锶、钕、铅同位素样品准备方法介绍

针对同位素样品粉末化过程中易受污染的特点，详细介绍了夏威夷大学同位素实验室所使用的方法，包括样品的选取、切割、粗碎、净化、挑选以及粉末化过程。该方法的优点是尽可能地保证样品在粉碎过程中不受外界物质的污染，并去除一些蚀变及氧化物的影响。     

长江水氢、氧同位素组成的时空变化及其环境意义

在2003～2007年间,在长江干流的25个水文站及主要支流的13个水文站系统采样,进行了氢氧同位素研究。观测到的D变化范围为-30‰～-112‰,变化范围为-3.8‰～-15.4‰。从长江源头到河口,不同时期的样品均显示相同的氢氧同位素沿程变化特征。从源头到攀枝花,长江干流的D与逐步下降;而由攀枝花到入海口,D与值逐渐升高。 研究发现,控制长江水的氢氧同位素组成的主要因素是大气降水。长江干流D与值所展现的从攀枝花至河口逐渐升高的趋势就是对流域大气降水的D与变化趋势的响应。长江各支流在氢氧同位素组成上的差别及其对干流的影响也反映大气降水对长江水的制约。 蒸发作用对长江水的氢氧同位素组成也有重要影响。长江源头地处青藏高原,高原湖泊和沼泽星罗棋布。由于气候干燥、日照强烈,湖沼水经过长期的蒸发,盐度逐渐加大,D和18O值也逐渐升高。这些湖水的加入对长江水的氢氧同位素组成也造成一定影响。蒸发作用在枯水期也使洞庭湖与鄱阳湖的D和18O值升高,进而提高长江相关河段的D和18O值。 冰雪融化是影响长江水的氢氧同位素组成的另一重要因素。在长江源头和所有左岸支流的源头,冰川融雪都是重要的水源之一。由于冰川水在氢氧同位素组成上的特殊性,其对河水贡献的大小将影响河水的氢氧同位素组成。 三峡大坝对于长江的水动力体系影响巨大,三峡水库对长江水资源的调控作用有待长期观测研究。从本次的研究资料来看,三峡大坝在丰水期对相应河段的氢氧同位素变化趋势影响不大。但在枯水季节,三峡水库蓄水使下游的宜昌和沙市的水源发生明显变化,导致D和18O值的显著降低。 长江水资源状况及其演变趋势是受到各方面高度关注的重要研究课题。为深入探讨这一问题,需要了解长江水资源的变化与各种气象与水文要素之间的关系,查明大气降水、地下水、冰川水、湖水与河水之间的交互作用。而氢氧同位素示踪技术在这方面可以发挥关键性的作用。由于现有资料有限,目前还无法利用氢氧同位素组成来追溯其气候条件的详细演化过程。但若能在进行系统水文测量的同时,适当开展氢氧同位素测定,将对研究长江水资源状况及其演变趋势大有脾益。     

阿尔金铅、钕、锶、氩、氧同位素研究及其早期演化

根据铅、钕、锶、氩、氧等同位素体系及其年代学研究，阿尔金在其早期演化阶段中存在２７９０—２５９０、１８８３—１７０４、５７５和４７０—４２０Ｍａ４个构造热事件，各自具有不同的性质和时代意义。     

西南极长城湾NG93-1沉积柱样碳、氧、锶、铅同位素地球化学研究及其古环境意义

对西南极西北海域乔治王岛和纳尔逊岛之间长城湾浅水海区柱长８３ｃｍ的沉积柱样ＮＧ９３－１进行了矿物学、Ｓｒ、Ｐｂ、Ｏ、Ｃ等同位素地球化学研究。揭示了沉积物以陆源碎屑物为主，证实南设德兰群岛火山岩是该海区沉积物的重要控制源。Ｏ、Ｃ同位素记录了早全新世以来两次冰期，一次高温的气候变动信息，并指出Ｓｒ、Ｐｂ同位素组成的剖面变化具有气候演变的示踪意义。     

