Rhenium–Osmium Isotope Measurements in Marine Shale Reference Material SBC‐1: Implications for Method Validation and Quality Control

In this study, the USGS black shale reference material SBC‐1 was investigated as a matrix‐matched reference material for both intra‐laboratory calibration and inter‐laboratory comparison of high‐precision Re‐Os dating for organic‐rich sedimentary rocks. This reference material was analysed for Re‐Os isotopic composition by three digestion protocols – inverse aqua regia, CrO₃‐H₂SO₄ and H₂O₂‐HNO₃. The results for SBC‐1 obtained by inverse aqua regia digestion yielded similar Re mass fractions but slightly (~ 5%) higher Os mass fractions and lower ¹⁸⁷Os/¹⁸⁸Os values than the CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions. The data set of inverse aqua regia digestion exhibited strong correlations in plots of ¹⁸⁷Os/¹⁸⁸Os vs. 1/¹⁹²Os and ¹⁸⁷Os/¹⁸⁸Os vs. ¹⁸⁷Re/¹⁸⁸Os, which may signify the incorporation of detrital Re and Os into organic matter in the Re‐Os system. Similar correlations were also observed for the CrO₃‐H₂SO₄ digestion data set, but not for that of H₂O₂‐HNO₃. The data indicate that there is an amount of non‐hydrogenous Os in SBC‐1 and that CrO₃‐H₂SO₄ and H₂O₂‐HNO₃ digestions would minimise liberation of the non‐hydrogenous Os component. We propose that SBC‐1 may be a more suitable reference material to monitor the influence of detrital Re and Os on Re‐Os isochron age data, especially for samples with less organic matter and more siliceous detritus.     

187Re-187Os in Lesser Himalayan sediments: Measurement techniques and preliminary results

The applications of the¹⁸⁷Re-¹⁸⁷Os isotope pair as a petrogenetic and geologic tracer are increasing in recent years due to several advances in the chemical extraction and purification of Re and Os, occurring at ppb levels in environmental samples, and in the precise determination of the Os isotope composition. We have established in our laboratory; based on available methods, chemical procedures and Negative Thermal Ionisation Mass Spectrometric techniques for the measurement of Re-Os concentrations in environmental samples and the Os isotope composition in them. Using these techniques, we are able to determine¹⁸⁷Os/¹⁸⁶Os ratios with a precision of ∼ 1% (±2σ_μ; twice the standard error of the mean) in several tens of picogram of Os. Preliminary analysis of black shales from the Lower Tal section of the Maldeota phosphorite mine yields a mean¹⁸⁷Re-¹⁸⁷Os model age of 597 ± 30 Ma. The¹⁸⁷Os/¹⁸⁶Os and Os concentration in black shales of the Lesser Himalaya range from 8 to 96 and 0.02 to 13 ng g^-1 respectively. The mean¹⁸⁷Os/¹⁸⁶Os in these samples is ∼ 25, significantly higher than the crustal value of ∼ 10.5, suggesting that these black shales could be an important source of radiogenic Os to the rivers draining the Himalaya and to the steady increase in¹⁸⁷Os/¹⁸⁶Os of the oceans through the Cenozoic.     

Os and Os enrichments and high-He/He sources in the Earth’s mantle: Evidence from Icelandic picrites

Picrites from the neovolcanic zones in Iceland display a range in ¹⁸⁷Os/¹⁸⁸Os from 0.1297 to 0.1381 (γ_Os = + 2.1 to +8.7) and uniform ¹⁸⁶Os/¹⁸⁸Os of 0.1198375 ± 32 (2σ). The value for ¹⁸⁶Os/¹⁸⁸Os is within uncertainty of the present-day value for the primitive upper mantle of 0.1198398 ± 16. These Os isotope systematics are best explained by ancient recycled crust or melt enrichment in the mantle source region. If so, then the coupled enrichments displayed in ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os from lavas of other plume systems must result from an independent process, the most viable candidate at present remains core-mantle interaction. While some plumes with high ³He/⁴He, such as Hawaii, appear to have been subjected to detectable addition of Os (and possibly He) from the outer core, others such as Iceland do not.A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He from 9.6 to 19 Ra in Iceland picrites is best modeled as mixtures of 1 Ga or older ancient recycled crust mixed with primitive mantle or incompletely degassed depleted mantle isolated since 1-1.5 Ga, which preserves the high ³He/⁴He of the depleted mantle at the time. These mixtures create a hybrid source region that subsequently mixes with the present-day convecting MORB mantle during ascent and melting. This multistage mixing scenario requires convective isolation in the deep mantle for hundreds of million years or more to maintain these compositionally distinct hybrid sources. The ³He/⁴He of lavas derived from the Iceland plume changed over time, from a maximum of 50 Ra at 60 Ma, to approximately 25-27 Ra at present. The changes are coupled with distinct compositional gaps between the different aged lavas when ³He/⁴He is plotted versus various geochemical parameters such as ¹⁴³Nd/¹⁴⁴Nd and La/Sm. These relationships can be interpreted as an increase in the proportion of ancient recycled crust in the upwelling plume over this time period.The positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/⁴He demonstrates that the Iceland lava He isotopic compositions do not result from simple melt depletion histories and consequent removal of U and Th in their mantle sources. Instead their He isotopic compositions reflect mixtures of heterogeneous materials formed at different times with different U and Th concentrations. This hybridization is likely prevalent in all ocean island lavas derived from deep mantle sources.     

