铼—锇同位素分析中样品的预处理

文章对近年来在Ｒｅ＿Ｏｓ同位素质谱分析中样品的预处理方法进行了介绍和总结评述，重点介绍了样品的分解和元素的分离纯化。引用主要文献１８篇。     

铼-锇同位素地球化学进展

Re和Os是强亲铁元素。Re同位素有：^185Re(37．07％)和^187Re(62．93％)。Os有7个同位素：^184Os(0．018％)、^186Os(1．59％)、^187Os(1．64％)、^188Os(13．20％)、^189Os(16．10％)、^180Os(26．40％)和^192Os(41．0％)。^186Os和^187Os为放射性衰变产物。^186Os由^190Pt通过α衰变而成,^187Os由^187Re通过β衰变而成。     

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。     

镁铁-超镁铁岩铼-锇同位素体系分析方法

通过试验建立了镁铁-超镁铁岩Re-Os同位素体系分析方法，包括Re-Os的化学分离纯化流程，Re同位素比值的电感耦合等离子体质谱测量方法和Os同位素比值的负离子热电离质谱测量方法。化学流程包括Carius管溶样，小型蒸馏分离Os，微蒸馏纯化Os，阴离子交换法分离、纯化Re。用该流程测定了汉诺坝幔源橄榄岩、辉石岩捕虏体和大别山饶拔寨超镁铁岩样品的Re、Os含量和Os同位素比值。     

辉钼矿铼—锇同位素年代学研究简介

辉钼矿铼－锇同位素年代学测定依据该矿物中含有由＾１８７Ｒｅ通过β＾－衰变而形成的放射性成因＾１８７Ｏｓ这一同位素年代学方法的由于８０年代以来微量铼，锇同位素质谱技术的成熟而逐浙应用于研究中，获得了具有地质意义的年龄值，对辉钼矿年龄测定的成功与否，选择适当的样品至关重要，一般而言，红外透光性大于３．５的辉钼矿样品的适合于铼－锇同位素年代学研究，其辉钼矿的铼－锇同位素年龄值十分接近于围岩的钾－氩或其它     

铼-锇同位素定年方法及分析测试技术的进展

铼-锇同位素定年已经成为矿床学乃至于地质学领域最重要的定年技术之一。文章简略地回顾了铼-锇同位素体系技术方法的发展过程;介绍了准确测定187Re衰变常数的发展历史,铼-锇同位素定年和同位素示踪的基本原理,铼与锇的基本化学性质、在自然界的分布、地球化学行为、赋存状态和样品采集应注意的问题。结合作者实验室10余年的铼-锇同位素体系分析经验,较系统地总结了常用的样品分解和化学分离方法;介绍了负离子热表面电离质谱和电感耦合等离子体质谱测定铼、锇同位素的方法原理、特点和应注意的技术细节,以及近年来用于准确测定锇稀释剂的锇标准参考物质的选择、化学组分测定和铼-锇标准参考物质的研究进展。     

186锇和188锇双同位素稀释法在辉钼矿铼—锇测年中的应用

以经过负离子热表面电离质谱仪准确标定的＾１８６Ｏｓ和＾１８８Ｏｓ双同位素作为稀释剂,利用＾１８６Ｏｓ和＾１８８Ｏｓ计算＾１８７Ｏｓ的含量,能有效地减少用等离子体质谱仪测定＾１８７Ｏｓ时由于仪器本身的不稳定性及质量歧视效应所产生的误差,使测量准确度比用单同位素作为稀释剂有明显提高。方法应用于辉钼矿Ｒｅ－Ｏｓ年龄标准参考物及样品的测定,结果与参考值一致,５份试样测定的ＲＳＤ〈３％。     

铼—锇同位素体系在基性—超基性岩中应用现状的综述

综述了该同位素体系晚侏罗世以来，尤其是现代地幔岩石的研究成果表明，地幔在晚侏罗世以来在１８７Ｏｓ／１８７Ｏｓ比值方面显示出非均一性，其比值从０．９０－１．２６，但此类岩石的１８７Ｏｓ／１８６Ｏｓ比值分别与各个不同研究者所确定的地幔演化线相到致；来自较古老正常地幔或贫化地幔的岩石，在锇同位素方面体现为１８７Ｏｓ／１８６Ｏｓ初始比值接或低于Ｒｅ－Ｏｓ同位素体系地幔演化线值。在此类岩石中，Ｒｅ－Ｏｓ同位     

湘东南将军寨钨矿花岗岩地球化学特征及铼-锇同位素定年

将军寨钨矿是湘东南白云仙矿田中一个典型的石英脉型黑钨矿床。岩石学和岩石地球化学研究表明,将军寨钨矿花岗岩体为一复式岩体,是同源岩浆演化的产物,具有壳源花岗岩的特征。文章研究了白云仙矿田将军寨钨矿花岗岩的地球化学特征,并进行石英脉型黑钨矿石中辉钼矿的铼-锇同位素定年,以精确厘定将军寨钨矿的形成时间,揭示湘东南地区钨、锡等有色金属成矿的时限及其地球动力学背景。铼-锇同位素定年结果表明,辉钼矿中铼的含量偏低,表明将军寨钨矿的成矿物质来源可能是以上地壳为主。4件辉钼矿样品的铼-锇同位素模式年龄为(151.3±2.5)Ma～(163.6±2.3)Ma,其等时线年龄为(169.6±2.7)Ma,这表明将军寨钨矿形成于燕山早期,为华南中生代大规模成矿作用的产物。     

