Reference Materials for Geochemical Studies: New Analytical Data by ICP-MS and Critical Discussion of Reference Values

Abundances of twenty four trace elements, including Y and fourteen rare earth elements (REE), are reported for eighty six geological reference materials and four proficiency testing samples. Analytical data were obtained by ICP-MS using solution nebulisation after mixed acid digestion (HF-HClO₄) under pressure. Analysed samples cover a wide range of element concentrations and mineralogical compositions, including samples for which there are few previously published data. Precision for elemental determinations in nearly 90% of the samples analysed is better than 5%. Accuracy, estimated by comparison with data from compilations is better than 6% for well characterized reference materials. Results obtained for samples that are low in trace elements are often significantly lower than compiled reference values. A critical discussion of the compiled data sets, especially for Y and the REEs, indicates that some reference values seem to be erroneous.     

Compilation Report (1966–1987) on Trace Elements in five CRPG Geochemical Reference Samples: Basalt BR; Granites, GA and GH; Micas, Biotite Mica-Fe and Phlogopite Mica-Mg

The five CRPG geochemical reference samples (BR, GA, GH, Mica-Fe and Mica-Mg) have been distributed as reference samples for more than twenty years. All data on trace elements in these samples available to the authors since their first reports have been compiled and evaluated. It has been possible to assign working values for more than forty elements in BR, GA, GH and Mica-Fe and for twenty-three elements in Mica-Mg. The samples are expected to last for another twenty years.     

First Co-Operative Study on Four Tropical Soil Samples and One Lateritic Bauxite (Suriname) Proposed as Geochemical Reference Samples

Five samples from Suriname have been analysed for their chemical composition by 18 laboratories. The proposed reference samples are four soil samples and one lateritic bauxite. The samples were analyzed for major and minor elements as well as for 36 trace elements. More data are needed for better characterization of these samples, particularly for trace elements.     

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.     

PROVISIONAL ELEMENTAL VALUES FOR FOUR NEW GEOCHEMICAL SOIL AND TILL REFERENCE MATERIALS, TILL-1, TILL-2, TILL-3 AND TILL-4

The collection and preparation of two soil reference samples and two till reference samples are described. Like their predecessors the LKSD series and the STSD series, the TILL series are characterized for total elements and for elements derived by partial extractions. Provisional data are presented for major, minor and trace elements. In addition, information data from a single source are provided for a number of elements derived by EPA digestions 3050 and 3051; these data allow a comparison with other partial extractions reported herein.     

Report (1984) on Two GIT-IWG Geochemical Reference Samples: Albite from Italy, AL-I And Iron Formation Sample from Greenland, IF-G

Two reference samples, Albite AL-I and Iron Formation sample IF-G were analysed for their chemical composition by the International Working Group "Analytical Standards of Minerals, Ores and Rocks" (GIT-IWG). AL-I was processed in 189 kg and IF-G and 760 kg. 103 GIT-IWG laboratories participated in this collaborative study along with 171 geoanalysts. This study lasted 15 months (September 1982 - December 1983) and is the second undertaken by the GIT-IWG. Over 2400 units of data were collated. As a result of this international study, the major and minor elements have been well characterized in both the samples; however, more data on trace elements will be very welcome for a better definition of trace elements, although working values have been proposed for about forty trace elements in each sample. The first and the second collaborative studies undertaken by GIT-IWG demonstrate well the immense analytical potential of the GIT-IWG.     

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.     

Report (1973–1984) on Two ANRT Geochemical Reference Samples: Granite GS-N and Potash Feldspar FK-N

Granite GS-N and Potash Feldspar FK-N are two ANRT reference samples prepared in 1973 in 960 and 567 kg, respectively. All data reported since 1973 are compiled in this report. GS-N and FK-N are now well characterized for major and minor elements. As for trace elements, working values have been assigned for 36 elements in GS-N and for 30 elements in FK-N. We need much more data on trace elements for characterizing them better. As GS-N and FK-N are still available in large quantities and are certain to remain so for two or three decades to come, a plea is made for contribution of more data on trace elements.     

