Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

激光剥蚀等离子体质谱分析中激光剥蚀参数对信号响应的影响

探讨了激光剥蚀等离子体质谱固体微区分析中激光剥蚀参数对元素分析信号灵敏度及稳定性的影响。这些参数包括激光功率、脉冲频率、剥蚀孔经、散焦距离、剥蚀方式等。讨论了优化的激光剥蚀等离子体质谱信号采集及数据处理方式。在全质量范围内选用具有代表性的元素作为研究对象,建立了激光剥蚀的一般性特征规律和266nm紫外激光系统的最佳操作条件。在选定的激光剥蚀参数下,大多数被测元素的检出限为22.8~457ng/g,能够满足固体微区分析的要求。     

Advances in energy-dispersive X-ray fluorescence

Recently, two new instruments for X-ray fluorescence analysis (XRF) with interesting features for geochemical applications came to the market. Both instruments were designed to improve the peak to background ratio, the principal factor limiting the sensitivity of XRF. Total reflection XRF (TXRF) was designed to analyse extremely small sample amounts. An instrument, using polarised X-rays (P-XRF) for excitation, is designed to reduce scattered background in spectra of bulk samples. The performance of both instruments was compared with conventional XRF-methods and ICP/MS. Results for GXR-1, GXR-2, GXR-3, GXR-4 and GXR-6 obtained with TXRF and P-XRF are in good agreement with literature data. The effective amount of sample, analysed by TXRF was 200 μg only and detection limits of ~ l μg/g were achieved. P-XRF shows considerable improved detection limits (0.25–0.5 μg/g) for bulk samples for elements with atomic numbers 42–51 (Mo-Sb) compared with conventional XRF-methods.     

粤西庙山铜多金属矿床硫化物微量元素LA-ICP-MS原位测定及S同位素对矿床成因的制约

庙山铜多金属矿床是在粤西阳春盆地内新近发现的一处铜多金属矿床。矿体主要呈似层状和透镜状产于泥盆系的陆源碎屑岩和含泥质的碳酸盐岩中。本文以矿石矿物黄铁矿和闪锌矿为研究对象,采用LA-ICP-MS原位微区分析新技术对其微量元素特征进行研究。结果表明,庙山铜多金属矿床中黄铁矿以富Se、Te和As,贫Ni元素为特征,其Co/Ni和S/Se比值特征指示其成因与岩浆热液型矿床密切相关;闪锌矿的微量元素组成指示其主要形成于中高温环境,以富Mn、In、Se,贫Ga、Ge、Tl等元素为特征,总体与国外一些典型的矽卡岩型矿床（如Baita Bihor、Majdanpek、Ocna de Fier和Valea Seaca）相似。同时,闪锌矿的部分微量元素比值（如Zn/Cd、Ga/In等）以及相关的微量元素图解（如Ge-In, Ge-Se等）均表明庙山矿床的成因类型与矽卡岩型矿床一致。硫同位素测试结果表明,矿石的δ34S值较为集中（-0.4‰ ~ +2‰）,平均0.69‰,具有较为明显的塔式分布特征,反映成矿物质具有岩浆来源的特征。以地质现象为基础,结合硫化物原位微区分析和硫同位素数据,我们认为庙山铜多金属矿床属于与岩浆热液有关的矽卡岩型矿床。     

铈硼硅石的微量化学分析法

铈硼硅石是一种罕见的稀土矿物,由于它含有某些化学性质近似的元素,故分析难度较大。本文研究了应用纸色层法和离子选择性电极法对铈硼硅石中某些主要成分和微成分的分离和测定条件,设计了较合理的铈硼硅石微量全分析流程。该流程也适合类似矿物的分析,与常法比较,本法具有快速、准确、成本低和用样少等优点。     

