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.     

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.     

Re–Os geochronology of the Cambrian stage-2 and -3 boundary in Zhijin County,Guizhou Province,China

The black shale series that formed in the Ediacaran–Cambrian transition are important stratigraphic records of the co-evolution of the paleo-ocean, -climate, and -biology. In this study, we measured Re–Os isotopic compositions of the black shale in the Niutitang Formation from the Gezhongwu section in Zhijin, Guizhou Province. The samples had high Re and Os contents, with Re ranging from 21.27 to 312.78 ng/g and Os ranging from 0.455 to 7.789 ng/g. The Re–Os isotope isochron age of 522.9 ± 8.6 Ma implies deposition of the Niutitang black shale predated the Chengjiang Fauna, providing an age constraint for the expansion of oceanic anoxia in the study area. The initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.826 ± 0.026 indicates that enhanced continental weathering might have triggered the expansion of the oceanic anoxia.     

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.     

Re-Os elemental and isotopic systematics in crude oils

Analysis of 12 worldwide oil samples show that Re and Os abundances are positively correlated with the asphaltene content of oil. Light oils with <1% asphaltene content have basically no measurable Re or Os. Within oil, Re and Os are present dominantly in the asphaltene fraction (>83%), with <14% Re and Os found in the maltene fraction, this distribution is similar to other trace metals such as V and Mo. Rhenium and Os could be present in oil as metalloporphyrin complexes, but given their abundance in the asphaltene component they are also likely bound by heteroatomic ligands. The ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values in asphaltene calculated at the estimated time of oil generation (Os_i) are similar to those of the whole oil, as expected from the elemental results. This suggests that the asphaltene fraction can be used to approximate the Re-Os isotopic compositions of the whole oil. Os isotopic compositions in oils show a considerable range, from ¹⁸⁷Os/¹⁸⁸Os of 1.9-6.0, and they correlate positively with the age of the proposed source rock. Re/Os ratios also show a large range and overlap the Re/Os ratios found in typical oil source rocks such as organic rich shale.     

Re-Os isotopic systematics and platinum group element composition of the Tagish Lake carbonaceous chondrite

The Tagish Lake meteorite is a primitive C2 chondrite that has undergone aqueous alteration shortly after formation of its parent body. Previous work indicates that if this type of material was part of a late veneer during terrestrial planetary accretion, it could provide a link between atmophile elements such as H, C, N and noble gases, and highly siderophile element replenishment in the bulk silicate portions of terrestrial planets following core formation. The systematic Re-Os isotope and highly siderophile element measurements performed here on five separate fractions indicate that while Tagish Lake has amongst the highest Ru/Ir (1.63 ± 0.08), Pd/Ir (1.19 ± 0.06) and ¹⁸⁷Os/¹⁸⁸Os (0.12564-0.12802) of all carbonaceous chondrites, these characteristics still fall short of those necessary to explain the observed siderophile element systematics of the primitive upper mantles of Earth and Mars. Hence, a direct link between atmophile and highly siderophile elements remains elusive, and other sources for replenishment are required, unless an as yet poorly constrained process fractionated Re/Os, Ru/Ir, and Pd/Ir following late accretion on both the Earth and Mars mantles.The unique elevated Ru/Ir combined with elevated ¹⁸⁷Os/¹⁸⁸Os of Tagish Lake may be attributed to Ru and Re mobility during aqueous alteration very early in its parent body history. The Os, Ir, Pt, and Pd abundances of Tagish Lake are similar to CI chondrites. The elevated Ru/Ir and the higher Re/Os and consequent ¹⁸⁷Os/¹⁸⁸Os in Tagish Lake, are balanced by a lower Ru/Ir and lower Re/Os and ¹⁸⁷Os/¹⁸⁸Os in CM-chondrites, relative to CI chondrites. A model that links Tagish Lake with CI and CM chondrites in the same parent body may explain the observed systematics. In this scenario, CM chondrite material comprises the exterior, grading downward to Tagish Lake material, which grades to CI material in the interior of the parent body. Aqueous alteration intensifies towards the interior with increasing temperature. Ruthenium and Re are mobilized from the CM layer into the Tagish Lake layer. This model may thus provide a potential direct parent body relationship between three separate groups of carbonaceous chondrites.     

