Highly siderophile element geochemistry of Os-enriched 2.8 Ga Kostomuksha komatiites, Baltic Shield

New analyses of highly siderophile elements (HSE; Re, Os, Ir, Ru, Pt, and Pd) obtained by Carius tube digestion isotope dilution inductively coupled plasma mass-spectrometry (ID-ICPMS) technique are reported for ¹⁸⁷Os-enriched 2.8 Ga komatiites from the Kostomuksha greenstone belt. As a result of a significant improvement in the yield over our previous digestions by the NiS fire-assay technique, these komatiites have now been shown to contain 22 to 25% more Os, Ir, and Pt and 34% more Ru. The emplaced komatiite lavas at Kostomuksha thus had siderophile element abundances comparable to those of the Abitibi belt. The discrepancies observed between the two techniques are interpreted to be the result of incomplete digestion of HSE carriers (particularly chromite) during the NiS fire-assay procedure. Our results for UB-N peridotite reference material agree well with those obtained by the high-pressure ashing digestion ID-ICPMS technique reported in the literature. Two types of komatiite lavas have been distinguished in this study based on the IPGE (Os, Ir, and Ru) behavior during lava differentiation. The Kostomuksha type is unique and is characterized by an incompatible behavior of IPGEs, with bulk solid-liquid partition coefficients for IPGEs being close to those for olivine. Cumulate zones in this type of komatiite lava occupy <20% of the total thickness of the flows. The Munro type exhibits a compatible behavior of IPGEs during lava differentiation. The cumulate zone in this type of komatiite occupies >20% of the total thickness of the flows. The calculated bulk partition coefficients indicate that, as with the other Munro-type komatiite lavas, the bulk cumulate contained an IPGE-rich minor phase(s) in addition to olivine. The non-CI chondritic HSE pattern for the source of the Kostomuksha komatiites calculated here is similar to that of Abitibi komatiites and to average depleted spinel lherzolite (ADSL) and supports the hypothesis of a non-CI chondritic HSE composition of the Earth’s mantle. The absolute HSE abundances in the source of the Kostomuksha komatiite have been demonstrated to be comparable to those of the source of Abitibi komatiites, even though the two komatiites contrast in their Os isotopic compositions. This supports the earlier hypothesis that if core-mantle interaction produced the ¹⁸⁷Os/¹⁸⁸Os radiogenic signature in the Kostomuksha source, it must have occurred in the form of isotope exchange at the core-mantle boundary. Other explanations of the radiogenic Os signature are similarly constrained to conserve the elemental abundance pattern in the mantle source of Kostomuksha komatiites.     

The Concentration of the Platinum-Group Elements in South African Komatiites: Implications for Mantle Sources, Melting Regime and PGE Fractionation during Crystallization

We have analysed 18 samples of komatiite from five consecutivelava flows of the Komati Formation at Spinifex Creek, BarbertonMountain Land. Our samples include massive komatiite, varioustypes of spinifex-textured komatiite, and flow-top breccias.The rocks have low platinum-group element (PGE) contents andPd/Ir ratios relative to komatiites from elsewhere, at 0·45–2ppb Os, 1–1·4 ppb Ir, <1–5 ppb Ru, 0·33–0·79ppb Rh, 1·7–6 ppb Pt, 1·6–6·1ppb Pd, and Pd/Ir 3·3. Pt/Pd ratios are c. 1·1.Platinum-group elements are depleted relative to Cu (Cu/Pd =15 300). They display a tendency to increase in the less magnesiansamples, suggesting that the magmas were S-undersaturated uponeruption and that all PGE were incompatible with respect tocrystallizing olivine. Komatiites from the Westonaria Formationof the Ventersdorp Supergroup and the Roodekrans Complex nearJohannesburg have broadly similar PGE patterns and concentrationsto the Komati rocks, suggesting that the PGE contents of SouthAfrican ultrabasic magmas are controlled by similar processesduring partial mantle melting and low-P magmatic crystallization.Most workers believe that the Barberton komatiites formed byrelatively moderate-degree batch melting of the mantle at highpressure. Based on the concentration of Zr in the Komati samples,we estimate that the degree of partial melting was between 26and 33%. We suggest that the low PGE contents and Pd/Ir ratiosof all analysed South African komatiites are the result of sulphideshaving been retained in the mantle source during partial melting.The difference in Pd/Ir between our samples and Al-undepletedkomatiites from elsewhere further suggests that the PGE arefractionated during progressive partial melting of the mantle.Thus, our data are in agreement with other recent studies showingthat the PGE are hosted by different phases in the mantle, withPd being concentrated by interstitial Cu-rich sulphide, andthe IPGE (Os, Ir, Ru) and Rh resting in monosulphide solid solutionincluded within silicates. Pt is possibly controlled by a discreterefractory phase, as Pt/Pd ratios of most komatiites worldwideare sub-chondritic. KEY WORDS: platinum-group elements; komatiites; Barberton; mantle melting; South Africa     

Geochemical study of peridotites from the Manipur Ophiolite Complex,Northeast India with special reference to their PGE concentration

The peridotites of the Manipur Ophiolite Complex (MOC) have been examined based on mineral chemistry, major elements and PGE contents. They represent high-magnesian cumulates with Mg# > 0.90 (Mg/Mg+Fe) in olivine and Cr# > 0.12 (Cr/Cr+Al) in spinel. High Mg* contents of the olivine show that these rocks are most likely derived from partial melting of the residual upper mantle. The peridotites contain higher concentration of Palladium Group PGE (PPGE) (Rh=4.4−6.6ppb; Pd=336−458ppb and Pt=14.6−36.4ppb) than the Iridium Group PGE (IPGE) (Os=2.4−5.8ppb; Ir=3.2−4.16ppb and Ru=5.2−7ppb). These are characterized by overall enrichment of PGE concentration (σPGE=365.8 − 516.6 ppb) and high ratio of (Pt+Pd)/(Os+Ir+Ru). This suggests that the rocks are formed by partial melting and crystal fractionation of olivine-rich (picritic) magma.     

