Platinum-group Elements Patterns Research Articles

Implications for the origins of Eoarchean ultramafic rocks of the North Atlantic Craton: a study of the Tussaap Ultramafic complex, Itsaq Gneiss complex, southern West Greenland

Ultramafic rocks found within the ~ 3.81 Ga Itsaq Gneiss Complex (IGC) have some mantle-like geochemical characteristics that have led to them being used to directly constrain the nature of the Eoarchean mantle. The discrimination of mantle peridotites that are the residues of partial melting, from cumulate peridotites generated by crystal accumulation from mantle-derived magmas can be difficult in ancient, altered ultramafic rocks whose field relations have been obscured by multiple tectonic episodes. Hence it is important to scrutinize significant individual occurrences of Eoarchean ultramafic rocks in some detail prior to using them to constrain the nature of Earth’s early mantle. Here we present mineral chemistry, whole rock major-, trace-, and platinum-group-element abundances, and Re–Os isotope compositions of a previously unstudied large ultramafic enclave in the IGC—the Tussaap Ultramafic Complex (TUC)—with the aim of documenting its origin. High FeO contents of up to 15.5 wt% and correlations between MgO and Os provide strong evidence that the TUC evolved through fractional crystallization rather than partial melt extraction. In addition, co-variations of major elements in the TUC lithologies can be modeled via fractional crystallization of picritic basalts using MELTS. Later alteration and metasomatism of these ultramafic rocks has largely overprinted primary mineral chemistry and resulted in a redistribution of light rare earth elements, rendering these tools ineffective for ascertaining the origin of the TUC or quantifying some of the petrogenetic processes that formed the body. In addition, it is clear that many geochemical features used to identify residual mantle peridotites can also be produced by cumulate or alteration processes, such as some variations in olivine and chromite chemistry, whole rock Al/Si vs Mg/Si systematics, and trace and platinum group element patterns. Finally, combined discrimination diagrams for high field strength elements and moderately high 187Os/188Os ratios suggest the parental melt of the TUC partially assimilated basaltic crust prior to precipitating the TUC cumulates. As such, these rocks represent a variably obscured record of Eoarchean crystal fractionation from mantle-derived melts. Despite not being prima facie mantle rocks, it is possible that such early formed ultramafic cumulates in nascent continents found their way into the later-stabilized roots of Archean cratons, helping to explain the high compositional variability of cratonic peridotites.

Uniform 182W isotope compositions in Eoarchean rocks from the Isua region, SW Greenland: The role of early silicate differentiation and missing late veneer

