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.     

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.     

Pt-Re-Os systematics of group IIAB and IIIAB iron meteorites

The Pt-Re-Os isotopic and elemental systematics of 13 group IIAB and 23 group IIIAB iron meteorites are examined. As has been noted previously for iron meteorite groups and experimental systems, solid metal-liquid metal bulk distribution coefficients (D values) for both IIAB and IIIAB systems show D_Os>D_Re>>D_Pt>1 during the initial stages of core crystallization. Assuming closed-system crystallization, the latter stages of crystallization for each core are generally characterized by D_Pt>D_Re>D_Os. The processes governing the concentrations of these elements are much more complex in the IIIAB core relative to the IIAB core. Several crystallization models utilizing different starting parameters and bulk distribution coefficients are considered for the Re-Os pair. Each model has flaws, but in general, the results suggest that the concentrations of these elements were dominated by equilibrium crystallization and subsequent interactions between solid metal and both equilibrium and evolved melts. Late additions of primitive metal to either core were likely minor or nonexistent.The ¹⁸⁷Re-¹⁸⁷Os systematics of the IIAB and IIIAB groups are consistent with generally closed-system behavior for both elements since the first several tens of Ma of the formation of the solar system, consistent with short-lived chronometers. The Re-Os isochron ages for the complete suites of IIAB and IIIAB irons are 4530 ± 50 Ma and 4517 ± 32 Ma, respectively, and are similar to previously reported Re-Os ages for the lower-Ni endmembers of these two groups. Both isochrons are consistent with, but do not require crystallization of the entire groups within 10-30 Ma of the initiation of crystallization.The first high-precision ¹⁹⁰Pt-¹⁸⁶Os isochrons for IIAB and IIIAB irons are presented. The Pt-Os isochron ages for the IIAB and IIIAB irons, calculated using the current best estimate of the λ for ¹⁹⁰Pt, are 4323 ± 80 Ma and 4325 ± 26 Ma respectively. The Re-Os and Pt-Os ages do not overlap within the uncertainties. The younger apparent ages recorded by the Pt-Os system likely reflect error in the ¹⁹⁰Pt decay constant. The slope from the Pt-Os isochron is combined with the age from the Re-Os isochron for the IIIAB irons to calculate a revised λ of 1.415 × 10⁻¹² a⁻¹ for ¹⁹⁰Pt, although additional study of this decay constant is still needed.     

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.     

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.     

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

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

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.     

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

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

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.     

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

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

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.     

Pt-Re-Os and Sm-Nd isotope and HSE and REE systematics of the 2.7 Ga Belingwe and Abitibi komatiites

High-precision Pt-Re-Os and Sm-Nd isotope and highly siderophile element (HSE) and rare earth element (REE) abundance data are reported for two 2.7 b.y. old komatiite lava flows, Tony’s flow (TN) from the Belingwe greenstone belt, Zimbabwe, and the PH-II flow (PH) from Munro Township in the Abitibi greenstone belt, Canada. The emplaced lavas are calculated to have contained ∼25% (TN) and ∼28% (PH) MgO. These lavas were derived from mantle sources characterized by strong depletions in highly incompatible lithophile trace elements, such as light REE (Ce/Sm_N = 0.64 ± 0.02 (TN) and 0.52 ± 0.01 (PH), ε¹⁴³Nd(T) = +2.9 ± 0.2 in both sources). ¹⁹⁰Pt-¹⁸⁶Os and ¹⁸⁷Re-¹⁸⁷Os isochrons generated for each flow yield ages consistent with respective emplacement ages obtained using other chronometers. The calculated precise initial ¹⁸⁶Os/¹⁸⁸Os = 0.1198318 ± 3 (TN) and 0.1198316 ± 5 (PH) and ¹⁸⁷Os/¹⁸⁸Os = 0.10875 ± 17 (TN) and 0.10873 ± 15 (PH) require time-integrated ¹⁹⁰Pt/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os of 0.00178 ± 11 and 0.407 ± 8 (TN) and 0.00174 ± 18 and 0.415 ± 5 (PH). These parameters, which by far represent the most precise and accurate estimates of time-integrated Pt/Os and Re/Os of the Archean mantle, are best matched by those of enstatite chondrites. The data also provide evidence for a remarkable similarity in the composition of the sources of these komatiites with respect to both REE and HSE. The calculated absolute HSE abundances in the TN and PH komatiite sources are within or slightly below the range of estimates for the terrestrial Primitive Upper Mantle (PUM). Assuming a chondritic composition of the bulk silicate Earth, the strong depletions in LREE, yet chondritic Re/Os in the komatiite sources are apparently problematic because early Earth processes capable of fractionating the LREE might also be expected to fractionate Re/Os. This apparent discrepancy could be reconciled via a two-stage model, whereby the moderate LREE depletion in the sources of the komatiites initially occurred within the first 100 Ma of Earth’s history as a result of either global magma ocean differentiation or extraction and subsequent long-term isolation of early crust, whereas HSE were largely added subsequently via late accretion. The komatiite formation, preceded by derivation of basaltic magmas, was a result of second-stage, large-degree dynamic melting in mantle plumes.     