Platinum-Group Element Geochemical Characteristics of the Picrites and High-Ti Basalts in the Binchuan Area,Yunnan Province

The Binchuan area of Yunnan is located in the western part of the Emeishan large igneous province in the western margin of the Yangtze Block.In the present study,the Wuguiqing profile in thickness of about 1440 m is mainly composed of high-Ti basalts,with minor picrites in the lower part and andesites,trachytes,and rhyolites in the upper part.The picrites have relatively higher platinum-group element（PGE） contents（ΣPGE=16.3-28.2 ppb）,with high Cu/Zr and Pd/Zr ratios,and low S contents（5.03-16.9 ppm）,indicating the parental magma is S-unsaturated and generated by high degree of partial melting of the Emeishan large igneous province（ELIP） mantle source.The slightly high Cu/Pd ratios（11 000-24 000） relative to that of the primitive mantle suggest that 0.007%sulfides have been retained in the mantle source.The PGE contents of the high-Ti basalts exhibit a wider range（ΣPGE=0.517-30.8 ppb）.The samples in the middle and upper parts are depleted in PGE and haveε_Nd（260 Ma） ratios ranging from -2.8 to -2.2,suggesting that crustal contamination of the parental magma during ascent triggered sulfur saturation and segregation of about 0.446%-0.554% sulfides,and the sulfide segregation process may also provide the ore-forming material for the magmatic Cu-Ni-PGE sulfide deposits close to the studied basalts.The samples in this area show Pt-Pd type primitive mantle-normalized PGE patterns,and the Pd/Ir ratios are higher than that of the primitive mantle（Pd/Ir=1）,indicating that the obvious differentiation between Ir-group platinum-group elements（IPGE） and Pd-group platinum-group elements（PPGE） are mainly controlled by olivine or chromites fractionation during magma evolution.The Pd/Pt ratios of most samples are higher than the average ratio of mantle（Pd/Pt=0.55）,showing that the differentiation happened between Pt and Pd.The differentiation in picrites may be relevant to Pt hosted in discrete refractory Pt-alloy phase in the mantle;whereas the differentiation in the high-Ti basalts is probably associated with the fractionation of Fe-Pt alloys,coprecipitating with Ir-Ru-Os alloys.Some high-Ti basalt samples exhibit negative Ru anomalies,possibly due to removal of laurite collected by the early crystallized chromites.     

Fractionation of the platinum-group elments and Re during crystallization of basalt in Kilauea Iki Lava Lake, Hawaii

Kilauea Iki lava lake formed during the 1959 summit eruption of Kilauea Volcano, then crystallized and differentiated over a period of 35 years. It offers an opportunity to evaluate the fractionation behavior of trace elements in a uniquely well-documented basaltic system. A suite of 14 core samples recovered from 1967 to 1981 has been analyzed for 5 platinum-group elements (PGE: Ir, Os, Ru, Pt, Pd), plus Re. These samples have MgO ranging from 2.4 to 26.9 wt.%, with temperatures prior to quench ranging from 1140 °C to ambient (110 °C). Five eruption samples were also analyzed.Osmium and Ru concentrations vary by nearly four orders of magnitude (0.0006–1.40 ppb for Os and 0.0006–2.01 ppb for Ru) and are positively correlated with MgO content. These elements behaved compatibly during crystallization, mostly likely being concentrated in trace phases (alloy or sulfide) present in olivine phenocrysts or included chromite. Iridium also correlates positively with MgO, although less strongly than Os and Ru. The somewhat poorer correlation for Ir, compared with Os and Ru, may reflect variable loss of Ir as volatile IrF₆ in some of the most magnesian samples.Rhenium is negatively correlated with MgO, behaving as an incompatible trace element. Its behavior in the lava lake is complicated by apparent volatile loss of Re, as suggested by a decrease in Re concentration with time of quenching for lake samples vs. eruption samples. Platinum and Pd concentrations are negatively, albeit weakly, correlated with MgO, so these elements were modestly incompatible during crystallization of the major silicate phases. Palladium contents peaked before precipitation of immiscible sulfide liquid, however, and decline sharply in the most differentiated samples. In contrast, Pt appears to have been unaffected by sulfide precipitation. Microprobe data confirm that Pd entered the sulfide liquid before Re, and that Pt is not strongly chalcophile in this system. Occasional high Pt values in both eruption and lava lake samples suggest the presence of unevenly distributed, unidentified Pt-rich trace phases in some Kilauea Iki materials.Estimated mineral (olivine + chromite)/melt D values for Os, Ir, Ru and Pt for equilibrium crystallization for samples from ~ 7 to 27 wt.% MgO are 26, 8.2, 19 and 0.55, respectively. These Os, Ir and Ru estimates are somewhat higher than previous estimates for similar systems. If fractional crystallization is instead assumed, D values are much more similar.Results confirm many prior observations in other mafic systems that olivine (together with included phases) has a major effect on absolute and relative abundances of Re and the PGE. The relatively linear correlations between these elements and MgO potentially permit accurate estimation of the concentrations of these elements in the primary melts of comparable systems, especially in instances where the MgO content of the primary melt is well constrained.     

