Geochemical and isotopic studies of aeolian sediments in China

The Sr and Nd isotopic, rare earth element (REE) and major element compositions, together with mineral and grain‐size proportions, are reported for aeolian loess deposits and desert sands from several Chinese localities. The study was carried out in order to examine regional variations in the isotopic and geochemical features of these aeolian sediments, and to constrain the provenance of Chinese loess. Samples include loesses from the Tarim and Junggar basins and desert sands from the Taklimakan desert in north‐west China, loess from the Ordos area and desert sands from the Tengger and Mu‐us deserts in north‐central China, as well as loess and desert sands from the Naiman area, north‐east China. REE distributions show minimal variation among the Chinese loess deposits, whereas those for the desert sands show regional variations. New isotopic data document a latitudinal variation in Sr and Nd isotopic features for the loesses and desert sands. The Naiman and Junggar loesses have distinctly lower ⁸⁷Sr/⁸⁶Sr ratios and higher ε_Nd(0) values than the loesses from the Tarim Basin, the Ordos area and the Loess Plateau. Among the desert sands, the Naiman samples have higher ε_Nd(0) values than the Taklimakan, Tengger and Mu‐us samples. Isotopic data suggest that loesses of the Loess Plateau were supplied from the Tarim Basin loesses and Taklimakan Desert sand, and that the Naiman loesses were supplied from the Junggar Basin loesses. The latitudinal variation in the loesses and desert sands may be partly explained by isotopic variations reported previously for moraines from the Tianshan and west Kunlun Mountains, which are possible sources for the loesses and desert sands. These inferences on the provenance of the loesses and desert sands are consistent with the dust transport pattern over East Asia.     

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.     

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

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

Re-Os 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.     

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.     

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.     

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 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.     

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.     

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

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

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.     

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.     

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.     

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

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

Os mobilization during melt percolation: The evolution of Os isotope heterogeneities in the mantle sequence of the troodos ophiolite, Cyprus

This study focuses on the origin of the Os isotope heterogeneities and the behaviour of Os and Re during melt percolation and partial melting processes in the mantle sequence of the Troodos Ophiolite Complex. The sequence has been divided into an eastern (Unit 1) and a western part (Unit 2) (Batanova and Sobolev, 2000). Unit 1 consists mainly of spinel-lherzolites and a minor amount of dunites, which are surrounded by cpx-bearing harzburgites. Unit 2 consists of harzburgites, dunites, and contains chromitite deposits.Unit 1 (¹⁸⁷Os/¹⁸⁸Os: 0.1169 to 0.1366) and Unit 2 (¹⁸⁷Os/¹⁸⁸Os 0.1235 to 0.1546) peridotites both show large ranges in their Os isotopic composition. Most of the ¹⁸⁷Os/¹⁸⁸Os ratios of Unit 1 lherzolites and harzburgites are chondritic to subchondritic, and this can be explained by Re depletion during ancient partial melting and melt percolation events. The old Os isotope model ages (>800 Ma) of some peridotites in a young ophiolitic mantle show that ancient Os isotopic heterogeneities can survive in the Earth upper mantle. Most harzburgites and dunites of Unit 2 have suprachondritic ¹⁸⁷Os/¹⁸⁸Os ratios. This is the result of the addition of radiogenic Os during a younger major melt percolation event, which probably occurred during the formation of the Troodos crust 90 Ma ago.Osmium concentrations tend to decrease from spinel-lherzolites (4.35 ± 0.2 ng/g) to harzburgites (Unit 1: 4.06 ± 1.12 ng/g; Unit 2: 3.46 ± 1.38 ng/g) and dunites (Unit 1: 2.71 ± 0.84 ng/g; Unit 2: 1.85 ± 1.20 ng/g). Therefore, this element does not behave compatibly during melt percolation as it is observed during partial melting, but becomes dissolved and mobilized by the percolating melt. The Os contents and Re/Os ratios in the mantle peridotites can be explained if they represent mixing products of old depleted mantle with cpx- and opx-veins, which are crystallization products of the percolating melt. This mixing occurred during the melting of a continuously fluxed mantle in a supra-subduction zone environment.This study shows that Unit 1 and Unit 2 of the Troodos mantle section have a complex and different evolution. However, the Os isotopic characteristics are consistent with a model where the harzburgites and dunites of both units belong to the same melting regime producing the Troodos oceanic crust.     

