Ppb Pd Research Articles

DISCRETE PT MICROCRYSTALS FIRSTLY FOUND IN LTI BASALTIC LAVA FLOWS, PARANÁ IGNEOUS PROVINCE, STATE OF PARANÁ, BRAZIL.

Platinum Group Elements (PGE) in basalt flows of the Paraná Igneous Province (the South American portion of the Paraná-Etendeka Igneous Province, one of the largest in the world) have been related in previous studies to a Norils'k-Talnak mineralization model, despite inconsistencies such as the lack of EGP-collecting Ni-sulfides, low levels of S and rare olivine. On the other hand, Licht (2018), Gomes et al. (2018), Lindsay et al. (2021) showed the occurrence of relatively high levels of EGP (up to 18 ppb Pt and 9 ppb Pd) in tholeiitic basalts flows of the geochemical types 1-CN, 2 and 3 (Licht 2018), all belonging to magma-type Paranapanema (Peate et al. 1992) and composing the magnetite and Ti-magnetite-rich Paranapanema Formation (Licht & Arioli 2018). The magnetite-PGM association in PIP had already been proposed by Arioli (2008).

PGE geochemical and Os-S-Sr-Nd isotopic constraints on the genesis of the Shitoukengde magmatic sulfide deposit in the East Kunlun Orogenic Belt, NW China

Numerous early Paleozoic mafic–ultramafic intrusions that host important Ni-Cu sulfide mineralization occur in the northern part of the Qinghai-Tibet Plateau, NW China. The sulfide-bearing Shitoukengde Ni-Cu deposit, which is hosted in a ∼424 Ma mafic–ultramafic intrusion, is one of the most represent magmatic sulfide deposits in the East Kunlun Orogenic Belt. The intrusion is composed of a large gabbroic body, cut by lherzolite, olivine websterite, websterite, and minor dunite. Disseminated and net-textured sulfide mineralization occurs as lenses in the center and towards the bottom of the ultramafic bodies. The sulfide mineralization has variable sulfur contents of 0.3 to 13.6 wt% with Ni grade of 0.41 wt% on average, and low platinum-group element (PGE) concentrations (<8.2 ppb Ru and <11.9 ppb Pd). Pd and Ru tenors of bulk sulfides in the deposit are characterized by a positive correlation, indicating that PGE tenor variations are mainly controlled by varying R-factors (magma/sulfide mass ratio). The estimated PGE concentrations in the Shitoukengde magma are about three orders of magnitude lower than those in continental tholeiites. The significant PGE depletions in the Shitoukengde deposit may be due to sulfide removal in the magma conduit at depth. Our new sulfur isotope data reported range in δ34S values from −5.0 to 4.9‰ for the sulfide minerals of the Shitoukengde deposit, clearly distinct from those of mantle-derived sulfur (0 ± 2‰) and immediate country rocks (1.1 to 2.0‰). This, together with the modeling for S isotope variation as a function of R-factor, suggest that the current δ34S range is attributed to the addition of external sulfides with anomalous δ34S into the magma at depth, followed by progressive modification to crustal signature by uncontaminated pulses of magma. The ultramafic rocks exhibit low εNd(t) values (−4.71 to 2.12) and high (87Sr/86Sr)i ratios (0.7073 to 0.7130), which are more enriched relative to the isotopic compositions of depleted mantle. Mixing calculations indicate that about 15 to 20 wt% of lower crustal contamination plus variable upper crustal contamination is required to explain the variations of Sr-Nd isotopes in the Shitoukengde intrusion. Significant crustal contamination is also supported by the mineralization at Shitoukengde having high (187Os/188Os)i (0.24 to 4.51) and γOs(t) values (0.24 to 2534) that are comparable to or higher than those of the important Ni-Cu deposits worldwide. Current results provide evidence that assimilation of crustal sulfur at deep crust and siliceous material with variable crustal contamination during magma ascent and emplacement played critical roles in the attainment of sulfide saturation in the parental magma and the formation of the Shitoukengde deposit.

Genesis and mechanisms of metal enrichment in the Baimazhai Ni-Cu-(PGE) deposit, Ailaoshan Orogenic Belt, SW China