Formation of pyroxenite layers in the Totalp ultramafic massif (Swiss Alps) - Insights from highly siderophile elements and Os isotopes

Pyroxenitic layers are a minor constituent of ultramafic mantle massifs, but are considered important for basalt generation and mantle refertilization. Mafic spinel websterite and garnet-spinel clinopyroxenite layers within Jurassic ocean floor peridotites from the Totalp ultramafic massif (eastern Swiss Alps) were analyzed for their highly siderophile element (HSE) and Os isotope composition.Aluminum-poor pyroxenites (websterites) display chondritic to suprachondritic initial γ_Os (160 Ma) of −2 to +27. Osmium, Ir and Ru abundances are depleted in websterites relative to the associated peridotites and to mantle lherzolites worldwide, but relative abundances (Os/Ir, Ru/Ir) are similar. Conversely, Pt/Ir, Pd/Ir and Re/Ir are elevated.Aluminum-rich pyroxenites (clinopyroxenites) are characterized by highly radiogenic ¹⁸⁷Os/¹⁸⁸Os with initial γ_Os (160 Ma) between +20 and +1700. Their HSE composition is similar to that of basalts, as they are more depleted in Os, Ir and Ru compared to Totalp websterites, along with even higher Pt/Ir, Pd/Ir and Re/Ir. The data are most consistent with multiple episodes of reaction of mafic pyroxenite precursor melts with surrounding peridotites, with the highest degree of interaction recorded in the websterites, which typically occur in direct contact to peridotites. Clinopyroxenites, in contrast, represent melt-dominated systems, which retained the precursor melt characteristics to a large extent. The melts may have been derived from a sublithospheric mantle source with high Pd/Ir, Pt/Ir and Re/Os, coupled with highly radiogenic ¹⁸⁷Os/¹⁸⁸Os compositions. Modeling indicates that partial melting of subducted, old oceanic crust in the asthenosphere could be a possible source for such melts.Pentlandite and godlevskite are identified in both types of pyroxenites as the predominant sulfide minerals and HSE carriers. Heterogeneous HSE abundances within these sulfide grains likely reflect subsolidus processes. In contrast, large grain-to-grain variations, and correlated variations of HSE ratios, indicate chemical disequilibrium under high-temperature conditions. This likely reflects multiple events of melt-rock interaction and sulfide precipitation. Notably, sulfides from the same thick section for the pyroxenites may display both residual-peridotite and melt-like HSE signatures. Because Totalp pyroxenites are enriched in Pt and Re, and depleted in Os, they will develop excess radiogenic ¹⁸⁷Os and ¹⁸⁶Os, compared to ambient mantle. These enrichments, however, do not possess the requisite Pt-Re-Os composition to account for the coupled suprachondritic ¹⁸⁶Os-¹⁸⁷Os signatures observed in some Hawaiian picrites, Gorgona komatiites, or the Siberian plume.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).     

Platinum-group element geochemistry of peridotite xenoliths from the Sierra Nevada and the Basin and Range, California

The nature of PGE-Re (PGE = Pt, Pd, Os, Ir, Ru) behavior in subcontinental lithospheric mantle was investigated using new, high precision PGE-Re abundance measurements and previously published Re-Os isotopic analyses of peridotite xenoliths from the Sierra Nevada and Mojave Province, California. Ru/Ir ratios and Ir concentrations are constant over a wide range in S content and major-element fertility indices (e.g., Mg/(Mg+Fe)), indicating that Ru and Ir are not only compatible during partial melting, but also that their partitioning behaviors may not be controlled entirely by sulfide. Pt/Ir, Pd/Ir, Os/Ir, and Re/Ir ratios range from slightly superchondritic to distinctly subchondritic for all xenoliths except for one anomalous sample (1026V), which is characterized by radiogenic ¹⁸⁷Os/¹⁸⁸Os, low Re/Os ratio, and large enrichments in Cu, Os, Pt, Pd, and S relative to Ir (COPPS metasomatism). Assuming chondritic initial relative abundances, the magnitudes of some of the depletions in Pt, Pd, Os, and Re relative to Ir and Ru require incompatible behavior or substantial secondary loss. In detail, some samples, which are otherwise characterized by fertile major-element indices, exhibit low S contents and subchondritic Os/Ir and Pd/Ir ratios, indicating that depletions in Pd and Os relative to Ir are not simple functions of the degree of melting as inferred from major elements. Possible mechanisms for depleting Pt, Pd, Os, and Re relative to Ir and Ru include partitioning into chromian spinels and alloys, partitioning between sulfide and sulfide liquids, mobilization by aqueous fluids, or secondary loss associated with late-stage sulfide breakdown. However, it is not possible to explain all of the depletions in Pt, Pd, Os, and Re by any single mechanism.The preferential enrichment in Os over Re and Ir in sample 1026V is somewhat paradoxical because this sample’s radiogenic ¹⁸⁷Os/¹⁸⁸Os requires a metasomatic agent, originating from a source with a high time-integrated Re/Os ratio. The abundant garnet websterite xenoliths may be a suitable source because they have high Re/Os ratios, radiogenic Os, and abundant garnet, which may sequester Re over Os during partial melting. However, their extremely low Os contents require the processing of large amounts of garnet websterite to concentrate enough Os into the metasomatic sulfides needed to enrich sample 1026V in Os. The homogeneity in ¹⁸⁷Os/¹⁸⁸Os ratio in the remaining xenoliths suggest that their Os isotopic compositions were not significantly affected by PGE metasomatism. The singular nature of 1026V’s composition emphasizes the rarity of COPPS metasomatism.     

