Total Platinum-group Elements Research Articles

Platinum-group elements in Late Quaternary high-Mg basalts of eastern Kamchatka: Evidence for minor cryptic sulfide fractionation in primitive arc magmas

The geochemical variations of magmas across and along supra-subduction zones (SSZ) have been commonly attributed to profound changes in the phase and chemical compositions of the mantle source and subduction-derived melt and fluid fluxes, as well as the physical parameters (e.g. depth, temperature, oxygen fugacity etc) of slab dehydration, mineral breakdown and melting. Here we test the variability of the Late Quaternary primitive magmas in the southern and northern parts of the meridionally oriented Eastern Volcanic Belt (EVB) of Kamchatka, with a slab depth varying from 60 to 160 km. Eight high-Mg (Mg# > 60 mol%) basalts were characterized for major, trace and platinum-group element (PGE) abundances, as well as the compositions of olivine phenocrysts and olivine-hosted spinel inclusions. The basalts in our study are geochemically typical of SSZ magmas and contain similar liquidus assemblages of forsteritic olivine (Mg# 78–92 mol%), low-Ti Cr-spinel and clinopyroxene. Although the absolute abundances of major and trace elements, and their ratios, in the basalts fluctuate to some extent, the observed variability cannot be correlated with any of considered parameters in the geometry of the Kamchatka SSZ and conditions of melting. This unexpected result led to the evaluation of the platinum-group element (PGE) systematics against the lithophile and chalcophile trace element geochemistry and the compositions of phenocrysts. Total whole-rock PGE content varies from 2.3 to 11.7 ppb, whereas the normalized PGE concentration patterns are typical for supra-subduction zones magmas and broadly similar in all studied samples. They are enriched in Rh, Pd and Pt relative to mid-ocean ridge basalts (MORB) and have nearly identical concentrations of Ir-group PGE. The only parameter that correlates well with PGE contents is the average Mg# of olivine phenocrysts from 84 to 90.3 mol%. This is interpreted to result from minor cryptic fractionation of sulfide melt, together with primitive olivine, in low-to-mid crustal conditions. Negative Ru anomalies on chondrite-normalized diagrams correspond to the Fe2+/Fe3+ ratios in spinel (a proxy for magma redox conditions), which reflects a replacement of monosulfide solid solution by laurite in the mantle wedge during oxidation.

Distribution and Mobility of Platinum‐Group Elements in the Late Cretaceous Ni‐Laterite in the Northern Oman Mountains

AbstractLow‐grade Ni‐laterite deposits are irregularly developed overlying mafic/ultramafic protoliths in the northern Oman Mountains. Concentrations, distribution patterns, and mobility of platinum‐group elements (PGEs) are investigated in some Ni‐laterite profiles from the Oman ophiolite as potential unconventional PGE resource. The ultramafic protoliths display the lowest PGE contents (average total = 35 ppb) that are similar to the PGE contents in the overlying saprolite zones. The PGE content increased upward in the laterite profile, where the highest total PGE contents (∼253 ppb) are recorded in the oxide and ferricrete/clay‐rich zones. The highest PGE content corresponds to Pt > Ru > Pd, while the lowest PGE content mostly corresponds to Os < Rh < Ir. The general positive correlation between PGE contents and both Cr2O3 and Fe2O3 contents and the positive trend of the chondrite‐normalized PGE patterns in the Ni‐laterite profiles reflect the formation of PGE‐Fe nanoparticle alloys that are hosted by Fe‐rich oxyhydroxides or due to the residual accumulation of chromite in the oxide/clay‐rich zone during the lateritization process. The PGE distribution patterns and positive correlation of total PGE content with the ultramafic index of alteration indicate that PGE can be mobilized in different proportions in the surficial environment upon progressive lateritization processes. The high content of total PGE in the Oman Ni‐laterite is in good agreement with PGE‐rich laterite deposits worldwide. Consequently, the Oman deposits can be considered as an unconventional PGE resource if adequate extraction and refining processes are applied for their recovery from the possible upcoming Ni production.

Platinum Group Elements in the South Transbaikalian Basanites (First Data)

Abstract —Study of the behavior and distribution of platinum group elements (PGE), along with other data, is necessary for geodynamic reconstructions. There are almost no PGE data for Transbaikalia, one of the large regions of Russia. This work presents the first data on the contents and behavior of PGE in the Cenozoic intraplate alkali basaltoids of southern Transbaikalia. The total PGE contents are 20–40 ppb. The PGE pattern of the studied basanites is similar to those of mafic OIB, including the Hawaiian ones, and rocks of large igneous provinces: tholeiitic basalts of the Siberian Platform and basaltoids of the West Siberian Plate. Based on this similarity and on the intraplate location of the South Transbaikalian basanites, we have concluded that the basanitic melts formed under mantle plume impact.