Carius管溶样-负离子热表面电离质谱准确测定辉钼矿铼-锇同位素地质年龄

将样品、混合稀释剂和逆王水加入到Carius管中,于230℃溶样10h.利用蒸馏法分离Os,萃取和阴离子交换法分离Re.采用负离子热表面电离质谱精确测定了所研制的年龄标准参考物辉钼矿(HLP)的Re-Os年龄.对取自12个小瓶中17个样品所测平均年龄为221.3±0.3Ma,置信度95%.中值年龄和平均绝对偏差为221.34±0.12Ma.美国克罗拉多州立大学AIRIE小组19次单独取样所测HLP的平均年龄为221.3±1.0Ma,置信度95%.中值年龄和平均绝对偏差为221.34±0.24Ma.     

改进的卡洛斯管溶样等离子体质谱法测定地质样品中低含量铂族元素及铼的含量

报道了一个改进的卡洛斯管溶样等离子体质谱法测定地质样品中铂族元素及Re含量的新方法。将封闭的卡洛斯管置于高压釜中,然后在高压釜中加水,密封在高压釜中的水在高温下产生的外压将会抵消卡洛斯管中由酸产生的内压,这样就可以避免传统的卡洛斯管在高温高压下可能发生爆炸的危险。由此可以加大取样量,降低铂族元素测定过程中的块金效应及检出限,使超低含量铂族元素的测定成为可能。12g样品在75mL卡洛斯管中用35mL王水于320℃溶解15h,基本上可以使各种地质样品中的铂族元素矿物完全溶解。一次溶样可以测定全部铂族元素及Re,全流程空白值极低,国际标样测定结果稳定可靠。     

Reassessment of Hydrofluoric Acid Desilicification in the Carius Tube Digestion Technique for Re–Os Isotopic Determination in Geological Samples

In this study, Re and Os isotopes were systematically determined in six geological reference materials (RMs; covering a wide range of lithologies) using the Carius tube (CT) digestion technique with and without hydrofluoric acid desilicification. Our results show that the HF desilicification increased the Re extraction efficiency (by 9–15%) evidenced from basaltic and andesitic rocks (e.g., BHVO‐2, TDB‐1 and AGV‐2). This implies that a small proportion of Re resides in silicate phases. For mafic–ultramafic rocks (e.g., BCR‐2, WGB‐1 and WPR‐1), Re extraction efficiencies obtained by the CT digestion with and without HF desilicification were similar. This may indicate that Re in these rocks may dominantly reside in some phases (e.g., magnetite and sulfides) that could be completely dissolved in aqua regia solutions without the aid of HF desilicification. Our results also show that the HF desilicification increased Os extraction efficiency (by 13–99%) in some RMs (e.g., BHVO‐2, WGB‐1 and AGV‐2). This observation suggests that a portion of Os‐rich trace phases may occur as inclusions in the silicate phases that act as isolators at ~ 200 mesh sizes. This study demonstrates that the HF desilicification step prior to CT digestion is important for complete extraction of Re and Os in geological samples.     

蒸馏法富集纯化Os实验条件研究及其在负离子热电离质谱测量中的应用

微蒸馏是富集纯化Os的一项重要化学前处理技术,提高Os回收率对提高Os的负离子热电离质谱(NTIMS)测量精度尤为重要。在微蒸馏过程中,蒸馏温度、吸收液体积、蒸馏时间等对Os回收率具有重要影响,但目前微蒸馏的实验条件不够明确,导致Os回收率不稳定,影响NTIMS测量精度,易增加所得Re-Os年龄误差。本文以自制的含Os溶液为对象,以ICP-MS为测量手段,对微蒸馏过程中多种实验条件对Os回收率的影响进行深入研究,以期获得最佳微蒸馏实验条件,满足后续NTIMS对Os信号强度的测量要求。结果表明:在溶液蒸干温度为120℃并保持15 min,微蒸馏温度为80℃,氢溴酸吸收液体积为15μL,微蒸馏时间为2 h的条件下,获得Os回收率为80%~90%,能够满足多种地质样品尤其是中酸性岩浆岩、热液硫化物等pg级地质样品的NTIMS测量要求,在保证Os信号强度的情况下提高了分析效率。     

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。     

A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

The Design of Re‐usable Carius Tubes for the Determination of Rhenium,Osmium and Platinum‐Group Elements in Geological Samples

The traditional Carius tube technique is cumbersome and requires skilful work to seal the Carius tube, which can be used only once. We describe a modification to the technique that does not require the use of a high‐temperature welding torch to melt the Carius tube to seal it. The newly designed Carius tube consists of a main body with a 3 mm‐thick glass wall, a neck and head with walls 4 mm in thickness, and an efficient screw‐thread stopper. These new features allowed the tube to be used repeatedly. We demonstrate relatively low procedural blanks derived for Re and Os, and platinum‐group elements (PGEs), using the redesigned tube. A temperature of 220 °C could be reached for about 5 ml of HNO₃ for a 47 ml tube and for 32 ml of inverse aqua regia for a 200 ml tube. This digestion technique can be used for routine analysis of Re and PGEs in geological samples.