地幔流体及其成矿作用

高灵敏度、高精密度、低检出限、多元素同时检测并可提供同位素组成比值信息的等离子体质谱与高空间分辨率的紫外激光采样技术结合 ,可定量地测定单个流体包裹体中常、微量元素含量 ,为成矿流体的研究提供了一个新的研究手段。文中简要地介绍了激光剥蚀电感耦合等离子体质谱 (LA ICP MS)分析仪器的发展 ,结合实验室的研究工作 ,就激光剥蚀池的设计、单个流体包裹体的剥蚀方法、元素的分馏效率、定量校正技术及其在成矿成因物理化学机制研究中的应用等进行评述 ,并阐述单个流体包裹体元素组成的LA ICP MS分析技术存在的局限和发展趋势。     

Biomass Burning in Southern Africa: Individual Particle Characterization of Atmospheric Aerosols and Savanna Fire Samples

Ambient atmospheric aerosols and savanna fireparticulate emission samples from southern Africa werecharacterised in terms of particle classes and theirnumber abundance by electron probe X-ray microanalysis(EPXMA). About ten particle classes were identifiedfor each sample. The major classes werealuminosilicates and sea salts for ambient coarse(2–10 m equivalent aerodynamic diameter (EAD))samples, and K-S and S-only particles for ambient fine(<2 m EAD) samples. The K-S particles are oneof the major products of biomass burning. The EPXMAresults were found to be consistent with the resultsfrom bulk analyses on a sample by sample basis. Forsavanna fire fine samples, quantitative EPXMA revealedthat many particles had a composition of simple saltssuch as KCl. Some particles had a deviatingcomposition in the sense that more ionic species wereinvolved in sustaining the balance between cations andanions, and they were composite or mixed salts.Because of extensive processing during the atmospherictransport, the composition of the K-S particles in theambient samples was different from K₂SO₄,and such particles were enriched with S. The finepyrogenic KCl particles and the fine sea-saltparticles were much depleted in chlorine.     

Evaluation of a Quality Control Monitor Material for the Routine Electron Probe Microanalysis of Kimberlite Exploration Garnets

Election probe microanalysis of indicator minerals is extensively used in the exploration for kimberlite deposits, the evaluation of specific kimberlite occurrences for their diamond bearing potential and to classify grains into different chemical and lithological mantle associations. Kimberlite exploration programmes can involve several tens of thousands of indicator mineral analyses. Procedures for monitoring data quality and consistency of analyses across large data sets are commonly absent. Suitable monitor minerals should be used to verify the data quality of kimberlite exploration and evaluation data sets. This material should have a suitable composition, be homogenous, be available in sufficient quantities and have a similar appearance to the unknown samples. Garnet P1, a megacryst garnet from the Premier kimberlite, was found to have a suitable composition as a monitor for kimberlite garnet analyses. Data were collected on the monitor material at regular intervals during routine analyses, over an extended period, both as a fixed grain mounted on the sample holder and as separate grains set within batches of routine samples. The data were evaluated to assess the quality and consistency in the analyses of large data sets over time. The monitor material was also analysed at independent laboratories using their routine analytical set-up and calibration procedures for comparative purposes. Values are given for the mean ± 2s range, which can serve as guide values for acceptable analyses for all elements.     

Homogeneity testing of microanalytical reference materials by electron probe microanalysis (EPMA)

Homogeneity testing of candidate reference materials requires distinguishing the effects of measurement uncertainty of the analytical method from true compositional variations within the material. Many in situ microanalytical techniques do not allow classical ANOVA homogeneity testing due to the infeasibility of truly replicated analyses on the same analysis volume. This also applies to the analysis of beam-sensitive and light element-bearing materials by electron probe microanalysis (EPMA). This reality has led me to reconsider the homogeneity index approach used in the testing of microanalytical reference materials by EPMA. Based on statistical considerations, I show that the homogeneity index is suitable for statistical significance testing using F and chi-squared statistics and allows estimating the contribution of compositional heterogeneity to the total uncertainty budget of the referenced values. However, there are problems of bias and masking of small compositional variations by measurement uncertainty. This contribution shows the strong impact of the total number of measurements on the resolution of a microanalytical homogeneity study and discusses how to quantify the relative contribution of heterogeneity to the total uncertainty budget. I present an example of EPMA to illustrate this approach and show some pitfalls and limitations in its application.