ABSTRACT The ∼259 Ma Baimazhai Ni-Cu-(platinum-group element) deposit is located in the Ailaoshan-Red River fault zone on the southwest margin of the Yangtze Plate in the Jinping area of southeastern Yunnan Province. The intrusion is lenticular (∼530 m long × 190 m wide × 24–64 m thick) and concentrically zoned (margin to core) from gabbro through pyroxenite to peridotite. It contains ∼50 kt of Ni-Cu-(platinum-group element) mineralization, concentrically zoned (margin to core) from disseminated through net-textured to massive sulfides with an average grade of 1.03 wt.% Ni, 0.81 wt.% Cu, and 0.02∼0.69 ppm Pd+Pt. The sulfide assemblage comprises pyrrhotite, chalcopyrite, and pentlandite, with lesser magnetite, violarite, galena, and cobaltite. The mineralization is enriched in Ni-Cu-Co relative to the platinum-group elements and the host rocks are enriched in highly incompatible lithophile elements relative to moderately incompatible lithophile elements with high Th/Yb and intermediate Nb/Yb ratios. These host rocks, and those at most other Ni-Cu-platinum-group element deposits in the Emeishan Large Igneous Province, have high γOs and intermediate εNd values, indicating that they crystallized from a magma derived from a subduction-modified pyroxenite mantle source and modified by crustal contamination. The initial concentrations of metals in the primary magma are estimated to have been on the order of 200 ppm Ni and 100 ppm Cu, but only 0.4 ppb Pd, 0.2 ppb Pt, 0.005 ppb Rh, 0.02 ppb Ru, and 0.01 ppb Ir. The δ34S values of ores and separated sulfides range from 5.8‰ to 8.6‰, between the ∼10‰ value of sulfides in the metasedimentary country rocks and the 0 ± 0.5‰ value expected for magmas derived from MORB-type mantle, or the –2.5 ± 0.3‰ value expected for subduction-modified mantle, consistent with equilibration at magma:sulfide mass ratios (R factors) of 100–1000. Variations in Ir100 and Pd100 (metals in 100% sulfide) are consistent with 40–60% fractional crystallization of monosulfide solid solution to form Ni-Co-intermediate platinum-group element (Ru, Os, Ir)-rich massive ores and Cu-palladium/platinum-group elements (Pt, Pd, Rh)-Au-rich residual sulfide liquids. This process is also recorded by magnetite: Type I (early magmatic), type II (late magmatic), and type III (secondary) magnetites exhibit progressively lower Cr-Ti-V concentrations. The platinum-group element contents in base-metal minerals are low, and only pentlandite, violarite, and cobaltite contain detectable concentrations of Pd, Rh, and Ru. There is abundant textural evidence for metamorphic-hydrothermal alteration of sulfides in the Baimazhai intrusion, with secondary violarite, chalcopyrite, and pentlandite being enriched (Ag, Sb, Au, Pb) or depleted (Sn) in more mobile chalcophile elements. The different tectonic and petrogenetic settings of the Baimazhai and other deposits in China highlight the potential of Ni-Cu-platinum-group element deposits to occur in subduction or post-subduction settings and demonstrate that the key controls are magma flux and access to crustal S. Exploration potential remains for the Ailaoshan orogenic belt to host additional magmatic Ni-Cu deposits.

Effective global mixing of the highly siderophile elements into Earth’s mantle inferred from oceanic abyssal peridotites

Late accretion occurred through addition of massive impactors to Earth, leading to potential heterogeneity in the distribution of highly siderophile elements (HSE: Os, Ir, Ru, Pt, Pd, Re) within the mantle. Abyssal peridotites sample the present-day convecting mantle, which make them useful for examining the distribution of the HSE within the mantle. Here we report new HSE abundance data and 187Os/188Os ratios, in conjunction with mineral chemistry and bulk rock major- and trace-element compositions for abyssal peridotites from the fast-spreading Pacific Antarctic Ridge (PAR) and East Pacific Rise (Hess Deep), and for slow to intermediate spreading ridges from the Southwest Indian Ridge, Central Indian Ridge and Mid-Atlantic Ridge. These analyses expand the global abyssal peridotite Os isotope and HSE database, enabling evaluation of potential variations with spreading rate, from ultraslow (<20 mm/yr, full spreading rate) to fast (135–150 mm/yr). Accounting for likely effects from seawater modification and serpentinization, the Pacific data reveals heterogeneous and sometimes significant melt depletion for PAR (3–23% melt depletion; 187Os/188Os from 0.1189 to 0.1336, average = 0.1267 ± 0.0065; 2SD) and Hess Deep abyssal peridotites (15–20% melt depletion; 0.1247 ± 0.0027). Abyssal peridotites from fast to intermediate spreading ridges reveal no systematic differences in the distribution and behavior of the HSE or Os isotopes, or in degrees of melt depletion, compared with slow to ultraslow spreading ridges. These observations arise despite significant differences in melt generation processes at mid-ocean ridges, suggesting that the effects of ancient melt depletion are more profound on HSE compositions in abyssal peridotites than modern melting beneath ridges. Using global abyssal peridotites with Al2O3 content > 2 wt.%, the average composition of the primitive mantle is 0.3 ppb Re, 4.9 ppb Pd, 7.1 ppb Pt, 7.2 ppb Ru, 3.8 ppb Ir and Os, showing no Pd/Ir, but a positive Ru/Ir anomaly, relative to chondrites. There is ∼50% variation of the HSE abundances in the oceanic mantle, with much of this variation being observed at small length scales (<1 km) and due entirely to both modern and more ancient partial melting effects. Consequently, any significant HSE heterogeneities formed during late accretion or early Earth differentiation processes are no longer recognizable in the mantle sampled within ocean basins, implying generally efficient mixing of Earth’s mantle for these elements. By contrast, relatively ancient heterogeneity in Os and other radiogenic isotopes has been effectively preserved in the convecting mantle over the last ∼2 Ga, through recycling processes and through preservation and isolation of melt-depleted refractory residues.