Subgrain-scale decoupling of Re and Os and assessment of laser ablation ICP-MS spot dating in molybdenite

Reproducibility of Re-Os molybdenite ages depends on sample size and homogeneity, suggesting that Re and Os are decoupled within individual molybdenite crystals and do not remain spatially linked over time. In order to investigate the Re-Os systematics of molybdenite at the subgrain (micron) scale, we report LA-ICP-MS Re-Os ages for an Archean molybdenite crystal from Aittojärvi, Finland, analyzed in situ in a white aplite matrix. A related Aittojärvi molybdenite (A996D), in the form of a very fine-grained mineral separate, is used as one of our in-house NTIMS standards, and thus its age of 2760 ± 9 Ma is well established. Measurements of (¹⁸⁷Re + ¹⁸⁷Os)/¹⁸⁵Re on micron scale spots along 200 μm traverses across the crystal yield a wide range of ages demonstrating that, in this case, microsampling of molybdenite does not produce geologically meaningful ages. Experimentation with mineral separations and sample size over a 7-yr period predicted that this would be the outcome. We suggest that ¹⁸⁷Os is more likely to be the mobile species, based on its charge and ionic radius, and that ¹⁸⁷Os becomes decoupled from parent ¹⁸⁷Re with time on the micron and larger scale. Incompatible charge and ionic radius for Os ions formed during reduction of molybdenite-forming fluids may explain the widely observed absence of common (initial) Os in molybdenite. Geologically accurate ages for molybdenite can only be obtained for fully homogenized crystals (or crystal aggregates) so that any post-crystallization ¹⁸⁷Re-¹⁸⁷Os decoupling is overcome.A growing number of geologically accurate ID-NTIMS ¹⁸⁷Re-¹⁸⁷Os ages for homogenized molybdenite suggest that postcrystallization mobility of radiogenic ¹⁸⁷Os must be limited to within the molybdenite mineral phase. We suggest that radiogenic ¹⁸⁷Os may be stored in micron scale dislocations, kink bands, and delamination cracks produced by deformation, and that the unusual structure and deformation response of molybdenite results in an increased chemical stability in this mineral. Migration of ¹⁸⁷Os into adjacent silicate phases is highly unlikely, but other contacting sulfides may take in Os. In an example from a Proterozoic skarn deposit at Pitkäranta (western Russia), we demonstrate minor loss of radiogenic ¹⁸⁷Os from molybdenite and a corresponding gain in adjacent chalcopyrite such that the molybdenite age is not perceptibly disturbed, whereas the resulting chalcopyrite ages are impossibly old. Therefore, it is unadvisable to perform Re-Os analytical work on any sulfide in contact or intimate association with molybdenite. In addition to large errors in the age, if the isochron method is employed, initial ¹⁸⁷Os/¹⁸⁸Os ratios could be erroneously high, leading to seriously errant genetic interpretations.     

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.     

Re-Os systematics of komatiites and komatiitic basalts at Dundonald Beach, Ontario, Canada: Evidence for a complex alteration history and implications of a late-Archean chondritic mantle source

Osmium isotopic compositions, and Re and Os concentrations have been examined in one komatiite unit and two komatiitic basalt units at Dundonald Beach, part of the 2.7 Ga Kidd-Munro volcanic assemblage in the Abitibi greenstone belt, Ontario, Canada. The komatiitic rocks in this locality record at least three episodes of alteration of Re-Os elemental and isotope systematics. First, an average of 40% and as much as 75% Re may have been lost due to shallow degassing during eruption and/or hydrothermal leaching during or immediately after emplacement. Second, the Re-Os isotope systematics of whole rock samples with ¹⁸⁷Re/¹⁸⁸Os ratios >1 were reset at ∼2.5 Ga, possibly due to a regional metamorphic event. Third, there is evidence for relatively recent gain and loss of Re in some rocks.Despite the open-system behavior, some aspects of the Re-Os systematics of these rocks can be deciphered. The bulk distribution coefficient for Os (D_Os^solid/liquid) for the Dundonald rocks is ∼3 ± 1 and is well within the estimated D values obtained for komatiites from the nearby Alexo area and stratigraphically-equivalent komatiites from Munro Township. This suggests that Os was moderately compatible during crystal-liquid fractionation of the magmas parental to the Kidd-Munro komatiitic rocks. Whole-rock samples and chromite separates with low ¹⁸⁷Re/¹⁸⁸Os ratios (<1) yield a precise chondritic average initial ¹⁸⁷Os/¹⁸⁸Os ratio of 0.1083 ± 0.0006 (γ_Os = 0.0 ± 0.6) for their well-constrained ∼2715 Ma crystallization age. The chondritic initial Os isotopic composition of the mantle source for the Dundonald rocks is consistent with that determined for komatiites in the Alexo area and in Munro Township, suggesting that the mantle source region for the Kidd-Munro volcanic assemblage had evolved with a long-term chondritic Re/Os before eruption. The chondritic initial Os isotopic composition of the Kidd-Munro komatiites is indistinguishable from that of the projected contemporaneous convective upper mantle. The uniform chondritic Os isotopic composition of the Kidd-Munro komatiites contrasts with the typical large-scale Os isotopic heterogeneity in the mantle sources for ca. 89 Ma komatiites from the Gorgona Island, arc-related rocks and present-day ocean island basalts. This suggests that the Kidd-Munro komatiites sampled a late-Archean mantle source region that was significantly more homogeneous with respect to Re/Os relative to most modern mantle-derived rocks.     

Dissolved rhenium in the Yamuna river system and the Ganga in the Himalaya: role of black shale weathering on the budgets of Re, Os, and U in rivers and CO2 in the atmosphere

Extensive measurements of dissolved Re and major ion abundances in the Yamuna River System (YRS), a major tributary of the Ganga, have been performed along its entire stretch in the Himalaya, from its source near the Yamunotri Glacier to its outflow at the foothills of the Himalaya at Saharanpur. In addition, Re analysis has been made in granites and Precambrian carbonates, some of the major lithologies of the drainage basin. These data, coupled with those available for black shales in the Lesser Himalaya, allow an assessment of these lithologies’ contributions to the Re budget of the YRS.The Re concentrations in the YRS range from 0.5 to 35.7 pM with a mean of 9.4 pM, a factor of ∼4 higher than that reported for its global average concentration in rivers. Dissolved Re and ΣCations∗ (= Na∗+K+Ca+Mg) are strongly correlated in the YRS, indicating that they are released to these waters in roughly the same proportion throughout their course. The Re/ΣCations∗ in most of these rivers are one to two orders of magnitude higher than the (Re/Na+K+Mg+Ca) measured in granites of the Yamuna basin. This leads to the conclusion that, on average, granites/crystallines make only minor contributions to the dissolved Re budget of the YRS on a basin-wide scale, though they may be important for rivers with low dissolved Re. Similarly, Precambrian carbonates of the Lesser Himalaya do not seem to be a major contributor to dissolved Re in these rivers, as their Re/(Ca+Mg) is much less than those in the rivers. The observation that Re concentrations in rivers flowing through black shales and in groundwaters percolating through phosphorite-black shale-carbonate layers in phosphorite mines are high, and that Re and SO₄ are significantly correlated in YRS, seems to suggest that the bulk of the dissolved Re is derived from black shale/carbonaceous sediments. Material balance considerations, based on average Re of 30 ng g⁻¹ in black shales from the Lesser Himalaya, require that its abundance in the drainage basin of the YRS needs to be a few percent to yield average Re of 9.4 pM. Furthermore, the positive correlation between Re and ΣCations∗ would require that these Re-rich sediments (e.g., black shales) and Re-poor lithologies (e.g., crystallines, Precambrian carbonates) contribute Re and cations in roughly the same proportion throughout the drainage basin. The available data on the abundance and distribution of black shales in the basin are not adequate to test if these requirements can be met.The annual fluxes of dissolved Re at the base of the Himalaya from the Yamuna are ∼150 mol at Batamandi and ∼100 mol at Saharanpur, compared to ∼120 mol from the Ganga at Rishikesh. The total flux from the Yamuna and the Ganga account for ∼0.4% of the global riverine Re flux, much higher than their contribution to global water discharge. This is also borne out from the mobilization rate of Re: ∼1 to 3 g km⁻² y⁻¹ in the Ganga and Yamuna basins in the Himalaya, compared to the global average of ∼0.1 g km⁻² y⁻¹.Black shale weathering can also significantly influence the budgets of Os and U in rivers and CO₂ in rivers and the atmosphere. Using dissolved Re in rivers as a proxy, it is estimated that ∼(6-9) × 10⁸ kg y⁻¹ of black shales are being weathered in the Ganga and Yamuna basins in the Himalaya. Weathering of such amounts of black shales can account for the reported concentrations of Os and U in these rivers. Furthermore, if the weathering results in the conversion of organic carbon in the black shales to CO₂, it would release ∼2 × 10⁵ mol of CO₂ km⁻² y⁻¹ in the Yamuna and Ganga basins in the Himalaya, comparable to the CO₂ consumption from silicate weathering.     