Abstract Eoarchean rocks from the Isua region in southern West Greenland are known to exhibit isotope anomalies of 182W and 142Nd. The excess 182W in many rocks from the Isua region have been explained by two endmember models: (1) missing late veneer or (2) silicate differentiation shortly after Earth’s formation. Furthermore, it has been proposed that pristine W isotope systematics in rocks from the Isua region (herein the Isua supracrustal belt and adjacent area) have been obscured by metamorphic disturbance. To address these issues, we present a comprehensive dataset, combining high precision 182W isotope data with trace element data, including high precision elemental W-Th-U-Ta abundance data. We present an improved analytical protocol that allows processing gram-sized samples with W abundances in the lower ng/g range. This protocol also results in markedly improved ion exchange column yields and cleaner W fractions, thereby minimizing nuclear volume effects on 183W. To compare with previous studies, our dataset includes some samples from previously investigated units in the Isua region (Isua Supracrustal Belt (ISB) mafic–ultramafic assemblages and Ameralik dikes). In addition, several Eoarchean key units in the Isukasia terrane (Isua region) and the Faeringehavn terrane (Nuuk region) have been examined for their W isotope composition in this study for the first time. These newly investigated units include recently recognized mantle-like peridotites from both terranes that display PGE abundances and patterns similar to modern depleted mantle peridotites, felsic lithologies from the ISB, as well as key amphibolite and TTG localities from low-strain domains south of the ISB. Virtually all rocks from the Isua region show significant W enrichment with W/Th of up to 160 in mafic to ultramafic samples. None of the samples from SW Greenland that were object of 182W isotope analysis in this study and virtually all previous studies appear to have preserved near canonical W/Th ratios (i.e., between 0.09 and 0.24). Independent of W enrichment, however, it can now be shown that there is a uniform 182W isotope excess in the different rock types from the Itsaq Gneiss Complex (IGC) (average 12.8 ppm ± 1 ppm, 95% confidence interval). Importantly, none of the rock suites investigated exhibit modern mantle-like 182W isotope signatures of µ182W = 0. By combining 182W signatures in the different lithologies with elemental W systematics, we therefore can infer that the 182W excess in Eoarchean rocks from the Isua region is widespread, and independent of W enrichment. Hence, we regard the 182W excess as an intrinsic feature of the Eoarchean assemblages in the Isua region. Notably, mantle-like peridotites from both the Isukasia and Faeringehavn terranes display the same 182W excess, as all other units, although they have been shown to display the full inventory of Highly Siderophile Elements (HSE) found in Phanerozoic mantle peridotites. Evidently, the W isotope budget in these rocks is clearly decoupled from HSE systematics, which hampers a straightforward explanation for 182W isotope excesses in terms of the missing late veneer model. As Platinum Group Element (PGE) patterns in mantle-like Eoarchean peridotites from the Isua region are similar to those in Phanerozoic rocks, we rather propose that to a large extent the 182W excesses are a vestige of early silicate differentiation processes, in line with positive 142Nd anomalies found in rocks from the Isua region, suggesting initial silicate differentiation prior to 4.50 Ga.

Mineralogy and geochemistry of peridotites and chromitites in the Aladag Ophiolite (southern Turkey): melt evolution of the Cretaceous Neotethyan mantle

The Aladag Ophiolite (also known as the Pozanti-Karsanti Ophiolite) is one of the largest Neotethyan ophiolites in Turkey and represents Cretaceous oceanic lithosphere derived from the Inner Tauride seaway of Neotethys. Its peridotites consist of spinel harzburgites, dunites and chromitites. The harzburgites display a depleted mineral and whole-rock geochemistry, indicating high degrees of partial melting. They contain Pd- and Pt-rich interstitial sulphides, which crystallized from S-saturated melts during melt–rock interactions. Their spoon-shaped rare earth element patterns indicate metasomatism by fluids, derived from a subducting slab, which were enriched in light rare earth elements. The chromitites in both the mantle and mantle–crust transition zone rock units show similar geochemical compositions, typical of high-Cr chromitites. They also show similar chondrite-normalized platinum group element patterns characterized by Os, Ir, Ru and Rh enrichments relative to Pt and Pd. The parental melts of the Aladag Ophiolite chromitites were S-undersaturated and boninitic in composition. The presence of microdiamond, moissanite, zircon and needle-shaped clinopyroxene exsolutions in chromite (chr) grains suggests that their formation might have originally involved high-temperature and high-pressure conditions within the mantle transition zone before their participation in further melting and the formation of oceanic crust at shallow depths in a forearc tectonic setting during the initiation of intra-oceanic subduction within the Inner Tauride seaway. Supplementary material: Sampling and analytical methods, representative microprobe analyses and whole-rock major and trace element compositions are available at https://doi.org/10.6084/m9.figshare.c.4153631 Thematic collection: This article is part of the ‘Tethyan ophiolites and Tethyan seaways collection’ available at: https://www.lyellcollection.org/cc/tethyan-ophiolites-and-tethyan-seaways

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.

