Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

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。     

Preliminary Results from a New 157 nm Laser Ablation ICP-MS Instrument: New Opportunities in the Analysis of Solid Samples

Preliminary results are given from an excimer 157 nm laser ablation multiple-collector inductively coupled plasma-mass spectrometer (LA-MC-ICP-MS), used for the isotopic measurements of solid materials. Elements of geological interest with different volatilities such as Pb and U (e.g. zircon geochronology) and Cu and Zn (as examples of geochemical/biochemical tracers) were analysed. The range of ablation rates of 20-150 nm s^-1 enabled us to ablate the sample down to a depth of 45 μm for a 50 μm diameter pit. The Cu and Zn isotopic measurements gave values that were very stable with, on average, a 0.01 % standard error, comparable with that achieved in liquid mode measurements.     

The Origin and Evolution of Silica-saturated Alkalic Suites: an Experimental Study

Experimental simulation of incremental crystal fractionationof a hy-normative hawaiite indicates that the spectrum of compositionsfrom mildly alkalic hawaiite to sodic rhyolite found in silica-saturatedalkalic suites of the ocean islands and continental hotspotsand rifts can be produced by fractionation at 9·3 kbarwith bulk water contents >     

A method for calculating effective bulk composition modification due to crystal fractionation in garnet-bearing schist: implications for isopleth thermobarometry

Quantitative P–T path determination in metamorphic rocks is commonly based on the variation in composition of growth‐zoned garnet. However, some component of growth zoning in garnet is necessarily the result of an effective bulk composition change within the rock that has been generated by crystal fractionation of components into the core of garnet. Therefore, any quantitative calculation of the P–T regime of garnet growth should be completed using an accurate assessment of the composition of the chemical system from which garnet is growing. Consequently, a method for calculating the extent of crystal fractionation that provides a means of estimating the composition of the unfractionated rock at any stage during garnet growth is developed. The method presented here applies a Rayleigh fractionation model based on measured Mn content of garnet to generate composition v. modal proportion curves for garnet, and uses those curves to estimate the vectors of crystal fractionation. The technique is tested by calculating the precision of the equilibrium between three garnet compositional variables within the chemical system determined to be appropriate for each of a series of microprobe analyses from garnet. Application of the fractionation calculations in conjunction with the P–T estimates based on intersecting compositional isopleths provides a means of calculating P–T conditions of garnet growth that is based on individual point‐analyses on a garnet grain. Such spatially precise and easily obtainable P–T data allow for detailed parallel studies of the microstructural, the P–T, and the chemical evolution of metamorphosed pelites. This method provides a means of studying the dynamics of orogenic systems at a resolution that was previously unattainable.     

对稳定同位素地球化学一个基本原理的反思

用基于Urey模型的量子化学从头计算,揭示Fe在FeCN63-和FeCN46-中的不同“自旋态”对同位素分馏行为的巨大影响,说明了只考虑“价态”的做法是不正确的,修正了关于“重同位素倾向于富集在高价化合物中”的这个广泛被接受的基本原理。并首次指出在压力导致自旋态变化的地质过程中,必定存在同位素分馏反常的复杂状况,是值得进一步研究的方向。     

稳定同位素分馏蒸汽压效应的计算方法

稳定同位素分馏的蒸汽压效应（vaporpressureisotopeeffects,简称VPIE）,在地球化学和天体化学上有着非常重要的研究意义。大部分情况下,由于轻重同位素体具有不同的蒸汽压,在经历挥发和蒸发过程时,含有重同位素的物种挥发得慢,轻同位素物种挥发得快,最终结果导致凝聚相富集重同位素,气相含有较多的轻同位素。在地球化学上,VPIE直接同非常重要的地学参数——同位素平衡分馏系数仅联系在一起。本文应用Bigeleisen提出的方法,直接将VPIE和约化配分函数比（RPFR）相联系,只需要通过理论计算获得两种物质的简谐振动频率,就能够得到非高压情况下该物质的VPIE。本文以水和硫镉矿（CdS）为例,详细介绍了如何计算蒸发和气化过程VPIE的方法,并指出了其在天体化学和矿床学中的一些潜在应用。     

有机碳同位素示踪古环境变化研究

对有机碳同位素示踪环境变化的原理、研究对象、取得的进展和存在的问题等进行了详细研究，认识到C～H键比C-O键有利于富集^12C，从而导致生物或有机碳δ^13C为极低的负值，使有机碳与无机碳之间存在显著的碳同位素差异。光合作用类型的不同使植物分为C3，C4和CAM3种类群，并导致不同类群的植物具有不同的碳同位素组成，C3植物δ^13C=-20‰～-32‰，平均-28‰，而C4植物δ^13C=-9‰～-17‰，平均-14‰。气候环境的差异影响了光合作用的类型和强度，使不同环境的植物类群特征不同，不仅造成植物组合的碳同位素组成不同，而且导致不同食性的动物牙齿等化石的碳同位素组成的差异，甚至相应的无机碳同位素的变化，因此生物链及其衍生物的碳同位素研究也就成为反演某一地区或某一时期气候环境的有效手段。被作为研究对象的地质记录可分为有机和无机两类，有机类主要包括树轮等植物化石、牙齿等动物化石、煤等陆相沉积有机质、海相沉积有机质、土壤(前者的衍生物)，这些研究对象分别适合于目的不同的环境研究，并获得了较好的效果。进而发现有机碳同位素在研究重大生物灭绝事件、C4植物起源、地球早期生命起源、地外生命存在与否、矿产资源形成时的有机质作用等问题上将有重要作为。     

多接收电感耦合等离子体质谱Cu同位素测定中的干扰评估

多接收电感耦合等离子体质谱（MC—ICP—MS）是高精度测定铜同位素的新方法,然而在测定中也可能存在干扰。为此对MC—ICPMS Cu同位素测定中的可能干扰进行了评估。主要包括以下方面的内容：（1）对所用标准物质和试剂进行了纯化,所用标准物质和试剂对Cu同位素的同质异位素干扰可以忽略;（2）运用K和／参数进行了讨论,其中K为样品中的Cu浓度与标准溶液中Cu浓度的比值,f为在一定Cu浓度的标准溶液中干扰信号相对于^63Cu真实信号的比值。理论模拟表明,当K值小于1时,即使在质量为63处的干扰很小,对ε^65 Cu的影响也可能很大;（3）通过对理论模拟结果与实际测定结果的对比,发现对所用的试剂而言质量数为65的干扰可以忽略不计;（4）实际测定结果表明,当样品中Cu的浓度是标样中Cu的浓度的0．5～4倍时,测试获得的样品的ε^65值与其真值在误差范围内一致;（5）对潜在的基质效应重点研究了Fe和Co对Cu同位素测定的影响。实验结果表明,当Fe／Cu〈100,Co／Cu〈7时,Fe,Co不影响Cu同位素比值的测定;（6）10个月的重现性研究结果为ε^65=3．5±1．0（2SD）。该测定值在误差范围内与文献报道的值一致     

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco,Guerrero (southern Mexico): A multi-isotopic approach

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments.