Himalayan uplift and osmium isotopes in oceans and rivers

Previous studies have shown that ¹⁸⁷Os/¹⁸⁸Os in seawater has become increasingly radiogenic over the last 40 Ma in a manner analogous to strontium. This rapid rise in the marine ¹⁸⁷Os/¹⁸⁸Os over the last 17 Ma has been attributed to an increase in the bulk silicate weathering rates resulting from the rise of the Himalayas and/or selective weathering and erosion of highly radiogenic organic rich ancient sediments. The key test of this hypothesis is the ¹⁸⁷Os/¹⁸⁸Os and the total osmium concentration of the Himalayan rivers. We report the concentration and isotopic composition of osmium in the Ganges, the Brahmaputra, and the Indus rivers. The ¹⁸⁷Os/¹⁸⁸Os of the Ganges close to its source (at Kaudiyal, 30°05′N, 78°50′E) is 2.65 and [Os] = 45 fM/kg. A second sample of the lower reaches of the Ganges at Patna (25°30′N, 85°10′E) gives ¹⁸⁷Os/¹⁸⁸Os =1.59 and [Os] = 171 fM/kg. The ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra at Guwahati (26°10′N, 91°58′E) is 1.07 and [Os] = 52 fM/kg. A sample of the Indus (Besham, 34°55′N, 72°51′E) has a ¹⁸⁷Os/¹⁸⁸Os of 1.2 and [Os] = 59 fM/kg. We infer that the Himalayas do not provide either a high flow of osmium or a highly radiogenic osmium component to the oceans. The overall trend for osmium and strontium could be explained by a regularly increasing input of global continental weathering sources but the Himalayas themselves appear not to be the dominant source.     

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.     

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.     

Re-Os isotope systematics of sediments of the Brahmaputra River system

Re-Os analyses were performed on suspended loads and coarser grained bank sediments of the Brahmaputra River system. Re and Os concentrations of these sediments vary from 7 to 1154 ppt and from 3 to 173 ppt, respectively. ¹⁸⁷Os/¹⁸⁸Os ratios range from 0.178 to 6.8, and thus vary from nearly mantle to very radiogenic crustal values. Nevertheless, most of the sediments have ¹⁸⁷Os/¹⁸⁸Os ratios less than 1.5, and nearly all of the samples of the Brahmaputra main channel have ratios less than 1.2. Thus, as previously suggested, the Brahmaputra is much less radiogenic than the Ganga. The Siang River, the northern extension of the Brahmaputra, is quite radiogenic in Os despite receiving sediments from the Tsangpo River, which flows along a suture zone with ultramafic outcrops. The Brahmaputra main channel has a fairly constant ¹⁸⁷Os/¹⁸⁸Os ratio even though its tributaries contribute sediments with very heterogeneous Os isotopic compositions. These data, along with the corresponding Nd isotopic compositions, suggest that about 60-90% of the sediment in the Brahmaputra system is derived from Himalayan formations (Higher Himalaya and Lesser Himalaya) whereas 10-40% comes from ophiolite-bearing sequences, perhaps eastern equivalents of those of the Transhimalayan Plutonic Belt. Os data also confirm previously published Sr and Nd results, indicating that about half of the sediments delivered to the Brahmaputra are supplied by the Siang River, while the Himalayan and the eastern tributaries account for 40 and 10%, respectively.The lower ¹⁸⁷Os/¹⁸⁸Os of the Brahmaputra River compared to that of the Ganga is due to two factors. One is the more limited presence of the Lesser Himalaya and hence the lower black shale content of the eastern Himalaya. The other is the non-radiogenic Os supplied by the eastern and southern tributaries, reflecting the presence of mantle-derived lithologies in this region. Despite the lower sediment supply from these tributaries, they contribute greatly to the Os budget of the Brahmaputra River. This study indicates that the Brahmaputra River has little effect on the present-day seawater Os budget. However, reconsideration of this budget suggests that the Ganga, which provides the most radiogenic Os of major rivers studied to date, may have significant impact on the marine Os isotopic composition. The Indo-Asian collision cannot be excluded as an important cause of the increase in the marine ¹⁸⁷Os/¹⁸⁸Os over the past 16 million years until the contributions of all of the rivers draining the Himalayan Tibetan Plateau are known.     