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

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

Geochemical investigation of the lower Cambrian mineralised black shales of South China and the late Devonian Nick deposit, Canada

Lower Cambrian (Tommotian) black shales of the Niutitang Formation, South China, host a thin accumulation (5–20 cm) of Ni, Mo, platinum group elements (PGE)-Au, Ni, As, Zn, Cu, V and rare earth elements (REE). Of all known deposits, the late Devonian Ni-Mo-PGE sulphide horizon in black shales of the Nick deposit, Selwyn Basin in Canadian Yukon, presents the strongest similarity with the Niutitang Formation polymetallic layer. In the present study, samples of the mineralised layer and host shales in South China from two mine sites (Zunyi and Sancha) were investigated in order to further characterise the prevailing redox conditions and mechanisms involved in the metal concentration process at both sites. Additional comparison with the Nick deposit mineralised layer was also undertaken. Bulk geochemical analysis (including PGE analysis) were conducted on all samples, along with μm-scale investigation of metal distributions and associations by X-ray fluorescence (XRF) mapping and Synchrotron XRF mapping. The comparison of the two sites from South China highlights strong similarities in metal enrichment factors. PGE and REE distribution patterns are also highly similar and suggest a source from seawater. Strong variations in elemental distributions at µm-scale were observed at both sites, most likely related to intense variations in redox conditions in the sediment. The comparison with the Nick deposit highlights a stronger enrichment in Ni and Zn in the Nick deposit and a greater variety of minerals in the Niutitang shales. The PGE and REE distributions of both the Nick deposit and the Niutitang shales, however, present highly similar patterns, and support an origin from seawater. The present study provides further insight into mineralisation style and processes in these mineralised black shales, highlighting the importance of redox conditions and re-emphasizing the role of organic matter in the formation of these mineralised layers.

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

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

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.

Mineralogy, geochemistry, and melt evolution of the Kalaymyo peridotite massif in the Indo-Myanmar Ranges (western Myanmar), and tectonic implications

We present new whole-rock major, trace, and platinum group element (PGE) and mineral chemistry data from the Kalaymyo peridotite massif in the central part of the Indo-Myanmar Ranges (western Myanmar) and discuss its mantle melt evolution. The Kalaymyo peridotites consist mainly of harzburgites, which show typical porphyroclastic or coarse-grained equigranular textures. They are composed of olivine (forsterite, Fo = 89.8–90.5), orthopyroxene (enstatite, En 86–91 , wollastonite, Wo 1–4 , ferrosilite, Fs 8–10 ; Mg# = 89.6–91.9), clinopyroxene (En 46–49 Wo 47–50 Fs 3–5 ; Mg# = 90.9–93.6), and spinel (Mg# = 67.1–78.9; Cr# = 13.5–31.5), and have relatively homogeneous whole-rock compositions with Mg#s of 90.1–90.8 and SiO 2 (41.5–43.65 wt%), Al 2 O 3 (1.66–2.66 wt%), and CaO (1.45–2.67 wt%) contents. They display light rare earth element (LREE)–depleted chondrite-normalized (CN) REE patterns with (La/Yb) CN = 0.04–0.21 and (Gd/Yb) CN = 0.40–0.84, and show a slight enrichment from Pr to La with (La/Pr) CN in the range of 0.98–2.36. The Kalaymyo peridotites are characterized by Pd-enriched chondrite-normalized PGE patterns with superchondritic (Pd/Ir) CN ratios (1.15–2.36). Their calculated oxygen fugacities range between the quartz-fayalite-magnetite (QFM) oxygen buffers, QFM–0.57 and QFM+0.90. These mineralogical and geochemical features collectively suggest that the Kalaymyo peridotites represent residual upper mantle rocks after low to moderate degrees (5%–15%) of partial melting at a mid-oceanic ridge environment. The observed enrichment in LREE and Pd was a result of their reactions with enriched mid-oceanic ridge basalt–like melts percolating through these already depleted residual peridotites. The Kalaymyo and other ophiolites in the Indo-Myanmar Ranges therefore represent mid-oceanic ridge–type Tethyan oceanic lithosphere derived from a downgoing plate and accreted into a westward-migrating subduction-accretion system along the eastern margin of India.

