铂族矿物中锇同位素比值的地质意义

铂族矿物中锇同位素比值的地质意义谢智（中国科技大学地球和空间科学系,合肥２３００２６）关键词锇同位素比值铂族矿物地幔地壳Ｏｓ元素是中等相容性元素,Ｒｅ是不相容性元素。在壳幔分异过程中,Ｒｅ／Ｏｓ分异很大,Ｏｓ倾向于存留在地幔中,而地壳中Ｏｓ的含量很低...     

铼—锇同位素和铂族元素分析方法及地学应用进展

近30年来,国内外铼—锇(Re-Os)同位素和铂族元素(PGE)分析方法及其地学应用取得了诸多研究进展.首先对铼—锇同位素和铂族元素分析的样品溶解、化学分离及质谱测定等方面的进展情况进行了综述;然后,对铼—锇同位素和铂族元素在天体化学、大陆岩石圈地幔定年、金属矿床定年、沉积地层定年及古环境,以及在油气系统定年与示踪等领域的应用进展情况进行了简要评述.可供地质分析工作者针对不同分析任务及分析对象,选择分析方法并进一步发展Re-Os-PGE分析技术时参考,也可供地质科研工作者开展Re-Os-PGE地球化学研究工作时借鉴.     

同位素稀释等离子体质谱法测定岩石中的铂

报道了以普通铂标准溶液标定198Pt稀释剂溶液的浓度,采用同位素稀释等离子体质谱法测定岩石中的Pt。稀释剂标定结果得到该198Pt稀释剂溶液的浓度为19.76μg/g(n=4,RSD=0.16%)。4次测定标准物质GBW07293(取样量约0.5g,推荐浓度440±37ng/g)中Pt含量,结果分别为412.0±2.6ng/g、495.9±2.7ng/g、519.6±3.5ng/g和677.3±3.8ng/g。单份试样重复测量的相对标准偏差<1%。由于铂族元素的块金效应,各份平行测定的结果较分散。     

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...     

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。     

锍试金富集贵金属元素1Ⅰ.等离子体质谱法测定地质样品中痕量铂族元素

纯化了捕集剂，用锍试金结合Ｔｅ共沉淀富集，等离子体质谱法测定了地质样品中的铂族元素。全流程铂族元素回收率大于９４％。一次熔样可同时测定６个铂族元素。按２０ｇ取样计算，方法检出限（ｎｇ／ｇ）分别为：００２４Ｒｕ，００１３Ｒｈ，０２０Ｐｄ，００３３Ｏｓ，０３９Ｉｒ，０１２Ｐｔ；对标准ＧＰｔ６平行测定５次，铂族元素相对标准偏差为１％（Ｏｓ）～８％（Ｐｔ）；对不同类型标样进行测定，测得结果与标准值基本吻合     

同位素稀释-等离子体质谱法快速测定铬铁矿中的铂族元素

目前测定铂族元素的方法主要有中子活化法和等离子体质谱法。后具有灵敏度高、检出限低、质谱图简单的特点,是铂族元素测定的有力工具。同位素稀释法具有准确度高、灵敏度好,不需要对分析元素进行严格的定量回收,已应用于铂族元素的测定。由于铂族元素在地质样品中含量极低,且分布不均匀,因此必须进行分离富集。目前国内外对铂族元素的富集方法主要有火试金法、     

锍镍试金-等离子体质谱法测定地球化学勘探样品中的铂族元素和金Ⅰ．分析流程的简化

报道了一个改进的锍镍试金一等离子体质谱测定铂族元素和金的分析流程，用封闭溶解贵金属硫化物滤渣与同位素稀释法测锇相结合，解决了包括锇在内的全部铂族元素和金的测定，避免了锇的蒸馏分离和（或）单独测定，简化了分析流程，以适应大批量化探样品的要求，用所拟方法分析了标准物质中铂族元素和金，其结果与参考值相符。     

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。     

The use of mantle normalization and metal ratios in the identification of the sources of platinum-group elements in various metal-rich black shales

It has been shown that Ni/Cu versus Pd/Ir and Cu/Ir versus Ni/Pd ratios, as well as mantle-normalized metal patterns can be successfully used to evaluate the effects of partial melting, crystal fractionation and sulfide saturation in mafic and ultramafic rocks. Platinum-group element (PGE) enrichments occur in Zn-, Cu- and Ni-rich black shales in a number of geological settings. These facies are generally associated with the development of continental rift structures, both without significant volcanic activity (examples in Canada, China, Finland and Poland) and with volcanic activity (Czech Republic and Namibia). Using the same element ratios as were used in mafic igneous rocks, it is evident that metal-rich black shales associated with volcanic rocks reflect the fractionation of PGEs in volcanogenic facies. It is further concluded that, in metal-rich black shales in which distributions of Ni and Cu have been altered by various processes, the Cu/Ir versus Ni/Pd and Ni/Cu versus Pd/Ir ratios plots are applicable for determination of the source of PGEs only after careful evaluation of Ni and Cu enrichments.Editorial handling: A. Brown, D. Lentz     

