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.     

松树沟超镁铁岩主量元素及Os同位素初步研究

本文利用 N-TIMS 方法测定了松树沟超镁铁岩的Os同位素组成，初步获得的Os同位素组成数据显示：残余型超镁铁岩的Os同位素比值明显低于岩浆型，表明松树沟岩体在岩浆演化过程中发生了 Re/Os分异；187Os/188Os与Al2O3、Al2O3/MgO正相关，与MgO负相关，表明在岩浆演化过程中，微量的 Re、Os元素分别与主要元素 Al2O3和MgO的性质相似。     

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。     

铼—锇同位素分析中试样化学预处理方法进展

评述了用于Re-Os同位素体系分析的化学前处理技术的发展。简要介绍了卡洛斯管熔样法、Os的CCl4提取、溴提取和微蒸馏方法。卡洛斯管封闭熔样方法，有效地防止了Os的挥发损失和保证了Os同位素平衡，是一种很有发展前景的熔样方法。蒸馏法仍是分离和纯化Os的有效方法，溶剂（CCl4)提取和溴提取法在许多实验室里应用，而微蒸馏则是Os的二次纯化的主要方法。Re的化学分离和纯化仍是离子交换和萃取法。引用主要文献29篇。     

铼-锇同位素分析样品预处理研究进展

文章评述并归纳了近年来地质样品中Re-Os同位素分析的化学前处理方法研究进展。总结了锍镍火试金法、碱熔法、Carius管溶样法以及HPA-S高温高压釜溶样法等常用的Re-Os同位素样品消解方法。归纳了离子交换、溶剂萃取富集Re以及蒸馏、萃取等分离富集Os的方法。由于地质样品的复杂性,Re、Os含量的不均一性及测试方法的多样性,要求在具体分析过程中不同的样品使用不同的消解方法和分离富集方法。当前国内应用较成熟的Re、Os分离方法是Carius管逆王水分解样品,原位蒸馏或CCl4萃取方法分离Os,阴离子交换法或丙酮萃取分离Re。     

Re-Os同位素组成测试方法及其应用进展

Re为中等不相容元素，Os则属强相容元素，与母子体均为不相容元素的Rb Sr、Sm Nd、U Th Pb等同位素体系相比，具亲铁、亲硫性的Re Os同位素体系在定年和示踪研究中显示出特殊性，受到了地学家高度重视，其应用正走向普及。总结和对比了近年来Re Os同位素分析中样品分解的不同方法（NiS火试金法、Carius管溶样法、高压灰化消解法、浸提法、水样处理法）、Os的分离（常规蒸馏、液溴和CCl4提取、快速低本底提取、小型蒸馏）与纯化流程（微蒸馏）、Os同位素比值质谱测定法（N TIMS、ICP MS、微区原位（in situ）分析）及随测定方法的改进Re Os同位素体系在地球科学研究中的应用进展。     

油气成藏定年的Re-Os同位素方法应用研究

Re和Os易于被有机物捕获而富集,并长期稳定地保存在烃源岩、原油和沥青中而保持良好的封闭体系.可以对烃源岩、原油和沥青进行Re-Os同位素直接定年,获得与油气成藏相关的精确的绝对年龄信息.Re-Os同位素实验分析包括样品的溶解、Re和Os的化学分离与纯化、Re和Os同位素的质谱测定.原油中沥青质组分的Re,Os同位素组成能够近似代表全油的Re,Os同位素组成,对原油进行Re-Os同位素分析实质就是对原油中的沥青质组分中的Re-Os同位素体系进行分析,其年龄记录的是油气生成的年龄,原油和烃源岩的187Os/188 Os比值的对比可以进行油源示踪.沥青Re-Os同位素等时线年龄揭示的是油气大量生成运移的时间,年龄数据分散的主要原因是具有不同187 Os/188 Os初始比值的烃源岩对Re-Os体系的贡献.川西龙门山北段矿山梁下寒武统沥青Re-Os同位素组成和等时线年龄指示了油气生成和运移的时间发生在～164 Ma,并来源于两种烃源岩.Re-Os同位素体系的封闭性、等时线年龄的精度和油气地质意义、烃源岩多期熟化作用和混源作用的影响等方面还值得进一步深入研究.Re-Os同位素方法将在油气成藏年代学领域,特别是在碳酸盐岩地区的油气成藏定年方面具有广泛的应用前景.     

铜镍硫化物的Re-Os同位素定年方法及应用实例

摘要本文介绍了含有普通Os的铜镍硫化物的Re-Os同位素定年方法及其在新疆黄山东和金川铜镍矿床的应用实例。样品采用Carius管溶解，Re采取丙酮萃取、阳离子树脂交换分离，Os则采取蒸馏分离方式，质谱测量为电感辆合等离子体质谱(ICP-MS)。结果表明，采用ICP-MS进行铜镍硫化物的Re-Os同位素定年研究，同样能得到令人满意的结果。     