Accretion of extraterrestrial matter during the last 80 million years and its effect on the marine osmium isotope record

The flux of particulate extraterrestrial (ET) matter to the deep-sea has been calculated using a four-component mixing model based on osmium concentrations and isotope ratios in slowly accumulating pelagic sediments from the Pacific Ocean. Nineteen published bulk-leach osmium isotope data pairs that cover the last 80 million years have been used for the calculation. The calculated annual particulate flux, averaged over several 100 ka by slow accumulation and bioturbation, ranges from ∼18,000 to ∼67,000 tons, with a mean value of ∼37,000 ± 13,000 tons. The data indicate no significant variability in the flux with time, except at the K-T boundary and are thus compatible with results based on Ir accumulation in deep-sea sediments. The inferred constancy of the ET matter flux is in contrast to recent results based on the ET ³He flux that integrates only a small size fraction of the entire ET matter flux. ³He data indicate variability by a factor of 6 over the past 70 Ma and a fivefold increase in the ET flux between 3 Ma and 1 Ma that is not seen in the bulk ET matter flux based on osmium isotope data.The apparent constancy of the cosmic matter flux over the past 80 Ma stands in marked contrast to the dynamic nature of the marine osmium isotope record and indicates that dissolution of cosmic matter does not drive changes in this record, except at the K-T boundary. A comparison between osmium isotope and Ir data from two pelagic sediment cores from the Pacific (DSDP Site 596 and LL44-GPC3) indicates that the seawater-soluble fraction of ET Os cannot exceed ∼36 kg/a and most likely is significantly smaller. The maximum value of 36 kg/a can account for approximately one half of the seawater-soluble ET matter flux necessary to balance the radiogenic continental runoff of Os without any additional unradiogenic source. Simple mass balance calculations indicate that an additional unradiogenic source of Os to the oceans, most likely alteration of oceanic crust, is required to balance the present-day seawater osmium-isotopic composition. This source is probably more important in balancing radiogenic continental runoff than is dissolution of cosmic matter in seawater.     

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.     

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.     

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.     

Sources of unique rhenium enrichment in fumaroles and sulphides at Kudryavy volcano

Rhenium (Re) is one of the least abundant elements in Earth, averaging 0.28 ppb in the primitive mantle. The unique occurrence of rheniite ReS₂ (74.5 wt% of Re) in Kudryavy volcano precipitates raises questions about recycling of Re-rich reservoirs within the Kurile-Kamchatka volcanic Island arc setting. The sources of this unique Re enrichment have been inferred from studies of Re-Os isotope systematic and trace elements in volcanic gases, sulphide precipitates and host volcanic rocks. The fumarolic gas condensates are enriched in hydrophile trace elements relative to fluid-immobile elements and exhibit high Ba/Nb (133-204), Rb/Y (16-406) and Th/Zr (0.01-0.25) ratios. They are characterised by high Re (7-210 ppb) and Os abundances (0.4-0.9 ppb), with ¹⁸⁷Os/¹⁸⁸Os ratios in a range 0.122-0.152. This Os isotopic compositional range is similar to that of the peridotite xenoliths from the metasomatised mantle wedge above the subducted Pacific plate, the radiogenic isotopic signature of which is probably due to radiogenic addition from a slab-derived fluid.Re- and Os-rich sulphide and oxide minerals precipitate from volcanic gases within fumarolic fields. Molybdenite (MoS₂), powellite (CaMoO₄) and cannizzarite (Pb₄Bi₆S₁₃) contain 1.5-1.7 wt%, 10 ppm, and 65-252 ppb of Re, respectively. Both molybdenite and rheniite contain normal Os concentrations, with total Os abundances in a range from 0.6 to 3.1 ppm for molybdenite, and 2.3-24.3 ppb for the rheniite samples. Repeated analyses of osmium isotope ratios for two rheniite samples form a best-fit line with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.32 ± 0.15 and an age of 79 ± 11 yr, which is the youngest age ever measured in natural samples. The high Re contents in molybdenite and rheniite led to high radiogenic ¹⁸⁷Os values, even in the limited period of time, with ¹⁸⁷Os/¹⁸⁸Os ratios up to 3.3 for molybdenite and up to 4.4 for rheniite.The Os isotopic compositions of andesite-basaltic rocks from the Kudryavy volcano (¹⁸⁷Os/¹⁸⁸Os up to 0.326) are more radiogenic than those of residual peridotites and fumarolic gas condensates that are mainly constituted from magmatic vapor. Such radiogenic values can be attributed either to the addition of a radiogenic Os-rich subduction component to the depleted mantle, or to the assimilation of older dacitic caldera walls (¹⁸⁷Os/¹⁸⁸Os = 0.6) during arc magma ascent and emplacement. The latter hypothesis is supported by the correlation between ¹⁸⁷Os/¹⁸⁸Os ratio and indicators of fractionation such as MgO or Ni, and by low contents of potentially hydrophile trace elements such as Ba, Rb and Th relative to fluid-immobile elements such as Nb, Zr and Y. The high Re flux in the Kudryavy volcano (estimated at ∼46 kg/yr) can be explained by remobilisation of Re by Cl-rich water from an underplated mantle wedge and subducted organic-rich sediments of the Pacific plate.     

