地质钻探中的井漏及堵漏材料研究

通过对钻探过程中井漏的复杂地质因素分析,提出了水化膨胀复合材料体系,并对该体系进行了膨胀性、封堵性及复合桥接堵漏模拟实验。实验结果表明,堵漏材料PAR具有很强的吸水膨胀性能,可膨胀至原体积的几十倍,且时间快有利于形成快速的封堵。材料PAR与稻谷和锯末形成的复合堵漏材料具有很强的堵塞率,可达70%以上。承压堵漏测量装置中测试表明:复合堵漏体系不仅能形成封堵,而且能够承受一定的压差。在云南临仓市勐简乡铅锌矿钻探过程中,运用复合堵漏体系满足了该地区复杂地矿钻探需要。     

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.     

GGR Biennial Review: Atomic Absorption,Inductively Coupled Plasma-Atomic Emission Spectrometry,Neutron Activation Analysis and X-Ray Fluorescence Spectrometry Review for 2008–2009

This review describes developments major and in trace element determination using atomic absorption spectroscopy (AAS), inductively coupled plasma-atomic emission spectrometry (ICP-AES), instrumental neutron activation analysis (INAA), and X-ray fluorescence (XRF) spectrometry that were reported in 2008 and 2009. Publication levels were comparable to those of previous years, except for XRF which showed an increase in the number of articles published in the past 2 years. In terms of number of publications and impact, the most active field was AAS, while INAA was the least active. As expected for well-established and mature methods, novel developments for all four analytical techniques were relatively sparse. For AAS, the most notable publications concerned developments in sample introduction, particularly focussing on solid samples, increasing analyte sensitivity, and higher sample throughput. For ICP-AES, publication of developments in sample introduction, remediation of matrix effects and calibration continues. Compared with past years, there was a clear focus on sample preconcentration methods, but very few publications reporting new hyphenated speciation methods. For INAA, there were several publications exploring the accuracy and robustness of the method, as well as the requirements for INAA to meet criteria for a primary method of measurement. Two other related techniques, delayed neutron activation analysis, and prompt gamma activation analysis, were also described. Hyphenated XRF techniques showed interesting developments in enabling XRF and XRD analysis on the same spot, and further work characterising and calibrating three-dimensional micro-XRF shows promising results for investigating sample heterogeneity.     

Accurate and Precise Elemental Abundance of Zinc in Reference Materials by an Isotope Dilution Mass Spectrometry TIMS Technique

A thermal ionisation mass spectrometric technique enabled the abundance of Zn in geological and biological reference materials and water samples to be measured by double spiking isotope dilution mass spectrometry enriched in the ⁶⁷Zn and ⁷⁰Zn isotopes. In the past, thermal ionisation mass spectrometry proved to be difficult for low-level zinc isotopic measurements. The size of Zn samples used for isotopic determination, in particular the biological RMs, represents an important breakthrough. These results represent the most accurate and precise concentrations measured for Zn in these samples. The maximum fractional uncertainty was that for TILL-3 (2%), while the minimum fractional uncertainty was 0.7% for both BCR-1 and W-2. The inhomogeneity of Zn in HISS-1 was revealed while other reference materials appeared homogeneous at the 95% confidence uncertainty. The certified concentration of Zn in HISS-1 and IMEP-19 by their producers are 28% and 3.8% higher than the values measured in this work. These are the first Zn concentration measurements in these materials by the isotope dilution-TIMS technique, except for BCR-1, NIES N^o 9 and IMEP-19. Reducing the blank enabled accurate measurement in water at the ng g^-1 level demonstrating the applicability of the technique for low-level Zn samples.     

Sulfur Concentration in Geochemical Reference Materials by Solution Inductively Coupled Plasma‐Mass Spectrometry