Re–Os systematics of the Raobazhai peridotite massifs from the Dabie orogenic zone, eastern China

The Raobazhai ultramafic massif of the ultrahigh pressure Sulu–Dabie orogenic belt, central China, is thought to be a segment of subcontinental lithospheric mantle that was subducted and exhumed during the Triassic collision of the North China and Yangtze cratons. We performed a Re–Os isotopic study of peridotites from the massif, associated with major and trace element analysis and textural examination. Os (1.02 to 6.28 ppb) and Re (0.004 to 0.376 ppb) concentrations are typical of orogenic lherzolite values, and ¹⁸⁷Os/¹⁸⁸Os ratios (0.1157 to 0.1283) are all similar to or lower than the proposed primitive upper mantle value. ¹⁸⁷Os/¹⁸⁸Os is roughly correlated with ¹⁸⁷Re/¹⁸⁸Os, and strongly correlated with Al₂O₃. These correlations can be explained by radiogenic ingrowth of ¹⁸⁷Os since an ancient partial melting event. T_MA model ages (1.7 to 2.0 Ga) of refractory peridotites from the lower massif are consistent with the model age (1.8 Ga) obtained from the ¹⁸⁷Os/¹⁸⁸Os vs. Al₂O₃ correlation at ~1% Al₂O₃. This age cannot distinguish the cratonic provenance of the Raobazhai massif, since similar Re–Os model ages have been obtained from both the North China and the Yangtze cratons. The poor quality of the ¹⁸⁷Os/¹⁸⁸Os vs. ¹⁸⁷Re/¹⁸⁸Os correlation indicates that the Re/Os ratios were disturbed, perhaps during Triassic subduction. The mainly lherzolitic samples of the upper massif, which were most strongly affected by this process, have porphyroclastic textures with fine-grained olivine, pyroxene and amphibole neoblasts, suggesting Re mobility during recrystallization in the presence of fluids.Previous studies of ultramafic xenoliths from arc volcanics demonstrate that slab-derived melts or fluids can both scavenge mantle Os and add substantial amounts of radiogenic Os to the suprasubduction mantle. In Raobazhai, both trace element patterns and the abundance of hydrous phases provide evidence for extensive interaction with fluids during subduction and/or exhumation. Nevertheless, the strong correlation between ¹⁸⁷Os/¹⁸⁸Os and Al₂O₃, and the high Os concentrations of these rocks indicate that Os isotopic ratios, and probably even Os concentrations, were essentially unaffected by this process. Assuming that the arguments favoring a suprasubduction setting for the Raobazhai massif are valid, these data provide evidence that Os systematics are sometimes surprisingly robust, even above subduction zones.     

The Coupled Re—Os and Pt—Os Systematics：A Theoretical Consideration

The ^190Pt-^186Os system should be a unique tracer for mantle processes be-cause both Pt and Os are concentrated in the mantle.The ^190Pt-^186Os system will also be a good supplement to the ^187Re-^187Os system for dating and tracing mantle pro-cesses because the ^190Pt-^186Os system is not so easily contaminated by crustal materials as the ^187Re-^187Os system.In turn,the application of the ^187Re-^187Os system to Pt-enriched materials uncontaminated by crustal materials will indirectly refine the half life of ^190Pt.The ^190Pt is refined.In the coupled ^187Re-^187Os and ^190Pt-^186Os sys-tematics,an ^186Os*/^190Pt-^187Os*/^187Re Concordia diagram similar to the ^206Pb*/^238U-^208Pb*/^232Th Concordia can be constructed.In such a Concordia diagram,a date will be obtained so long as the ^190Pt-^186Os system remains closed even if the ^187Re-^187Os sys -tem is contaminated by crustal materials.In addition ,for the coupled ^190Pt-^186Os and ^187Re-^187Os systematics,the mantle processes and the interactions between the mantle and the crust will be described by two ratios:^186Os/^188Os and ^187Os/^188Os .The coupled ^187Re-^187Os and ^190Pt-^186Os systematics will be a powerful tool in the investigation of the geodynamic history of the Earth because the ^187Re-^187Os system is sensitive to the interactions between the mantle and the crust,while the ^190Pt-^186Os system is a good tracer for mantle processes.     

