金川铜镍硫化物样品中锇同位素比值的高精度分析

采用两种独立的190Os稀释剂、4个不同的化学流程,用等离子体质谱仪、TRITON热表面电离质谱仪和MAT-262固体质谱仪3种质谱仪器,在4个实验室分别对采自金川铜镍硫化物样品的187Os/188Os同位素比值进行分析,样品分析数量达到56个。4个实验室获得的结果分别为0.3356±0.0018(n=12,2s)、0.3363±0.0008(n=6,2s)、0.3363±0.0010(n=18,2s)和0.3353±0.0034(n=20,2s)。采用ISOPLOT软件对所得56个数据进行加权平均计算,得到187Os/188Os同位素比值为0.33602±0.00022(置信度95%)。两台TRITON热表面电离质谱仪测量的结果几乎完全一致,且精度高于MAT-262固体质谱仪和等离子体质谱仪。比较了碱熔和Carius管两种溶样方法,结果表明,对于所研究的样品,用Carius管溶矿方式可以将含锇矿物完全溶解。     

Re-Os同位素稀释N-TIMS测定计算方法

为了更好地实现Re-Os同位素实验室之间数据比对,本实验室在了解国内外部分实验室的数据处理方法的基础上,提出了本实验室的N-TIMS Re、Os同位素计算方法。本文所涉及到的Re、Os同位素计算方法包括氧同位素干扰校正、Re同位素比值和含量计算、Os同位素测定质量分馏校正方法、三峰法和全峰法Os同位素比值和含量计算、测定结果的不确定度、Isoplot作图基本参数介绍和相关系数Rho的计算。对于辉钼矿和普通Os信号弱(~(187)Os/~(188)Os2000)的样品适合采用三峰法计算Os同位素比值,普通Os信号强(~(187)Os/~(188)Os2000)的样品应该采用全峰法计算同位素比值。在全峰法计算中,按照指数分馏规律以迭代计算方式校正Os同位素比值的质量分馏,采用5iso方法进行样品中Os和稀释剂中Os的摩尔比(N_(5iso)/S)_(Os)的计算。     

苏皖地区幔源橄榄岩捕瞄虏体的锇同位素组成、模式年龄及其意义

苏皖地区发育的新生代玄武岩中富含地幔橄榄岩捕虏体，测定了25个橄榄岩全岩的锇同位素组成。结果表明大部分样品呈亏损特征,187Os/188Os=0.119～0.129.Os同位素比值与主量成分之间有显著的相关性.采用187Os/188Os-Al2O3代用等时线方法,由截距得到初始值(187Os/188Os)0=0.109,在对流地幔的187Os/188Os比值演化线上获得模式年龄t=2.5(±0.1)Ga,为晚太古-早元古代。用样品组中最低的锇同位素组成,即187Os/188Os=0.119,计算Re亏损模式年龄,t=1.2Ga,为中元古代。表明苏皖地区新生代玄武岩中的地幔橄榄岩捕虏体具有古老的形成年龄,它们是经过显生宙减薄作用后的残余地幔的碎片。大陆岩石圈地幔的古老形成年龄与上覆地壳克拉通的古老稳定年龄相耦合。     

微量地质样品铼锇含量及其同位素组成的高精度测定方法

报道了采用新型IsoProbe—T热电离质谱计测定Os含量及其同位素组成和Neptune多接收器等离子体质谱仪（MC—ICPMS）测定Re含量的分析方法。样品化学处理采用Carius管溶样、小型蒸馏法分离和微蒸馏法纯化提取Os以及阴离子树脂交换分离Re的方法。采用IsoProbe—T质谱计测定Os同位素组成具有灵敏度高和精度高的特点。对溶液标样，采用多法拉第接收器系统测定Os总量低至0．2ng的样品时，平均^192Os^16O3-离子流强度可达100mV以上并可维持约20min，其^187Os／^188Os同位素比值的测定精度可优于0．1％（1RSD）。采用所建立的化学分离流程和高精度质谱测量方法，测定了铂族元素橄榄岩标样WPR-1中Re、Os含量和Os同位素组成，测定结果与文献报道值在误差范围内吻合。     