Comparative Re-Os systematics of chondrites: Implications regarding early solar system processes

A suite of 47 carbonaceous, enstatite, and ordinary chondrites are examined for Re-Os isotopic systematics. There are significant differences in the ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites compared with ordinary and enstatite chondrites. The average ¹⁸⁷Re/¹⁸⁸Os for carbonaceous chondrites is 0.392 ± 0.015 (excluding the CK chondrite, Karoonda), compared with 0.422 ± 0.025 and 0.421 ± 0.013 for ordinary and enstatite chondrites (1σ standard deviations). These ratios, recast into elemental Re/Os ratios, are as follows: 0.0814 ± 0.0031, 0.0876 ± 0.0052 and 0.0874 ± 0.0027, respectively. Correspondingly, the ¹⁸⁷Os/¹⁸⁸Os ratios of carbonaceous chondrites average 0.1262 ± 0.0006 (excluding Karoonda), and ordinary and enstatite chondrites average 0.1283 ± 0.0017 and 0.1281 ± 0.0004, respectively (1σ standard deviations). The new results indicate that the Re/Os ratios of meteorites within each group are, in general, quite uniform. The minimal overlap between the isotopic compositions of ordinary and enstatite chondrites vs. carbonaceous chondrites indicates long-term differences in Re/Os for these materials, most likely reflecting chemical fractionation early in solar system history.A majority of the chondrites do not plot within analytical uncertainties of a 4.56-Ga reference isochron. Most of the deviations from the isochron are consistent with minor, relatively recent redistribution of Re and/or Os on a scale of millimeters to centimeters. Some instances of the redistribution may be attributed to terrestrial weathering; others are most likely the result of aqueous alteration or shock events on the parent body within the past 2 Ga.The ¹⁸⁷Os/¹⁸⁸Os ratio of Earth’s primitive upper mantle has been estimated to be 0.1296 ± 8. If this composition was set via addition of a late veneer of planetesimals after core formation, the composition suggests the veneer was dominated by materials that had Re/Os ratios most similar to ordinary and enstatite chondrites.     

含有普通锇的辉钼矿Re-Os同位素定年研究

通过大量数据统计,表明较高比例的辉钼矿中存在普通锇。普通锇可能以类质同像形式存在于辉钼矿样品中,理论上辉钼矿中可能含有较高含量普通锇。辉钼矿样品含有较高含量普通锇可能对Re-Os定年结果产生很大影响,从原理上并结合实例证实了普通锇含量对辉钼矿Re-Os年龄影响程度。对于一般辉钼矿样品来讲,如果187Os总量(放射成因187Os与非放射成因187Os之和)与普通锇比值小于20,需要考虑普通锇对Re-Os模式年龄的影响,并提出了对于含有普通锇辉钼矿模式年龄的计算方法。先做出187Os/188Os-187Re/188Os等时线,求得初始187Os/188Os值,再根据初始187Os/188Os值和单个样品的普Os含量求得非放射成因的普Os中187Os的量。最后根据Re含量以及放射成因187Os含量得到模式年龄。     

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 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.     

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.     

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.     

Re-os isotope systematics of the Taklimakan Desert sands, moraines and river sediments around the taklimakan desert, and of Tibetan soils

Reported here are the first ¹⁸⁷Os/¹⁸⁸Os ratios and abundances of Os and Re for Taklimakan Desert sands and glacial moraines from the Kunlun Mountains. Osmium isotopic data are also reported for river sediments around the Taklimakan Desert, river sediments from the Kunlun and Tianshan Mountains, Tibetan soils and loesses from the Loess Plateau, as well as Sr and Nd isotopic data for these samples. The Taklimakan Desert sands from various regions show surprisingly homogeneous Os isotopic ratios (¹⁸⁷Os/¹⁸⁸Os = 1.29 ± 0.08) and abundances (Os = 11 ppt), with some variations in Re abundances (Re = 130 to 260 ppt) and ¹⁸⁷Re/¹⁸⁸Os ratios (60 to 140). The ¹⁸⁷Os/¹⁸⁸Os ratios for the Taklimakan Desert sands are close to the average for Kunlun moraines, river sediments around the Taklimakan Desert sands, and the Tibetan soils, supporting the idea that the Taklimakan Desert sands are derived from moraines and river sediments around the desert or from Tibetan soils and are homogenized by aeolian activity in the desert. Furthermore, the Os isotopic data for the sediments studied here are compared with those (¹⁸⁷Os/¹⁸⁸Os = 1.04, Os = 32 ppt, Re = 206 ppt, ¹⁸⁷Re/¹⁸⁸Os = 35) of loesses from the Loess Plateau reported elsewhere, and it is concluded that the Re-Os data for the loess can be used as proxy for the upper continental crust.     

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

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