The partitioning of Pt-Re-Os between solid and liquid metal in the Fe-Ni-S system at high pressure: Implications for inner core fractionation

Coupled ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os enrichments of plume-derived lavas have been suggested to reflect contributions of materials from the outer core (Brandon et al., 1998). This hypothesis is based on the assumption that the Earth’s liquid outer core has high Pt/Os and slightly high Re/Os ratios as a result of the crystallization of the solid inner core, and shows coupled enrichments in the ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios, reflecting the decay of ¹⁹⁰Pt and ¹⁸⁷Re to ¹⁸⁶Os and ¹⁸⁷Os, respectively. Partitioning experiments of Pt-Re-Os between solid and liquid metal were performed at 5-20 GPa and 1250-1400 °C, to examine the effects of pressure in the Fe-Ni-S system. The ratios (D_Os/D_Pt, D_Os/D_Re) of measured partition coefficients of Pt, Re and Os are almost constant with increasing pressure. D_Os/D_Pt increases significantly, whereas D_Os/D_Re decreases, with increasing sulphur content in the liquid metal. On the basis of the present experimental results, it is unlikely that the required Pt-Re-Os fractionation is generated during inner core crystallization, assuming that the light element in the Earth’s core is sulphur.     

Os-Os systematics of Hawaiian picrites revisited: New insights into Os isotopic variations in ocean island basalts

Eighteen picrites (MgO > 13 wt.%) and three related basalts from six Hawaiian volcanoes were analyzed for ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os. Variations in these ratios reflect long-term Re/Os and Pt/Os differences in the mantle source regions of these volcanoes. ¹⁸⁷Os/¹⁸⁸Os ratios vary from ∼0.129 to 0.136, consistent with the range defined by previous studies of Hawaiian picrites and basalts. Samples with lower ¹⁸⁷Os/¹⁸⁸Os are mainly from Kea trend volcanoes (Mauna Kea and Kilauea), and the more radiogenic samples are mainly from Loa trend volcanoes (Mauna Loa, Hualalai, Koolau and Loihi). As previously suggested, differences in ¹⁸⁷Os/¹⁸⁸Os between volcanic centers are most consistent with the presence of variable proportions of recycled materials and/or pyroxenitic components in the Hawaiian source.¹⁸⁶Os/¹⁸⁸Os ratios vary from 0.1198332 ± 26 to 0.1198480 ± 20, with some samples having ratios that are significantly higher than current estimates for the ambient upper mantle. Although the range of ¹⁸⁶Os/¹⁸⁸Os for the Hawaiian suite is consistent with that reported by previous studies, the new data reveal significant heterogeneities among picrites from individual volcanoes. The linear correlation between ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os reported by a previous study is no longer apparent with the larger dataset. The postulated recycled materials and pyroxenites responsible for the dominant variations in ¹⁸⁷Os/¹⁸⁸Os are likely not responsible for the variations in ¹⁸⁶Os/¹⁸⁸Os. Such materials are typically characterized by both insufficiently high Os concentrations and Pt/Os to account for the ¹⁸⁶Os/¹⁸⁸Os heterogeneities. The lack of correspondence between ¹⁸⁶Os/¹⁸⁸Os variations and the Kea and Loa trends supports this conclusion.The primary cause of ¹⁸⁶Os/¹⁸⁸Os variations are evaluated within the framework of two mixing scenarios: (1) metasomatic transport of Pt and/or ¹⁸⁶Os-rich Os into some portions of the Hawaiian source, and (2) interaction between an isotopically complex plume source with a common, Os- and ¹⁸⁶Os-enriched reservoir (COs). Both scenarios require large scale, selective transport of Pt, Re and/or Os. Current estimates of HSE concentrations in the mantle source of these rocks, however, provide little evidence for either process, so the dominant cause of the ¹⁸⁶Os/¹⁸⁸Os variations remains uncertain.     

Reconstructing the marine Os/Os record and the particulate flux of meteoritic osmium during the late Cretaceous