Application of the Pt–Re–Os isotopic systems to mantle geochemistry and geochronology

The Re–Os system has now been applied to a wide variety of problems in the solid earth sciences. This review concentrates on applications of the Re–Os system to understanding the age and composition of the mantle and the role that various materials in the mantle play in generating surface magmas. The progress in understanding Re–Os systematics in natural materials has accompanied dramatic advances in the understanding of the geochemical behavior of Re and the platinum group elements. This group of elements and the two isotopic systems (Pt–Os and Re–Os) they contain provide a view of Earth processes that are controlled not by the silicate phases the make up most of the outer portion of Earth, but by sulfide, oxide and metal phases that constitute but a trace of the mantle and crust. These phases are sensitive to oxygen and sulfur fugacities in ways that silicates are not. Consequently, the Re–Os and Pt–Os systems provide a new view into the geochemical evolution of the solid Earth that is complementary to that obtained through the study of traditional radiometric systems that are based on lithophile elements.     

Metasomatism and sulfide mobility in lithospheric mantle beneath eastern Australia: Implications for mantle Re–Os chronology

Spinel lherzolite xenoliths from Tertiary basaltic host magmas at Allyn River, eastern Australia reveal two distinct petrographic and geochemical types. One group is distinguished by xenoliths with undeformed, equilibrated microstructures and interstitial melt patches; The second group shows deformation and contains abundant fluid inclusions but no melt patches. Trace-element signatures of clinopyroxene in these xenoliths provide evidence for metasomatism by a silicate agent with hydrous component and by a carbonate-rich agent respectively.

Melt patches in the undeformed xenoliths contain secondary minerals including clinopyroxene, olivine, feldspar, Mg- and Ca-rich carbonate, apatite, ilmenite and spinel. They are interpreted to represent volatile-rich melt captured shortly prior to entrainment in the host basalt. Sulfide globules, now recrystallised to discrete sulfide phases but inferred to be molten at lithospheric mantle T and P, are closely associated with the melt patches. The close association between sulfide and highly mobile, volatile-bearing fluid has important implications for the mobility of Re and Os, the use of their isotopes in dating mantle events, and the possible effect of volatile-bearing metasomatic agents on their composition.     

特提斯洋对流上地幔Os同位素组成估算的新方法及初步运用

对流上地幔Os同位素组成的准确估算是运用Re-Os同位素体系探讨地幔演化的基础。前人研究主要是以地幔橄榄岩为研究对象,由于地幔橄榄岩Os同位素存在明显的不均一性,因而直接影响估算值的准确性。对流上地幔中包含的不同亏损程度的难熔组分在部分熔融过程中难以熔融,对形成的熔体相的Os同位素组成贡献很少或者没有。因此,与对流上地幔具有相同的Os同位素组成初始值的早期分离结晶岩石(如堆晶岩),结合堆晶岩中锆石的准确定年,可以用来估算对流上地幔Os同位素组成。本文根据这一方法测试了那曲地区弧后盆地堆晶岩的Os同位素组成和锆石U-Pb年龄,推测那曲地区新特提斯洋对流上地幔Os同位素组成为碳质球粒陨石型的。根据这一模型,对比了罗布莎和东巧铬铁矿岩、含矿围岩以及不含矿围岩的Os同位素特征,揭示出矿石及围岩均具有古老大陆岩石圈地幔信息,而不含矿围岩(泽当岩体)的Os同位素组成为碳质球粒陨石型的,无古老大陆岩石圈地幔信息。     

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.     

(LP)MCICPMS方法精确测定液体和固体样品的Sr同位素组成

MCICPMS是近年发展起来的高精度固体同位素分析仪器,利用MCICPMS可以精确测定Sr同位素组成,与TIMS相比,分析效率明显提高;对于含有Rb的实际样品,在Rb/Sr比值较小时(Rb/Sr<0.001),可以通过Rb扣除获得准确的87Sr/86Sr比值,而当Rb含量较高时,可以通过建立Rb/Sr与87Sr/86Sr偏差值的线性关系进行再一次校正,同样也可以获得准确的87Sr/86Sr比值.通过这种校正关系,可以直接分析固体微区的Sr同位素组成.     

