Inductively Coupled Plasma Determination Of Nine Rare-Earth Elements In Sixty International Geochemical Reference Samples

Data for nine rare-earth elements (REE) determined by inductively coupled plasma spectrometry (ICP-AES) in sixty international geochemical reference samples (igneous and sedimentary rocks, soils and sediments) are presented. The method is based on acid digestion of the sample and cation-exchange separation from matrix elements. Good agreement is generally achieved between the results of this work and the recent compilation values. The present paper includes analytical data on several reference materials for which existing data are rather scarce or even inexistent     

高温熔融研制岩石标准玻璃方法初步研究:以玄武岩为例

探索了利用高温炉合成玄武岩玻璃制作原位微区主微量元素含量分析的标准物质的实验条件.选取玄武岩标准物质GBW07105(GSR-3)进行高温熔融、淬火实验研究,获得玄武岩玻璃,为合成其他地质样品微区分析标准参考物质的研制提供了参考方法.用激光剥蚀-四极杆等离子体质谱(LA-Q-ICPMS)对样品微区46个主元素和微量元素...     

DETERMINATION OF NINE RARE EARTH ELEMENTS IN EIGHT USGS REFERENCE SAMPLES AND IN THE ANRT GLAUCONITE, GL-O, BY SEQUENTIAL INDUCTIVELY COUPLED ARGON PLASMA SPECTROMETRY

Nine rare earth elements have been determined by inductively coupled plasma spectrometry (ICP) in eight USGS reference samples, MAG-1, SCo-1, SDC-1, BIR-1, DNC-1, W-2, BCR-1 and BHVO-1 and in the ANRT Glauconite, GL-O. Along with these new data, updated compilations are presented for these samples. Good agreement is observed between the present work and the compiled values.     

Candoluminescence Emission Analysis of Cerium in Thirty-Six International Geochemical Reference Samples

Cerium has been determined in thirty-six international geochemical reference samples using candoluminescence emission analysis. Samples are fused with sodium peroxide in nickel crucibles and interfering elements are removed by an ion exchange technique.
Cerium values obtained in the present work generally lie within ranges reported in the literature or close to the upper or lower ends of these ranges. Candoluminescence values for cerium compare favourably with previously reported INAA values for most of the geochemical reference samples analysed in the present study.     

Sixteen Statistical Tests for Outlier Detection and Rejection in Evaluation of International Geochemical Reference Materials: Example of Microgabbro PM-S

A totally objective procedure involving sixteen statistical tests (a total of thirty four single or multiple outlier versions of these tests) for outlier detection and rejection in a univariate sample is applied to a data base of sixty four elements in a recently issued international geochemical reference material (RM), a microgabbro PM-S from Scotland. This example illustrates the relative importance and usefulness of these tests in processing modern geochemical data for possible outliers and obtaining mean concentration and other statistical parameters from a final normal sample of univariate data. The final mean values are more reliable (characterized by smaller standard deviations and narrower confidence limits) than those obtained earlier using an accommodation approach (robust techniques) applied to this data base. Very high quality (certified value equivalent, cve) mean data are now obtained for eleven elements as well as high quality recommended values (rv) for thirty three elements in PM-S. Earlier work using the accommodation approach failed to establish even one cve value for any of the sixty four elements compiled here. The present procedure of outlier detection and elimination is therefore recommended in the study of RMs     

A SELF-CONSISTENT COMPILATION OF ELEMENTAL CONCENTRATION DATA FOR 93 GEOCHEMICAL REFERENCE SAMPLES

Concentration data obtained by instrumental neutron activation analysis (INAA) are presented for up to 36 chemical elements in 93 geochemical reference samples, including some for which there are little previous data. Because all data are based on at least three independent analyses, and for many of the data the uncertainty associated with counting is an insignificant source of error, the values presented here are considered of higher precision than generally reported by INAA. Information on subsampling error (sample heterogeneity) is also presented.     