Paired analyses of Os isotope composition and concentration of bulk sediment and leachable Os in a metalliferous pelagic clay sequence from the North Pacific, ODP Site 886C, are used to reconstruct the marine Os isotope record and the particulate meteoritic Os flux between 65.5 and 78 Ma. Measured ¹⁸⁷Os/¹⁸⁸Os of bulk sediments ranges from approximately 0.64 to 0.32 and those of leach analyses are very similar to bulk analyses. Hydrogenous Os dominates the sedimentary Os inventory throughout most of the studied interval. As a result the measured ¹⁸⁷Os/¹⁸⁸Os of leachable Os approximates that of contemporaneous seawater. The ODP 886C record shows rising ¹⁸⁷Os/¹⁸⁸Os in the deepest portion of the core, with a local maximum of 0.66 close to 74 Ma. The 67-72 Ma portion of the record is characterized by nearly constant ¹⁸⁷Os/¹⁸⁸Os ratios close to 0.6. The structure of the marine Os isotope record from ODP 886C differs markedly from the seawater ⁸⁷Sr/⁸⁶Sr curve, which rises monotonically throughout the time interval studied here. Calculated particulate meteoritic Os fluxes are between 0.5 and 2 pg cm⁻² kyr⁻¹ throughout most of the studied interval. Two discrete intervals of the core (one of which is within Cretaceous Tertiary, boundary KTB interval) are characterized by higher fluxes of meteoritic Os. Excluding these two intervals, the average background flux of particulate meteoritic Os is roughly half of that estimated from analyses of Cenozoic marine sediments. These are the first Os isotope data to provide evidence of resolvable temporal variations in the background flux of particulate meteoritic material to the Earth.     

Re–Os isotope evidence from Mesozoic and Cenozoic basalts for secular evolution of the mantle beneath the North China Craton

The mechanism and process of lithospheric thinning beneath the North China Craton (NCC) are still debated. A key criterion in distinguishing among the proposed mechanisms is whether associated continental basalts were derived from the thinning lithospheric mantle or upwelling asthenosphere. Herein, we investigate the possible mechanisms of lithospheric thinning based on a systematic Re–Os isotopic study of Mesozoic to Cenozoic basalts from the NCC. Our whole-rock Re–Os isotopic results indicate that the Mesozoic basalts generally have high Re and Os concentrations that vary widely from 97.2 to 839.4 ppt and 74.4 to 519.6 ppt, respectively. They have high initial ¹⁸⁷Os/¹⁸⁸Os ratios ranging from 0.1513 to 0.3805, with corresponding variable γ_Os(t) values (+20 to +202). In contrast, the Re–Os concentrations and radiogenic Os isotope compositions of the Cenozoic basalts are typically lower than those of the Mesozoic basalts. The lowest initial ¹⁸⁷Os/¹⁸⁸Os ratios of the Cenozoic basalts are 0.1465 and 0.1479, with corresponding γ_Os(t) values of +15 and +16, which are within the range of ocean island basalts. These new Re–Os isotopic results, combined with the findings of previous studies, indicate that the Mesozoic basalts were a hybrid product of the melting of pyroxenite and peridotite in ancient lithospheric mantle beneath the NCC. The Cenozoic basalts were derived mainly from upwelling asthenosphere mixed with small amounts of lithospheric materials. The marked differences in geochemistry between the Mesozoic and Cenozoic basalts suggest a greatly reduced involvement of lithospheric mantle as the magma source from the Mesozoic to the Cenozoic. The subsequent lithospheric thinning of the NCC and replacement by upwelling asthenospheric mantle resulted in a change to asthenosphere-derived Cenozoic basalts.     

Platinum-osmium isotope evolution of the Earth’s mantle: Constraints from chondrites and Os-rich alloys

Separation of a metal-rich core strongly depleted the silicate portion of the Earth in highly siderophile elements (HSE), including Pt, Re, and Os. To address the issues of how early differentiation, partial melting, and enrichment processes may have affected the relative abundances of the HSE in the upper mantle, ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os data for chondrites are compared with data for Os-rich alloys from upper mantle peridotites. Given that ¹⁸⁷Os and ¹⁸⁶Os are decay products of ¹⁸⁷Re and ¹⁹⁰Pt, respectively, these ratios can be used to constrain the long-term Re/Os and Pt/Os of mantle reservoirs in comparison to chondrites. Because of isotopic homogeneity, H-group ordinary and other equilibrated chondrites may be most suitable for defining the initial ¹⁸⁶Os/¹⁸⁸Os of the solar system. The ¹⁸⁶Os/¹⁸⁸Os ratios for five H-group ordinary chondrites range only from 0.1198384 to 0.1198408, with an average of 0.1198398 ± 0.0000016 (2σ). Using the measured Pt/Os and ¹⁸⁶Os/¹⁸⁸Os for each chondrite, the calculated initial ¹⁸⁶Os/¹⁸⁸Os at 4.567 Ga is 0.1198269 ± 0.0000014 (2σ). This is the current best estimate for the initial ¹⁸⁶Os/¹⁸⁸Os of the bulk solar system. The mantle evolution of ¹⁸⁶Os/¹⁸⁸Os can be defined via examination of mantle-derived materials with well-constrained ages and low Pt/Os. Two types of mantle-derived materials that can be used for this task are komatiites and Os-rich alloys. The alloys are particularly valuable in that they have little or no Re or Pt, thus, when formed, evolution of both ¹⁸⁷Os/¹⁸⁸Os and ¹⁸⁶Os/¹⁸⁸Os ceases. Previously published results for an Archean komatiite and new results for Os-rich alloys indicate that the terrestrial mantle evolved with Pt-Os isotopic systematics that were indistinguishable from the H-group ordinary and some enstatite chondrites. This corresponds to a Pt/Os of 2.0 ± 0.2 for the primitive upper mantle evolution curve. This similarity is consistent with previous arguments, based on the ¹⁸⁷Os/¹⁸⁸Os systematics and HSE abundances in the mantle, for a late veneer of materials with chondritic bulk compositions controlling the HSE budget of the upper mantle. It is very unlikely that high pressure metal-silicate segregation leading to core formation can account for the elemental and isotopic compositions of HSE in the upper mantle.     