Oxidation of the deep big mantle wedge by recycled carbonates: Constraints from highly siderophile elements and osmium isotopes

Widespread Cenozoic intraplate basalts from eastern China offer the opportunity to investigate the consequences of interaction between the stagnant Pacific slab and overlying asthenosphere and chemical heterogeneity within this “big mantle wedge”. We present and compile a comprehensive study of highly siderophile elements and Mg-Zn isotopes of this magmatic suite (60 samples including nephelinites, basanites, alkali basalts and tholeiites). The large-scale Mg-Zn isotopic anomalies documented in these basalts have been ascribed to mantle hybridization by recycled Mg-carbonates from the stagnant western Pacific plate. Our results reveal that the nephelinites and basanites are characterized by unfractionated platinum-group element (PGE) patterns normalized to primitive upper mantle (PUM) (e.g., PdN/IrN normalized to PUM = 1.1 ± 0.8, 1σ), relatively high total PGE contents (e.g., Ir = 0.25 ± 0.14 ppb) and modern mantle-like 187Os/188Os (0.142 ± 0.020). These characteristics are coupled with lighter Mg isotope (δ26Mg = −0.48 ± 0.07‰) and heavier Zn isotope (δ66Zn = +0.46 ± 0.06‰) compositions compared to the mantle values (δ26Mg: −0.25 ± 0.07‰; δ66Zn: +0.18 ± 0.05‰). Together, these data are interpreted to reflect the oxidative breakdown of low proportions of mantle sulfides in the sources of these small-degree melts, likely caused by recycled carbonates, which then release chalcophile-siderophile elements into carbonatitic melts. By contrast, the contemporaneous alkali basalts and tholeiites are characterized by highly fractionated PGE patterns (e.g., PdN/IrN = 4.4 ± 3.3; Ir = 0.037 ± 0.027 ppb) and radiogenic 187Os/188Os (0.279 ± 0.115) coupled with less fractionated Mg-Zn isotope compositions (δ26Mg: −0.39 ± 0.05‰; δ66Zn: +0.35 ± 0.03‰). In combination with other isotopic (e.g., Sr-Nd) and chemical (SiO2, Ce/Pb, Ba/Th, Fe/Mn) constraints, the alkali basalts and tholeiites were derived from higher degree melting of ancient pyroxenite-bearing mantle in addition to mixing with the aforementioned nephelinitic and basanitic melts. Collectively, we suggest that deep recycled carbonates promoted melting within the “big mantle wedge” leading to the generation of Cenozoic intraplate basalts across eastern China and the “redox freezing of carbonates” may cause the oxidation of Fe0 and S2-. This process may provide an important mechanism to oxidize mantle sulfides and transfer precious metals from deep mantle to crust.

Base metal sulphide geochemistry of southern African mantle eclogites (Roberts Victor): Implications for cratonic mafic magmatism and metallogenesis

Platinum-group elements (PGE) display a chalcophile behaviour and are largely hosted by base metal sulphide (BMS) minerals in the mantle. During partial melting of the mantle, BMS release their metal budget into the magma generated. The fertility of magma sources is a key component of the mineralisation potential of large igneous provinces (LIP) and the origin of orthomagmatic sulphide deposits hosted in cratonic mafic magmatic systems. Fertility of mantle-derived magma is therefore predicated on our understanding of the abundance of metals, such as the PGE, in the asthenospheric and lithospheric mantle. Estimations of the abundance of chalcophile elements in the upper mantle are based on observations from mantle xenoliths and BMS inclusions in diamonds. Whilst previous assessments exist for the BMS composition and chalcophile element budget of peridotitic mantle, relatively few analyses have been published for eclogitic mantle. Here, we present sulphide petrography and an extensive in situ dataset of BMS trace element compositions from Roberts Victor eclogite xenoliths (Kaapvaal Craton, South Africa). The BMS are dominated by pyrite-chalcopyrite-pentlandite (± pyrrhotite) assemblages with S/Se ratios ranging 1200 to 36,840 (with 87% of analyses having S/Se <10,000. Total PGE abundance in BMS range from 0.17 to 223 ppm. We recognise four end-member compositions (types i to iv), distinguished by total PGE abundance and Pt/Pd and Au/Pd ratios. The majority of BMS have low PGE abundances (< 10 ppm) but Type iv BMS have the highest concentration of PGE recorded in eclogites so far (> 100 ppm) and are characteristically enriched in Os, Ir, Ru and Rh. Nano- and micron-scale Pd-Pt antimonide, telluride and arsenide platinum-group minerals (PGM) are observed spatially associated with BMS. We suggest that the predominance of pyrite in the xenoliths reflects the process of eclogitisation and that the trace element composition of the eclogite BMS was inherited from oceanic crustal protoliths of the eclogites, introduced into the SCLM via ancient subduction during formation of the Colesberg Magnetic Lineament c. 2.9 Ga and the cratonisation of the Kaapvaal Craton. Crucially, we demonstrate that the PGE budget of eclogitic SCLM may be substantially higher than previously reported, akin to peridotitic compositions, with significant implications for the PGE fertility of cratonic mafic magmatism and metallogenesis. We quantitatively assess these implications by modelling the chalcophile geochemistry of an eclogitic melt component in parental magmas of the mafic Rustenburg Layered Suite of the Bushveld Complex.

