稳定氯同位素地球化学研究进展

地球卤素元素含量相对稀少,相对而言氯为最常见的卤素元素。氯是一种挥发性元素,具有强烈的亲水性。自然界氯两个稳定同位素³⁵Cl和³⁷Cl,其相对丰度分别为75.76%和24.24%。文章综述了氯在各个地质储库的特征、稳定氯同位素分馏的控制因素以及氯同位素的地质应用三大方面的研究进展。地球主要储库中蒸发岩、海水、岩浆岩、沉积物、变质岩、地幔的氯同位素组成分别为-0.5‰~+0.8‰、0.00±0.05‰、-1.12‰~+0.79‰、-3.0‰~+2.0‰、-3.6‰~0、-1.9‰~+7.2‰。地外(月球、火星及其他小行星4-Vesta)氯同位素组成变化范围分别为-4‰~+81.1‰、-5.6‰~+8.6‰、-3.8‰~+7.7‰。相对地球上氯同位素(δ³⁷Cl)的变化范围(-14‰~+16‰),月球和火星δ³⁷Cl的变化范围可达-5.6‰~+81‰,表明挥发分氯在地内和地外迁移循环过程中有显著不同同位素分馏主控机制。已经探明氯同位素分馏受控于物理过程(如扩散、离子过滤、沉淀溶解作用、火山作用)和化学作用(如水岩作用、变质作用,尤其是蛇纹石化作用)等。扩散作用、淋滤作用和火山作用富集重同位素,沉淀作用结晶盐δ³⁷Cl先减小后上升,而蛇纹石化过程中多种因素共同影响。与其他指标结合,氯同位素地球化学可用于有效指示钾盐矿床远景区,评估示踪地下水的来源和演化路径、示踪污染物源区和量化生物修复、探究矿化流体来源、指示行星演化岩浆海洋脱气等过程。     

锌稳定同位素地球化学综述

锌是生物生命必需的微量元素和与人类活动息息相关的金属元素。随着样品纯化技术的提高和新一代质谱仪的开发应用,锌同位素体系已成为近年发展起来的金属(非传统)稳定同位素地球化学的一个热点领域,得到国内外学者的广泛研究。对最新的锌稳定同位素研究结果进行了系统总结,分别从分析方法、分馏理论、储库同位素组成以及应用等方面进行了论述。锌同位素已被广泛应用到天体化学、海洋、大气以及地球深部等诸多地球科学研究领域,大大提高人们对全球锌及其他重金属元素生物地球化学循环的认识。锌同位素在宇宙化学、环境地球化学、古气候环境重建以及健康及生物医学领域将具有非常大的应用前景。     

硒同位素地球化学研究进展与应用

多接收杯电感耦合等离子体质谱仪(MC ICPMS)与氢化物发生系统(HG)在线联机自动测样的实现,极大提高了硒(Se)同位素的分析精度和效率,推进了Se同位素地球化学的发展。本文综述了Se稳定同位素研究的最新进展及其在地质与环境中的应用。自然界中Se同位素(δ82/76Se)的变化范围可达-12.40‰~11.37‰。其同位素分馏主要取决于硒氧阴离子团的氧化还原反应,而地表水体与氧化海洋环境中的硒同位素分馏极可能与铁氧化物吸附、浮游生物的吸收有关,均可引起约1‰的分馏,且在吸附/吸收相中均倾向富集Se的轻同位素。黑色岩系中Se同位素尚未明确对古海洋还原环境的指示,但近地表中Se同位素存在的强烈分馏,指示大陆地表发生的氧化还原事件极可能导致Se同位素的明显分馏,使河流相倾向富集Se的重同位素。因此,Se同位素有可能成为了解局域至区域沉积环境的氧化还原条件以及古海洋化学演化的潜在指标。随着其分馏机制的进一步阐明,Se同位素有可能在地球、环境与生命科学中得到更为广泛的应用。     

Stable isotope geochemistry of coals, humic kerogens and related natural gases

Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ¹³C_org, δD_org and δ¹⁵N_org values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C₁/(C₂ + C₃) and by comparing their stable isotope compositions, especially δ¹³C_CH4 and δD_CH4. The δ¹³C_C2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires     