Origin of Peridotites and Chromitites in the Pozanti‐kar Santi Ophiolite, Turkey

The Pozanti‐Karsanti ophiolite (PKO) in Turkey's eastern Tauride belt comprises mantle peridotites, ultramafic to mafic cumulates, isotropic gabbros, sheeted dikes and pillow lavas. The mantle peridotites are dominated by spinel harzburgites with minor dunites. The harzburgites and dunites have quite depleted mineral and whole‐rock chemical composition, suggesting high degrees of partial melting. Their PGEs vary from Pd‐depleted to distinct Pd‐enriched patterns, implying the crystallization of interstitial sulphides from sulphur‐saturated melts (e.g. MORB‐like forearc basalt). U‐shaped or spoon‐shaped REE patterns indicate that the PKO peridotites may have also been metasomatized by the LREE‐enriched fluids released from a subducting slab in a suprasubduction zone. Based on the mineral and whole‐rock chemical compositions, the PKO peridotites show affinities to forearc peridotites. Chromitites occur both in the mantle peridotites and the mantle‐crust transition zone horizon (MTZ). Chromitites from the two different horizons have different textures but similar mineral compositions, consistent with typical high‐Cr chromitites. Chromitites hosted by mantle harzburgites generally have higher total platinum‐group element (PGE) contents than those of the MTZ chromitites. However, both chromitites show similar chondrite‐normalized PGE patterns characterized by clear IPGEs, Rh‐enrichments relative to Pt and Pd. Such PGE patterns indicate no or only minor crystallization of Pt‐ and Pd enriched sulphides during formation of chromitites from a sulphur‐undersaturated melt (e.g. boninitic or island arc tholeiitic melt). Dunite enveloping chromitite lenses in the hosting harzburgite resulted from melt‐rock reaction.We have performed mineral separation work on samples of podiform chromitite hosted by harzburgites. So far, more than 200 grains of microdiamond and more than 100 grains of moissanite (SiC) have been separated from podiform chromitites. These minerals have been identified by EDX and Laser Raman analyses. The diamonds and moissanite are accompanied by large amounts of rutile. Additionally, zircon, monazite and sulphides are also common phases within the heavy mineral separates. Both diamond and moissanite have been analyzed for carbon and nitrogen isotopic composition using the CARMECA 1280‐HR large geometry Secondary Ion Mass Spectrometer at the Helmholtz Zentrum Potsdam. In total, 61 δ13CPDB results for diamond were acquired, exhibiting a range from −28.4 ‰ to −18.8 ‰. 31 δ13CPDB results for Moissanite vary between −30.5 ‰ to −27.2 ‰, with a mean value of −29.0 ‰. Diamond has relatively large variation in nitrogen isotopic composition with 40 δ15NAIR results ranging from −19.1 ‰to 16.6 ‰.The discovery of diamond, moissanite and the other unusual minerals from podiform chromitite of the Pozanti‐Karsanti ophiolite provides new support for the genesis of ophiolitic peridotites and chromitites under high‐pressure and ultra‐high reducing conditions. Considering the unusual minerals, the high Mg# silicate inclusions, and the needle‐shaped exsolutions in the PKO chromitites, the parental melts of these chromitites may have been mixed with deep asthenospheric basaltic melts that had assimilated materials of the descending slab when passing through the slab in a subduction zone environment. We suggest melt‐rock reactions, magma mixing and assimilation may have triggered the oversaturation of chromites and the formation of PKO chromitites.

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.

Chemical homogeneity of high-Cr chromitites as indicator for widespread invasion of boninitic melt in mantle peridotite of Bir Tuluha ophiolite, Northern Arabian Shield, Saudi Arabia