Siderophile and chalcophile elements in spinels, sulphides and native Ni in strongly metasomatised xenoliths from the Bultfontein kimberlite (South Africa)

The metasomatised continental mantle may play a key role in the generation of some ore deposits, in particular mineral systems enriched in platinum-group elements (PGE) and Au. The cratonic lithosphere is the longest-lived potential source for these elements, but the processes that facilitate their pre-concentration in the mantle and their later remobilisation to the crust are not yet well-established. Here, we report new results on the petrography, major-element, and siderophile- and chalcophile-element composition of native Ni, base metal sulphides (BMS), and spinels in a suite of well-characterised, highly metasomatised and weakly serpentinised peridotite xenoliths from the Bultfontein kimberlite in the Kaapvaal Craton, and integrate these data with published analyses. Pentlandite in polymict breccias (failed kimberlite intrusions at mantle depth) has lower trace-element contents (e.g., median total PGE 0.72 ppm) than pentlandite in phlogopite peridotites and Mica-Amphibole-Rutile-Ilmenite-Diopside (MARID) rocks (median 1.6 ppm). Spinel is an insignificant host for all elements except Zn, and BMS and native Ni account for typically <25% of the bulk-rock PGE and Au. High bulk-rock Te/S suggest a role for PGE-bearing tellurides, which, along with other compounds of metasomatic origin, may host the missing As, Ag, Cd, Sb, Te and, in part, Bi that are unaccounted for by the main assemblage.The close spatial relationship between BMS and metasomatic minerals (e.g., phlogopite, ilmenite) indicates that the lithospheric mantle beneath Bultfontein was resulphidised by metasomatism after initial melt depletion during stabilisation of the cratonic lithosphere. Newly-formed BMS are markedly PGE-poor, as total PGE contents are <4.2 ppm in pentlandite from seven samples, compared to >26 ppm in BMS in other peridotite xenoliths from the Kaapvaal craton. This represents a strong dilution of the original PGE abundances at the mineral scale, perhaps starting from precursor PGE alloy and small volumes of residual BMS. The latter may have been the precursor to native Ni, which occurs in an unusual Ni-enriched zone in a harzburgite and displays strongly variable, but overall high PGE abundances (up to 81 ppm). In strongly metasomatised peridotites, Au is enriched relative to Pd, and was probably added along with S. A combination of net introduction of S, Au +/− PGE from the asthenosphere and intra-lithospheric redistribution, in part sourced from subducted materials, during metasomatic events may have led to sulphide precipitation at ~80–120 km beneath Bultfontein. This process locally enhanced the metallogenic fertility of this lithospheric reservoir. Further mobilisation of the metal budget stored in these S-rich domains and upwards transport into the crust may require interaction with sulphide-undersaturated melts that can dissolve sulphides along with the metals they store.

Geochemical characteristics of platinum-group elements in polymetallic nodules from the Northwest Pacific Ocean

Polymetallic nodules and cobalt (Co)-rich crusts are enriched in platinum-group elements (PGEs), especially platinum (Pt) and may be important sinks of PGEs. At present, little information is available on PGEs in polymetallic nodules, and their geochemical characteristics and the causes of PGEs enrichment are unclear. Here, PGEs of polymetallic nodules from abyssal basin in the Marcus-Wake Seamount area of the Northwest Pacific Ocean are reported and compared with the published PGEs data of polymetallic nodules and Co-rich crusts in the Pacific. The total PGEs (LPGE) content of polymetallic nodules in study area is 258×10−9 in average, markedly higher than that of Clarion-Clipperton Zone (CCZ) nodules (ΣPGE=127×10−9) and lower than that of Co-rich crusts in the Marcus-Wake Seamount (ΣPGE=653×10−9), similar to that of Co-rich crusts in the South China Sea (ΣPGE=252×10−9). The CI chondrite-normalized PGEs patterns in different regions of polymetallic nodules and cobalt-rich crusts are highly consistent, with all being characterized by positive Pt and negative Pd anomalies. These results, together with those of previous studies, indicate that PGEs in polymetallic nodules and Co-rich crusts are mainly derived directly from seawater. Pt contents of polymetallic nodules from the study area are negatively correlated with water depth, and Pt/ΣPGE ratios in nodules there are also lower than those of the Co-rich crusts in the adjacent area, indicating that sedimentary water depth and oxygen fugacity of ambient seawater are the possible important controlling factors for Pt accumulation in crusts and nodules.