Highly siderophile element composition of the Earth’s primitive upper mantle: Constraints from new data on peridotite massifs and xenoliths

Osmium, Ru, Ir, Pt, Pd and Re abundances and ¹⁸⁷Os/¹⁸⁸Os data on peridotites were determined using improved analytical techniques in order to precisely constrain the highly siderophile element (HSE) composition of fertile lherzolites and to provide an updated estimate of HSE composition of the primitive upper mantle (PUM). The new data are used to better constrain the origin of the HSE excess in Earth’s mantle. Samples include lherzolite and harzburgite xenoliths from Archean and post-Archean continental lithosphere, peridotites from ultramafic massifs, ophiolites and other samples of oceanic mantle such as abyssal peridotites. Osmium, Ru and Ir abundances in the peridotite data set do not correlate with moderately incompatible melt extraction indicators such as Al₂O₃. Os/Ir is chondritic in most samples, while Ru/Ir, with few exceptions, is ca. 30% higher than in chondrites. Both ratios are constant over a wide range of Al₂O₃ contents, but show stronger scatter in depleted harzburgites. Platinum, Pd and Re abundances, their ratios with Ir, Os and Ru, and the ¹⁸⁷Os/¹⁸⁸Os ratio (a proxy for Re/Os) show positive correlations with Al₂O₃, indicating incompatible behavior of Pt, Pd and Re during mantle melting. The empirical sequence of peridotite-melt partition coefficients of Re, Pd and Pt as derived from peridotites () is consistent with previous data on natural samples. Some harzburgites and depleted lherzolites have been affected by secondary igneous processes such as silicate melt percolation, as indicated by U-shaped patterns of incompatible HSE, high ¹⁸⁷Os/¹⁸⁸Os, and scatter off the correlations defined by incompatible HSE and Al₂O₃. The bulk rock HSE content, chondritic Os/Ir, and chondritic to subchondritic Pt/Ir, Re/Os, Pt/Re and Re/Pd of many lherzolites of the present study are consistent with depletion by melting, and possibly solid state mixing processes in the convecting mantle, involving recycled oceanic lithosphere. Based on fertile lherzolite compositions, we infer that PUM is characterized by a mean Ir abundance of 3.5 ± 0.4 ng/g (or 0.0080 ± 0.0009*CI chondrites), chondritic ratios involving Os, Ir, Pt and Re (Os/Ir_PUM of 1.12 ± 0.09, Pt/Ir_PUM = 2.21 ± 0.21, Re/Os_PUM = 0.090 ± 0.002) and suprachondritic ratios involving Ru and Pd (Ru/Ir_PUM = 2.03 ± 0.12, Pd/Ir_PUM = 2.06 ± 0.31, uncertainties 1σ). The combination of chondritic and modestly suprachondritic HSE ratios of PUM cannot be explained by any single planetary fractionation process. Comparison with HSE patterns of chondrites shows that no known chondrite group perfectly matches the PUM composition. Similar HSE patterns, however, were found in Apollo 17 impact melt rocks from the Serenitatis impact basin [Norman M.D., Bennett V.C., Ryder G., 2002. Targeting the impactors: siderophile element signatures of lunar impact melts from Serenitatis. Earth Planet. Sci. Lett, 217-228.], which represent mixtures of chondritic material, and a component that may be either of meteoritic or indigenous origin. The similarities between the HSE composition of PUM and the bulk composition of lunar breccias establish a connection between the late accretion history of the lunar surface and the HSE composition of the Earth’s mantle. Although late accretion following core formation is still the most viable explanation for the HSE abundances in the Earth’s mantle, the “late veneer” hypothesis may require some modification in light of the unique PUM composition.     

Petrogenesis and mineralization of the Hulu Ni-Cu sulphide deposit in Xinjiang,NW China: constraints from Sr-Nd isotopic and PGE compositions