The Bir Tuluha ophiolite is one of the most famous chromitite-bearing occurrences in the Arabian Shield of Saudi Arabia, where chromitite bodies are widely distributed as lensoidal pods of variable sizes surrounded by dunite envelopes, and are both enclosed within the harzburgite host. The bulk-rock geochemistry of harzburgites and dunites is predominately characterized by extreme depletion in compatible trace elements that are not fluid mobile (e.g., Sr, Nb, Ta, Hf, Zr and heavy REE), but variable enrichment in the fluid-mobile elements (Rb and Ba). Harzburgites and dunites are also enriched in elements that have strong affinity for Mg and Cr such as Ni, Co and V. Chromian spinels in all the studied chromitite pods are of high-Cr variety; Cr-ratio (Cr/(Cr+Al) atomic ratio) show restricted range between 0.73 and 0.81. Chromian spinels of the dunite envelopes also show high Cr-ratio, but slightly lower than those in the chromitite pods (0.73–0.78). Chromian spinels in the harzburgite host show fairly lower Cr-ratio (0.49–0.57) than those in dunites and chromitites. Platinum-group elements (PGE) in chromitite pods generally exhibit steep negative slopes of typical ophiolitic chromitite PGE patterns; showing enrichment in IPGE (Os, Ir and Ru), over PPGE (Rh, Pt and Pd). The Bir Tuluha ophiolite is a unimodal type in terms of the presence of Ru-rich laurite, as the sole primary platinum-group minerals (PGM) in chromitite pods. These petrological features indicates that the Bir Tuluha ophiolite was initially generated from a mid-ocean ridge environment that produced the moderately refractory harzburgite, thereafter covered by a widespread homogeneous boninitic melt above supra-subduction zone setting, that produced the high-Cr chromitites and associated dunite envelopes. The Bir Tuluha ophiolite belt is mostly similar to the mantle section of the Proterozoic and Phanerozoic ophiolites, but it is a “unimodal” type in terms of high-Cr chromitites and PGE-PGM distribution.

Modification of an ancient subcontinental lithospheric mantle by continental subduction: Insight from the Maowu garnet peridotites in the Dabie UHP belt, eastern China

Orogenic mantle-derived peridotites commonly originate from the subcontinental lithospheric mantle (SCLM) and thus provide a key target to investigate the modification of the SCLM by a subducting slab. The Maowu ultramafic rocks from the Dabie ultrahigh-pressure (UHP) metamorphic belt have formerly been debated as representing cumulates or mantle-derived peridotites. Detailed petrological and geochemical data presented in this study provide new constraints on the origin and formation of the peridotites involving melt depletion in the ancient SCLM and deep crustal metasomatism. The Maowu garnet dunites have refractory bulk compositions characterized by high Mg# (91.9–92.0) and Ni (2537–2892ppm) values and low Al2O3 (0.26–0.76wt.%), CaO (0.05–0.32wt.%), TiO2 (<0.03wt.%), Pd/Ir (0.40–0.46) and 187Os/188Os (minimum 0.11461) values. The Paleoproterozoic model ages (TRD=2.1Ga, TMA=2.3Ga) of the most refractory dunites represent minimum estimates for the age of the initial melt extraction. The extremely depleted nature, high olivine Fo (92.7–93.9), high Cr# (82–87) of spinel, and Re–Os isotopic data suggest that the Maowu garnet dunites are the residues of ~40% partial melting and represent a Paleoproterozoic fragment of the SCLM beneath the southeastern margin of the North China craton. Many garnet orthopyroxenite veins crosscutting the Maowu dunites preserve abundant metasomatic textures and show variable enrichment in incompatible elements. Mineral and whole-rock chemistry indicate that these veins represent metasomatic products between the wall dunites and silica-rich hydrous melts under UHP conditions. The veins show large variations in platinum-group element (PGE) signatures and Re–Os isotopes. The garnet-poor orthopyroxenite veins are characterized by low Al2O3 (<2wt.%) and S (<31ppm) contents and have PGE patterns and 187Os/188Os ratios similar to the wall dunites, whereas the garnet-rich orthopyroxenite veins have high Al2O3 (>6wt.%) and S (99–306ppm) contents and show melt-like PGE patterns and high 187Os/188Os ratios (up to 0.36910). These features, combined with the occurrence of interstitial sulfides in the garnet-rich orthopyroxenite veins, suggest that crust-derived sulfur-saturated silicate melts may have significantly modified the PGE signature and destroyed the Re–Os systematics of the SCLM. However, when the crust-derived silicate melts became sulfur-depleted, such melts would not significantly modify the PGE patterns, radiogenic Os-isotope compositions or the Re-depletion model ages of the SCLM. Consequently, deep crust-mantle interactions in continental subduction zones could induce high degrees of Os isotopic heterogeneity in the SCLM wedge.