Geochemical characteristics of the platinum-group elements in the Abulangdang ultramafic intrusion,Sichuan Province,China

The contents of the platinum-group elements (PGEs: Os, Ir, Ru, Rh, Pt, Pd) in the Abulangdang ultramafic intrusion have been determined using ICP-MS after nickel sulfide fire assay preconcentration. Different samples show significant differences in absolute PGE abundance. They display a pronounced negative incline in mantle-normalized patterns which are characterized by strong enrichment in IPGEs (Os, Ir, Ru) and depleting to slight enrichment in PPGEs (Rh, Pt, Pd). The characteristics of PGE distribution in the Abulangdang rocks are due to the combined action of sulfide and non-sulfide (spinel/chromite or alloy or micro-granular aggregation of metals). In comparison with the mafic-ultramafic rocks which host Ni-Cu-PGE deposits in the Emeishan Large Igneous Province (ELIP), it is assumed that the Abulangdang ultramafic intrusion may be the product of early-stage magma activity in the ELIP.     

非洲铂族金属矿产资源禀赋特征、成矿潜力及开发利用

铂族元素（Platinum group elements,PGEs）作为地壳最稀缺的一类金属元素,是重要的战略性矿产资源,与金一样,具有经济和科技双重的功能。非洲铂族金属矿产资源丰富且高度集中,占世界资源量> 80 %,主要集中在南非和津巴布韦。本文在前人研究基础上,对非洲PGEs矿床主要成矿类型、时空分布特点和开发利用现状进行了总结,研究认为：（1）非洲大型-超大型PGEs矿床成因类型主要为岩浆型,在时空上与世界级铁质-镁铁质大火成岩省（南非布什维尔德和津巴布韦大岩墙）密切相关,可细化分为脉状铜镍硫化物型、整合接触型铜镍硫化物型、脉状铬铁矿型和钒钛磁铁矿型。依据区域构造演化及其所产出的矿化特征,认为以铁质-镁铁质岩有关的岩浆型矿床仍具有较大的找矿潜力。(2)非洲铂族金属矿产勘查开发程度相对较高,近十年是全球勘查资金投入最多的地区,同时也是世界第一大Pt生产地和第二大Pd生产地。从事勘查开发的主要为世界顶级PGEs矿业寡头。（3）非洲是全球一次性铂族金属矿产品主要供应国,主要出口至美国、日本、中国、德国和英国。加强与南非、津巴布韦等国家之间的合作,保障PGEs资源供应的安全对我国尤为重要。     

High‐Precision Measurement of 187Os/188Os Isotope Ratios of Nanogram to Picogram Amounts of Os in Geological Samples by N‐TIMS using Faraday Cups Equipped with 1013 Ω Amplifiers

N(¹⁸⁷Os)/N(¹⁸⁸Os) ratios of six geological reference materials were measured using static Faraday cups (FCs) with 10¹³ Ω amplifiers by N‐TIMS. Our results show that the repeatability precision was 2–3‰ (2 RSD, n = 3), when taking ~ 1 g of BHVO‐2 with 76 pg g^?1 of Os mass fraction and ~ 2 g of BCR‐2 with 21 pg g^?1 of Os mass fraction for each sample, whether measured by FCs or by secondary electron multiplier. The repeatability precision measured by FCs was 1–0.2‰ (2 RSD, n = 3) when taking ~ 1 g of BIR‐2 with 350 pg g^?1 of Os mass fraction, ~ 1 g of WGB‐1 with 493 pg g^?1 of Os mass fraction or ~ 0.5 g of WPR‐1 with 13.3 ng g^?1 of Os mass fraction for each sample, which is much better than those measured by secondary electron multiplier. Instead, when taking ~ 2 g of AGV‐2 with 4 pg g^?1 Os mass fraction, the repeatability precision measured by secondary electron multiplier is 3–4‰ (RSD, n = 3), which is better than those measured by FCs. Of the six reference materials analysed, WPR‐1 and BIR‐1a are the most homogeneous with regard to Os isotopic composition (2 RSD of 0.08% and 0.23%, respectively) when test portion masses are 0.5–1 g.     

Precise determination of SmNd ratios,Sm and Nd isotopic abundances in standard solutions

The methods used for precise calibrations of $\text{Sm}\text{Nd}$ ratios and the average isotopic abundances obtained for normal Sm and Nd are given. A mixed Sm-Nd normal solution with a precisely known ${}^{147}\text{Sm}{}^{144}\text{Nd}$ ratio close to the nominal average chondritic value is described and the calibration discussed. Aliquots of this standard solution are available on request and may be useful for precise interlaboratory calibration of Sm and Nd.