, PGE depleted and crustally contaminated. The IOG volcanic rocks correspond to intraoceanic arc with polygenetic crustal signatures, and show affinity towards arc-generated calc-alkaline basalts. The low- and high MgO basalts of Malangtoli are affiliated to transitional arc to rift-controlled back arc tectonic setting in a basinal environment that developed proximal to an active convergent margin.

Platinum Group Elements (PGE) geochemistry of komatiites and boninites from Dharwar Craton, India: Implications for mantle melting processes

High MgO volcanic rocks having elevated concentrations of Ni and Cr are potential hosts for platinum group elements (PGE) owing to their primitive mantle origin and eruption at high temperatures. Though their higher PGE abundance is economically significant in mineral exploration studies, their lower concentrations are also valuable geochemical tools to evaluate petrogenetic processes. In this paper an attempt has been made to evaluate the PGE geochemistry of high MgO volcanic rocks from two greenstone belts of western and eastern Dharwar Craton and to discuss different mantle processes operative at diverse geodynamic settings during the Neoarchean time. The Bababudan greenstone belt of western and Gadwal greenstone belt of eastern Dharwar Cratons are dominantly composed of high MgO volcanic rocks which, based on distinct geochemical characteristics, have been identified as komatiites and boninites respectively. The Bababudan komatiites are essentially composed of olivine and clinopyroxene with rare plagioclase tending towards komatiitic basalts. The Gadwal boninites contain clinopyroxene, recrystallized hornblende with minor orthopyroxene, plagioclase and sulphide minerals. The Bababudan komatiites are Al-undepleted type (Al2O3/TiO2=23–59) with distinctly high MgO (27.4–35.8wt.%), Ni (509–1066ppm) and Cr (136–3036ppm) contents. These rocks have low ΣPGE (9–42ppb) contents with 0.2–2.4ppb Iridium (Ir), 0.2–1.4ppb Osmium (Os) and 0.4–4.4ppb Ruthenium (Ru) among Iridium group PGE (IPGE); and 1.4–16.2ppb Platinum (Pt), 2.8–19ppb Palladium (Pd) and 0.2–9.8ppb Rhodium (Rh) among Platinum group PGE (PPGE). The Gadwal boninites are high-Ca boninites with CaO/Al2O3 ratios varying between 0.8 and 1.0, with 12–24wt.% MgO, 821–1168ppm Ni and 2307–2765ppm Cr. They show higher concentration of total PGE (82–207ppb) with Pt concentration ranging from 13 to 19ppb, Pd between 65 and 180ppb and Rh in the range of 1.4–3ppb compared to the Bababudan komatiites. Ir, Os and Ru concentrations range from 0.6 to 2.2ppb, 0.2 to 0.6ppb and 1.4 to 2.6ppb respectively in IPGE. The PGE abundances in Bababudan komatiites were controlled by olivine fractionation whereas that in Gadwal boninites were influenced by fractionation of chromite and sulphides. The Al-undepleted Bababudan komatiites are characterized by low CaO/Al2O3, (Gd/Yb)N, (La/Yb)N, with positive Zr, Hf, Ti anomalies and high Cu/Pd, Pd/Ir ratios at low Pd concentrations suggesting the derivation of parent magma by high degrees (>30%) partial melting of mantle under anhydrous conditions at shallow depth with garnet as a residual phase in the mantle restite. The komatiites are geochemically analogous to Al-undepleted Munro type komatiites and their PGE compositions are consistent with Alexo and Gorgona komatiites. The S-undersaturated character of Bababudan komatiites is attributed to decompression and assimilation of lower crustal materials during magma ascent and emplacement. In contrast, the higher Al2O3/TiO2, lower (Gd/Yb)N, for Gadwal boninites in combination with negative Nb, Zr, Hf, Ti anomalies and lower Cu/Pd at relatively higher Pd/Ir and Pd concentrations reflect high degree melting of refractory mantle wedge under hydrous conditions in an intraoceanic subduction zone setting. Higher Pd/Ir ratios and S-undersaturation of these boninites conform to influx of fluids derived by dehydration of subducted slab resulting into high fluid pressure and metasomatism of mantle wedge.