Behavior of Re and Os during low-temperature alteration: Results from Himalayan soils and altered black shales

Re-Os analyses were performed on five soil profiles developed on silicate lithologies in the Narayani drainage basin of the Himalayas, as well as on several altered black shales and associated alteration phases. The results indicate that all of these samples have lost large amounts of Re. This Re loss approached 100% in the black shale-derived soils, which also most probably lost substantial quantities of Os. The near constancy of Os and Re concentrations with depth indicates that this loss occurred quite early in the alteration process, rather than progressively during the course of soil development. A slight decrease in ¹⁸⁷Os/¹⁸⁸Os was observed toward the surface of the two black shale soil profiles, possibly indicating a minor preferential mobility of radiogenic ¹⁸⁷Os for this lithology. In the black shale-derived saprolite and soils, the loss of Re and Os was related to the loss of organic carbon. The importance of this phase is underscored by the fact that organic material separated from a black shale sample accounted for nearly all of the Os contained in the whole rock. Analysis of alteration phases from the surface of a weathered black shale showed that Os liberated during alteration was partially reprecipitated in Fe oxides, with Os isotopic compositions very similar to that of the original rock, whereas Re was removed with the fluid phase.These results demonstrate the disproportionately large role that black shale weathering may play in determining the Re and Os contents of continental runoff and, thus, ultimately of seawater, but they also emphasize the possible complexity of this process. The data suggest that a large fraction of the Os contained in black shales is released during chemical alteration, which is apparently not the case for most other silicate rocks. Therefore, the potential contribution of black shales to the dissolved Os budget of runoff and river water may be even greater than that expected from the high Os concentrations of these rocks. The extent to which this Os will affect the seawater Os composition depends on how efficiently it is recaptured by secondary phases such as Fe-Mn oxides in situ or during transport. These results also underscore the high mobility of Re with respect to Os at every stage in the erosional process, thus explaining the order of magnitude increase in Re/Os ratio from the black shale source rocks to seawater.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Geochemistry of basal Cambrian black shales and cherts from the Northern Tarim Basin,Northwest China: Implications for depositional setting and tectonic history

Black shales and thin-bedded cherts in the basal Cambrian are widespread worldwide and they carry important information on the formation of sedimentary basins and on the tectonic history. We studied the geochemical signatures of the early Cambrian black shales and bedded cherts from the Northern Tarim Basin, China, with the objectives of understanding the depositional setting of these rocks and inferring the tectonic history in the region. Twenty two black shales, ten cherts, and two nodular phosphorites were collected from two outcrops at Xiaoerbulake and Sugaitebulake in the Northern Tarim Basin, spanning vertical sections of 8.8 and 7.5 m, respectively. A suite of techniques, including field investigations, X-ray diffraction, electron microscopy, trace element, rare earth element (REE), and isotope geochemistry, were employed to characterize the geochemical signatures of these rocks. Field evidence indicates that the black shales and bedded cherts are over- and underlain by dolomites, suggesting a shallow marine depositional environment. Mineralogical and trace element data suggest that the Tarim black shales and cherts were deposited in a suboxic continental shelf environment, and hydrothermal activity may have extracted certain trace elements from mafic continental crust and concentrated them in the sedimentary basin. REE characteristics for the cherts are very similar to those that are known to be deposited in pelagic ocean floor settings, suggesting that the hydrothermal fluids may be derived from the infant southern Tianshan Ocean in the north of the Tarim Basin. Os isotope signatures at the time of deposition (¹⁸⁷Os/¹⁸⁸Os_i = 1.1–2.7) are typical of crustal signatures, and the radiogenic Os isotope signatures rule out the mantle as a possible source of Os and other metals. A positive correlation between ¹⁸⁷Os/¹⁸⁸Os and ε_Nd is consistent with upper crust-derived basin sediments that contain a variable contribution of hydrothermal fluids possibly derived from ancient mafic continental crust. These trace element, REE, and isotope systematics collectively suggest that incorporation of hydrothermal fluids derived from ancient, mafic continental crust combined with deposition in relatively reducing conditions may have controlled the chemical and isotopic compositions of these rocks. We infer that the hydrothermal fluid was carried to the continental shelf by upwelling during the initial stages of formation of the southern Tianshan Ocean, where the fluid interacted with thinned, mafic crustal basement lithologies and was subsequently incorporated into the black shales and bedded cherts in the Northern Tarim Basin. This study provides important geochemical evidence for the creation of the Tianshan Ocean, which is a result of break-up of the Rodinia Supercontinent during the early Cambrian.     

