Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

Use of Thermal Infrared Multispectral Scanner (TIMS) imagery to investigate upslope particle size controls on arid piedmont morphology

Geomorphic differences between slopes backing two distinct desert piedmont types provide a proxy indicator for the kind of landform developed at the corresponding mountain base. Here, the term ‘bedrock pediment’ describes subaerial bedrock platforms that emanate from a mountain base while ‘alluvial slope’ describes suballuvial bedrock platforms that extend from the mountain. Mountain slopes backing bedrock pediments have been demonstrated to be mantled by larger clast sizes than corresponding slopes backing alluvial slopes in the Phoenix region, Arizona, USA. The present research focuses on using the disparate particle sizes between slopes backing bedrock pediments and alluvial slopes as an indicator for the piedmont form developed at the mountain base, and uses high-resolution remotely sensed digital data as a medium for quantitative landform assessments. A gravel + bedrock versus soil index developed from airborne midinfrared multispectral imagery acquired by the Thermal Infrared Multispectral Scanner (TIMS) indicates the presence of slopes mantled with larger particle sizes versus slopes mantled with smaller particle sizes and greater soil coverage. Two test areas confirm the applicability of this method and further demonstrate the usefulness of high-resolution midinfrared multispectral imagery as a geomorphic tool in arid regions.     

中-浅正变质岩锆石SHRIMP法与TIMS法测年结果不一致处理——以滇东南南温河花岗岩为例

变质岩中的锆石大多遭受变质热事件的改造,但中-浅变质岩一般不甚发育新生锆石或变质增生边,不易通过现有的锆石测年技术获得该岩石的变质年龄。中-浅正变质岩的锆石为岩浆锆石与变质增生锆石的混合物,其U-Pb同位素组成可以采用二端元混合模式来表达。利用同位素稀释法(TIMS)可以获得混合锆石U-Pb年龄及对应的同位素组成;结合CL等内部结构分析,利用离子探针法(SHRIMP)可以获得岩浆锆石U-Pb年龄及对应的同位素组成,进而推算出变质增生锆石U-Pb年龄对应的同位素组成。在对滇东南南温河花岗岩锆石U-Pb年代学的研究中,我们发现同一样品的SHRIMP与TIMS U-Pb法测年结果不一致,根据上式推算出后期主变质年龄约为230 Ma,与前人利用其它测年方法获得的结果基本一致,符合研究区主变质期为印支期的区域地质背景。该方法为中-浅正变质岩年代学研究提供了一种新思路。     

Albany K-Feldspar: A New Pb Isotope Reference Material

Lead isotopes are a powerful and versatile tool to elucidate fundamental geological problems related to the formation and evolution of continental crust. K-feldspar is a popular target for Pb isotope measurement as it is prevalent in many rock types and tends to capture the initial Pb isotope composition of its parental magma. We present data for a new Pb isotope reference material: Albany K-feldspar; as well as updated data for Shap K-feldspar. Results of Pb double-spike TIMS for Albany K-feldspar are ²⁰⁶Pb/²⁰⁴Pb = 16.7872 ± 0.0062, ²⁰⁷Pb/²⁰⁴Pb = 15.5640 ± 0.0056, and ²⁰⁸Pb/²⁰⁴Pb = 36.6600 ± 0.0168 (2s). TIMS measurement results for Shap K-feldspar indicate two isotopically distinct Pb populations. LA-MC-ICP-MS, with a spatial resolution as high as 15 μm, indicates a homogeneous Pb isotopic composition in Albany K-feldspar. In accord with previous studies, our results show that scatter in the measured Pb isotope ratios, related to the low natural isotopic abundance of ²⁰⁴Pb, along with the effect of isobaric ²⁰⁴Hg-²⁰⁴Pb interference, increases at lower count rates. However, the mean Pb isotope ratios measured via LA-MC-ICP-MS using a range of spot sizes are in excellent agreement with TIMS results thus highlighting the feasibility of Pb isotope determination via LA-MC-ICP-MS to access geological information preserved in small crystals, including mineral inclusions.     