铜同位素地球化学及研究新进展

多接收杯电感耦合等离子体质谱仪(MC-ICPMS)的应用极大地提高了铜(Cu)同位素的分析精度和效率,推进了铜同位素地球化学的发展和应用。文中对Cu同位素地球化学进行了全面的综述,并更新了铜同位素研究的最新进展及其在地质与环境过程中的应用。自然界中铜同位素(δ65Cu)的变化范围可达20‰以上,高温下铜同位素分馏较小,而在低温条件下,铜同位素能产生巨大的同位素分馏,其主要取决于低温下铜的氧化还原反应。作为最重要的金属成矿元素之一、重要的重金属元素和重要的挥发性元素,铜同位素在矿床地球化学、环境地球化学和天体化学领域均显示了巨大的应用潜力。     

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.     

The geochemistry of tungsten in Bulgarian coals

This paper discusses the tungsten geochemistry in coal, based on the behavior of this element in 14 Bulgarian deposits. The W contents range from 0.5–4335 ppm in the ash and from 0.01–784 ppm in the coals. In four of the deposits the tungsten content proved to be 16 to 100 times higher than the Clarke value for sedimentary rocks. No correlation has been found between the W concentration and either the age of the coal-bearing strata or the coal rank. The deposits were divided in three groups on the basis of the relationship between tungsten and ash content. The role of sorption ash and terrigenous ash in tungsten binding was evaluated for each group. The correlation between tungsten and organic matter is demonstrated by the increased contents of tungsten in the ash of the low-ash coals, its concentration in the lighter coal fractions, its extraction from the coals by HF and NaOH only, and by model experiments. Sorption ash concentrates tungsten; terrigenous ash is a carrier of tungsten.Of the petrographic constituents of coal, vitrain was found to concentrate the largest amounts of tungsten.In two of the deposits richest in tungsten, there is a very distinct zonality in its vertical distribution — tungsten concentration decreases from the bottom to the top of the coal bed. This zonality might be explained by the diffusion (syngenetic or diagenetic with respect to the coal-forming process) through the coal bed of aqueous solutions enriched in tungsten.The wide range of variation of the tungsten concentrations, the considerable differences in the mean contents and the dispersions between the individual deposits show that tungsten is very sensitive to the differences of the source area.Coal deposits enriched in tungsten may be expected in the following favourable environments: (1) in areas with nitrogen-bearing thermal waters containing increased amounts of tungsten; (2) source areas with tungsten mineralizations; and (3) country rocks consisting of acid granitoids whose Clarke values of tungsten are the highest as compared to the other types of rocks.     

A contribution to the stable carbon isotope geochemistry of iron meteorites

For most iron meteorites studied, the carbon isotopic composition of nodular graphite falls in the range ?4.8 to ?8.2%. vs PDB and shows a mode between ?5 and ?6%.. Fourteen cohenite analyses from the Magura meteorite fall between ?18.1 and ?19.2%. with a pronounced clustering around ?18.5%.. Carbon of a taenite separate from the same meteorite has an isotopic composition of ?18.8%.; compositions between ?19.7 and ?22.1%. were found for taenite carbon in five other octahedrites. It is suggested that the ¹²C enrichment in cohenite and taenite relative to the nodular graphite is a general phenomenon in iron meteorites, and that the study of ¹³C abundances in iron meteorites may aid in the elucidation of their history. To this end an experimental study of carbon isotope fractionations in the system Fe-Ni-C is essential. The ¹³C content of carbon from several silicate inclusions in the Four Corners and ‘El Taco’ (Campo del Cielo) meteorites is generally similar to the nodular graphite, the ¹²C enrichment (?13%.) in one specimen may be interpreted in terms of a mixing model involving an original inclusion carbon and carbon exsolved from the taenite upon cooling.     

稀有气体与轻稳定同位素气体地球化学的应用研究

稀有气体与CO2、CH4、N2等气体及其同位素的结合研究是近年迅速发展的研究体系。本文综述了2种体系的同位素指标以及CO2/3He、CH4/3He、N2/Ar等比值指标在地质领域的研究与应用情况,简述了N2、O2等气体与稀有气体在探索地球大气演化模式方面的概况。     

Application of heavy stable isotopes in forensic isotope geochemistry: A review

Light stable isotopes have been used for many years to characterize the source and transport of materials. More recently heavy isotope systems such as Sr, Nd and Pb have been added to this list in order to aid source identification. With the advent of multiple collector ICP-MS, the range of isotopic tools now available has increased considerably, however, until the isotope systematics of these new non-traditional isotope systems have become better understood, they will not be as useful in characterizing material source and transportation. Applications using heavy metal stable isotopes (mostly traditional heavy isotopes) have reached most avenues in science, including earth sciences, archaeology, anthropology, animal physiology, ecology and toxicology. This field will continue to grow as new applications are developed and techniques become simpler and quicker. This paper provides a review of how this field has grown and presents two new applications using Pb and Sr isotopes in glazes to determine the source of ore used in glazes, and using Sr isotopes to determine the origin of undocumented deceased Mexican border crossers.     