Constraints on mantle evolution from Os/Os isotopic compositions of Archean ultramafic rocks from southern West Greenland (3.8 Ga) and Western Australia (3.46 Ga)

Initial ¹⁸⁷Os/¹⁸⁸Os isotopic compositions for geochronologically and geologically well -constrained 3.8-Ga spinel peridotites from the Itsaq Gneiss Complex of southern West Greenland and chromite separates from 3.46-Ga komatiites from the Pilbara region of Western Australia have been determined to investigate the osmium isotopic evolution of the early terrestrial mantle. The measured compositions of ¹⁸⁷Os/¹⁸⁸Os(0) = 0.10262 ± 2, from an olivine separate, and 0.10329 ± 3, for a spinel separate from ∼3.8-Ga peridotite G93/42, are the lowest yet reported from any terrestrial sample. The corrections for in situ decay over 3.8 Ga for these low Re/Os phases are minimal and change the isotopic compositions by only 0.5 and 2.2% for the spinel and the olivine, respectively, resulting in ¹⁸⁷Os/¹⁸⁸Os_{(3.8 Ga)} = 0.1021 ± 0.0002 and 0.1009 ± 0.0002, respectively. These data extend direct measurement of Os isotopic compositions to much earlier periods of Earth history than previously documented and provide the best constraints on the Os isotopic composition of the early Archean terrestrial mantle. Analyses of Pilbara chromites yield 3.46-Ga mantle compositions of 0.1042 ± 0.0002 and 0.1051 ± 0.0002.These new data, combined with published initial Os isotopic compositions from late Archean and early Proterozoic samples, are compatible with the mantle, or at least portions of it, evolving from a solar system initially defined by meteorites to a modern composition of ¹⁸⁷Os/¹⁸⁸Os(0) = 0.1296 ± 0.0008 as previously suggested from peridotite xenolith data ( Meisel et al., 2001); the associated ¹⁸⁷Re/¹⁸⁸Os(0) = 0.435 ± 0.005. Thus, chondritic ¹⁸⁷Os/¹⁸⁸Os compositions were a feature of the upper mantle for at least 3.8 billion years, requiring chondritic Re/Os ratios to have been a characteristic of the very early terrestrial mantle. In contrast, nonchondritic initial compositions of some Archean komatiites demonstrate that Os isotopic heterogeneity is an ancient feature of plume materials, reflecting the development of variable Re/Os mantle sources early in Earth history.The lower average ¹⁸⁷Os/¹⁸⁸Os = 0.1247 for abyssal peridotites (Snow and Reisberg, 1995) indicate that not all regions of the modern mantle have evolved with the same Re/Os ratio. The relative sizes of the various reservoirs are unknown, although mass balance considerations can provide some general constraints. For example, if the unradiogenic ¹⁸⁷Os/¹⁸⁸Os modern abyssal peridotite compositions reflect the prevalent upper mantle composition, then the complementary high Re/Os basaltic reservoir must represent 20 to 40% by mass of the upper mantle (taken here as 50% of the entire mantle), depending on the mean storage age. The difficulties associated with efficient long-term storage of such large volumes of subducted basalt suggest that the majority of the upper mantle is not significantly Re-depleted. Rather, abyssal peridotites sample anomalous mantle regions.The existence of 3.8-Ga mantle peridotites with chondritic ¹⁸⁷Os/¹⁸⁸Os compositions and with Os concentrations similar to the mean abundances measured in modern peridotites places an upper limit on the timing of a late accretionary veneer. These observations require that any highly siderophile element -rich component must have been added to the Earth and transported into and grossly homogenized within the mantle by 3.8 Ga. Either large-scale mixing of impact materials occurred on very short (0-100 myr) timescales or (the interpretation preferred here) the late veneer of highly siderophile elements is unrelated to the lunar terminal cataclysm estimated to have occurred at ∼3.8 to 3.9 Ga.     

