Boron Isotopic Analysis of Proposed Borosilicate Mineral Reference Samples

This brief contribution presents new boron isotopic data for a set of proposed borosilicate reference minerals, most of which are described in the companion paper by Dyar et al.²⁰⁰¹. The results for a variety of minerals (tourmalines, danburite, prismatine, serendibite, ferroaxinite and a Li mica) show that it is generally possible to reproduce the ¹¹ B/¹⁰ B ratio within ± 0.5 per mil with replicate chemistry and mass spectrometry over long time spans. Because the accuracy of boron isotopic analysis is commonly determined by reference to secondary standards, it is suggested that some of the samples used in this study be adopted for interlaboratory comparisons and for quality control on boron isotopic analyses produced by a variety of analytical methods.     

Boron Determination in Twenty One Silicate Rock Reference Materials by Isotope Dilution ICP-MS

The concentration of boron was determined in twenty one geochemical reference materials (silicate rocks) by isotope dilution inductively coupled plasma-mass spectrometry. Boron was extracted from the rocks using HF digestion, suppressing boron volatilisation through boron-mannitol complexation. Sample solutions, in a diluted HCl matrix, were analysed by ICP-MS without any separation of boron from the matrix elements. The results obtained were in agreement with the literature data and indicate that using the described procedure, trace amounts of boron can be very easily determined in complex matrices with rapidity and precision. With the instrumentation and reagents used in this study, this procedure can be used for the determination of 0.5 μg g⁻¹ boron in a 15 0 mg silicate rock sample. Replicate analyses of the twenty one geochemical reference materials (GRM), ranging in boron concentration from 1.35 to 15 7 μg g⁻¹, yielded precisions (relative standard deviation) varying between 0.9 and 9.8%.     

A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

长江口咸淡水混合过程中溶解态硼的含量及同位素组成特征

采用Cs2BO2^ -石墨技术对长江口咸淡水混合过程中溶解态的硼同位素组成进行了测定,得到混合水的δ^11B的变化范围是39．9‰～12．δ^11‰,硼浓度的变化范围是2．07～O．0429μg／mL。结果表明,混合水的硼浓度和δ^11B均随离长江口岸距离的增加而增加,但硼浓度与其它所有水化学成分一样,只呈线性关系而增加。而δ^11B值是呈对数关系而增加,即在混合的初期,混合水的δ^11B值随海水的掺入而急剧增加至海水的δ^11B值后趋于稳定。混合水δ^11B值的这种变化是长江淡水与海水简单混合的结果。     

GeoReM: A New Geochemical Database for Reference Materials and Isotopic Standards

We have developed a new database named GeoReM ( http://georem.mpch-mainz.gwdg.de ) for reference materials and isotopic standards of geochemical and mineralogical interest. Reference samples include rock powders originating from the USGS, GSJ, GIT-IWG, synthetic and natural reference glasses originating from NIST, USGS, MPI-DING, as well as mineral (e.g., 91500 zircon), isotopic (e.g., La Jolla, E&A, NIST SRM 981), river water and seawater reference materials. GeoReM is a relational database, which strongly follows the concept of the three EARTHCHEM databases. It contains published analytical and compilation values (major and trace element concentrations, radiogenic and stable isotope ratios), important metadata about the analytical values, such as uncertainty, uncertainty type, method and laboratory. Sample information and references are also included. Three different ways of interrogating the database are possible: (1) sample names or material types, (2) chemical criteria and (3) bibliography. Some typical applications are described. GeoReM currently (October 2005) contains more than 750 geological reference materials, 6000 individual sets of results and references to 650 publications.     

Compilation of Boron Concentration Data for NBS, USGS and CCRMP Reference Materials

Boron concentration data on 69 different biological, coal and geological reference materials issued by NBS, USGS and CCRMP have been collected from 1951-1986. Data from 135 journal articles and technical reports are included. These data are summarized in consensus (mean) values with uncertainties expressed as pm one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables.     

有孔虫中硼的分离及其同位素组成测定的初步研究

本文初步建立了一种用硼特效树脂和阴、阳混和离子交换树脂相结合进行有孔虫中硼的分离和同位素测定的方法。该方法适用低硼含量 (纳克级 )的微体古生物中的硼的分离和同位素测定 ,分离过程不产生同位素分馏 ,满足了正热电离质谱法测定硼同位素的要求。     

微区原位Sm-Nd同位素体系分析技术及其地质应用

微区地球化学是近年来迅速发展的地球化学分支.系统介绍了矿物微区原位Sm-Nd同位素分析技术的发展过程与现状,重点总结了目前主要的适用测试对象(如磷灰石、榍石、独居石和褐帘石等)和质谱测量过程中同量异位素干扰(包括144Sm对144Nd,130Ba16O对146Nd等)的校正方法,并展示了应用微区原位Sm-Nd分析进行年代学和造山带隆升-剥蚀定量研究的部分成果,这些应用实例充分显示了该方法在地球科学研究中所具有的重要意义.     

Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

Multi-Element Isotope Dilution Sector Field ICP-MS: A Precise Technique for the Analysis of Geological Materials and its Application to Geological Reference Materials

We present a multi-element technique for the simultaneous determination of twelve trace elements in geological materials by combined isotope dilution (ID) sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) following simple sample digestion. In addition, the concentrations of fourteen other trace elements have been obtained using the ID determined elements as internal standards. This method combines the advantages of ID (high precision and accuracy) with those of SF-ICP-MS (multi-element capability, fast sample processing without element separation) and overcomes the most prevailing drawbacks of ICP-MS (matrix effects and drift in sensitivity). Trace element concentration data for BHVO-1 (n = 5) reproduced to within 1–3% RSD with an accuracy of 1–2% relative to respective literature values for ID values and 2–3% for all other values. We have applied this technique to the analysis of seventeen geological reference materials from the USGS, GSJ and IAG. The sample set also included the new USGS reference glasses BCR-2G, BHVO-2G and BIR-1G, as well as the MPI-DING reference glasses KL2-G and ML3B-G, and NIST SRM 612. Most data agreed within 3–4% with respective literature data. The concentration data for the USGS reference glasses agreed in most cases with respective data of the original rock powder within the combined standard uncertainty of the method (2–3%), except the U concentration of BIR-1G, which showed a three times higher concentration compared to BIR-1.     

黔西罐子窑铅锌矿床Pb同位素研究及地质意义

罐子窑铅锌矿床位于川、滇、黔铅锌成矿区东缘,矿体赋存于上泥盆统-下石炭统的白云质灰岩和白云岩中,呈似层状或陡倾斜脉状产出。在分析该矿床成矿地质条件的基础上,系统研究了矿石和围岩的Pb同位素组成特征,探讨了成矿时代与成矿物质来源。研究结果表明,该矿床矿石Pb同位素组成稳定,属于正常普通铅,利用H-H法计算获得了矿脉铅的主模式年龄150~169 Ma。研究表明该矿石Pb模式年龄应该代表矿床成矿年龄,反映Pb主成矿期在燕山期,燕山期NE向断裂(带)控制着本区铅锌矿体(点)的分布。同位素示踪结果显示本区矿石Pb同位素具有多来源特征,不同时代的碳酸盐岩围岩和基底岩石均为罐子窑铅锌矿床提供了成矿物质。综合研究认为,川、滇、黔铅锌成矿区内铅锌成矿具有多阶段、多旋回性,构造与同位素年代学均揭示,该成矿区存在较大规模的燕山期铅锌成矿作用,在今后的找矿研究工作中应当充分重视。     

Comprehensive Chemical and Isotopic Analyses of Basalt and Sediment Reference Materials

Geochemical studies of geological samples require the precise determination of their major and trace element contents and, when measured, of their isotopic compositions. It is now commonly accepted that the accuracy and precision of geochemical analyses are best estimated by the concomitant analysis of international reference materials run as unknown samples. Although the composition of a wide selection of basalts is relatively well constrained, this is far from being the case for sedimentary materials. We present here a comprehensive set of major and trace element data as well as Nd, Hf, Sr and Pb isotopic compositions for thirteen commonly used international reference materials – eight magmatic rocks (BHVO‐2, BR, BE‐N, BR 24, AGV‐1, BIR‐1, UB‐N, RGM‐1) and five sediments (JLk‐1, JSd‐1, JSd‐2, JSd‐3, LKSD‐1). We determined the concentrations of over forty elements in the magmatic rocks together with Sr, Nd, Hf and Pb isotopic compositions. Our trace element results were both accurate (difference ≤ 3%) and precise (reproducibility at 1s ≤ 3%) and the isotopic results were very similar to other published values. In contrast, we observed a significant chemical and isotopic variability in the sedimentary materials, which we attribute to mineral heterogeneities in the powders. Despite the limitation imposed by this heterogeneity, our work presents a complete set of data determined with a precision not yet achieved in the literature for sedimentary material. We also provide the first Nd, Hf and Pb isotopic measurements for the five sediments, which are commonly used by the geochemical community. Our study of both basalt and sediment reference materials represents a comprehensive and self‐consistent set of geochemical data and can therefore be considered as a reference database for the community.     

直接熔融热电离质谱法测定硼硅玻璃中硼同位素比值

硼硅玻璃是目前压水堆应用最多的可燃毒物材料,产品中硼同位素组成的准确测定对燃耗预估及产品质量判定具有重要意义。文章基于直接熔融热电离质谱法,首先探讨了硅元素对硼酸中硼同位素测量结果的影响,结果表明:Si/B质量比小于9时,硅对NIST 951a硼酸标准物质测量结果无显著干扰,采用直接熔融热电离质谱法测定核电用硼硅玻璃中硼同位素比值具有可行性;随后,详细分析了Na/B摩尔比、甘露醇和石墨加入量3个参数对测试结果的影响,得到的最佳参数为Na/B摩尔比9、加入甘露醇及3μL石墨发射剂;最后,采用优化测试参数,对实际硼硅玻璃样品进行了测试,并以NIST 951a硼酸标准物质为外标对测量结果进行分馏校正,结果发现分馏校正后样品的不确定度来源主要是标准物质。研究成果可满足硼硅玻璃的燃耗预估及产品质量的快速判定需要。