A radiogenic Os component in the oceanic lithosphere? Constraints from Hawaiian pyroxenite xenoliths

Platinum Group Element (PGE) concentrations in garnet pyroxenite xenoliths from Oahu, Hawaii, are significantly lower than those in mantle peridotites and show fractionated patterns (e.g. Pd_N/Os_N = 2-10, Pd_N/Ir_N = 4-24; N = chondrite normalized) and very high Re_N/Os_N ratios (∼9-248). Mass balance calculations show that the bulk rock pyroxenite PGE inventory is controlled by the presence of sulfide phases. The ¹⁸⁷Os/¹⁸⁸Os ratios of these pyroxenites vary from subchondritic to suprachondritic (0.123-0.164); and the ¹⁸⁷Os/¹⁸⁸Os ratios show good correlations with bulk rock and clinopyroxene major and trace element compositions, and bulk rock PGE and sulfur abundances. These observations suggest that the Os isotope compositions in these pyroxenites largely reflect primary processes in the oceanic mantle and Pacific lithosphere.In contrast, bulk rock ¹⁸⁷Os/¹⁸⁸Os ratios do not correlate with other lithophile isotopic tracers (e.g. Rb-Sr, Sm-Nd, Lu-Hf) which show limited isotopic variability (Bizimis et al., 2005). This and the lack of ¹⁸⁷Os/¹⁸⁸Os vs. Re/Os correlations suggest that the range in Os isotope ratios is not likely the result of mixing between long-lived depleted and enriched components or aging of these pyroxenites within the Pacific lithosphere after its formation at a mid-oceanic ridge setting some 80-100 million years ago. We interpret the Os isotopes, PGE and lithophile element systematics as the result of melt-lithosphere interaction at the base of the Pacific lithosphere. The major and trace element systematics of the clinopyroxenes and bulk rock pyroxenites and the relatively constant lithophile element isotope systematics are best explained by fractional crystallization of a rather homogenous parental magma. We suggest that during melt crystallization and percolation within the lithosphere, the parental pyroxenite melt assimilated radiogenic Os from the grain boundaries of the peridotitic lithosphere. This radiogenic Os component may reside in the grain boundary sulfides or other trace phases, and may be due to fluids or melts that had previously percolated through the basal part of the lithosphere during its transit from a mid-oceanic ridge to its present position above the Hawaiian plume. As the solidus of the parental pyroxenite melt is lower than the solidus of the lithospheric peridotite, we envision that the pyroxenite-parent melt selectively assimilated the grain boundary sulfide phases with lower melting temperature as it percolated through the lithosphere, without significantly reacting with the silicate minerals. Thus while the parental melt of these pyroxenites originate within the Hawaiian plume, melt-lithosphere interaction during progressive crystallization may have selectively enriched the resulting melts with radiogenic Os, thereby decoupling Os from the lithophile element isotopes, but retaining a link between Os, PGE and fractional crystallization systematics. In this model, Oahu pyroxenites essentially represent melts from different stages of this melt-mantle reaction process at the base of the lithosphere, and we suggest that this process may also explain the similar Os vs. lithophile element decoupling seen in the rejuvenated volcanism in Oahu and Kauai. We further show that the pyroxenites do not posses the requisite Pt/Re ratios, where upon, recycling and aging would generate the coupled enrichments of ¹⁸⁶Os-¹⁸⁷Os isotope ratios observed in Hawaiian and other lavas.     