A Matrix‐Matched Reference Material for Validating Petroleum Re‐Os Measurements

This study presents two matrix‐matched reference materials developed for petroleum Re‐Os measurements. We present the Re and Os mass fractions and ¹⁸⁷Re/¹⁸⁸Os and ¹⁸⁷Os/¹⁸⁸Os values (ratio of the number of atoms of the isotopes) for repeatedly measured aliquots (ca. 120–150 mg test portions) of the NIST Research Material 8505 (RM 8505) crude oil, and its asphaltene and maltene fractions, and ~ 90 g of homogeneous asphaltene powder isolated from this oil. Measurements were performed using the Carius tube‐isotope dilution negative‐thermal ionisation mass spectrometry methodology. The RM 8505 crude oil contains 1.98 ± 0.07 ng g^?1 Re and 25.0 ± 1.1 pg g^?1 Os, with Re‐Os isotope amount ratios of 452 ± 6 for ¹⁸⁷Re/¹⁸⁸Os and 1.51 ± 0.01 for ¹⁸⁷Os/¹⁸⁸Os (n = 20, 95% conf.). The homogeneous asphaltene sample contains 16.52 ± 0.10 ng g^?1 Re and 166.0 ± 0.9 pg g^?1 total Os, and possesses isotope amount ratios of 574 ± 3 for ¹⁸⁷Re/¹⁸⁸Os and 1.64 ± 0.01 for ¹⁸⁷Os/¹⁸⁸Os (n = 24, 95% conf.). The intermediate precision of these data makes the RM 8505 whole oil and the (~ 90 g) homogenised asphaltene appropriate petroleum matrix‐matched reference materials for Re‐Os measurements. The asphaltene fraction of the oil is the main carrier of Re and Os of the RM 8505 whole oil, and caution is suggested in using asphaltene and maltene fractions of a single oil for Re‐Os geochronology.     

U–Pb baddeleyite ages linking major Archean dyke swarms to volcanic-rift forming events in the Kaapvaal craton (South Africa), and a precise age for the Bushveld Complex

The Archean basement in the northeastern part of the Kaapvaal craton is intruded by a large number of mafic dykes, defining three major dyke swarms, which collectively appear to fan out from the Bushveld Complex. Herein we present U–Pb baddeleyite ages for two of these dyke swarms, the northwest trending Badplaas Dyke Swarm and the east-west trending Rykoppies Dyke Swarm, and infer their correlation with tectonic events in the Kaapvaal craton. We also present a U–Pb baddeleyite age for a noritic phase of the Marginal Zone of the Rustenburg Layered Suite (Bushveld Complex).     

微量萤石样品消解技术及其Sm-Nd同位素高精度热离子质谱法测试

Sm-Nd同位素被广泛地应用于萤石样品的定年和示踪。萤石样品Sm-Nd同位素测试的化学分离中,一般采用酸溶解样品,但氢氟酸和硝酸与萤石反应不完全,由于萤石(CaF_2)特殊化学结构导致氟离子会和稀土元素离子形成难溶稀土氟化物,易导致Sm-Nd亏损,因而对于Sm、Nd含量较低的萤石样品,Sm-Nd同位素测试需要较大样品用量(100~200 mg)。本研究建立了一种利用HNO_3+HClO_4+H_3BO_3溶解萤石样品的消解方法,在萤石溶解过程中加入H_3BO_3可有效提高Sm-Nd回收率。实验表明,利用5 mL浓硝酸和0.015 mL高氯酸溶解萤石样品过程中加入1 mL 0.49 mol/L H3BO3效果最佳,结合高灵敏度热电离质谱仪(Triton)可实现微量萤石样品高精度Sm-Nd同位素测试。较先前已有的溶解方法,本方法大大降低萤石样品用量。     

沥青铀矿的年龄测定方法改进

本文对核行业标准方法“沥青铀矿、晶质铀矿的年龄测定方法”进行了改进。主要采用同位素稀释高分辨等离子体质谱法（HR-ICP-MS)测定铀矿物中的铀含量，提高了测量的准确度，提高了分析速度。此外，改进了铀铅分离流程，降低了全流程本底，大大减小了样品用量，提高了TIMS法测定铅同位素组成的准确度。     

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.     

热电离质谱法测定锂同位素的研究进展

锂的两种稳定同位素6Li和7Li存在很大的相对质量差,质量分馏效应十分明显,因此要精确地测定锂同位素比值十分困难。近年来,随着质谱测定方法的发展,锂同位素的测定取得了长足进展。目前,使用热电离质谱仪(TIMS)和多接受电感耦合等离子质谱仪(MC-ICP-MS)测定锂同位素比值的较多。TIMS相比于MC-ICP-MS,其测定精度较高。主要对使用热电离质谱仪(TIMS)测定锂同位素进行了详细的介绍,主要包括带材料和带结构、涂样形式以及电离温度这3方面的研究进展,并指出了此方法存在的一些问题。