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.     

Variations in seawater osmium isotope composition since the last glacial maximum: A case study from the Japan Sea

Concentrations of Re and Os, and the isotopic composition of Os have been measured in the Japan Sea sediments to assess the response of the Japan Sea to glacial–interglacial climate change and associated weathering fluxes. The osmium concentrations in the sediment samples analyzed vary from 59 to 371 pg/g, and ¹⁸⁷Os/¹⁸⁸Os from 0.935 to 1.042. Only ¹⁸⁷Os/¹⁸⁸Os of sediment samples from dark laminations deposited under suboxic to anoxic conditions and having elevated concentrations of Re and Os, and with ≥ 80% hydrogenous Os are explained in terms of seawater composition. Lower ¹⁸⁷Os/¹⁸⁸Os were observed for sediments deposited during the last glacial maximum (LGM) when planktonic foraminifera from the Japan Sea recorded lighter oxygen isotopic composition. Decrease in dissolved Os fluxes from continents and/or change in the composition of the dissolved load to the Japan Sea are suggested as the driving mechanisms for the observed lower LGM ¹⁸⁷Os/¹⁸⁸Os. The results of this study, coupled with lower ¹⁸⁷Os/¹⁸⁸Os during the last glacial observed at other sites from ocean basins with different lithology and contrasting sediment accumulation rates, suggest that this trend is characteristic of the global oceans.

Data from this study show that the Japan Sea recorded higher ¹⁸⁷Os/¹⁸⁸Os during the current interglacial coinciding with excursions of oxygen isotopic compositions of planktonic foraminifera to heavier values. This is explained in terms of preferential release of ¹⁸⁷Os during deglacial weathering and/or higher continental Os flux driven by warm and wet climate. This study demonstrates that Os isotopic composition of reducing margin sediments has immense potential to track variations in the seawater composition. In addition, ¹⁸⁷Os/¹⁸⁸Os of reducing sediments may be used to draw inferences about local paleoceanographic processes in semi-enclosed basins such as the Japan Sea.     

Melt/mantle mixing produces podiform chromite deposits in ophiolites: Implications of Re-Os systematics in the Dongqiao Neo-tethyan ophiolite, northern Tibet

Podiform chromite deposits occur in the mantle sequences of many ophiolites that were formed in supra-subduction zone (SSZ) settings. We have measured the Re-Os isotopic compositions of the major chromite deposits and associated mantle peridotites of the Dongqiao Ophiolite in the Bangong-Nujiang suture, Tibet, to investigate the petrogenesis of these rocks and their genetic relationships.The ¹⁸⁷Os/¹⁸⁸Os ratios of the chromite separates define a narrow range from 0.12318 to 0.12354, less variable than those of the associated peridotites. Previously-reported ¹⁸⁷Os/¹⁸⁸Os ratios of the Os-rich alloys enclosed in the chromitites define two clusters: 0.12645 ± 0.00004 (2 s; n = 145) and 0.12003 to 0.12194. The ultra-depleted dunites have much lower ¹⁸⁷Os/¹⁸⁸Os (0.11754, 0.11815), and the harzburgites show a wider range from 0.12107 to 0.12612. The average isotopic composition of the chromitites (¹⁸⁷Os/¹⁸⁸Os: 0.12337 ± 0.00001) is low compared with the carbonaceous chondrite value (¹⁸⁷Os/¹⁸⁸Os: 0.1260 ± 0.0013) and lower than the average value measured for podiform chromitites worldwide (0.12809 ± 0.00085). In contrast, the basalts have higher ¹⁸⁷Os/¹⁸⁸Os, ranging from 0.20414 to 0.38067, while the plagioclase-bearing harzburgite and cumulates show intermediate values of ¹⁸⁷Os/¹⁸⁸Os (0.12979 ~ 0.14206). Correspondingly, the basalts have the highest ¹⁸⁷Re/¹⁸⁸Os ratios, up to 45.4 ± 3.2, and the chromites have the lowest ¹⁸⁷Re/¹⁸⁸Os ratios, down to 0.00113 ± 0.00008. We suggest that melts/fluids, derived from the subducting slab, triggered partial melting in the overlying mantle wedge and added significant amounts of radiogenic Os to the peridotites. Mass-balance calculations indicate that a melt/mantle ratio of approximately 15:1 (melt: ¹⁸⁷Re/¹⁸⁸Os: 45.4, ¹⁸⁷Os/¹⁸⁸Os: 0.34484; mantle peridotite: ¹⁸⁷Re/¹⁸⁸Os: 0.0029, ¹⁸⁷Os/¹⁸⁸Os: 0.11754) is necessary to increase the Os isotopic composition of the chromitite deposits to its observed average value. This value implies a surprisingly low average melt/mantle ratio during the formation of the chromitite deposits. The percolating melts probably were of variable isotopic composition. However, in the chromitite pods the Os from many melts was pooled and homogenized, which is why the chromitite deposits show such a small variation in their Os isotopic composition. The results of this study suggest that the ¹⁸⁷Os/¹⁸⁸Os ratios of chromitites may not be representative of the DMM, but only reflect an upper limit. Importantly, the Os-isotope compositions of chromitites strongly suggest that such deposits can be formed by melt/mantle mixing processes.     