Environmental geochemistry of calcium isotopes： Applications of a new stable isotope approach

1IntroductionIn nature, calcium has six naturally occurring sta-ble isotopes with atomic mass units (amu) and the a-bundances of40Ca (96.941%),42Ca (0.647%),43Ca (0.135%),44Ca (2.086%),46Ca (0.004%)and48Ca (0.187%) are presented in this paper.These analyt…     

The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.     

海南岛西南几个金矿床成矿流体与稳定同位素地球化学

二甲、抱板、不磨三个金矿床位于海南岛西部，沿北东向戈枕断裂带分布，含金脉体产于中元古代抱板群中，受韧性剪切带控制。其成矿流体是中温（２５０－３５０℃）、低盐度（４ｗｔ％－１０ｗｔ％Ｎａｃｌ）、较富ＣＯ２＋ＣＨ４的流体，氢、氧、硫同位素研究证明主要为变质－混合岩化热液矿床，成矿物质大多来自抱板群矿源层。雅亮伴生金矿位于海南岛南部，沿东西向九所－陵水深断裂分布，同位素研究表明该矿床为一低温（１５０－２     

安徽铜陵小铜官山铜矿床稀土元素和稳定同位素地球化学研究

安徽铜陵铜官山铜矿田是中国长江中、下游铁、铜、硫、金成矿带中著名的夕卡岩型矿床.小铜官山铜矿床位于安徽铜陵铜官山矿田,侵入岩体为铜官山石英二长闪长岩.成矿过程包括夕卡岩阶段、石英-硫化物阶段和石英-碳酸盐阶段3个主要成矿阶段.笔者通过对小铜官山铜矿床的氢、氧、碳、硫、硅同位素组成和稀土元素地球化学特征研究,探讨成矿溶液中水、硅和硫的来源以及成矿溶液的演化问题.研究表明,成矿热液早期以岩浆热液为主,随着成矿过程的进行,加入的大气降水比重越来越大,到晚期可能主要以大气降水为主.硫的来源主要有两个方面,即地层和岩浆热液,但以后者为主.硅具深部岩浆或岩浆热液水来源的特点.稀土元素球粒陨石标准化组成模式为右倾型,夕卡岩、矿石的稀土配分曲线类似于铜官山岩体石英二长闪长岩,故认为形成本区的夕卡岩型矿床的热液流体主要来源于闪长质熔体.     

钙同位素地球化学综述

钙是主要的造岩元素之一,也是生物必需的元素之一,在地球各圈层广泛分布,因此研究钙同位素的地球化学行为有助于提高我们对各种地质过程的认识。特别的是,地表碳酸盐主要是以碳酸钙的形式存在,很大程度上决定了碳循环与钙循环是耦合的。因此,钙同位素是研究碳的再循环的重要示踪剂,可以直接提供深部碳循环的准确信息。和其他非传统稳定同位素体系一样,随着实验技术的进步及多接收电感耦合等离子体质谱(MC ICP MS)和热电离质谱(TIMS)的发展,钙同位素分析方法取得了较大的进步,但目前的测试精度(2 sd)约0.1‰,尚有提升的必要,还需开展更详细的实验工作。目前钙同位素的地质应用主要集中在地球表生低温过程,但高温地质过程中钙同位素的研究越来越引起研究者的兴趣。     

铬稳定同位素地球化学

随着多接收质谱仪分析技术的进步,铬稳定同位素体系在最近二十几年的环境科学和地球化学中得到了越来越广泛的应用。铬元素属于氧化还原敏感元素,在氧化还原反应过程中伴随着较大的同位素分馏。因此,铬同位素在指示现代或古代环境的氧化还原状态方面有着重要的应用。同时,铬也是中度相容和轻度亲铁元素,使得铬稳定同位素体系也可用来制约高温地质过程(如核幔分异、地幔熔融和岩浆分异结晶等)以及地外行星的演化。本综述首先介绍铬稳定同位素体系,随后讲述分析方法、铬同位素分馏原理以及铬同位素在高温、低温地球化学中的应用。     