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.     

Osmium isotope systematics of ureilites

The ¹⁸⁷Os/¹⁸⁸Os for 22 ureilite whole rock samples, including monomict, augite-bearing, and polymict lithologies, were examined in order to constrain the provenance and subsequent magmatic processing of the ureilite parent body (or bodies). The Re/Os ratios of most ureilites show evidence for a recent disturbance, probably related to Re mobility during weathering, and no meaningful chronological information can be extracted from the present data set. The ureilite ¹⁸⁷Os/¹⁸⁸Os ratios span a range from 0.11739 to 0.13018, with an average of 0.1258 ± 0.0023 (1σ), similar to typical carbonaceous chondrites, and distinct from ordinary or enstatite chondrites. The similar mean of ¹⁸⁷Os/¹⁸⁸Os measured for the ureilites and carbonaceous chondrites suggests that the ureilite parent body probably formed within the same region of the solar nebula as carbonaceous chondrites. From the narrow range of the ¹⁸⁷Os/¹⁸⁸Os distribution in ureilite meteorites it is further concluded that Re was not significantly fractionated from Os during planetary differentiation and was not lost along with the missing ureilitic melt component. The lack of large Re/Os fractionations requires that Re/Os partitioning was controlled by a metal phase, and thus metal had to be stable throughout the interval of magmatic processing on the ureilite parent body.     

Re-Os-Isotope Systematics of Sulfides from Base-Metal Porphyry and Manto-Type Mineralization in Chile

Chile is a major world producer of copper, most of which occurs in base-metal porphyry and in manto deposits. A fundamental difference between these two types of deposits is the relative importance of intrusions spatially associated with the mineralization. The porphyry deposits are set within Mesozoic to Tertiary intrusive complexes. The manto-type deposits are restricted to volcanic and volcano-sedimentary sequences of Middle-Late Jurassic, Early Cretaceous, Late Cretaceous, and Early Tertiary times. Large intrusive centers are not spatially associated with these deposits, although minor intrusions are common. A central question in the metallogenesis of these deposits is the source of ore-forming components, in particular the ore metals. Initial 187Os/188Os isotopic data from sulfides from the El Teniente, La Disputada, and Andacollo base-metal porphyry deposits range from 0.19 to 1. These data indicate that the Os (and, by inference, Cu) is mostly crustally derived, since it is more radiogenic than that of the mantle, which has a ¹⁸⁷Os/¹⁸⁶Os ratio of ～0.12. The isotopie data for El Soldado, which is an important example of manto-type mineralization, are significantly more radiogenic, with ¹⁸⁷Os/¹⁸⁸Os ratios greater than 3. These radiogenic values require that the Os come from a crustal reservoir with a high Re/Os ratio, such as black shales. The Os-isotopic data indicate that the source for these two types of base-metal deposits is different, but that both Os reservoirs reside in the crust.     

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.     

Re–Os age of non-mineralized black shale from the Kupferschiefer, Poland, and implications for metal enrichment

Six samples of non-mineralized black shale from a Kupferschiefer section in the northern part of the Polish Zechstein Basin (Zdrada IG-8 drill hole: 1026.16–1026.90 m) were studied for Re–Os isotopes and selected major and trace elements. These black shales, averaging 5.82 wt.% C_org and 1.69 wt.% S_tot, display very low base metal values (up to 106 ppb Cu, 792 ppb Pb, and 144 ppb Zn) and have abundances of 64–1376 ppb Re and 0.37–1.25 ppb Os, with a ¹⁸⁷Os/¹⁸⁸Os ratio of 6.95–22.5. The regression of all Re–Os data yields an age of 247 ± 20 Ma, which is within the range of uncertainties of previous Rb–Sr and K–Ar geochronological studies. The scatter in the Re–Os data can be explained in terms of fluctuations in sedimentary conditions, i.e., restricted basin with terrestrial influence.     

