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

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

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 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.     

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.     

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.     

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.     

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。     

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

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

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.     

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 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.     

In situ measurement of Re-Os isotopes in mantle sulfides by laser ablation multicollector-inductively coupled plasma mass spectrometry: analytical methods and preliminary results

A method has been developed for the in situ determination of Re-Os isotopes in single grains of sulfides in mantle-derived peridotites using a laser ablation microprobe attached to a multicollector-induced coupled plasma mass spectrometer (MC-ICPMS). High-precision Os isotope analysis by MC-ICPMS is demonstrated by the measurement of interlaboratory Os standards. Evaluation of mass bias correction procedures shows that the exponential law provides the best fit to the Os isotope data and that the ratio of the mass fractionation coefficients for Re and Os remains constant for the range of typical instrument operating conditions. This relationship enables the accurate and precise correction of the isobaric interference of ¹⁸⁷Re on ¹⁸⁷Os for ¹⁸⁷Re/¹⁸⁸Os values up to 1.6.Results are presented for single sulfide inclusions in olivine macrocryts from kimberlites in the Siberian and Slave Cratons, and sulfides enclosed in silicates and interstitial to silicates in peridotite xenoliths from the Slave Craton and Massif Central, France. Enclosed sulfides larger than 50 μm in diameter and with Os contents ≥40 ppm give ¹⁸⁷Os/¹⁸⁸Os ratios with a precision of 0.1% (2 SE), which is equivalent to N-TIMS whole-rock data. Interstitial sulfides typically have lower Os (10 to 30 ppm) and give analyses with lower precision (∼1 to 2%) but still provide valuable information on the movement of Os within the lithosphere. The sulfide inclusions in silicates preserve significantly less radiogenic Os isotopic compositions than interstitial sulfides and accordingly produce significantly older and more realistic Re-Os age information. Whole-rock Os isotope compositions reflect the proportions of different generations of enclosed and interstitial sulfides; this calls into question the significance of many published “depletion ages.”     

Limited Recycling of Crustal Osmium in Forearc Mantle During Slab Dehydration

Elevated ¹⁸⁷Os/¹⁸⁸Os ratios compared to ambient oceanic mantle, i.e.,¹⁸⁷Os/¹⁸⁸Os>0.13, have been reported for both arc lavas and mantle wedge xenoliths, which have been ascribed to the addition of crustal Os through slab dehydration or melting. By contrast, much lower ¹⁸⁷Os/¹⁸⁸Os ratios of spinels from Izu‐Bonin‐Mariana boninites indicate slight or no crustal Os was transferred from the slab to the forearc mantle. Here we report Os isotopic compositions of peridotites from New Caledonia ophiolites, which represent relics of a forearc mantle. Some New Caledonia peridotites are characterized by Os concentrations of <1 ppb, yet have¹⁸⁷Os/¹⁸⁸Os ratios comparable to the ambient oceanic mantle (i.e., ¹⁸⁷Os/¹⁸⁸Os<0.13). This confirms that little crustal Os was transported to the forearc mantle via slab dehydration. Contrasting Os isotopes between forearc peridotites and mantle wedge xenoliths may reflect the changing behavior of Os in diverse agents released from the descending slab as a function of depth, which is mainly controlled by the stability of sulfides in the slabs. During dehydration at shallow depths, sulfides keep stable and thus little Os is transported to the overlying mantle. In comparison, sulfides become unstable and tend to break down at deeper depths where slab melting or supercritical fluid generation occurs, and thus Os behaves like a mobile element.     

Osmium isotope systematics of ureilites

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

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.     

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.     

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.     

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.