Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

Molybdenum Concentrations Measured in Eleven USGS Geochemical Reference Materials by Isotope Dilution Thermal Ionisation Mass Spectrometry

Molybdenum concentrations in eleven USGS geochemical reference materials AGV-1, BCR-1, BHVO-1, BIR-1, DNC-1, DTS-1, G-2, GSP-1, MAG-1, PCC-1 and W-2 were measured by isotope dilution thermal ionisation mass spectrometry (ID-TIMS). In every case but one, the concentrations determined in this study were significantly lower than the current consensus values. Molybdenum concentrations determined by ID-TIMS are inherently more accurate and precisions may be up to an order of magnitude higher than those measured by other analytical techniques.     

Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

1988 COMPILATION OF ELEMENTAL CONCENTRATION DATA FOR USGS AGV-1, GSP-1 AND G-2

Concentration data on up to 90 individual constituents in USGS AGV-1, GSP-1, and G-2 have been collected from 1270 journal articles and technical reports. These data are summarized in consensus (mean) values with uncertainties expressed as +/- one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables. Recommended values are proposed based upon data criteria used by NIST (National Institute of Standards and Technology, formerly the National Bureau of Standards or NBS).     

Germanium Contents of USGS Standard Rocks by Flameless Atomic Absorption

Germanium in 13 USGS standard silicate rooks was determined by flameless atomic absoprtion using a procedure which permits the determination of 0.2 ppm of germanium in as little as 50 mg of sample. The mean germanium content found is (in ppm Ge) for the new USGS standards: BHVO-1, 1.60; SDC, 1. 51; STM-1, 1. 32; QLO-1, 1. 28; RGM-1, 1. 24; and for- the older USGS standards: W-l, 1.S3; BCR-1, 1.39; G-l, 1.19; GSP-1, 1.16; AGV-1, 1.06; G-2, 0.96; PCC-1, 0.80; DTS-1, 0.72.     

1982 Compilation of Elemental Concentrations in Eleven United States Geological Survey Rock Standards

Elemental composition data on eight older (AGV-1, BCR-1, DTS-1, G-1, G-2, GSP-1, PCC-1 and W-1) and three newer (BIR-1, DNC-1 and W-2) USGS rock standards have been collected from institutional reports and journal articles from 1972–1981. This collection was combined with data from previous compilations and "consensus values" for up to 79 elements determined by comparing overall means, medians, and individual means based on analytical techniques.     

Sr and Pb isotopic composition of five USGS glasses (BHVO-2G, BIR-1G, BCR-2G, TB-1G, NKT-1G)

Sr isotopic compositions and Rb / Sr ratios of three USGS glasses (BHVO-2G, BIR-1G, BCR-2G) are identical to those of the original USGS reference materials. NKT-1G and TB-1G give values of 0.70351 and 0.70558, respectively. Pb isotopic ratios were measured by the standard-sample bracketing technique on an MC-ICP-MS, which give results that are comparable in accuracy and reproducibility to double spike analyses. However, assessment of the reproducibility of the technique is hampered by inhomogeneous contamination of all USGS reference materials analysed. This contamination is likely to be the reason why the USGS glasses do not all have the same Pb isotopic composition as their unfused originals. Powdered glasses, distributed for characterisation of the glasses by bulk analytical techniques, do not all have the same Pb isotopic compositions as the solid glass material, and can therefore not be used for this purpose.     

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.     

Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.     

Gold in BHVO-1, BIR-1, DNC-1 and BCR-1 by Fire-Assay Preconcentration Neutron Activation Analysis: Sample Size vs. Accuracy

Four mafic USGS rock standards (BHVO-1, BIR-1, DNC-1, BCR-1) were analyzed at three sample sizes (1, 5, and 10 g) for gold by neutron activation analysis subsequent to fire-assay concentration. The results indicate that large samples, in the order of 10 g, are required to produce consistent results, although analyses of variance indicate that sample sizes of 5 g may be used effectively. The analysis of 1 g samples resulted in a large range of values and high standard deviations. BCR-1 was found to be the most homogeneous of the four standards for gold, followed in decreasing order by BIR-1, DNC-1, and BHVO-1. Data for Ir in BIR-1 and DNC-1 are also presented.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.     

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.     

Reproducibility Tests for INAA Determinations With AGV-I, BCR-I and GSP-I and New Data For 17 Geochemical Reference Materials

During 1975–1977, the USGS reference rocks GSP-1, BCR-1 and from 1977 onwards AGV-1 have been systematically analysed in routine INAA as test samples. The results are given for up to 26 elements per sample and the reliability of our setup is demonstrated. For further 17 geochemical reference samples, new results are presented and compared with available data.     