Evaluation of osmium isotopes and iridium as paleoflux tracers in pelagic carbonates

New osmium (Os) isotope and platinum group element (PGE) concentration data are used in conjunction with published ³He and Th isotope data to determine the relative proportions of lithogenic, extraterrestrial and hydrogenous iridium (Ir) in a Pacific pelagic carbonate sequence from the Ocean Drilling Program (ODP) Site 806 on the Ontong Java Plateau (OJP). These calculations demonstrate that lithogenic and extraterrestrial contributions to sedimentary Ir budget are minor, while hydrogenous Ir accounts for roughly 85% of the total Ir. Application of analogous partitioning calculations to previously reported data from a North Pacific red clay sequence (LL44-GPC3) yields very similar results. Total Ir burial fluxes at Site 806 and LL44-GPC3 are also similar, 45 and 30 pg cm⁻² kyr⁻¹, respectively. Average Ir/³He and Ir/xs²³⁰Th_initial ratios calculated from the entire Site 806 data set are similar to those reported earlier for Pacific sites. In general, down-core profiles of Ir, ³He and xs²³⁰Th_initial, are not well correlated with one another. However, all three data sets show similar variance and yield sediment mass accumulation rate estimates that agree within a factor of two. While these results indicate that Ir concentration has potential as a point-paleoflux tracer in pelagic carbonates, Ir-based paleoflux estimates are likely subject to uncertainties that are similar to those associated with Co-based paleoflux estimates. Consequently, local calibration of Ir flux in space and time will be required to fully assess the potential of Ir as a point paleoflux tracer. Measured ¹⁸⁷Os/¹⁸⁸Os of the OJP sediments are systematically lower than the inferred ¹⁸⁷Os/¹⁸⁸Os of contemporaneous seawater and a clear glacial-interglacial ¹⁸⁷Os/¹⁸⁸Os variation is lacking. Mixing calculations suggest Os contributions from lithogenic sources are insufficient to explain the observed ¹⁸⁷Os/¹⁸⁸Os variations. The difference between the ¹⁸⁷Os/¹⁸⁸Os of bulk sediment and that of seawater is interpreted in terms of subtle contributions of unradiogenic Os carried by particulate extraterrestrial material. Down-core variations of ¹⁸⁷Os/¹⁸⁸Os with Pt/Ir and Os/Ir also point to contributions from extraterrestrial particles. Mixing calculations for each set of several triplicate analyses suggest that the unradiogenic Os end member cannot be characterized by primary extraterrestrial particles of chondritic composition. It is noteworthy that in efforts aimed at determining the effect of extraterrestrial contributions, ¹⁸⁷Os/¹⁸⁸Os of pelagic carbonates has greater potential compared to abundances of PGE. An attempt has been made for the first time to estimate sediment mass accumulation rates based on amount of extraterrestrial Os in the OJP samples and previously reported extraterrestrial Os flux. Throughout most of the OJP record, Os isotope-based paleoflux estimates are within a factor of two of those derived using other constant flux tracers. Meaningful flux estimates cannot be made during glacial maxima because the OJP sediments do not record the low ¹⁸⁷Os/¹⁸⁸Os reported previously. We speculate that this discrepancy may be related to focusing of extraterrestrial particles at the OJP, as has been suggested to explain down-core ³He variations.     

Investigation of an early Pleistocene marine osmium isotope record from the eastern equatorial Pacific