Depositional Age of a Fossil Whale Bone from São Paulo Ridge,South Atlantic Ocean,Based on Os Isotope Stratigraphy of a Ferromanganese Crust

Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (¹⁸⁷Os/¹⁸⁸Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. ¹⁸⁷Os/¹⁸⁸Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.     

Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the ¹⁸⁷Re–¹⁸⁷Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(¹⁸⁷Os/¹⁸⁸Os) expressed as ¹⁸⁷Os/¹⁸⁸Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of ¹⁹⁰Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H₂O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of ¹⁸⁷Os/¹⁸⁸Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting ¹⁸⁷Os/¹⁸⁸Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.     

Evaluation of Simultaneous Analyte Leaching/Vapour Phase Introduction for Direct Osmium Isotope Ratio Measurements in Solid Samples by Double-Focusing Sector Field ICP-MS

The analytical performance of a method for Os isotope ratio measurement by double‐focusing, sector field ICP‐MS (ICP‐SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by the formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic determination by ICP‐SFMS. Due to the very efficient utilisation of analyte (approaching 0.5‰), Os isotope ratio measurement could be performed at low pg levels. Combined with an ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub pg g^?1 range could be determined by this method. Given that two complete digestion/distillation systems were available for interchangeable use, throughputs of up to fifteen samples per 8 hour shift could be achieved. The method precision, evaluated as the long‐term reproducibility of ¹⁸⁷ Os/¹⁸⁸Os ratio measurements in a commercial Os reference sample containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1s). The method has been applied to perform replicate ¹⁸⁷ Os/¹⁸⁸ Os ratio measurements on a suite of fifty reference materials of various origins and matrix compositions, with Os concentrations varying from < 0.1 pg g^?1 to > 100 ng g^?1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi‐quantitative determination of Os concentrations.     

Osmium isotope systematics of historical lavas from Piton de la Fournaise (Réunion Island, Indian Ocean)