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.     

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.     

Pt-Os and Re-Os systematics of the Sudbury Igneous Complex, Ontario

We measured by negative thermal ionization mass spectrometry (NTIMS) Re, Os and ¹⁸⁶Os/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os in 26 samples of 18 Ni-Cu sulfide ores from the Falconbridge, McCreedy West, and Strathcona mines at Sudbury, Ontario. At McCreedy West and Falconbridge, the isochron Re-Os ages are 1835 ± 70 Ma and 1827 ± 340 Ma, and the initial ¹⁸⁷Os/¹⁸⁸Os ratios 0.514 ± 0.019 and 0.550 ± 0.024, respectively. The ages agree with the canonical value of 1850 ± 1 Ma for the Sudbury Igneous Complex (SIC). For Hangingwall and Deep Zone ores at Strathcona, the age of 1780 ± 7 Ma may reflect resetting by dyke activity. The high initial ¹⁸⁷Os/¹⁸⁸Os of 0.934 ± 0.005 in these ores is distinct from those at McCreedy West and Falconbridge. Strathcona Deep Copper Zone ores have highly radiogenic Os giving a mean model age of 1883 ± 54 Ma that is similar to ages at McCreedy West and Falconbridge, but distinct from other Strathcona sulfides. Initial ¹⁸⁶Os/¹⁸⁸Os in two Strathcona ores with low ¹⁹⁰Pt/¹⁸⁸Os average 0.119 826 ± 0.000 009 (n = 3) and 0.119 827 ± 0.000 004 (n = 3), respectively, with a grand mean of 0.119 827 ± 0.000 003. This ratio may be slightly lower than the chondritic value at that time. Similar ores at Falconbridge and McCreedy West show more scatter, averaging 0.119 855 ± 0.000 008 (n = 6) and 0.119 867 ± 0.000 020 (n = 3), respectively. These values are substantially suprachondritic. The Re-Os isotope systematics of Sudbury ores are clearly of crustal origin and may be derived from a binary mixture of Superior Province and Huronian metasedimentary rocks, with Strathcona, Falconbridge, and McCreedy West ores containing, respectively, 55%, 16%, and 12% of Os from Superior sediments. The suprachondritic ¹⁸⁶Os/¹⁸⁸Os at McCreedy West and Falconbridge may be due to admixture of Archean or Paleozoic mafic rocks with ¹⁹⁰Pt/¹⁸⁸Os ≈ 0.1. No trace of the asteroid that produced the Sudbury Structure has been reported. At the Whistle mine S-poor olivine melanorite inclusions with high Ni and Os and low ¹⁸⁷Os/¹⁸⁸Os may contain the signature of a magmatically fractionated asteroidal core contributing 1 to 2.5 % metal. The S-poor melanorite Ni and Os data are equally well explained by admixture of ≈40% mantle peridotite, however.     

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.     

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.     

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

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