关于《新疆喀拉通克铜镍硫化物矿床Re-Os同位素测年及成矿物质来源示踪》一文中γOs值计算错误的更正

笔者发表于本刊2005年第4期上《新疆喀拉通克铜镍硫化物矿床Re_Os同位素测年及成矿物质来源示踪》一文由于在计算γOs值时,误将(187Os/188Os)样品以(187Os/188Os)样品(t)代入公式计算,导致判断岩体形成过程中壳幔混染程度时出现错误,作者特刊登此更正声明,希望得到编辑部和学者们的谅解。由公式(187Os/188Os)(t)=(187Os/188Os)-(187Re/188Os)·(eλt-1)计算的样品的(187Os/188Os)(t)结果及利用公式γOs(t)=100·[(187Os/188Os)(t)/(187Os/188Os)球粒陨石(t)-1]重新计算的γOs(t)与原结果一起列于下表。重新计算的γOs值为100.6～12…     

上地幔Os同位素组成的演化

Re-Os同位素体系为研究地幔的成分-结构-演化提供了新的地球化学示踪和定年的工具.上地幔Os同位素组成演化的球粒陨石模型是Re-Os体系用于地幔物质定年的基础, 尤其在采用Re亏损模式年龄和Os同位素代理等时线年龄时.综合了铁陨石和各类球粒陨石、地幔橄榄岩包体和蛇绿岩豆荚状铬铁矿的Re-Os同位素体系研究的近期成果, 为认识对流上地幔Os同位素组成的演化提供了制约.对河北遵化蛇绿岩豆荚状铬铁矿岩的研究, 获得新太古代(2.5 Ga)时形成豆荚状铬铁矿的对流上地幔的187Os/188Os=0.110 2, 与球粒陨石型模式的一致.文献中常用的球粒陨石模式的参数如下: 地球形成时(4.558 Ga)初始值187Os/186Os为0.095 31, 现代值分别采用碳质球粒陨石的187Os/186Os比值为0.127 0和原始上地幔(PUM)的187Os/186Os比值为0.129 6, PUM与普通球粒陨石和顽火球粒陨石的187Os/186Os比值接近.      

岩石样品中低含量铂族元素和锇同位素比值的高精度测量方法

铂族元素（Os,Ir,Pt,Ru,Rh,Pd)具有强亲铁性和强亲铜性，为一组地球化学性质相近的相容元素，铂族元素包含两个同位素衰变体系（^190Pt-^186Os和^187Re-^187Os)。近年来，铂族元素和Re-Os同位素在研究各类不同地持作用过程中，尤其是在地幔岩石的研究中，作用独特，效果显著。由于地幔岩石的铂族元素含量较低，因此高精度，高灵敏度的分析测试方法的研究就显得十分重要。以往的分析方法（如常规的ICP－MS和中子活化分析方法），对含10^-9-10^012级低含量铂族元素的产品分析精度一般较差（＞15％－100％）。所采用的分析流程通常也无法同时获得样品的铂族元素含量和Os同位素比值。本文采用新的熔样方法（HAP－S高温高压釜酸溶法），新的化学流程（溶剂萃取和阴离子交换树脂柱）和新的分析仪器（多接收等离子体质谱MC－ICPMS和负离子热电离质谱N－TIMS）。用同位素稀释法对低含量地幔橄榄岩样品同时测定的铂族元素含量和Os同位素比值，获得了高精度的分析结果。对所分析的地橄榄样品中的铂族元素分配曲线和Os同位素组成的地质意义进行了初步探讨。     