The komatiite-mantle platinum-group element paradox

The platinum-group element (PGE) contents of komatiites have been used to estimate the PGE contents of their mantle sources and investigate temporal variations in the PGE systematics of the mantle throughout Earth history. However, the use of mantle melts to investigate source characteristics is critically dependent on understanding the fractionation of the elements in question between mantle sources and their derived magmas. We present new PGE and Re abundance data, together with Re-Os isotope data for the pristine 1.9 Ga Winnipegosis komatiites, Canada. Whole rock Re-Os isotope data define a 1865 ± 40 Ma isochron, consistent with previous age estimates, with initial γOs of +0.9 ± 1.4. The PGE and Re variations in these komatiites were controlled by fractionation of olivine, chromite, Os-Ir alloys, a Ru-Os rich phase (possibly laurite) from the komatiite melt. The calculated parental melt composition at 23.6 ± 1.6 wt% MgO has 1.1 ± 0.1 ppb Os, 0.91 ± 0.08 ppb Ir, 4.0 ± 0.5 ppb Ru, 7.0 ± 0.8 ppb Pt, 7.2 ± 0.7 ppb Pd, and 0.53 ± 0.06 ppb Re. The calculated PGE contents are low relative to many komatiites; using existing methods for calculating the PGE contents of mantle sources suggests the Winnipegosis source had PGE contents from 25 ± 19 wt% to 57 ± 7 wt% of primitive mantle values. This surprising finding substantiates a growing ‘PGE paradox’, where almost all komatiites appear to have formed from PGE-depleted mantle sources. We suggest the simplest resolution to this paradox is that current methods systematically underestimate mantle source PGE contents. We test the assumptions implicit in these methods by comparing detailed models of PGE behaviour during mantle melting to a large database of parental melt compositions of high degree melts. Ruthenium behaviour in high degree melts can be adequately modelled using our current understanding of Ru partitioning. However, the Ru contents of high degree mantle melts are strongly dependent on the degree of melting, as Ru-rich melts formed after sulphide exhaustion are increasingly mixed into early-formed Ru-poor melts. Platinum and Pd behaviour during mantle melting cannot be successfully modelled under the widespread assumption that they are strongly incompatible following sulphide exhaustion, suggesting that these elements cannot be used to estimate PGE contents of the mantle sources of high degree melts. Parental melt Pt and Pd in many high degree lavas are correlated with Al2O3/TiO2, suggesting a pressure control on their partitioning. We attribute the relatively low PGE contents of the Winnipegosis komatiites to their moderate degrees and depth of melting compared to other komatiites, rather than invoking a PGE-depleted mantle source. More broadly, the complex controls (T, P, fO2, S content, prior depletion) on the PGE contents of komatiites mean that most komatiites can be reconciled with being derived from sources with primitive mantle-like PGE contents, and few komatiites can be confidently asserted to come from PGE-depleted mantle sources. Pending a better understanding of PGE behaviour during mantle melting, we recommend caution when using komatiite PGE systematics to infer the highly siderophile element evolution and accretionary history of Earth’s mantle.

Mineralogical and geochemical constraints on the origin of the Sohland-Rožany Ni-Cu-(PGE) sulfide mineralization (Lausitz Block, Bohemian Massif, Germany/Czech Republic)

The Sohland-Rožany Ni-Cu-(PGE) sulfide mineralization is hosted by a small gabbroic dike that is one of several Ni-Cu sulfide-bearing gabbroic intrusions in the northern Bohemian Massif. The intrusions are associated with a Middle Devonian to Early Carboniferous mafic–ultramafic plumbing system that emplaced within Cadomian granodiorites of the Lausitz Block. The Sohland-Rožany dike comprises varitextured olivine- and hornblende-bearing gabbro and hornblende gabbro which originated from differently fractionated magma batches. Fractionation likely took place in deeper parts of the magmatic systems, e.g. within staging magma chambers. Mineralogical features like Ti-rich primary brown hornblende and diopsidic clinopyroxene as well as overall enriched incompatible element contents suggest moderate alkaline basaltic parental magmas with relatively high volatile contents.The magmatic sulfide mineralization is exclusively hosted by the olivine- and hornblende-bearing gabbro and include disseminated, net-textured and massive sulfides. The ore types are predominated by pyrrhotite-pentlandite-chalcopyrite assemblages accompanied by secondary violarite and pyrite as well as by accessory Pt, Pd, Au and Ag phases. The disseminated and net-textured sulfides have highly variable modal proportions of base-metal sulfides with pyrrhotite-dominated beside chalcopyrite-dominated aggregates on the hand specimen scale. The platinum-group mineral (PGM) assemblage includes Pd-Pt-Ni-bearing bismuthotellurides of the melonite–merenskyite and michenerite–testibiopalladite solid solution series as well as sperrylite. The sulfide ores feature predominantly elevated Ni and highly variable Cu and Pt, Pd and Au tenors (3.5–6.4 wt.% Ni, 0.1–16.6 wt.% Cu, 80–3080 ppb Pt, 50–5320 ppb Pd and 20–3770 ppb Au). The magmatic sulfides are locally characterized by a late-stage hydrothermal overprint where sulfides were replaced by hydrous secondary phases (e.g. actinolite–tremolite and chlorite). A significant redistribution of the PGE due to hydrothermal alteration is unlikely as the majority of PGM show a close spatial association to the base-metal sulfides.Textures and chemical compositions of the sulfides suggest that repeated magma batches eroded already fractionated sulfide pools and entrained early crystalized cumulates of monosulfide solid solution (MSS) together with variable fractionated sulfide melts. Sulfide saturation in the Sohland-Rožany magmas was locally controlled by assimilation of the granodioritic wall-rock in the course of thermomechanical erosion. This process was amplified by high mica contents of the granodiorites. Sulfur isotope signatures (–2.0 to –1.2‰ VCDT) and the S-poor nature of the hosting granodiorites exclude a significant contribution of S from the country rocks.