Re–Os geochronology of organic rich sediments: an evaluation of organic matter analysis methods

Rhenium and osmium in organic-rich sedimentary rocks are dominantly hydrogenous, but any nonhydrogenous component will influence the accuracy and precision of the Re–Os date obtained. To minimize the influence of any nonhydrogenous Re and Os, we evaluate analysis of isolated organic matter from the whole rock, together with whole rock analysis using a CrO₃–H₂SO₄ digestion medium instead of inverse aqua regia, for a black shale unit of the Exshaw Formation, Canada. This unit previously returned a whole rock Re–Os date of 358±10 Ma (Model 3) [Geochim. Cosmochim. Acta (2002)] using inverse aqua regia dissolution. Organic matter isolated from the whole rock matrix using the HF–BF₃ technique [Org. Geochem. 20 (1993) 249] yields scattered data and a Re–Os date of 449±220 Ma (Model 3, MSWD=616). The organic matter analyses show similar ¹⁸⁷Os/¹⁸⁸Os values, but significantly lower ¹⁸⁷Re/¹⁸⁸Os values in comparison to the whole rock analyses. We show that the Re–Os systematics of organic matter are altered during chemical isolation, and as such we suggest that the HF–BF₃ method should not be used for Re–Os analysis of organic matter. Whole rock Re–Os analysis using a CrO₃–H₂SO₄ digestion medium yields significantly better regression analysis compared with the inverse aqua regia method, and the Re–Os data identify two distinct initial ¹⁸⁷Os/¹⁸⁸Os values for the sample set. Separate regressions of these data yield precise dates [366.1±9.6, MSWD=2.2 and 363.4±5.6 Ma, MSWD=1.6 (Model 3)], which are indistinguishable from the age constraints for this formation (363.4±0.4 Ma, U–Pb monazite). Comparison of the Re–Os dates obtained from aqua regia and CrO₃–H₂SO₄ methods suggests that the former may contain nonhydrogenous Re and Os, whereas the CrO₃–H₂SO₄ method dominantly liberates hydrogenous Re–Os from organic matter, allowing for better stratigraphic age determinations and evaluation of the Os isotope composition of seawater.     

Sulfides in mantle peridotites from Penghu Islands, Taiwan: Melt percolation, PGE fractionation, and the lithospheric evolution of the South China block

Major elements, highly siderophile elements (HSE) and Re-Os isotope ratios were analysed in situ on individual sulfide grains in spinel peridotite xenoliths hosted by Miocene intraplate basalts from the Penghu Islands, Taiwan. The xenoliths represent texturally and compositionally different mantle domains, and the geochemical characteristics of the sulfides show changes in HSE distribution and Re-Os isotope systematics, produced as their host rocks were metasomatised by percolating fluids/melts. In prophyroclastic and partly metasomatised peridotites from the Kueipi (KP) locality, the sulfides have subchondritic to superchondritic ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios. Many of these sulfides reflect fluid/melt interaction with residual MSS and/or crystallization of fractionated sulfide melts, which produced high contents of Cu and PPGEs and high Re/Os; inferred melt/rock ratios are low. In contrast, sulfides in equigranular and extensively metasomatised peridotites from the Tungchiyu (TCY) locality are mainly more sulfur-rich Ni-(Co)-rich MSS, with subchondritic to chondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os. These sulfides are interpreted as products of interaction between pre-existing MSS and percolating silicate melts. Melt/rock ratios were high and the percolating melt was less differentiated than the melt that percolated the KP peridotites. Sulfides in a TCY pyroxenite are mainly MSS; they have the lowest HSE contents, subchondritic to superchondritic ¹⁸⁷Os/¹⁸⁸Os and subchondritic ¹⁸⁷Re/¹⁸⁸Os, and may have precipitated from sulfide melts that segregated from basaltic melts under S-saturated conditions. In most sulfides melt percolation appears to have induced fractionation among the HSEs and disturbed Re-Os isotope compositions. Despite the metasomatic effects, rare residual MSS, sulfides that from crystallised sulfide melts and sulfides modified by addition of Re (with no evidence for Os addition) can still provide useful chronological information. Such sulfides yield T_RD age peaks of 1.9, 1.7-1.6, 1.4-1.3 and 0.9-0.8 Ga, which may record the timing of melt extraction and/or metasomatic events in the mantle. These periods are contemporaneous with the major crustal events recorded by U-Pb dates and Nd and Hf model ages in the overlying crust. This close correspondence indicates that the sulfide T_RD ages reflect the timing of lithosphere-scale tectonothermal events (such as melting and metasomatism) that affected both the lithospheric mantle and the overlying crust. The sulfide T_RD ages, taken together with the crustal data, suggest that most of the Cathaysia block had formed at least by Paleo-Proterozoic time, and that some domains are Archean in age.     