Osmium isotope composition (¹⁸⁷Os/¹⁸⁸Os) and concentrations of Os, Ir and Pt are reported for an early Pleistocene section from the ODP Site 849 in the eastern equatorial Pacific. Using the data obtained in this study, the contributions from detrital and extraterrestrial particulate matter to Os concentration and ¹⁸⁷Os/¹⁸⁸Os of sediment are estimated. Our calculations show that detrital contributions to sedimentary Os are too small (<2%) to significantly shift measured bulk sediment ¹⁸⁷Os/¹⁸⁸Os away from seawater values. A moderate but significant negative correlation between ¹⁸⁷Os/¹⁸⁸Os and ³He/¹⁸⁸Os indicate that the average particulate extraterrestrial Os flux to this site is 1.21 ± 0.47 pg cm⁻² kyr⁻¹, which constitutes ?3% of total Os burial flux. The estimates of detrital and extraterrestrial Os are used to calculate the seawater ¹⁸⁷Os/¹⁸⁸Os in the early Pleistocene. The most notable features of this early Pleistocene ¹⁸⁷Os/¹⁸⁸Os record are: (1) glacial-interglacial ¹⁸⁷Os/¹⁸⁸Os differences are insignificant within errors of estimates, (2) glacial ¹⁸⁷Os/¹⁸⁸Os values are higher compared to those reported for the late Pleistocene glacials. Comparison of ¹⁸⁷Os/¹⁸⁸Os values at Site 849 to the late Pleistocene records suggests that average seawater ¹⁸⁷Os/¹⁸⁸Os change has been modest (∼5%) since the early Pleistocene. Assuming that ¹⁸⁷Os/¹⁸⁸Os difference between the glacial periods of the late and the early Pleistocene results solely from temperature dependence of weathering rates, it has been calculated that average surface temperature during the late Pleistocene glacials was 0.8 ± 0.2 °C lower than glacials in the early Pleistocene. This inference is consistent with temperature estimates based on a recent study of pCO₂ reconstruction in the Pleistocene. This observation based on limited studies of marine ¹⁸⁷Os/¹⁸⁸Os records seems to suggest that temperature played an important role in influencing chemical weathering during the Pleistocene glacials. However, more studies are needed to confirm if this temperature-weathering feedback was operational throughout the Pleistocene. A significant down core Ir-³He co-variation coupled with similar burial fluxes of Ir at Site 849 and at LL44 GPC-3 in the north Pacific point to the utility of Ir concentration as a point paleoflux tracer. However, a twofold difference in Ir burial fluxes between the eastern and the western equatorial Pacific suggests that calibration in space and time is required to use Ir concentration as a robust indicator of paleoflux through time. Significant co-variation of concentrations of Os and total alkenone during the glacials coupled with lighter δ¹³C of benthic foraminifera indicates that productivity and carbon burial played a dominant control on scavenging of Os at Site 849. In a broader context, this data set encourages future investigation of response of PGE behavior to paleoceanographic processes.     

Sources of osmium to the modern oceans: new evidence from the Pt-Os system

High precision Os isotope analysis of young marine manganese nodules indicate that whereas the composition of modern seawater is radiogenic with respect to ¹⁸⁷Os/¹⁸⁸Os, it has ¹⁸⁶Os/¹⁸⁸Os that is within uncertainty of the chondritic value. Marine Mn nodule compositions thus indicate that the average continental source of Os to modern seawater had long-term high Re/Os compared to Pt/Os. Analyses of loess and freshwater Mn nodules support existing evidence that average upper continental crust (UCC) has resolvably suprachondritic ¹⁸⁶Os/¹⁸⁸Os, as well as radiogenic ¹⁸⁷Os/¹⁸⁸Os. Modeling the composition of seawater as a two-component mixture of oceanic/cosmic Os with chondritic Os compositions and continentally-derived Os demonstrates that, insofar as estimates for the composition of average UCC are accurate, congruently weathered average UCC cannot be the sole continental source of Os to seawater. Our analysis of four Cambrian black shales confirm that organic-rich sediments can have ¹⁸⁷Os/¹⁸⁸Os ratios that are much higher than average UCC, but ¹⁸⁶Os/¹⁸⁸Os compositions that are generally between those of chondrites and average-UCC. Preferential weathering of black shales can result in dissolved Os discharged to the ocean basins that has a much lower ¹⁸⁶Os/¹⁸⁸Os than does average upper crust. Modeling the available data demonstrates that augmentation of estimated average UCC compositions with less than 0.1% additional black shale and 1.4% additional ultramafic rock can produce a continental end-member Os isotopic composition that satisfies the requirements imposed by the marine Mn nodule data. The interplay of these two sources provides a mechanism by which the ¹⁸⁷Os/¹⁸⁸Os of seawater can change as sources and weathering conditions change, yet seawater ¹⁸⁶Os/¹⁸⁸Os varies only minimally.     

A comparison of selected Precambrian Brazilian chromitites: Chromite, PGE-PGM, and Re/Os as parental source indicators