Re–Os isotope and elemental data have been obtained for 20 historical picrites and basalts (1931–2006) from the Piton de la Fournaise volcano on Réunion Island and two old (>0.78?Ma) cumulates from a drill hole in the eastern part of the volcano. The ¹⁸⁷Os/¹⁸⁸Os ratios of the historical lava samples, selected to cover the MgO concentration and Pb isotopic ranges of Piton de la Fournaise lavas, range from 0.1311 to 0.1374. This result, together with previous results on 66-Ma-old lavas from the Deccan Traps (Allègre et al. in. Earth Planet Sci Lett, 170:197–204, 1999), supports the idea that the Os isotopic signature of the Réunion plume is relatively uniform and is at the less radiogenic end of the ocean island basalt spectrum. In detail, lavas erupted before 1992 seem to have higher ¹⁸⁷Os/¹⁸⁸Os than the lavas erupted after the 1992–1998 period of quiescence. Comparison of ¹⁸⁷Os/¹⁸⁸Os ratios with Pb, Sr and Nd isotopic data on the same set of samples shows no correlation between Os and Sr–Nd isotopes, whereas a broad positive relationship with Pb isotopes is observed, which is interpreted to reflect coupled fractionation of Re/Os and U–Th/Pb in the mantle due to the partitioning of Pb and Os into sulphides. Lavas inferred to be recording the Os isotopic signature of the Réunion plume source have higher ¹⁸⁷Os/¹⁸⁸Os ratios than the primitive mantle values. While this might be ascribed to melting of a lithologically heterogeneous source comprising recycled oceanic crust and/or continental sediment, the expected coupled Os–Sr–Nd–Pb isotopic variations are not observed. It is thus proposed that the mantle source for Piton de la Fournaise has inherently slightly radiogenic ¹⁸⁷Os/¹⁸⁸Os values that could reflect a mantle domain almost isolated from recycling processes.     

A Matrix‐Matched Reference Material for Validating Petroleum Re‐Os Measurements

This study presents two matrix‐matched reference materials developed for petroleum Re‐Os measurements. We present the Re and Os mass fractions and ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values (ratio of the number of atoms of the isotopes) for repeatedly measured aliquots (ca. 120–150 mg test portions) of the NIST Research Material 8505 (RM 8505) crude oil, and its asphaltene and maltene fractions, and ~ 90 g of homogeneous asphaltene powder isolated from this oil. Measurements were performed using the Carius tube‐isotope dilution negative‐thermal ionisation mass spectrometry methodology. The RM 8505 crude oil contains 1.98 ± 0.07 ng g^?1 Re and 25.0 ± 1.1 pg g^?1 Os, with Re‐Os isotope amount ratios of 452 ± 6 for ¹⁸⁷Re/¹⁸⁸Os and 1.51 ± 0.01 for ¹⁸⁷Os/¹⁸⁸Os (n = 20, 95% conf.). The homogeneous asphaltene sample contains 16.52 ± 0.10 ng g^?1 Re and 166.0 ± 0.9 pg g^?1 total Os, and possesses isotope amount ratios of 574 ± 3 for ¹⁸⁷Re/¹⁸⁸Os and 1.64 ± 0.01 for ¹⁸⁷Os/¹⁸⁸Os (n = 24, 95% conf.). The intermediate precision of these data makes the RM 8505 whole oil and the (~ 90 g) homogenised asphaltene appropriate petroleum matrix‐matched reference materials for Re‐Os measurements. The asphaltene fraction of the oil is the main carrier of Re and Os of the RM 8505 whole oil, and caution is suggested in using asphaltene and maltene fractions of a single oil for Re‐Os geochronology.     

苏皖地区幔源橄榄岩捕瞄虏体的锇同位素组成、模式年龄及其意义

苏皖地区发育的新生代玄武岩中富含地幔橄榄岩捕虏体，测定了25个橄榄岩全岩的锇同位素组成。结果表明大部分样品呈亏损特征,187Os/188Os=0.119～0.129.Os同位素比值与主量成分之间有显著的相关性.采用187Os/188Os-Al2O3代用等时线方法,由截距得到初始值(187Os/188Os)0=0.109,在对流地幔的187Os/188Os比值演化线上获得模式年龄t=2.5(±0.1)Ga,为晚太古-早元古代。用样品组中最低的锇同位素组成,即187Os/188Os=0.119,计算Re亏损模式年龄,t=1.2Ga,为中元古代。表明苏皖地区新生代玄武岩中的地幔橄榄岩捕虏体具有古老的形成年龄,它们是经过显生宙减薄作用后的残余地幔的碎片。大陆岩石圈地幔的古老形成年龄与上覆地壳克拉通的古老稳定年龄相耦合。     

Comparison of reductive accumulation of Re and Os in seawater-sediment systems

In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO₂, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high ¹⁸⁷Re/¹⁸⁸Os ratio can occur only in reducing sediments, such as black shales. The high¹⁸⁷Re/¹⁸⁸Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower ¹⁸⁷Re/¹⁸⁸Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the ¹⁸⁷Os/¹⁸⁸Os ratio cannot grow significantly due to its extremely low ¹⁸⁷Re/¹⁸⁸Os ratio.     

