Re-evaluation of Reference Materials, IGS 21-39

The 20 ore and concentrate reference materials originally issued by the Institute of Geological Sciences (as it then was) in 1977 have been reevaluated using robust as opposed to classical statistical techniques. The opportunity has also been taken to correct minor errors and to incorporate any new data. One material, the nickel concentrate, IGS 20, has been withdrawn due to incipient oxidation. A total of 24 elemental concentrations in the remaining 19 samples have received revised values.     

疑源类Ammonidium Lister 1970与相关种的厘定及其生物地层和古地理意义

许多可归为疑源类Ammonidium Lister 1970的种被前人划为Multiplicisphaeridium Staplin,1961、Baltisphaeridium Eisenack 1958 ex Eisenack 1959及其他相似属,在某种程度上缩小了其原有定义范围. 报道了采自新疆西准噶尔洪古勒楞组下段保存良好的Ammonidiumloriferum、A. sprucegrovense,通过相关文献引证对比,并结合剖面部分该属标本化石,对Ammonidium属征作了修订.根据新属征特点,将Caiacorymbifer Tappan and Loeblich, 1971,Gracilisphaeridium Eisenack and Cramer, 1973,Naevisphaeridium Wicander, 1974, Puteoscortum Wicander and Loeblich, 1977,Craterisphaeridium Deunff, 1981, Pertusisphaeridium Turner,1986和Martinsphaeridium Sarjeant and Vavrdová,1997等相似属纳入Ammonidium属的晚出异名.Ammonidium sprucegrovense var. polyankistrum Wicander and Loeblich, 1977由种级降为了变种级.建立1个新种:Ammonidium levigatum n. sp.,前人报道的部分标本被误归为A.loriferum或A. sprucegrovense.新种Ammonidium levigatum n. sp.在全球晚泥盆世古大陆边缘具有全球分布特征,是识别晚泥盆世疑源类的标准化石之一.      

发射光谱法测定岩石中十五个痕量稀土元素

岩石中稀土元素的配分可作为地壳、地幔演化的标志,尤其是元素Eu,就是地质时代和物质来源的指示剂。因此,岩石中痕量稀土元素的测定越来越引起地质工作者的关注。     

The determination of chlorine in rocks and minerals by pyrohydrolytic method

In this paper a porcedute of pyrohydrolysis spectrophotometric determination has been established for chlorine in rocks and minerals. The selection of accelerator and its required quantity, the time and temperature of sample decomposition and the influence of interferring elements and other factors are also discussed in detail. Because samples are usually fused with alkalis, higher blank is an insurmountable problem. However, with our procedure, the above-mentioned drawback can be effectively overcome, and the determination of trace chlorine either in large or in minor quantities of samples also is rather ideal. The determined results indicate that the relative standard deviations are 8.7% in the former and 4.5% in the latter case. This procedure is simple, rapid and well reproduceable. The detection limit of the method is 10 ppm. The results obtained by our procedure are in good agreement with the proposed values from two reference samples in China (DZΣ-1 and DZΣ-2) and one international geochemical reference sample (RGM-1). This method has proved itself to be reliable.     

Results for Fluorine in Coals and Other Reference Materials

Results of fluorine determinations by a pyrohydrolysis-ion selective electrode method are reported for four reference coals, two fly ashes and eight rock samples. These values were obtained during a study of Australian coals which showed that the standard oxygen bomb combustion method generally used for coals gives low results. The results are compared with available literature data for these reference samples which were obtained by a variety of methods.     

IRON-FORMATION SAMPLES AND THE FIVE-MODE METHOD

Newly available analytical data on iron-formation reference samples are combined with values published earlier, in order to test the effectiveness of a revised version of the 'five-mode" method of evaluation, with the well-established sample IF-G as reference. The same method is then applied to improve the earlier evaluation of samples FeR-1, -2, -3 and -4. The resulting values are compared with those in the original evaluations. Better results are obtained than were possible with earlier versions of the method, but some problems do persist.     

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.     

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.     

Chlorine in 27 Geochemical Reference Samples

27 reference samples have been analysed for Cl by automated photometric analysis following alkali fusion. The results are in general agreement with the compilation values listed. However, it is apparent that in the case of the six USGS samples included, values are generally lower than those previously quoted for photometric determinations, particularly for G-2 and AGV-1.     