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。     

利用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定镁铁-超镁铁质岩石中的铼-锇同位素组成

报道了用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定Re-Os同位素组成的质谱方法和化学分离方法,并应用该方法测定了天然镁铁-超镁铁质岩石样品中的Os同位素组成及Re、Os含量.Re同位素组成的MC-ICPMS测定利用膜除溶雾化器(Aridus)和静态法拉第杯接收的方式完成,采用Ir标准溶液在线校正仪器的质量分馏.Os同位素组成的MC-ICPMS测定采用常规雾化器和离子计数器静态接收的方式完成,并用10%的HCl-EtOH和10%的HCl溶液交替清洗进样系统来消除Os的"记忆效应".岩石样品的Re和Os化学分离采用Carius管溶样法,结合CCl4萃取以及微蒸馏的方法分离纯化Os,利用阴离子交换树脂的方法分离纯化Re.运用上述方法,对6个镁铁-超镁铁质岩石样品中的Re、Os含量和187Os/188Os同位素比值进行了测定,获得了理想的分析结果.     

铼-锇同位素体系、铂-锇同位素体系及二者的联合体系

本文对铼—锇同位素体系的基础原理进行了介绍,并提出了铂—锇同位素体系及其与铼—锇同位素体系进行联合应用的设想,在铼—锇和铂—锇的联合体系中,地幔作用过程及地壳—地幔之间的相互作用,将由~(187)Os/~(188)Os/~(186)Os/~(188)Os比值及其相应的γ_(UMR)~T(~(187)Os)和γ_(UMR)~T(~(186)Os)参数来进行描述。这一对比值和参数对地幔作用过程及地壳—地幔之间相互作用的描述,将会比目前所采用的单一~(187)Os/~(188)Os比值所作的描述更为深刻和准确。同时,在这两种同位素的联合体系中,由于铂及锇都聚集于地幔中,不易受地壳物质的污染,因而即使在铼—锇同位素体系受到地壳物质污染的情况下,我们仍可根据两个或两个以上的不合谐年龄值,通过与联合体系的合谐年龄曲线相交,而得到合谐年龄值。     

Refinement of the Micro‐Distillation Technique for Isotopic Analysis of Geological Samples with pg‐Level Osmium Contents

In recent years, the ¹⁸⁷Re–¹⁸⁷Os isotope system has been increasingly used to study samples containing very small quantities of Os. For such samples, optimisation of measurement procedures is essential to minimise the loss of Os before mass spectrometric measurements. Micro‐distillation is a necessary purification step that is applied after the main Os chemical separation procedure, prior to Os isotope ratio measurements by negative‐thermal ionisation mass spectrometry (N‐TIMS). However, unlike the other separation steps, this procedure has not yet been optimised for small samples. In this study, we present a refined micro‐distillation method that achieved higher yields and allowed high‐precision R(¹⁸⁷Os/¹⁸⁸Os) expressed as ¹⁸⁷Os/¹⁸⁸Os measurements for small‐sized geological samples that contain only a few pg Os. The Os recovery in the micro‐distillation step was tested by changing the operating conditions including heating time and temperature, and amounts of oxidant and reductant. Recoveries were measured by the isotope dilution ICP‐MS method after the addition of ¹⁹⁰Os‐enriched spike solution. We found that the most critical factor controlling the chemical yield of Os during micro‐distillation is the extent of dilution of the reductant (HBr) by H₂O evaporated from the oxidant. A refined micro‐distillation method, in which the amount of oxidant solution is reduced from the conventional method, achieved an improved chemical yield of Os (~ 90%). This refined method was applied to the measurement of ¹⁸⁷Os/¹⁸⁸Os by N‐TIMS of varying test portions of the geological reference material BIR‐1a. The resulting ¹⁸⁷Os/¹⁸⁸Os ratios of BIR‐1a matched the literature data, with propagated uncertainties of 0.2, 1.1 and 11% digested sample quantities containing 150, 10 and 1 pg of Os, respectively.     