A subduction wedge origin for Paleoarchean peridotitic diamonds and harzburgites from the Panda kimberlite, Slave craton: evidence from Re–Os isotope systematics

An extensive study of peridotitic sulfide inclusion bearing diamonds and their prospective harzburgitic host rocks from the 53 Ma Panda kimberlite pipe, Ekati Mine, NWT Canada, has been undertaken with the Re–Os system to establish their age and petrogenesis. Diamonds with peridotitic sulfide inclusions have poorly aggregated nitrogen (<30% N as B centers) at N contents of 200–800 ppm which differs from that of chromite and silicate bearing diamonds and indicates residence in the cooler portion of the Slave craton lithospheric mantle. For most of the sulfide inclusions, relatively low Re contents (average 0.457 ppm) and high Os contents (average 339 ppm) lead to extremely low ¹⁸⁷Re/¹⁸⁸Os, typically << 0.05. An age of 3.52 ± 0.17 Ga (MSWD = 0.46) and a precise initial ¹⁸⁷Os/¹⁸⁸Os of 0.1093 ± 0.0001 are given by a single regression of 11 inclusions from five diamonds that individually provide coincident internal isochrons. This initial Os isotopic composition is 6% enriched in ¹⁸⁷Os over 3.5 Ga chondritic or primitive mantle. Sulfide inclusions with less radiogenic initial Os isotopic compositions reflect isotopic heterogeneity in diamond forming fluids. The harzburgites have even lower initial ¹⁸⁷Os/¹⁸⁸Os than the sulfide inclusions, some approaching the isotopic composition of 3.5 Ga chondritic mantle. In several cases isotopically distinct sulfides occur in different growth zones of the same diamond. This supports a model where C–O–H–S fluids carrying a radiogenic Os signature were introduced into depleted harzburgite and produced diamonds containing sulfides conforming to the 3.5 Ga isochron. Reaction of this fluid with harzburgite led to diamonds with less radiogenic inclusions while elevating the Os isotope ratios of some harzburgites. Subduction is a viable way of introducing such fluids. This implies a role for subduction in creating early continental nuclei at 3.5 Ga and generating peridotitic diamonds.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Osmium mass balance in peridotite and the effects of mantle-derived sulphides on basalt petrogenesis

Analyses of enriched mantle (EM)-basalts, using lithophile element-based isotope systems, have long provided evidence for discrete mantle reservoirs with variable composition. Upon partial melting, the mantle reservoir imparts its isotopic fingerprint upon the partial melt produced. However, it has increasingly been recognised that it may not be simple to delimit these previously well-defined mantle reservoirs; the “mantle zoo” may contain more reservoirs than previously envisaged.Here we demonstrate that a simple model with varying contributions from two populations of compositionally distinct mantle sulphides can readily account for the observed heterogeneities in Os isotope systematics of such basalts without additional mantle reservoirs. Osmium elemental and isotopic analyses of individual sulphide grains separated from spinel lherzolites from Kilbourne Hole, New Mexico, USA demonstrate that two discrete populations of mantle sulphide exist in terms of both Re-Os systematics and textural relationship with co-existing silicates. One population, with a rounded morphology, is preserved in silicate grains and typically possesses high [Os] and low [Re] with unradiogenic, typically sub-chondritic ¹⁸⁷Os/¹⁸⁸Os attributable to long term isolation in a low-Re environment. By contrast, irregular-shaped sulphides, preserved along silicate grain boundaries, possess low [Os], higher [Re] and a wider range of, but generally supra-chondritic ¹⁸⁷Os/¹⁸⁸Os ([Os] typically ? 1-2 ppm, ¹⁸⁷Os/¹⁸⁸Os ? 0.3729; this study). This population is thought to represent metasomatic sulphide.Uncontaminated silicate phases contain negligible Os (<100 ppt) therefore the Os elemental and isotope composition of basalts is dominated by volumetrically insignificant sulphide ([Os] ? 37 ppm; this study). During the early stages of partial melting, supra-chondritic interstitial sulphides are mobilised and incorporated into the melt, adding their radiogenic ¹⁸⁷Os/¹⁸⁸Os signature. Only when sulphides armoured within silicates are exposed to the melt through continued partial melting will enclosed sulphides add their high [Os] and unradiogenic ¹⁸⁷Os/¹⁸⁸Os to the aggregate melt. Platinum-group element data for whole rocks are also consistent with this scenario. The sequence of (i) addition of all of the metasomatic sulphide, followed by (ii) the incorporation of small amounts of armoured sulphide can thus account for the range of both [Os] and ¹⁸⁷Os/¹⁸⁸Os of EM-basalts worldwide without the need for contributions from additional silicate mantle reservoirs.     