湖南鲁塘石墨矿Re-Os同位素研究

石墨具有较高的Re、Os含量,可望成为理想的Re-Os同位素测年对象,但迄今国内外研究较少,尤其在煤层经变质作用形成石墨过程中,其中Re-Os同位素体系的变化还有待研究。湖南鲁塘石墨矿是我国典型的隐晶质石墨矿床之一,矿体产于二叠系龙潭组煤系地层中。本文采用Carius管逆王水溶解样品,直接蒸馏、微蒸馏分离纯化Os,丙酮萃取法分离富集Re,热表面电离质谱法对鲁塘矿区石墨样品以及外围原煤进行了Re-Os同位素分析。结果表明:鲁塘石墨的Re含量为0.901~9.794 ng/g,Os含量为7.3~189.5 pg/g,Re-Os同位素等时线年龄为155.6±3.6 Ma,该年龄与鲁塘石墨矿东侧骑田岭岩体第二阶段中粒黑云母花岗岩锆石U-Pb年龄153~157 Ma一致,表明了龙潭组煤层受到骑田岭岩体"烘烤"作用,发生热接触变质作用,使得靠近骑田岭岩体原煤变质为石墨,形成石墨矿床。通过对比石墨、原煤和骑田岭岩体Re、Os含量及比值,发现石墨中的Re、Os主要来源于原煤,并根据石墨Re-Os等时线初始(187Os/188Os)i值(0.686±0.032),推测骑田岭岩体在侵入煤系地层过程中,有少量具有较低187Os/188Os值的Os被碳质吸附。     

云南潞西三台山超镁铁岩体Os-Nd-Pb-Sr同位素特征及地质意义

滇西地区特提斯造山带具有多块体拼合的构造特点,是东特提斯造山带的重要组成部分之一,其大地构造演化对理解全球特提斯造山带具有重要的地质意义.在腾冲和保山地块之间的龙陵-瑞丽断裂带中出露超镁铁质岩石,曾被解释为两个陆块缝合的证据.本文采用高灵敏度高精度超低本底Re-Os、Sm-Nd、Pb和Rb-Sr同位素分析技术,对采自该断裂带潞西三台山的超镁铁岩样品进行了Os-Nd-Pb-Sr同位素测定.分析结果表明,这些超镁铁岩石具有强烈富集特征.分析的5个岩石样品具有高的初始~(87)Sr/~(86)Sr值(0.71074～0.71444)、低的初始ε_(Nd)值(-6.2～-10.6)、低初始γ_(Os)值(-4.8～-8.8)和较高的初始铅同位素比值,其Os同位素模式年龄值(t_(RD))为0.97～1.71Ga.Nd-Os同位素组成特征表明,三台山超镁铁岩具有古老的富集大陆岩石圈地幔岩石的特征,不能作为腾冲和保山地块的缝合证据.     

Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

利用同一化学流程分析地质样品中的铂族元素含量和铼-锇同位素组成

报道了利用一次溶样和同一化学流程分离富集地质样品中铂族元素(Pt、Pd、Os、Ir和Ru)和Re的方法.该化学流程包括以下几个步骤:(1) Carius管溶样法分解岩石样品中富集铂族元素的矿物;(2)四氯化碳萃取法分离出Os;(3)微蒸馏法进一步纯化Os;(4)阳离子交换树脂法将铂族元素(Pt、Pd、Ir和Ru)以及R...     

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.     

石灰岩铼-锇同位素分析方法研究及应用初探

针对石灰岩样品Re-Os同位素分析,在选样和溶样方法上进行了改进,在Carius管封闭前加入HCl与石灰岩反应释放出大量CO2,然后加入氧化剂和稀释剂封闭Carius管溶解样品,大大增加了样品取样量。利用改进的方法对采自青海玉树地区二叠世九十道班组底部的灰黑色微细晶灰岩的Re-Os同位素体系进行了分析测定,得到了精确的沉积年龄(283.1±7.1)Ma(MSWD=0.61,Model1,n=7)。187Os/188Os同位素初始值为0.56±0.12,与二叠纪时海水的187Os/188Os值相一致,反映了石灰岩沉积时海水的187Os/188Os比值。所得石灰岩年龄与其中的生物化石年龄相吻合,并且与区域上岩浆岩锆石年龄相互印证,表明Re-Os同位素体系在该石灰岩中的封闭性较好。通过石灰岩中有机碳含量以及其中Re、Os含量关系研究,得出了Re、Os在灰岩中主要赋存于有机质中的结论。从原理上解释了Re-Os同位素体系在灰岩中的应用具有十分广泛的前景。     

铼-锇同位素测年法研究综述

Re-Os同位素测年的最合适的对象为辉钼矿,定年是基于放射性的187Re通过β衰变成为187Os而引起锇同位素异常来计算地质年代的。在目前的测试研究中,较常用的方案为Carius管溶样法-蒸馏分离Os-萃取分离Re-TJA PQ ExCell ICPMS测定同位素比值。在我国有许多成功用Re-Os同位素测定钼矿床成矿年龄的范例,对认识矿床特征及成因、总结区域的成矿演化规律、解决相关地质问题具有重要的理论意义,而且对于指导矿床的预测和勘查具有很高科学价值。     

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。     

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.     

Preservation of Re‐Os isotope signatures in pyrite throughout low‐T,high‐P eclogite facies metamorphism

Pyrite in LT–HP eclogites from the western Tianshan orogenic belt yields a Re‐Os age of 378.1 ± 8.9 Ma, which is 30–70 Ma older than ages previously obtained for the same rocks using the Rb–Sr, Sm–Nd, Ar–Ar, U–Pb, and Lu–Hf isotope systems. The Tianshan LT–HP eclogite experienced temperatures of up to ~570 °C combined with pressures of up to 2.1 GPa during metamorphism. These conditions are below the transition of pyrite to pyrrhotite, which defines both pyrite stability and possibly its closure temperature for Re‐Os. Pyrite can preserve Re‐Os signatures through eclogite facies peak metamorphic conditions, and thus allow determination of the formation age of pyrite in the protolith.     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.