Report (1967–1981) on Four ANRT Rock Reference Samples: Diorite DR-N, Serpentine UB-N, Bauxite BX-N and Disthene DT-N

All data reported by 200 analysts (106 laboratories) are presented for the four ANRT samples: Diorite DR-N, Serpentine UB-N, Bauxite BX-N and Disthène DT-N. Recommended values are given for the major and minor elements. As far as the as trace elements are concerned, DR-N has been characterized for 35 elements whereas the other three samples have been for only 20 elements. Wherever possible, brief comments have been inserted so as to explain our way of assigning recommended or proposed values.
After more than a decade of existence the total number of data reported for all the four samples reach only 3200 units which are not sufficient enough for a valid evaluation of compiled data. It is also pointed out that these samples are most likely to be available even during the next century as they have been prepared in large quantities of the order of one ton. A plea is therefore made for contribution of more data particularly for trace elements and for major elements which are present as trace elements in UB-N, BX-N and DT-N.     

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.     

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.     

1986 Values for Fifteen GSJ Rock Reference Samples, "Igneous Rock Series"

During the five-year period (April 1981 - March 1986), a series of fifteen rock reference samples, "Igneous rock series", has been prepared by the Geological Survey of Japan (GSJ). Based on the data available (published and communicated), consensus values for major, minor and trace elements have been derived; these values are presented for this second series of samples as well as for the first series of two samples, Granodiorite JG-1 and Basalt JB-1.     

LA-ICP-MS微区原位准确分析含水硅酸盐矿物主量和微量元素

通过描述一种利用LA-ICP-MS准确测定含水硅酸盐矿物主量元素和微量元素含量的多外标、无内标分析方法.总结出该方法基于矿物化学计量式计算含水硅酸盐矿物中挥发分的相对含量,再将全部分析元素归一化到总金属氧化物含量(100%减含水量)的原理,利用多种天然成分的岩石标准玻璃(如MPI-DING玻璃和USGS玻璃)作为外标进行校正计算.利用该方法对角闪石、绿帘石、电气石和透闪石等含水硅酸盐矿物进行了分析,并与利用电子探针和微钻(直径300 μm)取样溶液-ICP-MS分析的结果进行了对比研究.研究结果表明:对于组成均一的主量元素的分析结果与电子探针分析数据一致,相对偏差集中在5%以内.除了那些分布异常不均一的元素(在300 μm尺度上),对微量元素的分析结果与溶液-ICP-MS分析结果具有很好的一致性,二者之间的相对偏差大部分集中在10%以内.研究结论为采用归一化校正策略,选择MPI-DING和USGS玻璃作为外标,利用LA-ICP-MS微区分析方法可以准确测定含水硅酸盐矿物中的主、微量元素含量.      

SECOND REPORT (1993) ON THE FIRST THREE GIT-IWG ROCK REFERENCE SAMPLES: ANORTHOSITE FROM GREENLAND, AN-G; BASALTE D'ESSEY-LA-CÔTE, BE-N; GRANITE DE BEAUVOIR, MA-N

The first report (1980) on the three samples, Anorthosite AN-G, Basalt BE-N and Granite MA-N resulted in the chemical characterization of major, minor and 30 trace elements. The present report confirms the validity of a great majority of these working values, in addition to presenting working values for 20 more trace elements for each sample. Only compiled data on trace elements are presented, followed by Tables of statistical parameters used as a basis for their evaluation, both statistical and subjective. A plea is made to obtain more data on platinum group elements and on other "difficult" trace elements (Au, B, Bi, Se, Te, TI, …). The three samples have been processed in 900 kg amounts and, therefore, they are likely to remain available for some decades to come. As such, it is certainly worthwhile to take pains to characterize them well for even these difficult trace elements.     