With implications for the origin of ore deposits, redox state of the atmosphere, and effects of volcanic outgassing, understanding the sulfur cycle is vital to our investigation of Earth processes. However, the paucity of sulfur concentration measurements in silicate rocks and the lack of well‐calibrated reference materials with concentrations relevant to the rocks of interest have hindered such investigations. To aid in this endeavour, this study details a new method to determine sulfur concentration via high mass resolution solution inductively coupled plasma‐mass spectrometry (ICP‐MS). The method is based on an aqua regia leach, involving relatively rapid sample preparation and analysis, and uses small test portion masses (< 50 mg). We utilised two independently prepared standard solutions to calibrate the analyses, resulting in 4% accuracy, and applied the method to eight geochemical reference materials. Measurements were reproducible to within ~ 10%. Sulfur concentrations and isotopes of six reference materials were measured additionally by elemental analyser‐combustion‐isotope ratio mass spectrometry to independently evaluate the accuracy of the ICP‐MS method. Reference materials that yielded reproducible measurements identical to published values from other laboratories (JGb‐1, JGb‐2 and MAG‐1) are considered useful materials for the measurement of sulfur. Reference materials that varied between studies but were reproducible for a given test portion perhaps suffer from sample heterogeneity and are not recommended as sulfur reference materials.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

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.     

国际标准物质数据库COMAR及有证标准物质

有证标准物质（CRMs）是具有准确量值的测量标准,在分析方法研究和评价、定性和定量分析、矿产勘查、仲裁检验、质量监督检验等领域发挥着重要的作用。20世纪80年代成立的国际标准物质数据库（COMAR）是目前国际上最大的CRMs数据库,收录来自25个成员国274个生产机构提供的CRMs数量超过10200种。本文从CRMs的数量、分类、发展变化等角度全面评述了国际数据库COMAR,阐述了欧盟组织、美国、中国、日本、澳大利亚等成员国的标准物质研究情况。英、美、法、德等国家的标准物质研究开展较早,研究水平高,处于世界领先地位;中国、日本等亚洲国家标准物质的发展虽起步晚,但发展迅速,已成为向COMAR提供CRMs最多的两个国家,分别为1194种和1456种（截至2013年8月）。COMAR建立以来,工业、有色金属和物理特性三大传统应用领域的CRMs占COMA数据库总CRMs的份额一直较大,比例始终保持50%以上,其中工业领域的CRMs数量最多,占19%;有机、生物与临床类CRMs所占份额最少,仅为7%和3%。随着社会需求的增加,生物与临床、生活质量领域标准物质成为未来标准物质发展的热点方向。本文指出,未来标准物质的发展将由过去的钢铁、有色金属、物理特性等传统领域逐渐转向食品安全、环境保护、气候变化、临床医学、制药产业、生物能源等新兴领域,标准物质的研究制备、定值及不确定度将面临新的技术挑战。     

脉状铅锌（铜、银）多金属热液矿床研究进展

目前在矿床学分类研究中对沉积岩容贱金属矿床的命名和分类尚未统一,其中一类赋矿围岩为沉积岩、矿体受构造(断层、褶皱等)控制呈脉状产出的、成矿金属为铅锌铜银多金属的矿床成为缺失环节,缺少系统的归纳总结。但该类矿床是造山作用的产物,对其进行归纳综合分析,有助于了解造山作用中的矿质迁移和沉淀过程。本文将该类矿床资料收集,对其成矿特征、控矿构造、成矿流体、矿质来源等进行分析总结。研究表明,此类矿床与造山作用或造山带有着紧密的联系。成矿物质表现为多源性,包括基底围岩、岩浆来源以及幔源贡献。成矿流体具有岩浆流体、变质流体、盆地卤水等多种来源,部分矿床的成矿流体受大气水影响。该类型矿床与MVT铅锌矿床有相似之处,但在成矿环境、控矿因素、金属来源以及成矿流体来源等方面有较大差异。     

Determination of trace and rare-earth elements in Chinese soil and clay reference materials by ICP-MS

Inductively coupled plasma mass spectrometry(ICP-MS) has become a powerful tool for providing reliable analytical results in many laboratories around the word. In this study, the mixture of HF and HNO3 acids in high-temperature and high-pressure closed-vessel digestion technique were used to decompose some Chinese reference materials, and thirty seven elements were determined by ICP-MS. Most of the results for Chinese soil reference materials were found to be in reasonable agreement with the reference values, except Cs, Ta, Li, Ge, Zn, Nd, Tb and Ta whose values need to be revised. Their precisions were typically lower than 5% RSD. However, the Precisions of Chinese clay reference materials, especially for GBW03102 and GBW03102a, were significantly different with reference values, probably reflecting the existence of a coarser-grained fraction(70 μm) in samples, and the formation of fluorides in Al-rich samples during sample decomposition by using the mixture of HF and HNO3 acids. Moreover, thirty-seven trace elements covering the mass range from Li to U in four Chinese clay reference materials were firstly provided with good precision and accuracy in this study.