汉诺坝玄武岩Re-Os同位素地球化学——Re的挥发性丢失和壳-幔相互作用的证据

本文报道了采自汉诺坝玄武岩区周坝和白龙硐剖面以及白布洛张20井等地29个玄武岩样品的Re、Os含量和~(187)Os/~(188)Os比值。Os含量为11×10~(-12)～314×10~(-12),Re含量为40×10~(-12)～238×10~(-12),Re和Os含量有正相关趋势。碱性玄武岩(AK)的Re、Os含量高于拉斑玄武岩(TH)和过渡玄武岩(TR),玄武岩Os含量变化与分离结晶作用有关,玄武岩的低Re含量与地面喷发的火山岩浆脱气过程中Re的挥发性丢失作用有关。玄武岩的~(187)Os/~(188)Os比值为0.14735～0.61136,AK的~(187)Os/~(188)Os比值比TH和TR低且变化小。玄武岩的~(187)Os/~(188)Os比值与Os含量有负相关性。随着Os含量降低到小于75×10~(-12),~(187)Os/~(188)Os比值迅速升高,反映了地壳混染在TH和TR成因中的贡献。在以往的研究中没有观察到类似的地壳混染作用,说明了Re-Os同位素体系在示踪壳源物质上的优势。一些Os含量较高的TH的~(187)Os/~(188)Os比值表明其地幔源区既非亏损的又非经交代富集的SCLM,可能是混入了地壳俯冲物质的"Marble cake"型地幔。总之,汉诺坝玄武岩的Re-Os同位素地球化学研究支持了以往研究的主要成果,两类玄武岩地球化学差异性和异源成因论;分离结晶和部分熔融过程在玄武岩成因中的重要作用;碱性玄武岩的成因与地幔柱的关系等。同时揭示了一些新的现象:汉诺坝玄武岩形成中存在少量的地壳混染作用;地面喷发的火山熔岩在脱气过程中Re的挥发性丢失;拉斑玄武岩的源区更有可能为"Marble cake"型地幔。     

Re-Os同位素在晚新元古代至早寒武世测年及古环境演绎中的应用进展

晚新元古代至早寒武世是地球演化历史上极其重要的时期,该时期地层年龄框架的厘定以及古海水、古大气、古气候等方面的研究一直是国际地学界的关注热点。Re-Os同位素测年法是近十几年来兴起的地层测年法,其对于晚新元古代至早寒武世重要时间节点上沉积的富有机质黑色页岩具有测年及示踪古环境的双重优势。本文以晚新元古代至早寒武世地层为例,阐述了Re-Os同位素测年法在年代地层学研究中的应用,通过与大量的、精确的锆石U-Pb年龄对比,论证了Re-Os同位素测定沉积地层年龄的可靠性。对于震旦系陡山沱组地层建阶及留茶坡组地层的年代学研究,黑色页岩Re-Os同位素测年法可发挥重要的作用。结合前人所做的Sr同位素变化曲线以及收集的晚新元古代—早寒武世Os同位素初始值的测试数据,阐述了Os同位素在该时段古环境演绎及Ni-Mo-V多金属层来源追溯上发挥的作用。黑色页岩难以进行~(87)Sr/~(86)Sr的分析,而Os同位素初始值能较好地弥补这一缺陷,二者的相互结合将为晚新元古代至早寒武世古环境演化的研究作出贡献。本文指出,随着Re-Os同位素分析技术的发展以及更多实验流程的建立,该项技术在未来年代地层学,尤其对一些古老地层的年代厘定具有广阔的应用前景。