Genetic classification, distribution and ore genesis of major PGE, Co and Cr deposits in China: A critical review

Major platinum-group element (PGE), cobalt (Co) and chromium (Cr) deposits in China are commonly associated with mafic-ultramafic rocks regardless magmatic or hydrothermal origins. Nearly all PGE and half of Co resources in China are from magmatic Ni-Cu-(PGE) sulfide deposits hosted in mafic-ultramafic intrusions. Major resources of Cr are from podiform chromite deposits associated with the mantle sequences of ophiolites, including the Luobusha chromite deposit in Tibet and the Sartohay chromite deposit in Xinjiang. However, there is a lack of large PGE and chromite deposits related to layered mafic-ultramafic intrusions. Sedimentary rock-hosted stratiform Cu deposits and Ni-Co laterites are two dominant types of Co-bearing deposits among terrestrial Co resources and are sporadically distributed in China, although these are insignificant. Platinum-group elements from three Ni-Cu-(PGE) sulfide-bearing mafic-ultramafic intrusions that formed within-plate settings account for 74% of the total PGE reserves of China. Among these, the Jinbaoshan and Yangliuping intrusions are parts of the Emeishan large igneous province (LIP) in SW China, and the Jinchuan intrusion emplaced in a rifting margin of the southern North China Craton. The Jinbaoshan intrusion hosts the only PGE-dominated deposit in China, but has not yet been mined due to the difficulty for access. In the Jinchuan and Yangliuping Ni-Cu deposits, PGEs are by-products. The Jinchuan intrusion is by far the largest PGE producer in China. Cobalt resources are from deposits associated with mafic-ultramafic rocks in China, including Ni-Cu sulfide deposits, Ni-Co laterites, volcanogenic massive sulfide (VMS) deposits and magmatic Fe-Ti oxide deposits, which make up 41% of total Co reserves of China. Major Ni-Cu sulfide deposits in both within-plate and convergent margin settings contain economic Co resources, such as the Jinchuan intrusion and those in the Emeishan LIP, and the Xiarihamu intrusion in the East Kunlun orogenic belt, the Jianchaling intrusion in a Neoproterozoic subduction zone in the northern margin of the Yangtze block and those in the central Asian orogenic belt. Ni-Co laterites that contain economic Co resource have been only discovered locally in Hannan, Yunnan and Taiwan. The Derni Cu-Co deposit in the A’nyemaqen suture zone of the East Kunlun orogenic belt is a special type of VMS deposits closely associated with ophiolite suites, which is also very rare worldwide. Magmatic Fe-Ti oxide deposits in the Emeishan LIP and hydrothermal iron oxide deposits in the East Tianshan orogenic belt have likely potential Co resources. Podiform chromite deposits in China occur in ophiolites, such as the Sartohay, Hegenshan and Suolunshan ophiolites in the central Asian orogenic belt, the Dadao Erji and Yushi ophiolites in the Qilian-Qinling orogenic belt, the Dongqiao ophiolite in the Bangong-Nujiang suture zone and Luobusha ophiolite in the Yarlung-Zangbo suture zone. Understanding the mechanisms of PGE enrichment in major Ni-Cu-(PGE) sulfide deposits such as the Jinchuan and Jinbaoshan intrusions has been a focus of studies in the past. The dissolution and re-precipitation processes that may lead to the enrichment of PGE and Co during hydrothermal overprints on magmatic Ni-Cu sulfide deposits have gained popularity. The origin of podiform chromite deposits is generally thought to be triggered by melt-mantle interaction and melt mixing. But it appears that such a traditional thought is challenged by the discoveries of various high-pressure and hydrous minerals that are trapped in chromite. Given PGE, Co and Cr are all strategic and critical metals to China, it is very important to conduct new exploration projects near active mines, such as those in the Emeishan LIP and the Jinchuan intrusion. However, additional experimental and mineralogical studies on the enrichment processes of PGE, Co and Cr are desired to make breakthroughs in order to better understand the behaviors of PGE, Co and Cr in magmatic-hydrothermal systems. Main issues that are worthy to be closely examined in the future include (1) micro- to nano-scale occurrence of PGE, (2) enrichment mechanism and occurrence of Co in mafic-ultramafic rocks and related ore deposits, and (3) mobilization and enrichment processes of Cr in the formation of podiform chromite deposits.