Age and sources of the ore at Tharsis and Rio Tinto, Iberian Pyrite Belt, from Re-Os isotopes

Re-Os isotopes were used to constrain the source of the ore-forming elements of the Tharsis and Rio Tinto mines of the Iberian Pyrite Belt, and the timing of mineralization. The pyrite from both mines has simila]r Os and Re concentrations, ranging between 0.05–0.7 and 0.6–66 ppb, respectively. ¹⁸⁷Re/¹⁸⁸Os ratios range from about 14 to 5161. Pyrite-rich ore samples from the massive ore of Tharsis and two samples of stockwork ore from Rio Tinto yield an isochron with an age of 346 ± 26 Ma, and an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.69. Five samples from Tharsis yield an age of 353 ± 44 Ma with an initial ¹⁸⁷Os/¹⁸⁸Os ratio of about 0.37. A sample of massive sulfide ore from Tharsis and one from Rio Tinto lie well above both isochrons and could represent Re mobilization after mineralization. The pyrite Re-Os ages agree with the paleontological age of 350 Ma of the black shales in which the ores are disseminated. Our data do not permit us to determine whether the Re-Os isochron yields the original age of ore deposition or the age of the Hercynian metamorphism that affected the ores. However, the reasonable Re-Os age reported here indicates that the complex history of the ores that occurred after the severe metamorphic event that affected the Iberian Pyrite Belt massive sulfide deposits did not fundamentally disturb the Re-Os geochronologic system. The highly radiogenic initial Os isotopic ratio agrees with previous Pb isotopic studies. If the initial ratio is recording the initial and not the metamorphic conditions, then the data indicate that the source of the metals was largely crustal. The continental margin sediments that underlie the deposits (phyllite-quartzite group) or the volcanic rocks (volcanogenic-sedimentary complex) in which the ores occur are plausible sources for the ore-forming metals and should constrain the models for the genesis of these deposits. Received: 15 March 1999 / Accepted: 26 July 1999     

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

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

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.     

Evidence for distinct proportions of subducted oceanic crust and lithosphere in HIMU-type mantle beneath El Hierro and La Palma, Canary Islands

Shield-stage high-MgO alkalic lavas from La Palma and El Hierro (Canary Islands) have been characterized for their O-Sr-Nd-Os-Pb isotope compositions and major-, trace-, and highly siderophile-element (HSE: Os, Ir, Ru, Pt, Pd, Re) abundances. New data are also reported for associated evolved rocks, and entrained xenoliths. Clear differences in Pd/Ir and isotopic ratios for high Os (>50 ppt) lavas from El Hierro (δ¹⁸O_olivine = 5.17 ± 0.08‰; ⁸⁷Sr/⁸⁶Sr = 0.7029 to 0.7031; ε_Nd = +5.7 to +7.1; ¹⁸⁷Os/¹⁸⁸Os = 0.1481 to 0.1750; ²⁰⁶Pb/²⁰⁴Pb = 19.1 to 19.7; Pd/Ir = 6 ± 3) versus those from La Palma (δ¹⁸O_olivine = 4.87 ± 0.18‰; ⁸⁷Sr/⁸⁶Sr = 0.7031 to 0.7032; ε_Nd = +5.0 to +6.4; ¹⁸⁷Os/¹⁸⁸Os = 0.1421 to 0.1460; ²⁰⁶Pb/²⁰⁴Pb = 19.5 to 20.2; Pd/Ir = 11 ± 4) are revealed from the dataset.Crustal or lithospheric assimilation during magma transport cannot explain variations in isotopic ratios or element abundances of the lavas. Shallow-level crystal-liquid fractionation of olivine, clinopyroxene and associated early-crystallizing minerals (e.g., spinel and HSE-rich phases) controlled compatible element and HSE abundances; there is also evidence for sub-aerial degassing of rhenium. High-MgO lavas are enriched in light rare earth elements, Nb, Ta, U, Th, and depleted in K and Pb, relative to primitive mantle abundance estimates, typical of HIMU-type oceanic island basalts. Trace element abundances and ratios are consistent with low degrees (2-6%) of partial melting of an enriched mantle source, commencing in the garnet stability field (?110 km). Western Canary Island lavas were sulphur undersaturated with estimated parental melt HSE abundances (in ppb) of 0.07 ± 0.05 Os, 0.17 ± 0.16 Ir, 0.34 ± 0.32 Ru, 2.6 ± 2.5 Pt, 1.4 ± 1.2 Pd, 0.39 ± 0.30 Re. These estimates indicate that Canary Island alkali basalts have lower Os, Ir and Ru, but similar Pt, Pd and Re contents to Hawai’ian tholeiites.The HIMU affinities of the lavas, in conjunction with the low δ¹⁸O_olivine and high ²⁰⁶Pb/²⁰⁴Pb for La Palma, and elevated ¹⁸⁷Os/¹⁸⁸Os for El Hierro implies melting of different proportions of recycled oceanic crust and lithosphere. Our preferred model to explain isotopic differences between the islands is generation from peridotitic mantle metasomatised by <10% pyroxenite/eclogite made from variable portions of similar aged recycled oceanic crust and lithosphere. The correspondence of radiogenic ²⁰⁶Pb/²⁰⁴Pb, ¹⁸⁷Os/¹⁸⁸Os, elevated Re/Os and Pt/Os, and low-δ¹⁸O in western Canary Island lavas provides powerful support for recycled oceanic crust and lithosphere to generate the spectrum of HIMU-type ocean island basalt signatures. Persistence of geochemical heterogeneities throughout the stratigraphies of El Hierro and La Palma demonstrate long-term preservation of these recycled components in their mantle sources over relatively short-length scales (∼50 km).