Cd, Gd and Sm Concentrations in BCR-1, BHVO-1, BIR-1, DNC-1, MAG-1, PCC-1 and W-2 by Isotope Dilution Thermal Ionisation Mass Spectrometry

Cadmium, gadolinium and samarium concentrations were determined in seven geochemical reference materials by isotope dilution thermal ionisation mass spectrometry. The results for all three elements in BCR-1 are in excellent agreement with the compiled values as well as the literature values dete-mined by isotope dilution mass spectrometry. The agreement with compiled values on the other material is generally good except for Cd where the values for BHVO-1, BIR-1, DNC-1 and W-2 need to be revised.     

Determination of Scandium, Yttrium and Rare Earth Elements in Rocks by High Resolution Inductively Coupled Plasma-Mass Spectrometry

The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to ⁴⁵Sc was completely resolved from ²⁹Si¹⁶O and ²⁸Si¹⁶O¹H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.     

Chemische und spektrochemische Analyse internationaler Referenzgesteinsproben

Zusammenfassung Siebzehn internationale Referenzgesteinsproben (USGS: G-1, G-2, W-1, GSP-1, AGV-1, PCC-1, DTS-1, BCR-1; ZGI: GM, BM, TB; CRPG: GR, GA, GH, BR; MRT: T-1; CSS: SY-1) wurden zum Teil naßchemisch auf Haupt- und Nebenbestandteile und emissionsspektrographisch mittels der Kohlenbogen- und Doppelbogenmethode auf 25 Spurenelemente unter Verwendung eines Spektrographen großer Dispersion quantitativ analysiert. Unter Einsatz eines thermochemischen Mischreagens (BaSO₄+LaF₃) wurden mit der Doppelbogenmethode Nachweisgrenzen von0,1 bis 5 ppm erreicht. Bei Mehrfachanalysen wurde mit dem Kohlebogen ein relativer Fehler von±4 bis±16% erhalten, bei der Doppelbogenmethode von±5 bis±30%. Es wird die Konzentrationsabhängigkeit des relativen Fehlers dargestellt.

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Chemical and spectrochemical analysis of international reference samples rocks

Summary Seventeen international reference samples of rocks (USGS: G-1, G-2, W-1, GSP-1, AGV-1, PCC-1, DTS-1, BCR-1; ZGI: GM, TB; CRPG: GR, GA, GH, BR; MRT: T-1; SSC: SY-1) were analysed partly for the main and minor constituents using methods of wet analysis. Twenty-five trace elements were determined with a large optical spectrograph using the carbon and double are methods. The double are methode gives detection limites of 0.1 up to 5 ppm, if thermochemical reagents (BaSO₄+LaF₃) are applicated. The carbon arc method shows a relative error of±4 up to±16% depending mostly on the concentration of the trace element, during the double arc methode results a relative error of±5 up to±30%.

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Mit 5 Abbildungen     

1988 Compilation of Elemental Concentration Data for USGS DTS-1, G-1, PCC-1 and W-1

Concentration data on up to 91 individual constituents in USGS DTS-1, G-1, PCC-1, and W-1 have been collected from 1647 journal articles and technical reports. These data are summarized in consensus (mean) values with uncertainties expressed as one standard deviation. Mean values are also calculated as a function of analytical procedure and all raw data are given in the tables. Recommended values are proposed based upon data criteria used by NIST (National Institute of Standards and Technology, formerly the National Bureau of Standrds or NBS).     

地质样品中Pb同位素分析的高效酸淋洗流程

针对地质样品的Pb同位素分析提出了一种简化淋洗法, 以去除样品碎样过程引起的污染.相对前人的淋洗法而言, 简化淋洗法不仅能够得到地质样品中准确的Pb同位素组成, 而且降低了全流程本底并提高了样品处理效率.利用多接收等离子体质谱分析了5个美国地质调查局(USGS) 国际标准参考物质(AGV-1、AGV-2、BHVO-2、BCR-2和G-2) 中的Pb同位素组成, 结合前人的研究, 结果表明第一、二代USGS参考物质在制样过程中均受到不同程度的污染.第一代标准在碎样过程受到的污染比碎样环境造成的普通铅污染严重, 而第二代则相反.淋洗后各种参考物质分别具有相近且均一的Pb同位素组成, 表明对岩石粉末样进行溶样前的淋洗有助于获得样品真实的Pb同位素组成.      

Determination of Rb/Sr and 87Sr86Sr ratios of some standard rocks and evaluation of X-ray fluorescence spectrometry in Rb1bSr geochemistry

New isotope dilution results are presented for Rb and Sr concentrations in U.S.G.S. standard rocks and NBS-70a K-feldspar. The results (based on at least five analyses of each rock), are generally accurate to ± 0.5% and resolve discrepancies in previously published data. X-ray fluorescence analyses of the same samples yield Rb and Sr determinations which are only accurate to ± 5%, but Rb/Sr ratios which are as precise and in excellent agreement with the isotope dilution values. It is concluded that X.R.F. determination of Rb/Sr ratios is perfectly suitable for whole-rock Rb1bSr geochronology.${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios have been determined on G-2, GSP-1, BCR-1 and AGV-1 as well as the Eimer and Amend SrCO₃ standard.     

Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.