Evaluation of Simultaneous Analyte Leaching/Vapour Phase Introduction for Direct Osmium Isotope Ratio Measurements in Solid Samples by Double-Focusing Sector Field ICP-MS

The analytical performance of a method for Os isotope ratio measurement by double‐focusing, sector field ICP‐MS (ICP‐SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by the formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic determination by ICP‐SFMS. Due to the very efficient utilisation of analyte (approaching 0.5‰), Os isotope ratio measurement could be performed at low pg levels. Combined with an ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub pg g^?1 range could be determined by this method. Given that two complete digestion/distillation systems were available for interchangeable use, throughputs of up to fifteen samples per 8 hour shift could be achieved. The method precision, evaluated as the long‐term reproducibility of ¹⁸⁷ Os/¹⁸⁸Os ratio measurements in a commercial Os reference sample containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1s). The method has been applied to perform replicate ¹⁸⁷ Os/¹⁸⁸ Os ratio measurements on a suite of fifty reference materials of various origins and matrix compositions, with Os concentrations varying from < 0.1 pg g^?1 to > 100 ng g^?1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi‐quantitative determination of Os concentrations.     

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.”     

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 Method for Rapid Determination of Re and Os Isotope Compositions Using ID‐MC‐ICP‐MS Combined with the Sparging Method

A simple, rapid method for the determination of Re and Os concentrations and isotope compositions using isotope dilution multi‐collector inductively coupled plasma‐mass spectrometry (ID‐MC‐ICP‐MS) combined with Carius tube digestion and sparging introduction of Os was developed. For Os measurement, four channeltron ion counters to detect different Os isotopes were used simultaneously, which led to a drastic reduction in the measurement time. Rhenium isotopes were measured by means of eight Faraday cups with solution nebulisation and an ultrasonic membrane desolvator. The representative ¹⁸⁸Os count rate of an Os standard solution containing 50 pg of total Os was approximately 110000–120000 cps at the onset of measurement; the Re intensity of our in‐house 10 pg g^?1 standard solution reached 1820 V/μg g^?1 with a sample uptake rate of 95–99 μl min^?1. These values indicate that the sensitivity of the method was sufficient even for samples with low Re and Os concentrations, such as chert. As the temporal variations of the amplification efficiency of the ion counters differed from one another, we adopted a sample‐calibrator bracketing method to correct the measured Re and Os isotope ratios. The Re and Os concentrations via the isotope dilution method and the ¹⁸⁷Os/¹⁸⁸Os ratios of two sedimentary rock reference materials (JMS‐2 and JCh‐1) on the basis of the isotope ratios determined by the MC‐ICP‐MS and by negative thermal ionisation mass spectrometry (N‐TIMS) were comparable within their ranges. Based on Os isotope measurement of the IAG reference material [Durham Romil Os (DROsS)], the average difference from the recommended value and precision of Os isotope measurements by the sparging method in combination with multi‐ion‐counters were 0.72% and 0.76% [1RSD (%), n = 29], respectively. The precisions in the ¹⁸⁷Os/¹⁸⁸Os ratios [1RSD (%)] of JMS‐2, JCh‐1 and DROsS were 0.35–0.71, 1.56–3.31 and 0.99–1.28%, respectively, which depended on their Os ion intensities. No systematic difference was observed between the Re and Os geochemical compositions of JCh‐1 and JMS‐2 obtained by means of digestion with inverse aqua regia and CrO₃‐H₂SO₄ solutions, suggesting that either acid solution can be used for the sparging method of sedimentary rock samples. As CrO₃‐H₂SO₄ solution is believed to liberate predominantly the hydrogenous Re and Os fraction from organic‐rich sediment, the sparging method combined with CrO₃‐H₂SO₄ digestion and multi‐ion‐counters in the mass spectrometry is expected to be a powerful tool for reconstructing the secular change in marine Os isotope compositions with high sample throughput.     

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.     

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.     

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.     

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.