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.

Distinct sulfur saturation histories within the Palaeogene Magilligan Sill, Northern Ireland: implications for Ni – Cu – platinum group element mineralisation in the North Atlantic Igneous Province

The ∼60 m thick Magilligan Sill is part of the British Palaeogene Igneous Province in the North Atlantic. The sill comprises layers of dolerite and olivine gabbro, and it intrudes a thick sequence of Mesozoic mudstones and marls, which are locally baked at the sill margins. Since 2014, the sill has been an exploration target for orthomagmatic Ni – Cu – platinum group element (PGE) sulfide mineralisation analogous to the Noril’sk-Talnakh intrusion in Russia. We present new petrological, geochemical, and S isotope data to assess the prospectivity of the sill and the underlying magmatic plumbing system. Most sulfides in the dolerite portions of the sill are &lt;50 μm in size and comprise only pyrite with PGE abundances below the detection limit. In the olivine gabbros, &gt;150 μm size pentlandite, chalcopyrite, and pyrrhotite grains contain &lt;4 ppm total PGE, 1460 ppm Co, and 88 ppm Ag. Pyrite from the dolerites have δ34S ranging from −10.0‰ to +3.4‰ and olivine gabbro sulfides range from −2.5‰ to −1.1‰, suggesting widespread crustal contamination. The S/Se ratios of sulfides in the dolerites and olivine gabbros range from 3500 to 19 500 and from 1970 to 3710, respectively, indicating that the latter may have come from upstream in the magma plumbing system. The Magilligan Sill records multiple injections of mafic magma into an inflating sill package, each with distinct mechanisms towards S saturation. Whilst the sulfide minerals in the sill do not constitute significant mineralisation themselves, detailed in situ studies highlight a divergence in S saturation histories and suggest that a larger volume of olivine gabbro sulfides at depth may be prospective.

The Main Anorthosite Layer of the West-Pana Intrusion, Kola Region: Geology and U-Pb Age Dating

The West-Pana intrusion belongs to the Paleoproterozoic Fedorova-Pana Complex of the Kola Region in NW Russia, which represents one of Europe’s most significant layered complexes in terms of total platinum group element (PGE) endowment. Numerous studies on the age of the West-Pana intrusion have been carried out in the past; however, all published U-Pb isotope ages were determined using multi-grain ID-TIMS. In this study, the mineralized Main Anorthosite Layer from the upper portion of the intrusion was dated using SHRIMP-II for the first time. High Th/U (0.9–3.7) zircons gave an upper intercept age of 2509.4 ± 6.2 Ma (2σ), whereas the lower portion of the intrusion was previously dated at 2501.5 ± 1.7 Ma, which suggests an out-of-sequence emplacement of the West-Pana intrusion. Furthermore, high-grade PGE mineralization hosted by the anorthosite layer, known as “South Reef”, can be attributed to (1) downward percolation of PGE-enriched sulfide liquid from the overlying gabbronoritic magma or (2) secondary redistribution of PGEs, which may coincide with a post-magmatic alteration event recorded by low Th/U (0.1–0.9) zircon and baddeleyite at 2476 ± 13 Ma (upper intercept).

Platinum-group element and gold enrichment in soils monitored by chromium stable isotopes during weathering of ultramafic rocks

Weathering of ultramafic rocks can lead to the formation of soil profiles with high contents of Fe, Ni, Co, platinum-group elements (PGE) and gold. Traditionally, these metal-rich soils are known as “laterites” and are formed under tropical climates and stable tectonic conditions. However, little is known about their possible development in cold/humid regions, and the factors governing PGE and gold mobility and enrichment under these weathering conditions are poorly constrained. In this study, five soil profiles developed on serpentinized, chromite-bearing ultramafic rocks at La Cabaña, located in the Coastal Range of south-central Chile (38° S) were studied by combining major and trace element geochemistry with chromium stable isotope data. The results show that the soils developed at La Cabaña have higher PGE and Au contents than the parent serpentinite rock, with ∑PGE and Au reaching up to 160 ppb and 29 ppb in a limonitic soil horizon and clay saprolite, respectively. Most soil samples have slightly negative δ53/52CrSRM979 values, within a range of −0.089 ± 0.012‰ to −0.320 ± 0.013‰ (average of −0.178‰), and are in agreement with previous data reported for modern soils. A noteworthy relation between δ53/52Cr data and PGE + Au contents is observed in the studied soil horizons, where isotopically lighter values of δ53/52Cr match the higher contents of PGE and gold. These results show that pedogenetic processes operating at the cold and humid La Cabaña area are capable of increasing the total PGE and Au contents of certain soil horizons. Such processes are complex and multivariate but are primarily modulated by chromite dissolution and the formation of secondary phases such as clay minerals and oxy-hydroxide phases in the soil. These findings provide evidence that important weathering and PGE + Au supergene accumulation are not only restricted to tropical latitudes, and that the chromium isotope system is a useful proxy to track surface redox process and noble metal enrichment during pedogenesis.