Determination of Platinum-Group Elements and Gold in Geological Matrices by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) after Separation with Selenium and Tellurium Carriers

The present study describes a method for the extraction of Pt, Pd, Rh, Ru, Ir and Au from various geological materials after fusion with sodium peroxide in zirconium crucibles involving samples that vary in mass from 1 g to more than 20 g. Precipitation is brought about by reduction of the platinum-group elements (PGEs) with Sn²⁺, using selenium and tellurium as carriers in the presence of a catalyst (KI). The extraction yields obtained by this method are between 95 and 100% for PGEs. Gold is less well extracted (around 80%). Detection of the noble metals in the extraction residues is carried out by using ICP-MS. The results obtained by this technique are reported for five CCRMP certified reference materials and are close to their certified values. The elements were also determined in a natural glass sample melted during a meteoritic impact and contaminated by PGEs at ultra-trace concentrations.     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

Mass Fractions of Forty‐Six Major and Trace Elements,Including Rare Earth Elements,in Sediment and Soil Reference Materials Used in Environmental Studies

Development of new techniques, enabling simultaneous determination of large numbers of elements in environmental samples, can force analysts to use certified reference materials that do not contain all the elements of interest. In this paper, the mass fractions of forty‐six major and trace elements, including rare earth elements (REE), are presented in one soil (NCS DC 77302 also known as GBW 07410) and five sediment (Metranal‐1, IAEA 405, MESS‐3, NCS DC 73309 also known as GBW 07311 and NCS DC 75301 also known as GBW 07314) certified reference materials determined by high resolution inductively coupled plasma‐mass spectrometry. The selected certified materials represent a spectrum of geological matrices often analysed in environmental studies. Measured elements include certified elements, elements listed with information values as well as new elements absent from certificates, including REEs and some other elements. REE + Y mass fractions in the river sediment reference material Metranal‐1 are reported for the first time. The results obtained are in agreement with available certified or information values.     

1994 REPORT ON WHIN SILL DOLERITE WS-E FROM ENGLAND AND PITSCURRIE MICROGABBRO PM-S FROM SCOTLAND: ASSESSMENT BY ONE HUNDRED AND FOUR INTERNATIONAL LABORATORIES

This compilation report describes the field location, mineralogy, preparation and homogeneity testing of two new GIT-IWG reference materials: Whin Sill dolerite (WS-E) from England and Pitscurrie microgabbro (PM-S) from Scotland. The elemental composition of these two new reference materials has been established by an international cooperative analysis programme involving participation by 104 laboratories. A full assessment of these analytical results is presented, from which working values have been derived for the major elements as well as for 45 trace elements in WS-E and 44 trace elements in PM-S. Furthermore, isotopic ratios are presented for both samples, particularly for ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd.     

A Compilation of New and Published Major and Trace Element Data for NIST SRM 610 and NIST SRM 612 Glass Reference Materials

Microanalytical trace element techniques (such as ion probe or laser ablation ICP-MS) are hampered by a lack of well characterized, homogeneous standards. Two silicate glass reference materials produced by National Institute of Standards and Technology (NIST), NIST SRM 610 and NIST SRM 612, have been shown to be homogeneous and are spiked with up to sixty one trace elements at nominal concentrations of 500 μg g-1 and 50 μg g-1 respectively. These samples (supplied as 3 mm wafers) are equivalent to NIST SRM 611 and NIST SRM 613 respectively (which are supplied as 1 mm wafers) and are becoming more widely used as potential microanalytical reference materials. NIST however, only certifies up to eight elements in these glasses. Here we have compiled concentration data from approximately sixty published works for both glasses, and have produced new analyses from our laboratories. Compilations are presented for the matrix composition of these glasses and for fifty eight trace elements. The trace element data includes all available new and published data, and summaries present the overall average and standard deviation, the range, median, geometric mean and a preferred average (which excludes all data outside ± one standard deviation of the overall average). For the elements which have been certified, there is a good agreement between the compiled averages and the NIST data. This compilation is designed to provide useful new working values for these reference materials.     

New ID-TIMS, ICP-MS and SIMS Data on the Trace Element Composition and Homogeneity of NIST Certified Reference Material SRM 610-611

We present new concentration data for twenty four lithophile trace elements in NIST certified reference material glasses SRM 610-SRM 611 in support of their use in microanalytical techniques. The data were obtained by solution ICP-MS and isotope dilution TIMS analysis of two different sample wafers. An overall assessment of these new results, also taking into account ion probe studies that have been published in the literature, shows that these wafers can be considered to be homogeneous. Therefore, individually analysed wafers are believed to be representative of the entire batch of the SRM 610-611 glasses. Possible exceptions are the alkali metals (and a few volatile or non-lithophile trace elements). The analysed concentrations range between 370 μg g⁻¹ (Cs) and 500 μg g⁻¹ (Sr) and agree well with published values. On the basis of our new data and data recently published in the literature we propose "preferred average" values for the elements studied. These values are, within a few percent, identical to those proposed by other workers.     