The Permian Hulu intrusion is one of several sulphide-bearing Permian mafic–ultramafic intrusions in the eastern part of the eastern Tianshan located at the southern margin of the Central Asian Orogenic Belt (CAOB) in Xinjiang, NW China. The intrusion is composed of lherzolite, olivine websterite, gabbro, and gabbro-diorite. Disseminated and net-textured Ni-Cu sulphide ores are located at the bottom of the lopolith complex. Negative Zr, Hf, Nb, and Ta anomalies, whole-rock εNd(t) values of +5.7 to +8.8, and variable (Th/Nb)_PM values (from 1.06 to 8.13) suggest that the source of the Hulu complexes is depleted mantle metasomatized by subducted slab-derived fluid and/or melt (~5% global subducted sediment and 15% slab fluid) that has experienced approximately 3% lower crustal and 10% upper crustal contamination. The Hulu intrusion is characterized by low PGE abundances i.e. 0.03–1.08 ppb Ir, 0.04–0.69 ppb Ru, 0.02–2.15 ppb Rh, 0.30–48.71 ppb Pt, and 0.21–344 ppb Pd. Our calculations indicate that if the Pd, Os, Ir, and Cu contents of the primary magma were 2.1 ppb, 0.03 ppb, 0.05 ppb, and 200 ppm, respectively, a variable R-factor between 200 and 1600 with residual magma that had experienced 0.01% early-sulphide segregation can explain the variation in Pd, Os, and Ir contents of sulphide-poor and disseminated sulphide samples of the Hulu deposit. Basaltic magma fractionation and assimilation and/or contamination of sulphur-bearing crustal materials might have triggered sulphur saturation to form Cu-Ni sulphide ores. Tarim basaltic PGE contents cannot be used as the mineralized parent magma for the Hulu intrusion because of the differing evolutionary trends of the Ni/Pd and Cu/Ir values. However, similar Cu/Ni and Pd/Ir values in Tarim basalts and Hulu Cu-Ni sulphide ores, as well as the same early sulphide segregation process, show that certain genetic relationships between them and magma sources are probably similar to each other.     

Behaviour of Ni-PGE-Au-Cu in mafic-ultramafic volcanic suites of the 2.7 Ga Kambalda Sequence, Kalgoorlie Terrane, Yilgarn Craton

The 2.7 Ga Kambalda Sequence comprises a mafic to ultramafic dominated volcanic rock sequence of the Kalgoorlie Terrane, Yilgarn Craton, Western Australia. The Sequence is divided into Lower and Upper Units separated by the Kambalda Komatiite Formation. Five basalt suites of the Lower Unit are tholeiitic where MgO spans 5-10 wt.% MgO, with minor assimilation-fractional crystallization (AFC), whereas six volcanic suites identified in the Upper Unit are tholeiitic to komatiitic-basalts with MgO 24-5 wt.% having generally greater degrees of AFC. Upper suites plot at Al₂O₃/TiO₂ (17-26) close to the primitive mantle ratio of 21, and Pt + Pd (19-31 ppb), whereas the PGE-depleted Lower basalts plot at generally lower Al₂O₃/TiO₂ (<16) and Pt + Pd (<10 ppb). Most suites have an average Pt/Pd ratio of 1.11, despite large variations in MgO contents, broadly consistent with the Pt/Pd ratio in the primitive mantle. On primitive mantle-normalised PGE plots, Upper suites generally display less fractionated patterns of the IPGE (Os, Ir, Ru and Rh) from the PPGE (Pt and Pd) relative to the Lower basalts. Most suites exhibit patterns with positive slopes reflecting relative enrichment of Pd, Pt, Au and Cu relative to Ni and IPGE. In suites of both Units, the concentrations of Ir and Ru fall with decreasing MgO contents, indicating their broadly compatible behaviour during magmatic evolution that involved AFC. Platinum and Pd behave as incompatible elements in the high-MgO suites, whereas Pt and Pd behave compatibly during crystallisation of the Lower basalt magmas, an interpretation consistent with progressively higher Cu/Pt and Cu/Pd ratios at decreasing MgO contents, and with falling Pt/Ti, collectively due to sulphur saturation induced by AFC as recorded in an antivariance of Pd/Ir with Nb/Th, a monitor of AFC.Collectively, the data suggest that several of the Lower Basalt suites crystallised under sulphide-saturated conditions, whereas most of the Upper Basalt Sequences remained sulphur undersaturated during magmatic evolution. Alteration, and fractional crystallisation of silicate and oxide phases, can be ruled out as factors governing PGE distribution in these mafic-ultramafic suites. Instead, the data suggest that discrete PGE-bearing phase (s) fractionated from the magmas. Such phases could be platinum group minerals (PGM; e.g., laurite) and/or alloys, or discrete PGE-rich nuggets or sulphides.     

Platinum group element (PGE) geochemistry to understand the chemical evolution of the Earth’s mantle

Platinum group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd) are important geochemical and cosmochemical tracers. Depending on physical and chemical behaviour the PGEs are divided into two subgroups: IPGE (Ir, Os, Ru) and PPGE (Pd, Pt, Rh). Platinum group elements show strong siderophile and chalcophile affinity. Base metal sulfides control the PGE budget of the Earth’s mantle. Mantle xenoliths contain two types of sulfide populations: (1) enclosed within silicate minerals, and (2) interstitial to the silicate minerals. In terms of PGE characters the included variety shows IPGE enriched patterns — similar to the melt-depleted mantle harzburgite, whereas the interstitial variety shows PPGE enriched patterns — resembling the fractionated PGE patterns of the basalt. These PGE characters of the mantle sulfides have been interpreted to be representative of multi-stages melting process of the mantle that helped to shape the chemical evolution of the Earth.     

Highly siderophile element behaviour accompanying subduction of oceanic crust: Whole rock and mineral-scale insights from a high-pressure terrain

Highly siderophile element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust.Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (∼75% loss). In contrast, basaltic eclogites display significant depletion of Pt (?60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide.Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled ¹⁸⁶Os-¹⁸⁷Os enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of ¹⁸⁷Os-¹⁸⁶Os enrichment.     

