Ag, Te and Pd in 17 Geochemical Reference Materials by Mass Spectrometric Isotope Dilution Analysis

Seventeen geochemical reference samples have been analysed for Ag, Te, Pd using mass spectrometric isotope dilution analysis. For most samples, analytical data on these elements were lacking. The concentration range encountered was generally in the nanogram levels.     

1992 compilation of analytical data for rare-earth elements, scandium, yttrium, zirconium and hafnium in twenty-six GSJ reference samples

Abstract: Analytical data for fourteen rare-earth elements, scandium, yttrium, zirconium and hafnium, received by May 1992, have been compiled on twenty-six GSJ (Geological Survey of Japan) reference samples. Seventeen of them are 'Igneous rock series' and nine are "Sedimentary rock series". The reported data including personal communication were evaluated under the consideration on analytical methods and geochemical evidences. No significant difference has been observed between the values obtained by the different analytical methods. Based on the selected available data, 1992 compilation values were tabulated.     

Reference samples for use in analytical geochemistry: their availability, preparation, and appropriate use

A large number of certified and other reference samples are available for use in analytical geochemistry. Certified materials are preferred, but of much more limited availability than other reference samples for most geochemical applications. The availability of rock, sediment, soil, water, and plant reference samples is outlined; ore and mineral separate reference samples are not included in the discussion. The preparation of these materials, including the establishment of certified or recommended concentrations, is then reviewed. It is shown that comparable quality can be achieved for both certified and recommended concentrations, though it has not always been achieved in the past. Finally, the most appropriate ways to use reference samples in quality control and instrumental calibration are discussed.     

Preparation and Characterisation of Two Geochemical Reference Materials: DG‐H (Granite) and AM‐H (Amphibolite) from the Himalayan Orogenic Belt

Two geochemical reference materials of Himalayan origin named DG‐H (a granite) and AM‐H (an amphibolite) prepared by the Wadia Institute of Himalayan Geology Dehradun are described. Both samples were collected from the NW Himachal Himalaya in India. With the participation of analysts from more than forty international laboratories, element determination data collected during the past 10 years for characterisation of the samples was processed to assign working values using statistical procedures in use for this purpose. Earlier work published on these samples is incorporated in the present communication making it an updated document. The typical chemical and petrological characteristics of these two samples may prove useful for method validation and calibration of analytical instruments used for analysing similar rock types, and for widening the analytical range of several analytical methods used for geochemical analysis.     

Geochemical Reference Samples, Drainage Sediment GSD 1 - 8 from China

A set of eight geochemical standard reference samples of stream sediments was prepared. The original purpose was to use these samples as primary standards for the data quality monitoring of a nation-wide regional geochemical survey program in China. But their use has been soon extended to other fields. Forty-one laboratories in China have joined in a collaborative venture to analyse these samples, using a variety of analytical procedures. Recommended values for over 50 trace and minor elements were derived by a method of repetitive elimination of outliers and calculation of central "tendency" from several central values.     

USGS Reference Samples Attapulgite ATT-1 and Bentonite CSB-1

The U.S. Geological Survey has prepared an attapulgite and a bentonite as reference samples because of their economic importance. The attapulgite (ATT-1) is from the Meigs-Attapulgite-Quincy fuller's earth district of Georgia and Florida, and the bentonite (CSB-1) is from the Northern Black Hills bentonite district of Wyoming, Montana, and South Dakota. The chemical and mineralogical properties of these two samples are quite different. Provisional values calculated from the few analytical data and the X-ray diffraction mineralogy are presented for those who wish to use the clays as reference samples.     

Measurements of Rare Earth Element and Other Element Mass Fractions in Environmental Reference Materials (NIST SRM 1646a,NIST SRM 1400, IAEA‐395 and IAEA‐450) by INAA,ICP‐AES and ICP‐MS