Sample pretreatment for voltammetric determination of Pd - selective separation and preconcentration using Cellex-T

Constant increase of the content of platinum group elements in the environment creates the need for their analysis in natural samples. Especially determination of palladium is challenging: it occurs at ultra-trace levels, analytical techniques offer too high limits of detection and interferences from sample matrix limit the application of some analytical methods. The aim of this work was to propose a complete methodology of Pd determination, with special attention paid to establishing the conditions for efficient decomposition of thiourea. The analysis was performed using ICP MS and/or voltammetry in samples naturally containing traces of Pd. The procedure includes sample digestion in aqua regia, separation of Pd from a complex natural matrix simultaneously with its 10-fold preconcentration (SPE) on anion-exchanger Cellex-T (Pd elution with 0.10 mol L−1 TU in 0.10 mol L−1 HCl). Voltammetric determination of Pd is possible after mineralization of thiourea in conc. nitric acid or the mixture of nitric and perchloric acids. The recovery is very satisfying, reaching more than 90%. The proposed methodology can be applied for quartz sand samples containing at least 2 ppb Pd.

The geology and mineralogy of the Stypsi porphyry Cu-Mo-Au-Re prospect, Lesvos Island, Aegean Sea, Greece

The Stypsi Cu-Mo-Au-Re prospect, Lesvos island, is a shallow porphyry-epithermal system hosted within a middle Miocene microgranite porphyry, which was emplaced along NNE-, NW- and NE-trending structures, within trachyandesites to trachydacites and felsic pyroclastics of the Stypsi caldera. The mineralization comprises three stages: Stage I is characterized by magnetite-actinolite ± quartz in transitional and banded quartz veins mostly developed within the microgranite and the surrounding lavas related to calcic-potassic and propylitic alteration of the host rocks. In the banded veins, quartz is botryoidal, suggesting crystallization from a gel. Abundant vapor-rich inclusions in the bands produce a dark grey to black color. Within the veins, magnetite, chalcopyrite, bornite and native gold were followed in time by pyrite, hematite, sphalerite and galena. Stage I mineralization was synchronous and also postdates quartz formation in the veins, since it crosscuts and/or fills vugs in the center of the veins. Sulfides are associated with various combinations of K-feldspar, actinolite, epidote, chlorite, and calcite gangue minerals. Pyrite-molybdenite-chalcopyrite (Stage II) and late intermediate sulfidation epithermal veins (Stage III) overprint earlier mineralization and alteration, and are associated with sericite-calcite and sericite-kaolinite alteration of the porphyry system and spatially associated lavas, respectively. Molybdenite is widespread in the first two mineralization stages, with Re content ranging from about 0.3 wt% in Stage I to 1.96 wt% in Stage II. A barren silicic and advanced argillic (alunite-kaolinite) lithocap, is exposed on top of the porphyry-style mineralization and is crosscut by non-mineralized high-sulfidation epithermal chalcedony-barite veins. Bulk ore analyses of surface samples from the Stypsi prospect yielded values of up to 276 ppm Mo, 978 ppm Cu, up to 0.5 g/t Au, up to 3 g/t Ag, and up to 70 ppb Pd and Re.Fluid inclusion data indicate that the Stage I transitional and banded quartz veins were deposited at 420 °C–530 °C and at pressures up to 450 bars, from boiling hydrothermal fluids. The fluid in the veins consists of a brine (40–61 wt% NaCl equiv) that coexists with a lower salinity (6–14 wt% NaCl equiv) liquid phase and a low-density vapor-rich fluid. Fluid inclusions in quartz of the Stage III intermediate-sulfidation epithermal veins are characterized by relatively low homogenization temperatures (231 °C–288 °C) and salinities (up to 1.9 wt% NaCl equiv), which was the result of subsequent dilution of the moderately saline fluids by circulating meteoric water. This study verifies earlier works suggesting that Au-enriched felsic magmas are able to crystallize Re-rich molybdenite, and that Re may also be redistributed and enriched in later stages during the deposition of porphyry-style mineralization. The Stypsi prospect ressembles in many respects (e.g., Au grades, Cu/Mo ratios, the Re content of molybdenite and the presence of ore-grade calcic-potassic alteration), other porphyry Cu-Mo-Re-Au systems hosted in calc-alkaline rocks in northeastern Aegean, Greece.

Geology, sulfide mineralogy and petrogenesis of the Angstberg Ni-Cu-(PGE) sulfide mineralization (Lausitz Block, Bohemian Massif, Germany): A potential Ni-Cu exploration target in Central Europe?