Osmium isotope and highly siderophile element geochemistry of mantle xenoliths from NW Turkey: implications for melt depletion and metasomatic history of the sub-continental lithospheric mantle

Ultramafic xenoliths entrained in the late Miocene alkali basalts and basanites from NW Turkey include refractory spinel-harzburgites and dunites accompanied by subordinate spinel-lherzolites. Whole-rock major and trace element characteristics indicate that the xenoliths are mostly the solid residues of varying degrees of partial melting (～4–～15%), but some have geochemical signatures reflecting the processes of melt/rock interaction. Mantle-normalized trace element patterns for the peridotites vary from LREE-depleted to strongly LREE-enriched, reflecting multistage mantle processes from simple melt extraction to metasomatic enrichment. Rhenium and platinum group element (PGE) abundances and ¹⁸⁷Os/¹⁸⁸Os systematics of peridotites were examined in order to identify the nature of the mantle source and the processes effective during variable stages of melt extraction within the sub-continental lithospheric mantle (SCLM). The peridotites are characterized by chondritic Os/Ir and Pt/Ir ratios and slightly supra-chondritic Pd/Ir and Rh/Ir ratios, representing a mantle region similar in composition to the primitive mantle (PM). Moderate enrichment in PPGE (Pd–Pt–Rh)/IPGE (Ir–Os–Ru) ratios with respect to the PM composition in the metasomatized samples, however, reflects compositional modification by sulphide addition during possible post-melting processes. The ¹⁸⁷Os/¹⁸⁸Os ratios of the peridotites range from 0.11801 to 0.12657. Highly unradiogenic Os isotope compositions (γOs at 10 Ma from –7.0 to –3.2) in the chemically undisturbed mantle residues are accompanied by depletion in Re/Os ratios, suggesting long-term differentiation of SCLM by continuous melt extraction. For the metasomatized peridotites, however, systematic enrichments in PPGE and Re abundances, and the observed positive covariance between ¹⁸⁷Re/¹⁸⁸Os and γOs can most likely be explained by interaction of solid residues with basaltic melts produced by melting of relatively more radiogenic components in the mantle. Significantly, the wide range of ¹⁸⁷Os/¹⁸⁸Os ratios characterizing the entire xenolith suite seems to be consistent with multistage evolution of SCLM and suggests that parts of the lithospheric mantle contain materials that have experienced ancient melt removal (～1.3 Ga) which created time-integrated depletion in Re/Os ratios; in contrast, some other parts display evidence indicative of recent perturbation in the Re–Os system by sulphide addition during interaction with metasomatizing melts.     

Sulphide Segregation in Ferropicrites from the Pechenga Complex, Kola Peninsula, Russia

The Palaeoproterozoic Ni–Cu sulphide deposits of the PechengaComplex, Kola Peninsula, occur in the lower parts of ferropicriticintrusions emplaced into the phyllitic and tuffaceous sedimentaryunit of the Pilgujärvi Zone. The intrusive rocks are comagmaticwith extrusive ferropicrites of the overlying volcanic formation.Massive lavas and chilled margins from layered flows and intrusionscontain <3–7 ng/g Pd and Pt and <0·02–2·0ng/g Ir, Os and Ru with low Pd/Ir ratios of 5–11. Theabundances of platinum group elements (PGE) correlate with eachother and with chalcophile elements such as Cu and Ni, and indicatea compatible behaviour during crystallization of the parentalmagma. Compared with the PGE-depleted central zones of differentiatedflows (spinifex and clinopyroxene cumulate zones) the olivinecumulate zones at the base contain elevated PGE abundances upto 10 ng/g Pd and Pt. A similar pattern is displayed in intrusivebodies, such as the Kammikivi sill and the Pilgujärvi intrusion.The olivine cumulates at the base of these bodies contain massiveand disseminated Ni–Cu-sulphides with up to 2 µg/gPd and Pt, but the PGE concentrations in the overlying clinopyroxenitesand gabbroic rocks are in many cases below the detection limits.The metal distribution observed in samples closely representingliquid compositions suggests that the parental magma becamesulphide saturated during the emplacement and depleted in chalcophileand siderophile metals as a result of fractional segregationof sulphide liquids. Relative sulphide liquid–silicatemelt partition coefficients decrease in the order of Ir >Rh > Os > Ru > Pt = Pd > Cu. R-factors (silicate-sulphidemass ratio) are high and of the order of 10⁴–10⁵, andthey indicate the segregation of only small amounts of sulphideliquid in the parental ferropicritic magma. In differentiatedflows and intrusions the sulphide liquids segregated and accumulatedat the base of these bodies, but because of a low silicate–sulphidemass ratio the sulphide liquids had a low PGE tenor and Pt/Irand Cu/Ir ratios similar to the parental silicate melts. Duringcooling the sulphide liquid crystallized 40–50% of monosulphidesolid solution (mss) and the residual sulphide liquid becameenriched in Cu, Pt and Pd and depleted in Ir, Os and Ru. TheCu-rich sulphide liquid locally assimilated components of thesurrounding S-rich sediments as suggested by the radiogenicOs isotopic composition of some sulphide ores (     

Dispersion Pattern of PGE and Ag in Chromiferous Ultramafic Suite of Rocks in Sukinda Valley,India