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

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

Distribution of PGE in Permo-Triassic basalts of the Siberian Large Igneous Province

We have revealed the spatio-temporal regularities of distribution of platinum group elements (PGE) in basaltoids related to the activity of the Siberian mantle plume. As objects of study, we chose rift and flood basalts from the Norilsk district (sampled from the SD-9 borehole), flood basalts from the central part of the Tunguska syneclise (Lower Tunguska), Kuznetsk Basin traps, and subalkalic basalt from the Semeitau volcanoplutonic structure in eastern Kazakhstan. Based on the PGE patterns of basaltoids related to the activity of the Permo-Triassic Siberian plume, we have shown that the rocks that formed in the central part of the Siberian Large Igneous Province (LIP) at the early rift stage have low contents of PGE, whereas picrites and tholeiitic flood basalts have high contents. The rift (Semeitau structure) and flood (Kuznetsk Basin traps) basalts from the peripheral regions are characterized by extremely low PGE contents. The high PGE contents in magmas of the plume head are responsible for the high productivity of ultramafic-mafic trap magmatism. The elevated K contents in magmas and the high PGE contents in the mantle plume head are probably due to the ascent of deep-seated material from the core-lower-mantle boundary, as follows from the thermochemical model of the Siberian plume.

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

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

Age and evolution of the deep continental root beneath the central Rae craton, northern Canada

Canada is host to at least six separate cratons that comprise a significant proportion of its crustal extent. Of these cratons, we possess knowledge of the cratonic lithospheric roots beneath only the Slave craton and, to a lesser extent, the Superior craton, despite the discovery of many new diamond-bearing kimberlites in Canada's North. Here we present the first age, composition and geothermal information for kimberlite-borne peridotite xenoliths from two localities within the central Rae craton: Pelly Bay and Repulse Bay. Our aim is to investigate the nature and evolution of the deep lithosphere in these regions and to examine how events recorded in the mantle may or may not correlate with the complex history of crustal evolution across the craton.Peridotite xenoliths are commonly altered by secondary processes including serpentinization, silicification and carbonation, which have variably affected the major element compositions. These secondary processes, as well as mantle metasomatism recorded in pristine silicate minerals, however, did not significantly modify the relative compositions of platinum-group elements (PGE) and Os isotope ratios in the majority of our samples from Pelly Bay and Repulse Bay, as indicated by the generally high absolute PGE concentrations and mantle-like melt-depleted PGE patterns. The observed PGE signatures are consistent with the low bulk Al2O3 contents (mostly lower than 2.5%) of the peridotites, as well as the compositions of the silicate and oxide minerals. Based on PGE patterns and Os model ages, the peridotites from both localities can be categorized into three age groups: Archean (3.0–2.6Ga overall; 2.8–2.6Ga for Pelly Bay and 3.0–2.7Ga for Repulse Bay), Paleoproterozoic (2.1–1.7Ga), and “Recent” (<1Ga, with model ages similar to the ca. 546Ma kimberlite eruption age). The Archean group provides the first direct evidence of depleted Archean lithospheric mantle forming coevally with the overlying Archean crustal basement, indicating cratonization of the Rae during the Archean. The subtle difference in Os model ages between Pelly Bay and Repulse Bay coincides with the age difference between crustal basement rocks beneath these two areas, supporting the suggestion that the Rae craton was assembled by collision of separate two Archean blocks at 2.7–2.6Ga. The Paleoproterozoic peridotites are interpreted to represent newly formed lithospheric mantle, most likely associated with regional-scale underplating during the 1.77–1.70Ga Kivalliq-Nueltin event via removal of the lower portion of Archean lithospheric mantle followed by replacement with juvenile Paleoproterozoic lithospheric mantle. The existence of multiple age clusters in the lithosphere at each locality is consistent with the observation of present-day seismic lithospheric discontinuities (Snyder et al., 2013, 2015) that indicate two or more layers of fossil lithospheric mantle fabric beneath this region. Our data define a shallow mantle lithosphere layer dominated by Archean depletion ages underlain by a layer of mixed Archean and Paleoproterozoic ages. This lithospheric mantle structure is probably a response to complex tectonic displacement of portions of the lithospheric mantle during Paleoproterozoic orogeny/underplating. The best equilibrated Archean and Paleoproterozoic peridotites at both Pelly Bay and Repulse Bay define a typical cratonic geotherm at the time of kimberlite eruption, with a ∼200km thick lithospheric root extending well into the diamond stability field, in keeping with the diamondiferous nature of the kimberlites. Such thick lithosphere remains in place to the present day as suggested by seismic and magnetotelluric studies (Snyder et al., 2013, 2015; Spratt et al., 2014). The metasomatically disturbed peridotites in the Rae lithospheric mantle, yielding model ages indistinguishable from kimberlite eruption, may represent parts of the Rae craton mantle root that show anomalous magnetotelluric signatures.