Early Palaeozoic sub-arc chromitite-bearing peridotite in the Kudi ophiolite on the westernmost Tibetan Plateau

ABSTRACTA chromite deposit was discovered in the Kudi ophiolite in the Palaeozoic western Kunlun orogenic belt. Chromite forms elongated (<2 m in width) and banded chromitite bodies (<0.1 m in width for each band) in dunite and podiform chromitite bodies (<1.5 m in width) in harzburgite. Dunite is classified into two types. Type I dunite hosting massive and banded chromitites shows low Fo in olivine (88.1–90.9), moderate Cr# [=Cr/(Cr + Al), 0.47–0.56] in chromite, and a positively sloped primitive mantle-normalized platinum group elements (PGE) pattern, suggesting that it is a cumulate of a mafic melt. Harzburgite and type II dunite show olivine with high Fo (>91.1) and chromite with moderate to high Cr# (0.44–0.61), and flat to negatively sloped primitive mantle-normalized PGE patterns, indicating that they are residual mantle peridotite after partial melting. Chromite in all three types of chromitites has relatively uniform moderate values Cr# ranging from 0.43 to 0.56. Massive chromitite contains euhedral chromite with high TiO2 (0.40–0.43 wt.%) and has a positively sloped primitive mantle-normalized PGE pattern, suggesting that it represents a cumulate of a melt. Rocks containing disseminated and banded chromite show overall low total PGE, < 117 ppb, and a negatively sloped primitive mantle-normalized PGE pattern. Chromite grains in these two types of occurrences are irregular in shape and enclose olivine grains, suggesting that chromite formed later than olivine. We suggest that chromite-oversaturated melt penetrated into the pre-existing dunite and crystallized chromite. The oxygen fugacity (fO2 values of chromitites and peridotites are high, ranging from FMQ+0.8 (0.8 logarithmic unit above the fayalite-magnetite-quartz buffer) to FMQ+2.3 for chromitites and from FMQ+0.9 to FMQ+2.8 for peridotites (dunite and harzburgite). The mineral compositions and high fO2 values as well as estimated parental magma compositions of the chromitites suggest that the Kudi ophiolite formed in a sub-arc setting.

An assessment of the inhalation bioaccessibility of platinum group elements in road dust using a simulated lung fluid

Metal enrichment of road dust is well characterized but available data on the bioaccessibility of metals in particle size fractions relevant to human respiratory health remain limited. The study goal was to investigate the bioaccessibility of platinum group elements (PGE), which are used as catalysts in automotive exhaust converters, in the inhalable fraction of road dust. Street sweepings were provided by the City of Toronto, Canada, collected as part of its Clean Roads to Clean Air program.The particle size relevance of road dust for inhalation exposures was confirmed using a laser diffraction particle size analyzer (mean Dx(50): 9.42 μm). Total PGE were determined in both bulk and inhalable fractions using nickel sulfide (NiS) fire-assay and instrumental neutron-activation analysis (INAA). PGE lung solubility was examined for the inhalable fraction using Gamble’s extraction. Sample digests were co-precipitated with Te-Sn, to pre-concentrate and isolate PGE, prior to their measurement using inductively coupled plasma mass spectrometry (ICP-MS).Total PGE concentrations were enriched in the inhalable fraction of road sweepings. Geomean concentrations in the inhalable fraction were: palladium (Pd) (152 μg/kg), platinum (Pt) (55 μg/kg), rhodium (Rh) (21 μg/kg) and iridium (Ir) (0.23 μg/kg). Osmium (Os) concentrations were below the limit of detection (LOD). Bioaccessible PGEs (n = 16) using Gamble’s solution were below LOD for Ir and ruthenium (Ru). For the remainder, the geomean % bioaccessibility was highest for platinum (16%), followed by rhodium (14%) and palladium (3.4%). This study provides evidence that PGE in road dust are bioaccessible in the human lung.