扬子地台钾镁煌斑岩 Nd、Sr、Pb 同位素特征

扬子地台周缘钾镁煌斑岩 Nd、Sr同位素特征介于南非Ⅰ、Ⅱ型金伯利岩和西澳与北美钾镁煌斑岩两种变化趋势之间，不同岩区间同位素组成差异反映地台周边构造性质不同，Pb同位素特征表明晚太古代地幔岩石圈具U亏损特征。     

湖北省大幕山锑矿田硫、碳、氧同位素特征及其成矿意义

文中简要地叙述了大幕山锑矿田的地质条件,详细地说明了辉锑矿、黄铁矿、重晶石中硫同位素的组成;方解石中碳、氧同位素的组成和石英中氧同位素的组成,得出了关于热液和硫、锑来源的结论:成矿热液主要来源于下渗雨水;碳来源于雨水和主岩;硫、锑来源于震旦纪海水。根据石英和方解石的氧同位素组成算出了成矿热液温度为158℃。     

新疆西天山喇嘛萨依铜矿床地质和C、O、S、Pb同位素地球化学

喇嘛萨依铜矿是新疆西天山赛里木微地块内的一处典型铜矿床,关于其成因类型尚存争议。总结了该铜矿床的地质特征,测试围岩、脉石碳酸盐的C、O同位素和硫化物的S、Pb同位素组成,探讨其成因类型。研究表明,喇嘛萨依铜矿床具有后生矿床特征,发育矽卡岩化蚀变,脉石方解石的δ13C值变化范围为-1.04‰~-0.87‰,低于围岩灰岩的δ13C值(变化范围为3.51‰~5.47‰),δ18O值变化范围为9.33‰~9.61‰,明显低于正常的海相碳酸盐岩的O同位素(δ18O=20‰~26‰),C、O同位素组成反映喇嘛萨依铜矿成矿晚阶段流体来自岩浆水和地下水的混合水;硫化物的δ34S值主要变化范围为3.75‰~8.64‰,与区域上海西期斑岩的硫同位素组成(如达巴特斑岩铜钼矿床硫化物的δ34S变化范围为4.9‰~7.9‰)接近,反映硫来源于斑岩;黄铜矿的铅同位素为206Pb/204Pb=18.264~19.544,207Pb/204Pb=15.575~15.656,208Pb/204Pb=38.103~38.705,具有富含放射成因铅、两阶段异常铅特征,与区域上海西期斑岩(达巴特流纹斑岩)的铅同位素组成特征相似,反映成矿金属物质部分来源于斑岩。通过综合分析认为,喇嘛萨依铜矿是与斑岩有关的矽卡岩型矿床。     

稀有气体同位素地球化学研究的某些进展

稀有气体的化学惰性使其在示踪成矿流体方面具有明显的优越性,其与碳、氢、氧、硫、锶、钕、铅同位素方法,以及卤素方法等结合使用,不但可以避免单一方法的片面性,还可以相互补充,相互印证,更好地示踪成矿流体的来源与演化,进而探讨矿床的成矿机制。本文归纳了近年来稀有气体同位素与其他同位素体系联合应用的研究进展,及其存在的问题和发展趋势。     

固体样品中He、Ar同位素的质谱测定

在现有设备的基础上，经多年实验，以空气Ｈｅ、Ａｒ同位素作标准样，采用同位素峰高比分析方法，在国内首次建立了一次进样完成固体样品中Ｈｅ、Ａｒ同位素的测量技术。文中就该项技术的要点，包括样品的前期处理、空气标准样的使用、仪器空白与灵敏度的测定、固体样品进样量的估算方法、测量条件等予以说明与分析。对应用该项技术获取的固体样品中Ｈｅ、Ａｒ同位素首批数据及其偏差，文中也进行了讨论。该项技术方法的建立，将为与惰性气体同位素相关的研究领域提供新的实验技术支撑，推动相关领域基础研究的开展和水平的提高     