Mineralogical and geochemical studies were carried out in chromitites belonging to the mafic–ultramafic bodies of Niquelândia, Luanga, and Campo Formoso, which are, respectively, included in the Goiás Massif and the Amazon and São Francisco cratons. The main platinum-group minerals (PGM) included or associated with chromite grains are laurite in Niquelândia and Campo Formoso and sperrylite and braggite in Luanga. The most common primary base metal sulfides (BMS) are pentlandite, chalcopyrite, and minor pyrrhotite. Also present are base metal alloys (BMA), such as awaruite, and the BMS millerite, pyrite, and copper as secondary mineral phases linked to later alteration process. The Luanga chromites display the lowest Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios. The chondrite-normalized profiles are strongly enriched in the platinum PGE subgroup (PPGE, Pt, Pd, Rh). The average Pd/Ir ratio (24.2) and ¹⁸⁷Os/¹⁸⁸Os values (0.17869–0.18584) are very high. Niquelândia chromites have higher Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios than Luanga. Its PGE contents are low and chondrite-normalized profiles depleted, mainly in the PPGE subgroup. The average Pd/Ir ratio (0.45) and ¹⁸⁷Os/¹⁸⁸Os values (0.12598–0.12777) are low. Campo Formoso chromites have the highest Cr₂O₃/Al₂O₃ and Cr₂O₃/FeO_t ratios; its average Pd/Ir ratio (0.72) and chondrite-normalized profiles (except the pronounced Ru spike) are closer to those of Niquelândia. The remarkable differences in terms of chromite bulk-composition, PGE contents and patterns, Pd/Ir ratios, and ¹⁸⁷Os/¹⁸⁸Os values associated with probable distinctions in the inferred geochemical compositions of the respective parental magmas indicate that the Luanga and Niquelândia complexes originated from distinct parental sources. Geochemical and isotopic features indicate that Luanga chromitites and associated rocks are consistent with a parental magma, either originated from an enriched mantle reservoir or strongly contaminated, whereas Niquelândia derives from a depleted mantle source, which displays a slightly positive Os anomaly.     

云南马关地区岩石圈地幔组成和年龄:地幔橄榄岩包体的Re-Os同位素限制

本文对马关地区新生代碱性玄武岩中的地幔包体进行了系统的岩石学和地球化学研究,并首次进行了包体的Re-Os同位素测试。马关地区的橄榄岩包体主量成分上表现为饱满肥沃的特征;具有不同程度的轻稀土亏损特征,亏损Nb、Ti和Zr等高场强元素(HFSE)以及Ba等大离子亲石元素(LILE);橄榄岩包体的Nd同位素特征表明橄榄岩包体代表的是不均一的亏损地幔。5个橄榄岩全岩样品的Re-Os同位素分析结果表明,样品的Os含量总体较高(3.29×10^-9~3.78×10^-9),接近于造山带橄榄岩体的Os含量,Re含量变化范围较大(0.24×10^-9~0.54×10^-9),与Re的迁移能力较强有关。样品的¹⁸⁷Os/¹⁸⁸Os值在0.12295~0.12530之间变化,与¹⁸⁷Re/¹⁸⁸Os值和Al₂O₃含量之间都不存在较好的相关性,说明Re-Os体系不单纯由熔体抽取过程所控制。橄榄岩包体的Re亏损年龄t_RD为254~604Ma,说明马关地区岩石圈地幔形成的时代应该在新元古代之前。马关地区岩石圈地幔并非是由软流圈上涌新增生的地幔,而是经历了如下演化历史:在新元古代之前,由原始地幔的部分熔融和熔体抽取作用形成了岩石圈地幔,之后经历了熔/流体交代和改造而发生了再富集作用,导致部分地幔橄榄岩逐渐从亏损难熔的特征向饱满肥沃转变,而未遭受熔/流体的改造的橄榄岩仍然保持了难熔亏损的特征。这种熔/流体交代和改造作用很可能与晚二叠纪峨眉山地幔柱的活动有关,而新生代以来印度-亚洲大陆碰撞导致地幔物质向东南方向的侧向流动,诱发软流圈上涌和马关地区的钾质岩浆的活动,也对马关地区岩石圈地幔的改造具有重要的影响,但由于喷发时间较新对Os同位素组成的影响还未显现出来。     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

Osmium isotope ratios of PGM grains associated with the Freetown Layered Complex,Sierra Leone,and their origin

Osmium isotope ratios for two types of platinum group mineral (PGM) nuggets of eluvial (residual) origin, associated with the Freetown Layered Gabbro Complex, were determined in-situ using an ion microprobe. The values for erlichmanite nuggets are 1.08. Those for PGM inclusions in Pt–Fe alloy nuggets are higher, ranging from 1.2 to 2.1. Ratios of¹⁸⁷Os/¹⁸⁶Os vary between the nuggets, but they are consistent within individual nuggest. The data suggest early formation of the erlichmanite nuggets, prior to a postulated substantial contribution of crustal Os. The Pt–Fe alloy nuggets, on the other hand, were formed later in a residual melt which was contaminated by crustal Os due to the assimilation (<10%) or the gaseous/fluid transport of Os from Archaean host rocks into the magma. The lack of systematic mineralogical and chemical changes of the Complex and extensive granulitization in the adjacent host rocks and xenoliths may favor the latter process.The lack of high¹⁸⁷Os/¹⁸⁶Os ratios, consistent¹⁸⁷Os/¹⁸⁶Os values within individual nuggets and their textures and mineralogy suggest that the studied PGM nuggets were not formed during lateritization or in low-temperature depositional environments.     