Sulfur geochemistry of Jurassic high-sulfur coals from Egypt

Jurassic high-sulfur coals from the Maghara area in Egypt were analyzed for the abundance and isotopic composition of different forms of sulfur. Analyses indicated that the sulfur occurs in the form of organic, pyrite, and sulfate forms. Pyrite sulfur represents the major fraction, while sulfate sulfur is minor and could be formed during sample preparation for the analyses.The δ³⁴S CDT values of the organic sulfur are positive ranging between 1.0‰ and 13.5‰ with an average of 9.1‰. Pyrite δ³⁴S values are also positive ranging between 1.5‰ and 15.4‰ with an average of 6.6‰. The high δ³⁴S values of the organic sulfur in the Maghara coals suggest a freshwater origin of the organic components of these coals. The lack of correlation between pyrite and organic sulfur isotopes implies different incorporation mechanisms of sulfur. The high-sulfur contents along with the positive and high δ³⁴S values suggest a marine origin of pyrite sulfur and support the geological interpretation of marine invasion after the peat formation that was responsible for the incorporation of the pyrite sulfur.The occurrence of pyrite as euhedral crystals as well as the high and positive δ³⁴S values of the pyrite sulfur indicates the formation of pyrite during diagenesis as a result of marine water invasion of the preexisting peat in a brackish coastal plain environment.     

Sulphur isotope geochemistry of carbonatites

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

Molecular stable carbon isotope compositions of alkylphenanthrenes in coals and marine shales related to source and maturity

Phenanthrene (PHE) and methylphenanthrenes (MPs) extracted from coaly shale and coal samples containing terrestrial organic matter are compared with the same compounds from marine shales in terms of yields and δ¹³C values at marginally to fully mature stages of thermal evolution. The shales derived from four boreholes in the Hils Half-Graben area, northwestern Germany, were shown to be representative of a greater number of samples from the same sites. The δ¹³C values of extractable PHE and MPs are less negative in the terrestrial (−24.3 to −26.0‰) than in the marine (−28.8 to −30.5‰) samples. Since these values are unrelated to mean vitrinite reflectance (R_r) values in the range of 0.5–0.9%, it appears that the stable carbon isotope composition of PHE and MPs is controlled by organic matter type rather than maturity.     

The geochemistry of the stable isotopes of silicon

One hundred thirty two new measurements of the relative abundances of the stable isotopes of silicon in terrestrial materials are presented. The total variation of ^δ30Si found is 6.2%., centered on the mean of terrestrial mafic and ultramafic igneous rocks, δ³⁰Si = ?0.4%.. Igneous rocks show limited (1.1%.) variation; coexisting minerals exhibit small, systematic silicon isotopic fractionations that are roughly $\text{1}\text{3}$ the magnitude of concomitant oxygen isotopic fractionations at 1150°C. In both igneous minerals and rocks, δ³⁰Si shows a positive correlation with silicon content, as does δ¹⁸O. Opal from both sponge spicules and sinters is light, with $\text{}\text{?}\text{gd}{}^{30}\text{Si}\text{= ?2.3}$ and ?1.4%., respectively. Large ^δ30Si values of both positive and negative sign are reported for the first time from clay minerals (?2.3 to +1.8%.), opaline phytoliths (?1.4 to +2.8%.), and authigenic quartz (+ 1.4%.). All highly fractionated samples were precipitated from solution at low temperatures; however, aqueous silicon is not measurably fractionated relative to quartz at equilibrium. A kinetic isotope fractionation of ≈3.5%. is postulated to occur during the low temperature precipitation of opal and, possibly, poorly ordered phyllosilicates, with the silicate phase being enriched in ²⁸Si. This fractionation, coupled with a Rayleigh precipitation model, is capable of explaining most non-magmatic δ³⁰Si variations. Chert ^δ30Si values are largely inherited, but the primary opal ^δ30Si values can be modified by isotopic equilibration of silicate silicon and dissolved silicon during the transformation of opal into quartz.