中国东部新生代玄武岩的地球化学（Ⅱ）Sr、Nd、Ce同位素组成

对有代表性的中国东部新生代玄武岩的Ｓｒ、Ｎｄ和Ｃｅ同位素组成进行了系统的研究，结合系统的微量元素研究结果，进一步阐明其地幔源区同位素组成的不均一性；利用Ｃｅ、Ｎｄ同位素地球化学给出的信息，探讨富集Ⅰ型（ＥＭⅠ）地幔端元的成因。     

干法灰化和湿法消解植物样品的铜锌铁同位素测定对比研究

测定有机样品中元素含量和同位素时,处理样品常用的方法有干灰化法和湿法两种.目前,测定样品中Cu、Zn、Fe同位素时,多采用湿法处理样品.相对于湿法处理样品,干灰化法溶样迅速、耗酸量少,适合处理大量样品,但高温灼烧过程可能会导致样品中Cu、Zn、Fe同位素的分馏.本研究利用海州香薷植株,以湿法为基础,对干灰化法和湿法处理...     

Comparative stable isotope geochemistry of Ni, Cu, Zn, and Fe in chondrites and iron meteorites

High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes.The observed variations of the ⁶²Ni/⁵⁸Ni, ⁶¹Ni/⁵⁸Ni, and ⁶⁰Ni/⁵⁸Ni ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no ⁶⁰Ni anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45‰ per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation.     

过渡族金属元素同位素分析方法及其地质应用

由于同位素分析方法的改进和多接收电感耦合等离子体质谱仪 (MC ICP MS)的应用 ,近年来过渡族金属元素 (Cu ,Zn和Fe)同位素地球化学有了长足进步 ,成为国际地学领域的一个前沿研究方向。Cu同位素在自然界中的变化最大 ,δ65Cu值为 - 3.70‰～ +2 .0 5‰ ;Zn和Fe同位素变化比Cu同位素变化小 ,δ66Zn值为 - 0 .6 4‰～ +1.16‰ ,而δ56Fe值为 - 1.6 2‰～ +0 .91‰。自然界中各种无机过程 (从高温到低温 )和生物有机过程均能使Cu ,Zn和Fe同位素发生分馏。Cu、Zn和Fe在自然界中广泛分布于各类矿物、岩石、流体和生物体中 ,并广泛参与成岩成矿作用、热液活动和生命活动过程。因此 ,这些过渡族金属元素同位素已在陨石和宇宙化学、矿床学 ,海洋学和生物学等领域的研究中取得了显著成效 ,并将成为地球科学中具有巨大应用前景的一种新的地球化学手段。     

玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

Resolving impact volatilization and condensation from target rock mixing and hydrothermal overprinting within the Chicxulub impact structure