Platinum-group minerals in the LG and MG chromitites of the eastern Bushveld Complex, South Africa

The chromitites of the Bushveld Complex in South Africa contain vast resources of platinum-group elements (PGE); however, except for the economic upper group (UG)-2 chromitite seam, information on the distribution of the PGE in the ores and on the mineralogical nature, assemblages, and proportions of platinum-group minerals (PGM) is essentially missing. In the present geochemical and mineralogical study, PGE concentrates originating from the lower group (LG)-6 and middle group (MG)-1/2 chromitites were investigated with the intention to fill this gap of knowledge. Chondrite-normalized PGE patterns of bulk rock and concentrates are characterized by a positive slope from Os to Rh, a slight drop to Pt, and an increase to Pd again. The pronounced similarities of the PGE patterns indicate similar primary processes of PGE concentration in the chromitites, namely “sulfide control” of the PGE mineralization, i.e., co-precipitation of chromite and sulfide. Further, the primary control of PGE concentration in chromitites appears to be dual in character: (i) base-level concentrations of IPGE (up to ∼500 ppb) hosted within chromite and (ii) co-precipitation of chromite and sulfide, the latter containing virtually the entire remaining PGE budget. Sulfides (chalcopyrite, pentlandite, and pyrite; pyrrhotite is largely missing) are scarce within the chromitites and occur mainly interstitial to chromite grains. Pd and Rh contents in pentlandite are low and erratic. Essentially, the whole PGE inventory of the ores occurs in the form of discrete PGM. The PGM are almost always associated with sulfides. The dominant PGM are various Pt-Pd-Rh sulfides (cooperite/braggite [(Pt,Pd)S] and malanite/cuprorhodsite [CuPt2S4]/[CuRh2S4]), laurite [RuS2], the main carrier of the IPGE (Os, Ir, Ru), sulfarsenides [(Rh,Pt,Ir)AsS], sperrylite [PtAs2], Pt-Fe alloys, and a large variety of mainly Pd-rich PGM. The LG and MG chromitites have many characteristics in common and define a general, “typical” PGM spectrum of Bushveld chromitites. This PGM assemblage is characterized by the predominance of PGE-sulfides including elevated proportions of malanite, variable proportions of (sulf) arsenides, and Pt-Fe alloys in conjunction with a paucity of (bismutho)tellurides. The formation of this specific PGM spectrum is related to the distinct chromitite environment and its depositional and post-depositional history, whereby desulfurization reactions have probably played an important role. The LG-6 samples have higher contents of PGE-sulfides, including extraordinary high proportions of malanite but low PGE-arsenide and PGE-sulfarsenide contents compared to the MG-1/2 samples. This indicates a higher availability of arsenic either in the stratigraphically higher MG-1/2 samples (compared to the LG-6) or regionally in the chromitites south of the Steelpoort lineament.