Potential chromite ore deposits of India are situated in Sukinda, Odisha, which may also be considered as a potential resource for platinum group elements (PGEs). This paper reports on PGE geochemistry in twenty six samples covering chromite ores, chromitites and associated ultramafic rocks of the Sukinda ultramafic complex. Platinum group element contents range from 213 to 487 ppb in the chromite ore body, from 63 to 538 ppb in rocks that have chromite dendrites or dissemination and from 38 to 389 ppb in associated olivine–peridotite, serpentinite, pyroxenite and brecciated rocks. The PGEs are divided into two sub‐groups: IPGE (Ir, Os, and Ru) and PPGE (Pd, Pt, and Rh) based on their chemical behaviour. The IPGE and PPGE in these three litho‐members show a contrasting relationship e.g. average IPGE content decreases from chromite to chromitite and associated rocks while PPGE increases in the same order. Appreciable Ag in chromitite (270–842 ppb) is recorded. Positive correlation between IPGE with Cr₂O₃ and with Al₂O₃ is observed while these are negatively correlated with MgO. Covariant relationships between Au and Mg in rocks devoid of chromite and between Ag and Fe in chromitite sample are observed. Chromite in all seams and some chromitite samples exhibit an IPGE‐enriched chondrite normalized pattern while PPGE are highly fractionated and show a steep negative slope, thereby indicating that PGE in the parental melt fractionates and IPGE‐compatible elements prefer to settle with chromite. The rocks devoid of chromite and rocks containing accessory chromite exhibit a nearly flat pattern in chondrite‐normalized PGE plots and this suggests a limited fractionation of PGE in these rocks. Variation in the distribution pattern of PGE and Ag in three typical litho‐members of the Sukinda Valley may be related to multiple intrusion of ultramafic magma, containing variable volume percentage of chromite.     

北大别白垩纪镁铁－超镁铁岩的铂族元素地球化学研究

采用镍锍火试金法结合ICP-MS分析了12个北大别白垩纪镁铁-超镁铁岩样品的Ir,Ru,Rh,Pt和Pd的含量,结果显示铂族元素（PGE）的含量较低,原始地幔标准化后的PGE分布模式呈正斜率型,PPGE相对原始地幔略微亏损,而IPGE强烈亏损,Pd/Ir值远高于相应的地幔比值。这些镁铁-超镁铁岩中PGE的强烈分异是地幔低程度的部分熔融过程中,PPGE主要受硫化物控制,而Ir则存在于非硫化物相如尖晶石,可能还有合金之中造成的。同时,铂族元素的分布特征表明这些镁铁-超镁铁岩是岩浆结晶分异的产物。     

Laurite and Ir-Osmium from Plagioclase Lherzolite of the Yoko–Dovyren Mafic–Ultramafic Pluton,Northern Baikal Region

The near-bottom part of the Yoko-Dovyren layered ultramafic-mafic intrusion host the Baikal deposit of Cu–Ni sulfide ores with Pt–Pd mineralization, whereas horizons and pockets of low sulfide ores with Pt–Pd mineralization occur at higher stratigraphic levels, including the boundary between strata of troctolite and gabbronorite, within these rocks, as well as in strata of peridotite at the lower part of the intrusion. This paper represents a new (for the Yoko-Dovyren intrusion) type of “refractory IPGE-mineralization” discovered in the lower peridotite ranging from two-pyroxene-plagioclase-bearing lherzolite. This mineralization occurs in thin intercalations of plagioclase lherzolite containing as much as 7% of alumochromite, up to 50 ppb Ru, 15 ppb Ir, and 60 ppb Pt. Crystals of cumulate alumochromite with 0.2–0.8 wt % TiO₂ contain hexagonal plates of Ir-osmium up to 5 m in size. Crystals of cumulate alumochromite with 1.2–2.8 wt % TiO₂ host pentagonal dodecahedrons of laurite up to 4 m in size. One of the alumochromite crystals with an inclusion of Os-poor laurite was found inside a crystal of cumulate olivine Fo86. Intergrowth of laurite and Ir-osmium enclosed in alumochromite with 1.1% TiO₂ was observed in one case. Laurite from Yoko-Dovyren contains 93–66%, predominantly 92–82%, RuS₂ endmember (n = 10); 3–20, predominantly 5–12%, OsS₂ endmember; 4–5% IrS₂ endmember; and up to 0.7% Pd and 0.5% Au. Ir-osmium is divided into two groups by composition. The first group is enriched in Os (58–73 wt %, on average 64 wt %) and Ru (3–8 wt %, on average 5 wt %), contains 24–34 wt % Ir (n = 4), up to 1.4 wt % Au, and no Pt. Compositions of the second group have 57–58 wt % Os, 27–30 wt % Ir, 1.5–5.5 wt % Ru, approximately 10 wt % Pt (n = 3), and up to 0.2 wt % Pd. The Cr# and Fe²⁺/(Fe²⁺ + Mg) values, which range within 58–69 and 61–72, respectively, are identical in alumochromite with both enclosed laurite and Ir-osmium. Alumochromite, relatively enriched in Ti, crystallized slightly later, suggesting later crystallization for hosted laurite. Occurrence of Ir-osmium seems to indicate a picritic magma undersaturated with sulfide sulfur during bulk crystallization of alumochromite Judging from the diagram from (Brennan and Andrews, 2001), intergrowths of laurite and Ir-osmium, evidence that their probable crystallization temperature did not exceed 1250°C. The presence of own minerals of Ru, Os, Ir in the rocks, containing the first ppb of these PGE shows startling degree of magmatic differentiation. In the matrix of plagioclase lherzolites, containing laurite and Ir-osmium, in association with phlogopite, pargasite, pentlandite, troilite and chalcopyrite there were found the smallest crystals of geversite, sperrilite, insizwaite, niggliite, naldrettite, zvyagintsevite, in association with serpentine and chlorite–native platinum, Pd-platinum, osarsite, irarsite, platarsite.     