This work presents isotopic data for the non-traditional isotope systems Fe, Cu, and Zn on a set of Chicxulub impactites and target lithologies with the aim of better documenting the dynamic processes taking place during hypervelocity impact events, as well as those affecting impact structures during the post-impact phase. The focus lies on material from the recent IODP-ICDP Expedition 364 Hole M0077A drill core obtained from the offshore Chicxulub peak ring. Two ejecta blanket samples from the UNAM 5 and 7 cores were used to compare the crater lithologies with those outside of the impact structure. The datasets of bulk Fe, Cu, and Zn isotope ratios are coupled with petrographic observations and bulk major and trace element compositions to disentangle equilibrium isotope fractionation effects from kinetic processes. The observed Fe and Cu isotopic signatures, with δ^56/54Fe ranging from ?0.95‰ to 0.58‰ and δ^65/63Cu from ?0.73‰ to 0.14‰, mostly reflect felsic, mafic, and carbonate target lithology mixing and secondary sulfide mineral formation, the latter associated to the extensive and long-lived (>10⁵ years) hydrothermal system within Chicxulub structure. On the other hand, the stable Zn isotope ratios provide evidence for volatility-governed isotopic fractionation. The heavier Zn isotopic compositions observed for the uppermost part of the impactite sequence and a metamorphic clast (δ^66/64Zn of up to 0.80‰ and 0.87‰, respectively) relative to most basement lithologies and impact melt rock units indicate partial vaporization of Zn, comparable to what has been observed for Cretaceous-Paleogene boundary layer sediments around the world, as well as for tektites from various strewn fields. In contrast to previous work, our data indicate that an isotopically light Zn reservoir (δ^66/64Zn down to ?0.49‰), of which the existence has previously been suggested based on mass balance considerations, may reside within the upper impact melt rock (UIM) unit. This observation is restricted to a few UIM samples only and cannot be extended to other target or impact melt rock units. Light isotopic signatures of moderately volatile elements in tektites and microtektites have previously been linked to (back-)condensation under distinct kinetic regimes. Although some of the signatures observed may have been partially overprinted during post-impact processes, our bulk data confirm impact volatilization and condensation of Zn, which may be even more pronounced at the microscale, with variable degrees of mixing between isotopically distinct reservoirs, not only at proximal to distal ejecta sites, but also within the lithologies associated with the Chicxulub impact crater.     

Ion-exchange fractionation of copper and zinc isotopes

Whether transition element isotopes can be fractionated at equilibrium in nature is still uncertain. Standard solutions of Cu and Zn were eluted on an anion-exchange resin, and the isotopic compositions of Cu (with respect to Zn) of the eluted fractions were measured by multiple-collector inductively coupled plasma mass spectrometry. It was found that for pure Cu solutions, the elution curves are consistent with a ⁶³Cu/⁶⁵Cu mass fractionation coefficient of 0.46‰ in 7 mol/L HCl and 0.67‰ in 3 mol/L HCl between the resin and the solution. Batch fractionation experiments confirm that equilibrium fractionation of Cu between resin and 7 mol/L HCl is ∼0.4‰ and therefore indicates that there is no need to invoke kinetic fractionation during the elution. Zn isotope fractionation is an order of magnitude smaller, with a ⁶⁶Zn/⁶⁸Zn fractionation factor of 0.02‰ in 12 mol/L HCl. Cu isotope fractionation results determined from a chalcopyrite solution in 7 mol/L HCl give a fractionation factor of 0.58‰, which indicates that Fe may interfere with Cu fractionation.Comparison of Cu and Zn results suggests that the extent of Cu isotopic fractionation may signal the presence of so far unidentified polynuclear complexes in solution. In contrast, we see no compelling reason to ascribe isotope fractionation to the coexistence of different oxidation states. We further suggest that published evidence for iron isotopic fractionation in nature and in laboratory experiments may indicate the distortion of low-spin Fe tetrahedral complexes.The isotope geochemistry of transition elements may shed new light on their coordination chemistry. Their isotopic fractionation in the natural environment may be interpreted using models of thermodynamic fractionation.     

Application of the stable-isotope system to the study of sources and fate of Hg in the environment: A review

With the improvement of analytical methods and the development of multiple-collector inductively coupled plasma-mass spectrometry (MC-ICP/MS), research on non-traditional stable isotope (Cu, Zn, Fe, Se, Mo, Cr, Hg) in geochemistry has made tremendous progress in the past decade. Recent studies have demonstrated that both organic and inorganic reactions may cause Hg isotope fractionation, and variations of Hg isotopic composition in the environment have been successfully employed to explain Hg pollution history, Hg sources and tracking Hg pathways in nature. Furthermore, Hg isotopic fractionation studies can be a powerful tool in the calibration of global Hg cycling models. Stable isotope geochemistry of Hg is therefore becoming a new frontier subject in earth sciences. Based on summarizing previous research, this paper outlines the main advances in the study of Hg stable isotopes with particular emphasis placed on a brief explanation of Hg isotope analytical techniques, possible Hg isotope fractionation mechanisms observed in both natural and experimental processes, Hg isotope composition variations in different environmental matrices, and the application prospects of the Hg stable isotopes in environmental geosciences.     