INAA, ICP‐AES and ICP‐MS were used to elementally characterise four environmental reference materials – NIST SRM 1646a (Estuarine Sediment), NIST SRM 1400 (Bone Ash), IAEA‐395 (Urban Dust) and IAEA‐450 (Algae). An analytical scheme consisting of the three methods was first applied to NIST SRM 1646a to validate the methodology because it has been extensively analysed and has certified values for many elements. With repeated analyses of NIST SRM 1646a, the accuracy and measurement repeatability of the data obtained were evaluated based on two statistical calculations (zeta‐score and Horwitz ratio) and were observed to be good enough for the analytical scheme to be applied to similar sorts of environmental/geochemical samples. Applying the same approach to NIST SRM 1400, IAEA‐395 and IAEA‐450, enabled mass fractions of 29, 38 and 28 elements to be determined, respectively. Among these results, the data for rare earth elements are of particular interest, not only for IAEA‐450 but also for the other three reference samples. The data for Pr, Gd, Dy, Ho, Er and Tm in NIST SRM 1646a are newly reported in this study. By using small test portions (< 100 mg) for NIST SRM 1646a and IAEA‐395, and recommended minimum amounts for NIST SRM 1400 and IAEA‐450, sample homogeneity was evaluated.     

Strontium, Neodymium and Lead Isotope Analyses of NIST Glass Certified Reference Materials: SRM 610, 612, 614

The NIST glass certified reference materials, SRM 610-617, have been widely adopted by the geological community as calibration samples for a variety of in situ trace element analytical techniques. There is now an urgent requirement for similar reference materials for in situ isotopic analytical techniques. We have analysed SRM 610, 612 and 614 for their Pb, Sr and Nd isotopic compositions using thermal ionisation mass spectrometry. Large differences in isotopic composition were observed between each CRM, suggesting a significant trace element content in the initial starting material (base glass). As a result, isotopic compositions for one CRM cannot be extrapolated to another, and each must be calibrated for use independently. We present the first compilation of working values for these glasses.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

1994 COMPILATION OF ANALYTICAL DATA FOR MINOR AND TRACE ELEMENTS IN SEVENTEEN GSJ GEOCHEMICAL REFERENCE SAMPLES, "IGNEOUS ROCK SERIES"

Analytical data for minor and trace elements published or communicated to us, on seventeen GSJ (Geological Survey of Japan) reference samples, "Igneous rock series" received up to April 1994 are compiled. The data were evaluated statistically in consideration of analytical methods. Based on the selected available data, 1994 recommended and proposed values for 65 minor and trace elements are presented.     

Determination of Thirteen Rare-Earth Elements by High-Performance Liquid Chromatography in Thirty and of K, Rb, Cs, Sr and Ba by Isotope Dilution Mass Spectrometry in Eighteen International Geochemical Reference Samples

This study reports the results of thirteen rare-earth elements in thirty geochemical reference samples. Three alkali (K, Rb, Cs) and two alkaline earth (Sr, Ba) elements were also determined in eighteen reference samples. The analytical procedure involved is based on spiked samples and later measurement of the rare-earth elements by high-performance liquid chromatography and the alkalies and alkaline earths by thermo-quartz mass spectrometric isotope dilution (THQ-MSID). Whenever possible, the results are compared with literature values.     

1996 COMPILATION OF ANALYTICAL DATA ON NINE GSJ GEOCHEMICAL REFERENCE SAMPLES, "SEDIMENTARY ROCK SERIES"

Analytical data compiled on nine Geological Survey of Japan (GSJ) reference samples, "Sedimentary rock series" received by February 1996 are reported. After excluding outliers and examining critically the analytical procedures employed, the data were evaluated statistically. Recommended or preferable values for fifteen major and sixty minor and trace elements are proposed.     

区域地球化学样品分析质量管理计算机控制

使用通用的Microsoft Office系统中的Excel软件,根据不同项目及不同元素的内检质量和一级标准物质质量,判断分析测试质量。对区域地球化学样品分析测试质量进行计算机及局域网质量控制,利用Access工具建立数据库,编制一级标准物质质量控制表、密码检查质量控制表,制作质量监控图及打印检测报告等质量监控体系,实现对化探样品分析数据质量的管理。     

DETERMINATION OF MINOR AND TRACE ELEMENTS IN FOUR CANADIAN IRON FORMATION STANDARD SAMPLES FER-1, FER-2, FER-3 AND FER-4 BY INAA AND ICP-MS

Analytical data on samples FeR-1, FeR-2, FeR-3 and FeR-4 obtained by instrumental neutron activation analysis and by inductively coupled plasma mass spectrometry are presented. The applied methods are described, and the analytical problems associated with their use are discussed. The accuracy of the two methods is demonstrated by comparing the results with the recommended values of the iron formation reference sample, IF-G. For the four FeR samples a set of values summarizing all data obtained by the two analytical methods is also given.     