Germany’s largest known magmatic Ni-Cu-(PGE) sulfide enrichment is associated with the gabbroic Angstberg intrusion that is one of several small-scaled, Ni-Cu sulfide-bearing intrusions in the northern Bohemian Massif (Central European Variscan Belt). The intrusions are part of a Middle Devonian to Early Carboniferous, mafic-(ultramafic) magmatic system that emplaced within Cadomian granodiorites of the Lausitz Block. The Angstberg intrusion represents an exposed sub-vertical, dike-like body (320 × 60 m in plan view) and comprises olivine-gabbronorite, olivine-gabbro, gabbro, olivine-hornblende-gabbro, and hornblende-pyroxene-gabbro. The hornblende-bearing and hornblende-free lithologies originate from at least two variably fractionated basaltic parental magma batches which differ in their Ti, LREE, HREE and volatile contents. Fractionation probably took place in deeper-seated sections of the magmatic system, possibly within staging magma chamber(s). Overall enriched incompatible trace-element patterns suggest that the Angstberg lithologies are linked with intra-plate magmatism, likely associated with a transtensional setting in the course of the Variscan orogeny. The previously suggested Devonian age of the intrusion is confirmed by an 40Ar-39Ar biotite age of 373.4 ± 0.9 Ma for the olivine-gabbro. The magmatic sulfide mineralization is predominated by disseminated sulfides that are hosted in the olivine-richest parts of the olivine-gabbronorite and olivine-hornblende-gabbro lithologies. In addition, some sulfide-matrix breccias (up to 70 modal % sulfides) occur directly on the footwall contact of the intrusion to granodiorite. Both mineralization types are characterized by a predominance of pyrrhotite over pentlandite and chalcopyrite with minor secondary violarite and pyrite, and accessory PGE, Au, and Ag phases. Nickel-rich bismuthotellurides of the melonite–merenskyite solid-solution series and froodite are the most common platinum-group minerals. Disseminated sulfides are characterized by high Ni, moderate Cu, and low Pt and Pd tenors (∼4–9 wt% Ni, ∼2–6 wt% Cu, ∼200–800 ppb Pt, ∼200–1000 ppb Pd). Sulfide-matrix breccias feature comparable Ni, but lower Cu, Pt and Pd tenors (∼4–6 wt% Ni, ∼0.3–1 wt% Cu, ∼10–100 ppb Pt, ∼40–200 ppb Pd). Fractional crystallization and wall-rock assimilation of granodiorite are regarded as key factors for sulfide saturation in the magmas associated with the Angstberg intrusion. Sulfur isotope compositions of pyrrhotite-pentlandite-chalcopyrite assemblages (−1.4 to −0.2‰ VCDT) propose a mantle-origin of S, whereas addition of crustal S cannot be completely ruled out as the S isotope values of the sulfides overlap with those of the granodiorite (−7 to +4‰ VCDT). Olivine- and sulfide-textures suggest that disseminated sulfides likely originate from sulfide melts that were entrained in an olivine-rich crystal mush during magma rise to upper levels. The sulfide-matrix breccias also resulted from entrained sulfide melts, or from gravity-driven downward percolation of sulfide melts from stratigraphically higher, now-eroded levels. In both cases, the formation of sulfide-matrix breccias most likely was amplified by in-situ thermomechanical erosion of the granodioritic wall-rock, caused by flash-boiling of thermally dehydrating biotite. Despite spatial limitations of the mineralized zones and limited information about the architecture of the intrusions in the northern Bohemian Massif, the Angstberg intrusion, as well as other neighboring magmatic sulfide occurrences, may represent a new exploration target for Ni and Cu in Central Europe.

Multiple Magma Conduits Model of the Jinchuan Ni-Cu-(PGE) Deposit, Northwestern China: Constraints from the Geochemistry of Platinum-Group Elements

The giant Jinchuan nickel-copper-platinum-group element (PGE) deposit is hosted by two individual sub-vertical intrusions, referred to as the western and eastern intrusions (including segment II-W and segment II-E). Exactly how the Jinchuan deposit was formed by a system of sub-vertical magma conduits is still not well understood. This paper reports new major elements, trace elements and PGEs data from the Jinchuan deposit to study the formation mechanism of sulfide ores with different textures and their relationship with the magma conduit system. Our study shows that the PGE tenors of disseminated and net-textured sulfide in segment II-E are significantly lower than segment II-W and the western intrusion, but the Cu/Pd ratios are opposite. In addition, net-textured sulfides in segment II-W show a negative correlation between IPGE (Ir, Ru and Rh) and PPGE (Pt and Pd) in contrast to the positive correlation in segment II-E and the western intrusion. These features indicate the parental magma sources of the western intrusion, segment II-W and segment II-E were originally three different surges of PGE-depleted magma. Modeling of parental magma in the western intrusion, segment II-W and segment II-E suggests that they were formed by the same initial picritic basalt (100 ppm Cu, 1 ppb Ir and 10 ppb Pd) with different prior sulfide segregations (0.0075%, 0.0085% and 0.011%). The three parts of Jinchuan sulfides show that the Pt/Pd and (Pt + Pd)/(Ir + Ru + Rh) ratios decrease from section III-5 toward both sides in the western intrusion and decrease from section II-14 toward all sides, whereas no regular spatial variations occur in segment II-E, showing the different fractionation processes of sulfide melt. The massive sulfides in the western intrusion and segment II-E experienced a ~20% to 40% and ~40% to 60% fractionation of sulfide melt, respectively. We propose that the Jinchuan deposit was generated in a metallogenic system of multiple magma conduits, where sulfides entrained in parental magma experienced different amounts of prior removal.