Platinum-group minerals (PGM) in the chromitite from the Nuasahi massif, eastern India: further findings and implications for their origin

We report the first find of Al-rich chromitites in the Nuasahi massif located in the Singhbhum Craton, eastern India. Electron microprobe analyses yielded Al 2 O 3 contents between 19.86 and 25.86 wt%. The Cr 2 O 3 and Fe 2 O 3 concentrations vary (in wt %) from 34.8 to 40.67 and 5.38 to 7.05, respectively. TiO 2 content ranges from 0.04 to 0.71 wt%. The silicates interstitial to chromite consist of enstatite, magnesiohornblende and clinochlore. One sample contains 855 ppb of total platinum-group elements (PGE) and shows a chondrite-normalized PGE pattern with a slightly positive slope, with enrichment in Pt and Pd relative to Os and Ir. Ruthenium and Rh show positive and negative peaks, respectively. In agreement with the PGE distribution, the following platinum-group minerals (PGM) have been found: laurite ((Ru,Os)S 2 ), erlichmanite ((Os,Ru)S 2 ), irarsite (IrAsS), vysotskite ((Pd,Ni)S), braggite or cooperite ((Pt,Pd,Ni)S) and Pd-telluride. The PGM form small grains, less than 10 μm across, and occur associated with base metal sulphides (BMS) and rutile included in magmatic minerals, such as chromite and enstatite. The BMS occur exclusively included in chromite. Mineralogical observations suggest that the (Os, Ir, Ru), Pt- and Pd-bearing phases crystallized in the magmatic stage, before or during the precipitation of the host chromite, under relatively high sulphur fugacity. Part of the Pd, together with Te, was initially enclosed at high temperature as small clusters in the sulphide liquid and then incorporated in the crystallizing BMS. Finally, these elements precipitated as Pd-telluride blebs, as an exsolution product at lower temperatures. Rutile occurs as a minor phase in association with PGM, included in chromite or in the contact chromite–silicate. The mode of occurrence of rutile in the Nuasahi chromitite is similar to that reported from the stratiform chromitites emplaced in stable cratonic settings.

Ophiolitic Chromitites of Timor Leste: Their Composition, Platinum Group Element Geochemistry, Mineralogy, and Evolution

Ultramafic rocks that crop-out as fault-bounded blocks within Hili Manu, ∼50 km east of the capital Dili on the north coast of Timor Leste, have been a topic of considerable debate regarding their ophiolitic affiliation with the Banda Arc or Australian subcontinental lithosphere. Two discrete ultramafic massifs separated by amphibolite of undefined origin, Be Heda Hill and Kerogeol Hill in the east and Subao Highway in the west, have been identified and host tabular and vein-like chromitite morphologies, respectively. The chromitite bodies at Hili Manu occur as small lenses a few meters in size. This paper presents the first detailed investigation of the chromitites from the two massifs at Hili Manu, including their mineralogy, textures, and chemistry. Chemically, the primary chromites from the Hili Manu chromitites comprise both high-Cr type (Cr2O3 40.24–56.95 wt.% and Cr# [Cr/(Cr + Al)] > 0.6) that occur at Kerogeol Hill and Subao Highway and high-Al type (Cr2O3 35.70–37.38 wt.% and #Cr < 0.56) that are restricted to Be Heda Hill. Similarly, the accessory spinels of the enclosing wall rocks also show high-Cr (#Cr = 0.60–0.82) and high-Al varieties (#Cr = 0.17–0.48). Platinum-group minerals (PGM) such as laurite and possible erlichmanite-series minerals, silicates, base metal sulfides (BMS), and arsenides are found as inclusions and within fractures in the chromite or the serpentinite matrix. The platinum-group element (PGE) concentration of the Hili Manu chromitites and its immediate host peridotite at the three localities varies, with total PGE (Os + Ir + Ru + Rh + Pt + Pd) in the ranges 73.1–1295 ppb and 28.5–364 ppb, respectively. The total PGE content is higher and the Pd/Ir ratio is lower in the Cr-rich chromitites compared to the Al-rich ones. Most of the PGM are 3–10 μm in size and occur as primary or composite inclusions in IPGE-bearing phases, particularly Os-rich laurite, within unaltered chromite grains. Host peridotite major- and trace-element geochemistry coupled with the chemistry of chrome-spinels for both the chromitites and host peridotites in this study show evidence of formation of the Hili Manu peridotite in an upper mantle in a supra-subduction zone setting, part of the young oceanic lithosphere from the Banda Arc.

Homogenisation of sulphide inclusions within diamonds: A new approach to diamond inclusion geochemistry

Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100°C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages.We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source.