The marine osmium isotope record

Over the past decade the marine osmium isotope record has been developed into a new tracer in palaeoceanographic research. Several analytical developments, particularly in the past few years, have significantly increased our ability to study the behaviour of osmium in the surficial environment. The ¹⁸⁷Os/¹⁸⁸Os and osmium concentration of seawater, river water, rain, and hydrothermal vent fluids have been measured directly. Recently, the behaviour of osmium in estuaries–critical for estimating the marine residence time of osmium–has been studied. Our knowledge of the surficial osmium cycle has thus significantly improved. In addition, reconstructions of past variations in the marine ¹⁸⁷Os/¹⁸⁸Os recently have been extended back into the Mesozoic. This review attempts to summarize our current understanding of the marine osmium system–present and past. The ¹⁸⁷Os/¹⁸⁸Os of seawater during the Cenozoic to first order mimics the marine ⁸⁷Sr/⁸⁶Sr record. It is therefore tempting to interpret both records as reflecting increased input of radiogenic osmium and strontium resulting from enhanced continental weathering regulated by climatic/tectonic processes. However, the marine osmium isotope system differs fundamentally from the marine strontium isotope system. This review emphasizes three important differences. First, large impacts are capable of resetting the ¹⁸⁷Os/¹⁸⁸Os to unradiogenic values without significantly affecting the marine strontium system. Second, organic‐rich sediments are characterized by high ¹⁸⁷Re/¹⁸⁸Os; resulting ¹⁸⁷Os/¹⁸⁸Os ingrowth‐trajectories are similar to the average slope of the Cenozoic ¹⁸⁷Os/¹⁸⁸Os seawater record. Trends towards more radiogenic ¹⁸⁷Os/¹⁸⁸Os seawater therefore can be caused by weathering of organic‐rich sediments at a constant rate. Third, the marine residence time of osmium is sufficiently short to capture short‐periodic (glacial‐interglacial) fluctuations that are inaccessible to the buffered marine strontium isotope system. This offers the opportunity to discriminate between high‐frequency (climatic) and low‐frequency (tectonic) forcing.     

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.     

A major element,PGE and Re–Os isotope study of Middle Atlas (Morocco) peridotite xenoliths: Evidence for coupled introduction of metasomatic sulphides and clinopyroxene

We present major element and PGE (platinum-group-element) abundances in addition to Re–Os isotope data for 11 spinel-facies whole rock peridotites from a single maar from the Middle Atlas Mountains, Morocco.Major element systematics of these xenoliths are generally correlated with indices of depletion. FeO–MgO systematics appear to suggest spinel-facies melting in the range of 5 to 25%. However, Al₂O₃ abundances in these xenoliths appear elevated relative to primitive mantle (Prima). The Al₂O₃ abundances in conjunction with other major elements require distinct re-enrichment of the Middle Atlas continental mantle root due to melt/rock reaction and precipitation of amphibole and/or clinopyroxene from passing silicate melts akin to MORB or OIB that evolved in reverse direction along the melting curves in e.g. FeO–MgO space. Sc and V confirm the range of apparent depletion and also indicate that the currently preserved fO₂ in these peridotites is distinctly different from fO₂ conditions observed in subduction zones.The majority of these xenoliths have low Os and Ir (I-PGEs) concentrations relative to Prima and modelled sulphide- and clinopyroxene-depleted residues of mantle melting under low fO₂, mid-ocean ridge-like conditions. Moreover, Pt and Pd (P-PGE) abundances are elevated when compared to their expected abundances after substantial melt extraction. Importantly, the systematically low Ir abundances in the majority of samples show well-correlated trends with Al₂O₃, MgO and Cu that are inconsistent with established melting trends. Os isotopes in the Middle Atlas xenoliths range from ¹⁸⁷Os/¹⁸⁸Os = 0.11604 to 0.12664 although most samples are close to chondritic. The Os isotope ratios are decoupled from ¹⁸⁷Re/¹⁸⁸Os but, together with Re abundances, also exhibit a good correlation with Al₂O₃, MgO and Cu.The major element, I-PGE and Os isotope correlations suggest that the initial melt depletion led to the exhaustion of sulphide and clinopyroxene (20 to 30%) without significant stabilization of I-PGE-rich alloys. During later modal metasomatism of the refractory Middle Atlas continental mantle root with silicate melts akin to MORB or OIB the introduction of clinopyroxene/amphibole reduced the volume of the melt inducing sulphur saturation in these melts causing precipitation of secondary sulphides. This coupled crystallization of pyroxenes and sulphides (chalcopyrite) resulted in the two-component mixing systematics exhibited by I-PGEs, Os isotopes with major elements and Cu preserved in the Middle Atlas continental mantle root.