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.

Concentrations of platinum-group elements (PGE), Re and Au in arsenian pyrite and millerite from Mo–Ni–PGE-Au black shales (Zunyi region, Guizhou Province, China): results from LA-ICPMS study

Lower Cambrian Mo–Ni sulphidic black shales from the Huangjiawan mine (Guizhou Province, south China) have anomalous platinum-group element (PGE) concentrations (up to ∼1 ppm in total). We used LA-ICPMS to study the distribution of PGE in pyrite and Ni-sulphide (millerite) and FE-SEM/EDS for determination of As in pyrite. A sulphide concentrate was produced by innovative hydroseparation techniques from one representative sample, which contained 162 ppb Pt, 309 ppb Pd, 12.2 ppb Ru, 11.3 ppb Rh, 1.5 ppb Ir, 11 212 ppb Re and 343 ppb Au. Mineralogical analysis revealed that pyrite forms ∼12 vol%, which corresponds to a calculated ∼18.4 wt% of all mineral phases in mineralized black shale. We found that pyrite contains on average (144 analyses) 0.10 ppm Pt, 0.11 ppm Re and 1.40 ppm Au (Ru, Rh, Pd, Os and Ir were below detection limit). It also contains from ∼0.5 to ∼1.8 wt% As and can be therefore classified as arsenian pyrite. Millerite (77 analyses) showed PGE, Re and Au values below detection limit. We suggest that pyrite represents a dominant Au carrier, containing between 64 and 83% Au of the total Au mineralised rock budget. Conversely, pyrite does not bear any significant amount of Re and Pt, contributing up to ∼0.2% and ∼12.5% to their whole rock budgets, respectively. Time resolved LA-ICPMS spectra in pyrite indicate that Pt, Re and Au behave as typical lattice-bound elements, with only Re locally forming micro-inclusions. Arsenic is heterogeneously distributed in pyrite and the Au/As ratio (much lower than 0.02) is in support of Au to be structurally bound in solid solution.

Platinum-group element contents of Karelian kimberlites: Implications for the PGE budget of the sub-continental lithospheric mantle

We present high-precision isotope dilution data for Os, Ir, Ru, Pt, Pd and Re in Group I and Group II kimberlites from the Karelian craton, as well as 2 samples of the Premier Group I kimberlite pipe from the Kaapvaal craton. The samples have, on average, 1.38ppb Pt and 1.33ppb Pd, with Pt/Pd around unity. These PGE levels are markedly lower, by as much as 80%, than those reported previously for kimberlites from South Africa, Brazil and India, but overlap with PGE results reported recently from Canadian kimberlites. Primitive-mantle-normalised chalcophile element patterns are relatively flat from Os to Pt, but Cu, Ni and, somewhat less so, Au are enriched relative to the PGE (e.g., Cu/Pd>25.000). Pd/Ir ratios are 3,6 on average, lower than in most other mantle melts. The PGE systematics can be largely explained by two components, (i) harzburgite/lherzolite detritus of the SCLM with relatively high IPGE (Os-Ir-Ru)/PPGE (Rh-Pt-Pd) ratios, and (ii) a melt component that has high PPGE/IPGE ratios. By using the concentrations of iridium in the kimberlites as a proxy for the proportion of mantle detritus in the magma, we estimate that the analysed kimberlites contain 3–27% entrained and partially dissolved detritus from the sub-continental lithospheric mantle, consistent with previous estimates of kimberlites elsewhere (Tappe S. et al., 2016, Chem. Geol.http://dx.doi.org/10.1016/j.chemgeo.2016.08.019). The other major component in the samples is melt, modelled to contain an average of 0.85ppb Pt and 1.09ppb Pd. Assuming that Group II kimberlites are derived from relatively metasomatised SCLM, our data suggest that the metasomatised Karelian SCLM is relatively poor in Pt and Pd. If our data are representative of other Group II kimberlites elsewhere, this result could imply that the PGE enrichment in certain continental large igneous provinces, including Bushveld, is not derived from melting of metasomatised SCLM.

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.

Palladium and platinum in hydrothermal systems: The case of porphyry-Cu systems and sulfides associated with ophiolite complexes.