Fe-Cu-Zn-Mo同位素示踪氧化还原过程

非传统稳定同位素（Fe-Cu-Zn-Mo）理论与数据相结合提高了科研工作者对地质体系氧化还原过程的理解。本文对这一相对较新的领域进行了综述,包括与氧化还原过程相关的同位素分馏理论和实验约束、时空尺度下的氧逸度以及同位素示踪氧化还原过程。稳定同位素理论预测,Fe-Cu-Zn-Mo同位素应该对氧化还原状态的变化能够做出响应。结果表明,Fe同位素作为岩浆过程、表生过程、俯冲带流体性质"氧逸度计"应用前景广阔;Cu同位素在岩浆、热液、陆地系统可以很好地示踪氧化还原过程;Zn同位素由于络合过程分馏已经被用在许多不同环境中作为含硫/碳流体迁移的敏感示踪剂;Mo同位素作为古氧逸度计可有效重建古海洋-大气氧化还原状态。     

Investigation of matrix effects in the MC-ICP-MS induced by Nb, W, and Cu: Isotopic case studies of iron and copper

Some elements normally occur at trace levels while the majority of natural geological materials may be exceedingly enriched in some special cases, such as the Bayan Obo ore deposit where REE and Nb are extremely enriched. These elements may not be removed completely during purification. Therefore, matrix effects will be caused during stable isotope ratio measurement in the MC-ICP-MS. Experiments have shown that the established methods of chromatographic separation of Cu, Fe, and Zn using AG MP-1 Anion Exchange Resin cannot make ef-fective separation of Nb, W, and Cu from Fe using 20 mL 6 M HCl. It is also observed that the elution curves of W and Cu overlap at working conditions and thus W is present in measurable amounts in some sample solutions. Matrix effects in the MC-ICP-MS induced by Nb, W, and Cu during Fe isotope ratio measurements and by W during Cu isotope ratio measurements were thus investigated by examining their changes in delta values between doped and undoped standards. The results show that the effects of the matrix elements Nb, W, or Cu on Fe isotope ratio measurements are minimal in the case of m(Nb)/m(Fe)<0.005, m(W)/m(Fe)<0.01, or m(Cu)/m(Fe)<0.6. This finding, combined with the extremely low levels of W and Cu, and the fact that nearly 90% of Nb can be removed during purification, demonstrates that the methods of chromatographic separation of Fe established before are suitable for Bayan Obo ore samples and that the methods can be simplified when Cu elution is unnecessary. The effects of the matrix element W on Cu isotope determinations are minimal in the case of m(W)/m(Cu)<0.7. Therefore, W exerts no significant effect on the measurements of Cu isotopes for the majority of natural geological materials.     

Mo稳定同位素研究进展

随着表面热离子质谱(TIMS)和多接收器电感耦合等离子体质谱(MC-ICP-MS)的广泛应用以及同位素分析方法的改进,近10年来非传统稳定同位素(Cu、Zn、Fe、Se、Mo、Cr、Hg等)的研究得到迅速发展.其中,由于Mo同位素的分馏明显受氧化还原条件的控制,使其在指示古环境及古气候的变化方面有独特的地球化学指示意义.同时,Mo同位素在指示成矿物质来源和海洋Mo循环等方面也取得较大成果.因此,Mo同位素地球化学研究已成为国际地学领域的一个前沿和热点.本文综合前人的研究成果,结合近期自己的工作,论述了Mo同位素地球化学研究领域的一些重要进展,详细介绍了Mo同位素的化学分离、提纯和质谱分析技术,并对其应用前景进行了展望.