Preliminary Characterisation of New Reference Materials for Microanalysis: Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5

Four silicate glasses were prepared by the fusion of about 1 kg powder each of a basalt, syenite, soil and andesite to provide reference materials of natural composition for microanalytical work. These glasses are referred to as ‘Chinese Geological Standard Glasses’ (CGSG) ‐1, ‐2, ‐4 and ‐5. Micro and bulk analyses indicated that the glasses are well homogenised with respect to major and trace elements. Some siderophile/chalcophile elements (e.g., Sn, Pt, Pb) may be heterogeneously distributed in CGSG‐5. This paper provides the first analytical data for the CGSG reference glasses using a variety of analytical techniques (wet chemistry, XRF, EPMA, ICP‐AES, ICP‐MS, LA‐ICP‐MS) performed in nine laboratories. Most data agree within uncertainty limits of the analytical techniques used. Discrepancies in the data for some siderophile/chalcophile elements exist, mainly because of possible heterogeneities of these elements in the glasses and/or analytical problems. From the analytical data, preliminary reference and information values for fifty‐five elements were calculated. The analytical uncertainties [2 relative standard error (RSE)] were estimated to be between about 1% and 20%.     

Reference Samples in Geology and Geochemistry

The report discusses some history of analytical problems that resulted in early standards. Geologic samples of economic interest and general information are discussed by country of origin, whereas geochemical samples are mentioned by samples types and by their intended use. Numerous topics and problems for reference samples and their data are discussed.     

Report (1980) on Three GIT-IWG Rock Reference Samples: Anorthosite from Greenland, AN-G; Basalte d'Essey-la-Côte, BE-N; Granite de Beauvoir, MA-N

Three rock reference samples, Anorthosite AN-G, Basalt BE-N and Granite MA-N were analysed for their chemical composition by 122 laboratories belonging to the International Working Group "Analytical Standards of Minerals, Ores and Rocks" (IWG). 243 analysts took part in this first collaborative study which lasted only nine months, from June 1979 to March 1980. Despite this very short period, it has been possible to harvest over 6000 units of analytical data on major, minor and 53 trace elements. This excellent performance of the IWG members has rendered possible the chemical characterization of the three samples for not only the usual major and minor elements but also for 30 trace elements. This first study by the IWG Members demonstrates well their immense analytical potential and is exemplary in many respects.     

Determination of Trace Elements (Ag, B, Ge, Mo, Sn, W, Tl) in Reference Samples of Soils and Bottom Sediments by Atomic Emission Spectrometry: A Traceability and Fitness-for-Purpose Study

Reference samples of soils from the Institute of Applied Physics, Irkutsk (RIAP), the Institute of Geochemistry, Irkutsk (IGI) and the United States Geological Survey, Reston (USGS) were analysed with the aim of determining Ag, B, Ge, Mo, Sn, Tl and W abundances by an atomic emission method with air-stabilised D.C. arc excitation. Two series of reference samples of soils and bottom sediments, GSS-1-8 and GSD-1-12 (IGGE), were used to ensure the traceability link for the analytical results. Traceability was also demonstrated through the comparison of measured results by AES and ICP-MS methods. It is shown that the reference samples GSS-1-8 and GSD-1-12 satisfied the "fitness-for-purpose" criterion (uncertainty U of the certified value should be one-third to one-tenth the magnitude of routine laboratory data uncertainty S (S/U > 3-10)) and can be applied for calibrating AES techniques.     

Preparation of Reference Samples of Mineral Raw Materials and Their Use In Analytical Practice

47 reference samples of mineral raw materials were prepared by collaborative work of Czechoslovak geological laboratories; these reference samples include silicates, feldspars, kaolin, clays, fluorspars, baryta, carbonates, siliceous materials, ores of Pb-Zn, Cu, Sb, Eg, Sn-W and Ag-Au. The pulverized samples were tested for homogeneity using analysis of variance. The analytical results were evaluated statistically; arithmetic mean, its confidence interval and values of precision and accuracy of the individual determinations were computed. Some analytical problems which were encountered during this study and which require further research work are also reported.