Platinum group element and nickel sulphide ore tenors of the Mount Keith nickel deposit, Yilgarn Craton, Australia

A set of platinum group element (PGE) analyses of about 120 samples from a 250-m continuous drill core through the Mount Keith komatiite-hosted nickel orebody, combined with Ni, Cu, Co, S, and major elements, reveals a complex trend of covariance between the original cumulus components of a thick sequence of nearly pure olivine–sulphide liquid adcumulates. The intersection is divided into informal chemostratigraphic zones, defined primarily by combinations of fine-scale cyclicity in original olivine composition, defined by Mg#, and sulphide composition, defined by Pt/S and Ni/S. Contents of Ni and PGE in 100% sulphides (tenors) were determined from linear regressions of the Ni–S and PGE–S covariance for each zone. Inferred olivine compositions range from about Fo₉₂ to Fo_94.6 and show a broad decrease from bottom to top of the sequence complicated by numerous reversals, revealing crystallisation in an open conduit system. Ni and PGE tenors of Mount Keith sulphide ores have typical values similar to the type I deposits of the Kambalda Dome. Mobility of S, at least on the scale of 2-m sample composites, is evidently relatively minor. Tenors for the various zones range 12–22% Ni, 370–1540?ppb Pt, 970–3670?ppb Pd, 100–460?ppb Ir, 170–460?ppb Rh, and 710–1260?ppb Ru. Pt, Pd, and Rh tenors are very strongly correlated, but the iridium group of platinum group elements (IPGEs; Ir and Ru) less so. Tenor variations are predominantly controlled by variations in magma/sulphide ratio R (100–350), with a minor component of variance from equilibrium crystallisation trends in the parent magma. PGE depletion in the silicate melt due to sulphide liquid extraction is limited by entrainment of sulphide liquid droplets and continuous equilibration with the transporting silicate magma. Ratios of the PGEs to one another are similar to those in the host komatiite magma, with the exception of Pt, which is systematically depleted in ores, relative to Rh and Pd and relative to host magma, by a consistent factor of about 2 to 2.5. This anomalous Pt depletion relative to PGE element ratios in unmineralized komatiitic rocks matches that observed in bulk compositions of many komatiite-hosted orebodies. The highly consistent nature of this depletion, and particularly the very strong correlation between Pt, Pd, and Rh in the Mount Keith deposit, argue that this depletion is a primary magmatic signal and not an artefact of alteration. Differential diffusion rates between Pt and the other PGEs, giving rise to a low effective partition coefficient for Pt into sulphide liquid, is advanced as a possible but not definitive explanation.     

Distribution of platinum-group elements and Os isotopes in chromite ores from Mayarí-Baracoa Ophiolitic Belt (eastern Cuba)

The Mayarí-Baracoa ophiolitic belt in eastern Cuba hosts abundant chromite deposits of historical economic importance. Among these deposits, the chemistry of chromite ore is very variable, ranging from high Al (Cr#=0.43–0.55) to high Cr (Cr#=0.60–0.83) compositions. Platinum-group element (PGE) contents are also variable (from 33 ppb to 1.88 ppm) and correlate positively with the Cr# of the ore. Bulk PGE abundances correlate negatively with the Pd/Ir ratio showing that chromite concentrates mainly Os, Ir and Ru which gives rise to the characteristic negatively sloped, chrondrite-normalized PGE patterns in many chromitites. This is consistent with the mineralogy of PGEs, which is dominated by members of the laurite–erlichmanite solid solution series (RuS₂–OsS₂), with minor amounts of irarsite (IrAsS), Os–Ir alloys, Ru–Os–Ir–Fe–Ni alloys, Ni–Rh–As, and sulfides of Ir, Os, Rh, Cu, Ni, and/or Pd. Measured ¹⁸⁷Os/¹⁸⁸Os ratios (from 0.1304 to 0.1230) are among the lower values reported for podiform chromitites. The ¹⁸⁷Os/¹⁸⁸Os ratios decrease with increasing whole-rock PGE contents and Cr# of chromite. Furthermore, γOs values of all but one of the chromitite samples are negative indicating a subchondiritc mantle source. γOs decrease with increasing bulk Os content and decreasing ¹⁸⁷Re/¹⁸⁸Os ratios. These mineralogical and geochemical features are interpreted in terms of chromite crystallization from melts varying in composition from back-arc basalts (Al-rich chromite) to boninites (Cr-rich chromite) in a suprasubduction zone setting. Chromite crystallization occurs as a consequence of magma mixing and assimilation of preexisting gabbro sills at the mantle–crust transition zone. Cr#, PGE abundances, and bulk Os isotopic composition of chromitites are determined by the combined effects of mantle source heterogeneity, the degree of partial melting, the extent of melt-rock interactions, and the local sulfur fugacity. Small-scale (μm to cm) chemical and isotopic heterogeneities in the platinum-group minerals are controlled by the mechanism(s) of chromite crystallization in a heterogeneous environment created by the turbulent regime generated by successive inputs of different batches of melt.