1988 COMPILATION REPORT ON TRACE ELEMENTS IN SIX ANRT ROCK REFERENCE SAMPLES: DIORITE DR-N, SERPENTINE UB-N, BAUXITE BX-N, DISTHENE DT-N, GRANITE GS-N AND POTASH FELDSPAR FK-N

The six ANRT rock reference samples (DR-N, UB-N, BX-N, DT-N, GS-N, FK-N) have been distributed as reference samples for nearly twenty years. All available data on trace elements in these samples are presented and evaluated. It has been possible to assign working values for nearly 40 trace elements. These samples prepared in 600 to 1300 kg quantities are expected to last for some decades to come.     

Determination of the REE in Geological Reference Materials DTS-1 (Dunite) and PCC-1 (Peridotite) by Ultrasonic and Microconcentric Desolvating Nebulisation ICP-MS

Inductively coupled plasma-mass spectrometry is well suited for the precise, accurate and rapid determination of rare earth elements in most geological samples. However, determination of rare earth elements in certain mantle-derived materials, without applying preconcentration techniques, remains problematical due to low natural concentrations (generally < 1 ng g⁻¹). Consequently, USGS reference materials DTS-1 (a dunite) and PCC-1 (a partially serpentinized harzburgite) have only suggested rather than recommended values for the rare earth elements in reference material compilations. We compared results obtained using two ICP-MS instruments: a U-5000AT ultrasonic nebuliser coupled to a PQ2+ quadrupole ICP-MS and an ELEMENT sector field ICP-MS equipped with a MCN-6000 microconcentric desolvating nebuliser, with the suggested literature values for these two reference materials. Precision and accuracy of analytical methods employed by both instruments were demonstrated by excellent relative standard deviations (< 2%) and inter-laboratory agreement (< 5%) for numerous analyses of BHVO-1 and BIR-1, which are well established with rare earth elements contents at the μg g⁻¹ level. Repeat analyses of DTS-1 and PCC-1 at each laboratory indicate that each method is generally precise to better than 5% at sub-g g⁻¹ levels. Furthermore, values from both instruments generally agree to within 10%. Our DTS-1 and PCC-1 values agree reasonably well with selected data reported in the literature (except for Ce and Sm in DTS-1) but exhibit poorer agreement with reported compilation values. With the demonstrated level of precision and accuracy, we contend that these new values for DTS-1 and PCC-1, generated by two different instruments, are the best estimates of the true whole-rock composition of these samples reported to date.     

Neutron Activation Analysis of Nine GSJ Sedimentary Rock Reference Samples

Nine rock reference samples "Sedimentary rock series" issued by the Geological Survey of Japan (GSJ) were analysed for up to 31 elements by neutron activation analysis (NAA); 14MeV-NAA for Si and Al, fission track method for U, radiochemical and instrumental NAA for rare-earth elements, and instrumental NAA for the remaining elements, with reactor neutrons for the latter three. The present results are compared with reported values.     

Sequential Separation of Uranium,Hafnium and Neodymium from Natural Waters Concentrated by Iron Coprecipitation

A new ion exchange chromatography method is presented for the isolation of high field‐strength elements (HFSE) from freshwater and seawater samples that have undergone iron coprecipitation. Large volumes of water can be condensed through the application of iron coprecipitation, but clean separation of elements from the precipitate proves difficult. The technique described is a five‐column process designed to separate the HFSE, including rare earth elements such as neodymium and hafnium, before removing the iron and isolating uranium. Subsequent isolation of Nd and Hf was achieved using established ion exchange chromatography methods. The efficacy of our chemistry was verified by measurements of analytical reference materials – both reference solutions and seawater samples – subjected to the chemical separation methods described. Elution results indicate high yields (> 90%) determined by concentration measurements of a known reference material added to each column. Measurement results for isotopic compositions of seawater (U, Nd) and reference solutions (NIST SRM 960, U) were identical within uncertainty to previously published values. Compositions were identical between solutions (Spex CLMS3, Spex PLND2) that underwent different iron coprecipitation procedures. Isotopic determinations for reference materials JNdi‐1 and NIST SRM 960 measured with the mass spectrometers used in this study were in agreement with universally accepted values for these materials, and indicate high precision.     

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.     

SZ-1型同位素X射线荧光分析仪分析多金属结核中锰铁钴镍铜

采用低分辨率能量色散Ｘ射线荧光分析仪和偏最小二乘法对太平洋多金属结核中的Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ和Ｃｕ等元素进行了现场分析,并对所用仪器的性能和方法的可靠性作了评价。方法经国家级标准物质验证,其测定值与标准值相符,ＲＳＤ（ｎ＝４２）各元素均小于１．０％,分析结果满足现场分析中矿物品位的测定要求。