Platinum-group element and Re-Os geochemistry of lamprophyres in the Zhenyuan gold deposit, Yunnan Province, China: Implications for petrogenesis and mantle evolution

Cenozoic lamprophyres are widespread along the Ailaoshan suture, SW Yunnan, SW China, where there are also many important gold deposits, especially the Zhenyuan deposit. We have carried out a geochemical investigation of the Zhenyuan lamprophyres in terms of major and trace elements, platinum-group elements (PGE), and Os isotopes. The Zhenyuan lamprophyres can be classified into groups with high or low Os concentrations. The 187Os/188Os ratios, corrected for in situ growth, are highly variable in both types of lamprophyre, ranging from mantle values up to 1.13. The highly radiogenic Os isotopic signatures are interpreted as being due to long-term accumulation of elevated Re/Os in the lithospheric mantle, as a result of subduction-related metasomatism. The highly variable 187Os/188Os ratios of the low-Os lamprophyres might also have resulted from metasomatism of a deeply derived carbonate melt, which did not elevate Os concentrations significantly. The Zhenyuan lamprophyres feature low PGE contents and can be classified into two groups: A and B, based on their primitive-mantle-normalized PGE patterns. Group A is characterized by strongly negative Ru anomalies, while Group B is characterized by slightly negative Ru anomalies and low total PGE contents. The PGE characteristics may be explained by a two-stage model of magma evolution. Very high Cu/Pd and low Pt/Y ratios indicate the first stage involved sulfur saturation and sulfide removal, producing variable total-PGE concentrations, especially in Group B. The second stage involved S-undersaturation and the early crystallization of silicate minerals (e.g., olivine) along with laurite and/or Ru-Ir-Os alloy, fractionating PGEs and producing marked negative Eu anomalies.

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.

Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic)

Thick ferromanganese (Fe-Mn) crusts from four Cretaceous seamounts (The Paps, Tropic, Echo and Drago) at the southern Canary Island Seamount Province (CISP) in the northeastern tropical Atlantic were recovered along the flanks and summits from 1700 to 3000m water depths. CISP is composed of >100 seamounts and submarine hills, is likely the oldest hotspot track in the Atlantic Ocean, and is the most long-lived of known hotspots globally. The Fe-Mn crusts grow on basalt-sedimentary rock substrates below the northeastern tropical Atlantic core of the oxygen minimum zone (OMZ) with a maximum thickness of 250mm at a water depth of 2400m. The mineralogical and chemical composition of these Fe-Mn crusts indicate a hydrogenetic origin. The main Mn minerals are vernadite with minor interlayered todorokite and asbolane-buserite. Fe oxides are essentially ferroxyhyte and goethite. The Fe-Mn crusts show high average contents in Fe (23.5wt%), Mn (16.1wt%), and trace elements like Co (4700μg/g), Ni (2800μg/g), V (2400μg/g) and Pb (1600μg/g). Rare earth elements plus yttrium (REY) averages 2800μg/g with high proportions of Ce (1600μg/g). Total platinum group elements (PGEs) average 230ng/g, with average Pt of 182ng/g. Two main types of growth layers form the crusts: 1) a dense laminae of oxides with high contents in Mn, Co and Ni associated with vernadite and Cu, Ni, and Zn associated with todorokite; 2) botryoidal layers with high contents in Fe, Ti, V and REY associated with goethite. The Fe-Mn crusts from the CISP region show higher contents in Fe, V, Pb and REY but lower Mn, Co, Ni and PGEs contents than Pacific or Indian ocean seamount crusts. The oldest maximum age of initiation of crust growth was at 76Ma (Campanian, Late Cretaceous). Using a combination of high resolution Co-chronometer and geochemical data along an Electron Probe Micro Analysis (EPMA) transect, four stages in morphology, chemical contents and growth rates can be differentiated in the the Cenozoic crusts since 28Ma, which we interpret as due to changes in the ventilation of the North Atlantic OMZ and to the increase of Saharian dust inputs. An earliest growth period, characterized by similar contents of Fe and Mn in the interval 27.8–24.45Ma (late Oligocene-early Miocene) reflects slow precipitation related to a thick OMZ. An intermediate laminated zone with higher contents of Fe, Si and P, high growth rates reaching 4.5mm/Ma, and precipitation of Fe-Mn oxides during the interval 24.5–16Ma is related to periods of ventilation of the OMZ by intrusion of deep upwelling currents. Significant increase in Fe contents at ca. 16Ma correlates with the onset of incursions of Northern Component Waters into the North Atlantic. Finally, since 12Ma, the very low growth rates (<0.5mm/Ma) of the crust are related to a thick North Atlantic OMZ, an increase in Sahara dust input and a stable thermohaline circulation.