泡沫塑料富集分离—石墨炉原子吸收法测定化探样品中的痕量金

样品用1＋1王水分解样品,在王水介质中,用泡沫塑料吸附金。在聚四氟乙烯塑料瓶中进行水浴加热溶解,以1%硫脲络合解脱金,在石墨炉原子吸收分光光度计上,采用自动进样方式测定金。经国家一级分析标准样品验证,结果与标准值相符。     

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.     

THREE NEW GSJ ROCK REFERENCE SAMPLES: RHYOLITE JR-3, GABBRO JGB-2 AND HORNBLENDITE JH-1

Three new rock reference samples, Rhyolite JR-3, Gabbro JGb-2 and Hornblendite JH-1 have been prepared by the Geological Survey of Japan for collaborative studies on their chemical composition. Twenty-eight major, minor and trace elements were determined and presented. The results of homogeneity tests showed that all elements are considered to be distributed homogeneously in each reference sample. Geological and mineralogical characteristics are also described.     

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.     

GEOCHEMICAL STANDARD REFERENCE SAMPLES GSD 9–12, GSS 1–8 AND GSR 1–6

The 18 Chinese geochemical standard reference samples GSD 9-12 (stream sediments), GSS 1-8 (soils) and GSR 1-6 (rocks) were prepared after GSD 1-8 (stream sediments) for even wider and increasing needs of geology, exploration geochemistry and geochemical analysis. Usable values of 41 trace, minor and major elements of the 18 samples were published in 1984. In the following two years, efforts were concentrated on the determination of other elements, most of which are more difficult to determine accurately and hence not many data were available in the literature. At the same time, additional data on the 41 elements already evaluated were also submitted. In all, 155 234 results were available along with the 35 284 analytical data submitted. The processing of samples, the examination of sample homogeneity, the plan of collaborative analysis of the samples, and the criteria for defining the recommended values are described. The recommended or reference values of the 72 constituents, to-gether with the 35 284 analytical data of the 18 samples are published in this paper.     

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.     

NEW REFERENCE SAMPLES OF MAGMATIC ROCKS: QUARTZ DIORITE SKD-1 AND SVIATONOSSITE SSV-1

The preparation and study of the two rock reference samples, Quartz Diorite SKD-1 and Sviatonossite SSv-1, are described, along with mineralogical and petrographic features. After its homogeneity studies, the two samples were analysed by seventy-five former USSR laboratories in the framework of an interlaboratory analytical program. The two samples have been certified respectively for 41 and 39 major, minor and trace elements; additionally, values are proposed for about 20 trace elements. The compiled data on the two samples are presented as an Appendix. Both the samples, processed in about 280 kg, form now part of the set of eight magmatic rock reference samples prepared by the Institute of Geochemistry in Irkutsk.     

Elemental Concentrations in Nine New GSJ Rock Reference Samples "Sedimentary Rock Series"

Nine new rock reference samples of the "Sedimentary rock series", Chert JCh-1, Dolomite JDo-1, Lake sediment JLk-1, Limestone JLs-1, Stream sediments JSd-1 to JSd-3, and Slates JS1-1 and JSl-2 have been prepared by the Geological Survey of Japan(GSJ). Thirty major, minor and trace elements were determined using atomic absorption spectrometry, flame emission spectrometry, infrared absorption spectrometry and wet chemical techniques. The results of homogeneity tests showed that almost all elements, with a few exceptions, are considered to be distributed homogeneously in each reference sample.     

Determination of the platinum-group elements and gold in ferromanganese nodule reference material NOD-A-1

The concentrations of Ru, Pd, Ir, Pt, and Au were determined in a ferromanganese nodule reference sample NOD-A-1 by inductively coupled plasma mass-spectrometry. Sample preparation procedures include acid digestion and anion exchange preconcentration. Standard addition method was used to eliminate losses of the analyte during the chromatographic separation. The results are in agreement with previously published data. The low level of intermediate precision for Au between different subsamples of the same sample probably originates from the heterogeneous distribution of Au in ferromanganese nodules. The accumulation of PGE in ferromanganese nodules was studied using international reference samples.     

New Series of Rock and Sediment Geochemical Reference Materials

Certified or reference values for sixty six to sixty seven elements and element oxides are given for geochemical reference materials recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), including limestone (GSR-13), granitic gneiss (GSR-14), amphibolite (GSR-15), lake sediment (GSS-9) and stream sediments (GSD-1a, GSD-13, GSD-14). These samples supplement the GSR 1-6, GSD1-8 and GSD 9-12 certified reference materials already prepared and characterized by the IGGE.