Li2B4O7熔融玻璃-激光剥蚀等离子体质谱法测定水系沉积物国家标准定值样品中微量元素

建立了激光剥蚀等离子体质谱法直接测定Li2B4O7熔融玻璃中微量元素的分析方法。详细讨论了内标元素的选择及Li2B4O7熔融玻璃的均一性、背景空白对分析测定的影响。以Li2B4O7熔融玻璃中低同位素丰度的6Li作内标，水系沉积物国家标准参考物质熔融玻璃建立多元素标准校正曲线，用于标准参考物质及水系沉积物定值样品的分析，测定值与标准值或溶液雾化等离子体质谱结果比较，具有较好的一致性。     

The occurrence of potentially hazardous trace elements in five Highveld coals, South Africa

Permian coals of the southern hemisphere are generally considered to contain lower concentrations of sulfides, halogens, and trace elements when compared to northern hemisphere Carboniferous coals. Few studies have considered the trace element content in South African coals, and little or no work has been published for Highveld coals. Of the nineteen coal fields in South Africa, the Highveld coal field is one of the nine currently producing, and is second largest in terms of production. Five run of mine samples and a high ash middlings product from the Number 4 Lower seam were analyzed, totaling six sample sets. Fourteen trace elements (As, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, V, and Zn) were selected for this study based on the global perception that these elements may be hazardous to human health and/or the environment when they are released during coal utilization. Several sample preparation techniques were tested using certified reference materials (SARMs 18, 19 and 20) to determine the most repeatable technique for these coals. The samples were analyzed by ICP-AES and CVAA (Hg only). Microwave digestion proved to be generally unreliable despite the utilization of several different methods. A slurry direct injection method into the ICP-AES provided good correlations with the reference material, but requires further development to enhance the confidence level in this relatively unexplored technique. Samples prepared based on three ASTM standards for the determination of trace elements in coal provided repeatable results in most instances, and were the preparation methods utilized for the Highveld coals.The trace element values determined for the Highveld coals are generally in good agreement with values available in literature for South African coals, with the exception of Hg, Mn and Cr. Hg values reported here are lower, Cr and Mn higher. Results generally agree well with analyses on the same samples conducted by the United States Geological Survey. When considering the global ranges for trace elements, the Highveld range values are within Swaine's range boundaries with the exception of Cr. Compared to the cited global average values for the fourteen trace elements determined, the values obtained for the Highveld coals generally fall below or well below these average values, with the exception of Cr and Mn. Concentrations of Cd and Cu are lower compared to global average values, and As, Mo, Pb, Se, Sb, and Zn can be considered low to very low. Arsenic is ten times lower compared to typical USA values. Concentrations of Co and Ni are similar to global averages, with V and Hg being very slightly higher. The middlings samples reported higher concentrations of most elements, related to the higher ash content of these samples. Of interest, the chalcophile elements determined are all depleted in the Highveld coals compared to global averages, and the siderophile elements are enriched or comparable to global averages.Risk-based health studies in the USA on coals with similar or higher Hg and significantly higher As contents have not reported negative health effects, and therefore it could be assumed that the mobilization of these trace elements from the five Highveld coals are unlikely to cause human health problems. Work is ongoing to determine the modes of occurrence of these HAPs and to address the partitioning behaviors and speciation states of these elements during coal utilization.     

Solid Sampling Atomic Absorption Determination Of Silver in Silicate Rock Reference Samples. Application to a Homogeneity Study of Silver In a One-Ton Two-Mica Granite Reference Sample

Silver content of silicate rook samples rarely exceeds 200 ppb. For determining such low levels of silver, a solid sampling flame atomic absorption method has been developed and has been applied to the analysis of several silicate rock reference samples. These results are compared with the sparse published data. Using silver as an example, the usefulness of solid sampling procedures for testing the repartition of volatile trace elements during the processing of new rock reference samples is illustrated.     

Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

Studies in “Standard Samples” for Use In the General Analysis of Silicate Rocks and Minerals*

Reviews already published on the state of “standard samples” of silicate rocks and minerals, as well as of some samples of other materials that can be used as reference standards for the general analysis of silicate rocks and minerals, have been updated. Usable values of varying degrees of reliability are suggested for major, minor and trace constituents of nearly one hundred different samples. Presentation of the information has been improved with a view to making it more convenient for readers’use.