Data on the Pt and Pd contents in sea-floor massive sulfides related to ophiolite complexes indicated elevated Pt contents, up to 1 wt % Pt in sulfides from East Pacific Rise, up to 1000 ppb Pd or Pt in sulfides from mid-Atlantic Ridge and the Pindos ophiolite complex (Greece). Recently, elevated levels of Pd and Pt, have been reported from mineralization associated with alkaline porphyry deposits, such as the Skouries porphyry deposit (Greece), Cordillera of British Columbia, Elatsite (Bulgaria), Santo Tomas II in the Philippines and elsewhere. Current state of knowledge on the solubility of platinum-group elements was applied on hydrothermal systems related to the mineralization in ophiolite complexes and porphyry Cu-Mo-Au±Pd±Pt deposits toward a better understanding of the PGE mineralization in hydrothermal systems and the unknown Pd and Pt potential in porphyry-Cu systems. Ore reserves, mineralogical and geochemical ore data for porphyry-Cu systems are considered to be an encouraging factor for the presence of precious metals. In particular, the occurrence of merenskyite (palladium telluride) associated with chalcopyrite, coupled with the experimental data indicate that porphyry systems are capable to transport significant amounts of Pd and Pt.

Triggers on sulfide saturation in Fe–Ti oxide-bearing, mafic-ultramafic layered intrusions in the Tarim large igneous province, NW China

Three Fe–Ti oxide-bearing layered intrusions (Mazaertag, Wajilitag, and Piqiang) in the Tarim large igneous province (NW China) have been investigated for understanding the relationship of sulfide saturation, Platinum-group element (PGE) enrichment, and Fe–Ti oxide accumulation in layered intrusions. These mafic-ultramafic layered intrusions have low PGE concentrations (<0.4 ppb Os, <0.7 ppb Ir, <1 ppb Ru, <0.2 ppb Rh, <5 ppb Pt, and <8 ppb Pd) and elevated Cu/Pd (2.2 × 104 to 3.3 × 106). The low PGE concentrations of the rocks are mainly attributed to PGE-depleted, parental magma that was produced by low degrees of partial melting of the mantle. The least contaminated rocks of the Mazaertag and Wajilitag intrusions have slightly enriched Os isotopic compositions with γOs(t = 280 Ma) values ranging from +13 to +23, indicating that the primitive magma may have been generated from a convecting mantle, without appreciable input of lithospheric mantle. The Mazaertag and Wajilitag intrusions have near-chondritic γOs(t) values (+13 to +60) against restricted e Nd(t) values (−0.4 to +2.8), indicating insignificant crustal contamination. Rocks of the Piqiang intrusion have relatively low e Nd(t) values of −3.1 to +1.0, consistent with ∼15 to 25 % assimilation of the upper crust. The rocks of the Mazaertag and Wajilitag intrusions have positive correlation of PGE and S, pointing to the control of PGE by sulfide. Poor correlation of PGE and S for the Piqiang intrusion is attributed to the involvement of multiple sulfide-stage liquids with different PGE compositions or sulfide-oxide reequilibration on cooling. These three layered intrusions have little potential of reef-type PGE mineralization. Four criteria are summarized in this study to help discriminate between PGE-mineralized and PGE-unmineralized mafic-ultramafic intrusions.

A chilled margin of komatiite and Mg-rich basaltic andesite in the western Bushveld Complex, South Africa

A chill sequence at the base of the Lower Zone of the western Bushveld Complex at Union Section, South Africa, contains aphanitic Mg-rich basaltic andesite and spinifex-textured komatiite. The basaltic andesite has an average composition of 15.2 % MgO, 52.8 % SiO2, 1205 ppm Cr, and 361 ppm Ni, whereas the komatiite has 18.7 % MgO, 1515 ppm Cr, and 410 ppm Ni. Both rock types have very low concentrations of immobile incompatible elements (0.14–0.72 ppm Nb, 7–31 ppm Zr, 0.34–0.69 ppm Th, 0.23–0.27 wt% TiO2), but high PGE contents (19–23 ppb Pt, 15–16 ppb Pd) and Pt/Pd ratios (Pt/Pd 1.4). Strontium and S isotopes show enriched signatures relative to most other Lower Zone rocks. The rocks could represent a ~20 % partial melt of subcontinental lithospheric mantle. This would match the PGE content of the rocks. However, this model is inconsistent with the high SiO2, Fe, and Na2O contents and, in particular, the low K2O, Zr, Hf, Nb, Ta, Th, LREE, Rb, and Ba contents of the rocks. Alternatively, the chills could represent a komatiitic magma derived from the asthenosphere that underwent assimilation of the quartzitic floor accompanied by crystallization of olivine and chromite. This model is consistent with the lithophile elements and the elevated Sr and S isotopic signatures of the rocks. However, in order to account for the high Pt and Pd contents of the magma, the mantle must have been twice as rich in PGE as the current estimate for PUM, possibly due to a component of incompletely equilibrated late veneer.