Closed-system behaviour of the Re–Os isotope system recorded in primary and secondary platinum-group mineral assemblages: Evidence from a mantle chromitite at Harold's Grave (Shetland Ophiolite Сomplex,Scotland)

This study evaluates in detail the mineral chemistry, whole-rock and mineral separate Os-isotope compositions of distinct platinum-group mineral (PGM) assemblages in an isolated chromitite pod at Harold's Grave which occurs in mantle tectonite in the Shetland Ophiolite Complex (SOC), Scotland. This was the first ophiolite sequence worldwide that was shown to contain ppm levels of all six platinum-group elements (PGE) in podiform chromitite, including the contrasting type localities found here and at Cliff. At Harold's Grave the primary PGM assemblage is composed mainly of laurite and/or Os-rich iridium and formed early together with chromite, whereas the secondary PGM assemblage dominated by laurite, Os-rich laurite, irarsite, native osmium and Ru-bearing pentlandite is likely to reflect processes including in-situ serpentinization, alteration during emplacement and regional greenschist metamorphism. The osmium isotope data define a restricted range of ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for coexisting laurite and Os-rich alloy pairs from ‘primary’ PGM assemblage (0.12473–0.12488) and similar ‘unradiogenic’ ¹⁸⁷Os/¹⁸⁸Os values for both ‘primary’ and ‘secondary’ PGM assemblages (0.1242 ± 0.0008 and 0.1245 ± 0.0006, respectively), which closely match the bulk ¹⁸⁷Os/¹⁸⁸Os value of their host chromitite (0.1240 ± 0.0006). The unprecedented isotopic similarity between primary or secondary PGM assemblages and chromitite we report suggests that the osmium isotope budget of chromitite is largely controlled by the contained laurite and Os-rich alloy. This demonstrates that closed system behaviour of the Re–Os isotope system is possible, even during complex postmagmatic hydrothermal and/or metamorphic events. The preserved mantle Os-isotope signatures provide further support for an Enstatite Chondrite Reservoir (ECR) model for the convective upper mantle and are consistent with origin of the complex as a Caledonian ophiolite formed in a supra-subduction zone setting shortly before obduction.     

石灰岩铼-锇同位素分析方法研究及应用初探

针对石灰岩样品Re-Os同位素分析,在选样和溶样方法上进行了改进,在Carius管封闭前加入HCl与石灰岩反应释放出大量CO2,然后加入氧化剂和稀释剂封闭Carius管溶解样品,大大增加了样品取样量。利用改进的方法对采自青海玉树地区二叠世九十道班组底部的灰黑色微细晶灰岩的Re-Os同位素体系进行了分析测定,得到了精确的沉积年龄(283.1±7.1)Ma(MSWD=0.61,Model1,n=7)。187Os/188Os同位素初始值为0.56±0.12,与二叠纪时海水的187Os/188Os值相一致,反映了石灰岩沉积时海水的187Os/188Os比值。所得石灰岩年龄与其中的生物化石年龄相吻合,并且与区域上岩浆岩锆石年龄相互印证,表明Re-Os同位素体系在该石灰岩中的封闭性较好。通过石灰岩中有机碳含量以及其中Re、Os含量关系研究,得出了Re、Os在灰岩中主要赋存于有机质中的结论。从原理上解释了Re-Os同位素体系在灰岩中的应用具有十分广泛的前景。