The Interplay between Melting, Refertilization and Carbonatite Metasomatism in Off-Cratonic Lithospheric Mantle under Zealandia: an Integrated Major, Trace and Platinum Group Element Study

It is widely accepted that stabilization of the continental crust requires the presence of sub-continental lithospheric mantle. However, the degree of melt depletion required to stabilize the lithosphere and whether widespread refertilization is a significant process remain unresolved. Here, major and trace element, including platinum group elements (PGE), characterization of 40 mantle xenoliths from 13 localities is used to constrain the melt depletion, refertilization and metasomatic history of lithospheric mantle underneath the micro-continent Zealandia. Our previously published Re–Os isotopic data for a subset of these xenoliths indicate Phanerozoic to Paleoproterozoic ages and, reinterpreted with the new major and trace element data presented here, demonstrate that a large volume (>2 million km3) of lithospheric mantle with an age of 1·99 ± 0·21 Ga is present below the much younger crust of Zealandia. A peritectic melting model using moderately incompatible trace elements (e.g. Yb) in bulk-rocks demonstrates that these peridotites experienced a significant range of degrees of partial melting, between 3 and 28%. During subsolidus equilibration clinopyroxene gains significant rare earth elements (REE), which then leads to the underestimation of the degree of partial melting by ≤12% in fertile xenoliths. A new approach taking into account the effects of subsolidus re-equilibration on clinopyroxene composition effectively removes discrepancies in the calculated degree of melting and provides consistent estimates of between 4 and 29%. The estimated amount of melting is independent of the Re–Os model ages of the samples. The PGE patterns record simple melt depletion histories and the retention of primary base metal sulfides in the majority of the xenoliths. A rapid decrease in Pt/IrN observed at c. 1·0 wt % Al2O3 is a direct result of the exhaustion of sulfide in the mantle residue at c. 20–25% partial melting and the inability of Pt to form a stable alloy phase. Major elements preserve evidence for refertilization by a basaltic component that resulted in the formation of secondary clinopyroxene and low-forsterite olivine. The majority of xenoliths show the effects of cryptic metasomatic overprinting, ranging from minor to strong light REE enrichments in bulk-rocks (La/YbN = 0·16–15·9). Metasomatism is heterogeneous, with samples varying from those with weak REE enrichment and notable positive Sr and U–Th anomalies and negative Nb–Ta anomalies in clinopyroxene to those that have extremely high concentrations of REE, Th–U and Nb. Chemical compositions are consistent with a carbonatitic component contributing to the metasomatism of the lithosphere under Zealandia. Notably, the intense metasomatism of the samples did not affect the PGE budget of the peridotites as this was controlled by residual sulfides.

Re‐Os isotope and platinum group elements of a FOcal ZOne mantle source, Louisville Seamounts Chain, Pacific ocean

AbstractThe Louisville Seamount Chain (LSC) is, besides the Hawaiian‐Emperor Chain, one of the longest‐lived hotspot traces. We report here the first Re‐Os isotope and platinum group element (PGE) data for Canopus, Rigil, and Burton Guyots along the chain, which were drilled during IODP Expedition 330. The LSC basalts possess (187Os/188Os)i = 0.1245–0.1314 that are remarkably homogeneous and do not vary with age. A Re‐Os isochron age of 64.9 ± 3.2 Ma was obtained for Burton seamount (the youngest of the three seamounts drilled), consistent with 40Ar‐39Ar data. Isochron‐derived initial 187Os/188Os ratio of 0.1272 ± 0.0008, together with data for olivines (0.1271–0.1275), are within the estimated primitive mantle values. This (187Os/188Os)i range is similar to those of Rarotonga (0.124–0.139) and Samoan shield (0.1276–0.1313) basalts and lower than those of Cook‐Austral (0.136–0.155) and Hawaiian shield (0.1283–0.1578) basalts, suggesting little or no recycled component in the LSC mantle source. The PGE data of LSC basalts are distinct from those of oceanic lower crust. Variation in PGE patterns can be largely explained by different low degrees of melting under sulfide‐saturated conditions of the same relatively fertile mantle source, consistent with their primitive mantle‐like Os and primordial Ne isotope signatures. The PGE patterns and the low 187Os/188Os composition of LSC basalts contrast with those of Ontong Java Plateau (OJP) tholeiites. We conclude that the Re‐Os isotope and PGE composition of LSC basalts reflect a relatively pure deep‐sourced common mantle sampled by some ocean island basalts but is not discernible in the composition of OJP tholeiites.