Origin of anomalously Ni-rich parental magmas and genesis of the Huangshannan Ni–Cu sulfide deposit, Central Asian Orogenic Belt, Northwestern China

The Huangshannan Ni–Cu sulfide deposit at the southern margin of the Central Asian Orogenic Belt (CAOB) is an important recent discovery in the Eastern Tianshan Region, Northwestern China. The Huangshannan Intrusion is composed of mafic and ultramafic rocks, and its websterite and lherzolite sequences host the sulfide orebodies. Olivine is the dominant mineral in the Huangshannan Intrusion, occurring as olivine inclusions hosted by pyroxene oikocrysts, as olivine crystals in magmatic sulfides, and as poikilitic crystals in the lherzolite. Small olivine inclusions always coexist with large poikilitic olivine crystals in the same sample, resulting in a heterogeneous texture on the scale of the oikocrysts. The Ni abundance ranges from 1540 to 3772ppm in poikilitic olivine grains, from 2114 to 3740ppm in olivine grains hosted by sulfide minerals, and from 2043 to 4023ppm in olivine inclusions hosted by pyroxene oikocrysts. For the three types of olivine, the ranges in forsterite (Fo) content are 78.97–84.92mol.%, 81.57–84.79mol.%, and 80.33–84.68mol.%, respectively. The Ni content of olivine in the lherzolite is anomalously high relative to the range found in most within plate olivine-bearing mafic-ultramafic rocks. The composition of olivine is controlled mainly by that of the parental magma, fractional crystallization and reactions with interstitial silicate and sulfide melts. Both fractional crystallization and reaction with interstitial silicate may cause a decrease in the Ni content of olivine. The possibility that Ni–Fe exchange causes the anomalously high Ni contents in olivine can be excluded because the olivine grains contained in sulfide have similar or lower Ni content than the olivine grains hosted in the silicate rock. Most of the olivine grains are unzoned, and they have anomalously high Ni contents throughout the crystal. Assuming a partition coefficient of Ni between olivine and silicate magma to be 7, the measured Ni content of olivine in the lherzolite (1540–4023ppm with a mean of 2907ppm) indicates that the parental magma contains 220–575ppm (average of 415ppm) Ni. This value is higher than that found in basaltic magmas that crystallized olivine with similar Fo contents compared to the Huangshannan Intrusion. As mentioned above, the symmetric and reproducible variations in both Fo and Ni contents from core to margin in most of the olivine grains cannot be explained by fractional crystallization and reactions with interstitial silicate or sulfide melts but may reflect the equilibration of the olivine with new fluxes of magma as the chamber was replenished. The anomalously Ni-rich composition of the parental magmas of the Huangshannan Intrusion, relative to those of many other mineralized olivine-bearing mafic-ultramafic intrusions, may be produced by upgrading and scavenging of metals from a previously formed sulfide melts by a moderately Ni-rich magma. The mass-balance calculations of PGE data indicate that the parental magma that formed lherzolite contains 0.04ppb Os, 0.02ppb Ir and 0.4ppb Pd, whereas the parental magma that formed websterite has 0.02ppb Os, 0.009ppb Ir and 0.75ppb Pd. Rayleigh modeling using PGE tenors indicates that the massive sulfides may be produced by monosulfide solid solution (MSS)-sulfide liquid fractionation from the magma that formed the websterite. Rayleigh modeling of Fo and Ni contents of olivine shows that the parental magma that formed the lherzolite has experienced previous sulfide segregation and olivine crystallization.

The Giant Xiarihamu Ni-Co Sulfide Deposit in the East Kunlun Orogenic Belt, Northern Tibet Plateau, China

The Xiarihamu Ni-Co deposit, located in the East Kunlun orogenic belt, northern Tibet plateau, is the secondary largest Ni deposit in China and contains ~157 million metric tons (Mt) sulfide ores with average grades of 0.65 wt % Ni, 0.14 wt % Cu, and 0.013 wt % Co. The intrusion consists of gabbroic and ultramafic portions, the main orebody being hosted in the ultramafic portion. The zircons separated from the gabbronorite and websterite yield SHRIMP U-Pb ages of 405.5 ± 2.7 and 406.1 ± 2.7 Ma, indicating a genetic linkage with the Early Devonian regional magmatism (400–410 Ma). The main orebody includes two large ore pods comprising a pod of disseminated sulfides in the western portion grading into multiple ore sublayers to the east. The ore sublayers consist of net-textured and disseminated sulfides. The distribution and shape of the ore pods and sublayers of the orebody are conformable with the undulating roof and bottom of the ultramafic portion. The unusually high Ni/Cu ratios (~4–18) and extremely low tenors of platinum-group elements (PGE; <4 ppb Ir, <85 ppb Pt, and <115 ppb Pd) of the disseminated sulfides indicate a genetic relationship with low degrees of partial melting of a pyroxenite mantle source. The slightly higher Ir and Ru tenors suggest that the disseminated sulfides in the western portion of the main orebody were segregated from less evolved magma under higher mass ratios of silicate melt/sulfide liquid than the sulfides of the middle and eastern portions.

Textural Relationship of Sulfide Ores, PGE, and Sr-Nd-Os Isotope Compositions of the Triassic Piaohechuan Ni-Cu Sulfide Deposit in NE China

The ~216-Ma Piaohechuan no. 4 intrusion in northeastern China, situated in the easternmost part of the Central Asian orogenic belt, is composed of hornblende-olivine gabbro overlain by hornblende gabbro. The intrusion is about 630 m long, 40 to 250 m wide, and 50 to 150 m thick. Nickel sulfide mineralization is restricted to the lower part of the intrusion and contains 10,000 metric tons (t) of Ni with average PGE concentrations of 40 ppb Os, 30 ppb Ir, 36 ppb Ru, 26 ppb Rh, 255 ppb Pt and 161 ppb Pd in 100% sulfide.