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.     

Precise Determination of Rubidium in Geological Reference Materials by ID-TIMS and WD-XRF: A Discussion for the Basalt BIR-1

Data were obtained for rubidium in six geological reference materials by isotopic dilution thermal ionisation mass spectrometry (ID-TIMS) and wavelength dispersive X-ray fluorescence spectrometry (WD-XRF). The results found by one technique compare very well with the other within the respective analytical uncertainties and are also in good agreement with data from previously published values. The particular case of low Rb determinations in reference sample BIR-1 is discussed.     

Multi-Element Analysis of 15 International Standard Rocks by Isotope-Dilution Spark Source Mass Spectrometry

The concentrations of 25 trace elements have been determined in 15 international standard rock samples by isotope-dilution spark source mass spectrometry (ID-SSMS). This technique yields reliable data down to the ppb concentration range. The agreement between most of our data and recommended values is within 10%. However, for reference samples with low trace element contents (BIR-1, NIM-N, PCC-1, DTS-1), differences between our data and the literature can be as large as a factor of 80.     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.     

Multi-Element Isotope Dilution Sector Field ICP-MS: A Precise Technique for the Analysis of Geological Materials and its Application to Geological Reference Materials

We present a multi-element technique for the simultaneous determination of twelve trace elements in geological materials by combined isotope dilution (ID) sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) following simple sample digestion. In addition, the concentrations of fourteen other trace elements have been obtained using the ID determined elements as internal standards. This method combines the advantages of ID (high precision and accuracy) with those of SF-ICP-MS (multi-element capability, fast sample processing without element separation) and overcomes the most prevailing drawbacks of ICP-MS (matrix effects and drift in sensitivity). Trace element concentration data for BHVO-1 (n = 5) reproduced to within 1–3% RSD with an accuracy of 1–2% relative to respective literature values for ID values and 2–3% for all other values. We have applied this technique to the analysis of seventeen geological reference materials from the USGS, GSJ and IAG. The sample set also included the new USGS reference glasses BCR-2G, BHVO-2G and BIR-1G, as well as the MPI-DING reference glasses KL2-G and ML3B-G, and NIST SRM 612. Most data agreed within 3–4% with respective literature data. The concentration data for the USGS reference glasses agreed in most cases with respective data of the original rock powder within the combined standard uncertainty of the method (2–3%), except the U concentration of BIR-1G, which showed a three times higher concentration compared to BIR-1.     

ICP-MS ANALYSIS OF BASALT BIR-1 FOR TRACE ELEMENTS

The concentrations of 27 trace elements in the basalt BIR-1, as well as in other mafic rock reference materials, have been determined by ICP-MS, using pure elemental solutions for external calibration and standard additions. Concentrations of rare earth elements in BIR-1 for the new ICP-MS data, agree with compiled values, and previous ID-SSMS results, whereas ICP-MS data on HFSE's are systematically higher by about 40% to 70% than ID-SSMS, but are consistent with data generated at other ICP-MS laboratories.     

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.     

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.     

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock reference standards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BER-1/1 and W-2, together with NBS 981 using a micromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at the University of Queensland. 203Tl-205Tl isotopes were used as an internal standard to correct for mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standards AGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionization mass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2 are reproducibly higher for 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb than double-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR-1/1 and W-2, which may be used as reference values in future studies. It is found that linear correction for Pb isotopic fractionation is adequate with the results identical to those corre     

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.     

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.     

Determination of Rare Earth Elements, Sc, Y, Zr, Ba, Hf and Th in Geological Samples by ICP-MS after Tm Addition and Alkaline Fusion

We present a revised method for the determination of concentrations of rare earth (REE) and other trace elements (Y, Sc, Zr, Ba, Hf, Th) in geological samples. Our analytical procedure involves sample digestion using alkaline fusion (NaOH-Na₂O₂) after addition of a Tm spike, co-precipitation on iron hydroxides, and measurement by sector field-inductively coupled plasma-mass spectrometry (SF-ICP-MS). The procedure was tested successfully for various rock types (i.e., basalt, ultramafic rock, sediment, soil, granite), including rocks with low trace element abundances (sub ng g⁻¹). Results obtained for a series of nine geological reference materials (BIR-1, BCR-2, UB-N, JP-1, AC-E, MA-N, MAG-1, GSMS-2, GSS-4) are in reasonable agreement with published working values.     

Determination of Rare Earth Elements in Sixteen Silicate Reference Samples by Secondary Ion Mass Spectrometry Using Conventional Energy Filtering Technique*

Rare earth elements were determined by secondary ion mass spectrometry for 13 silicate rock samples, ranging from ultramafic-mafic to acidic compositions, 2 feldspar and 1 biotite separates. As a whole, the investigated samples are characterized by matrices and rare earth elements spectra covering most geological applications. The present data are compared with reference values. The advantage of using secondary ion mass spectrometry as a fundamental tool for trace element detection in bulk samples in the few ppm-ppb region is demonstrated.     

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.     

TRACE ELEMENT ANALYSIS OF TEN U.S. GEOLOGICAL SURVEY ROCK STANDARDS BY NEUTRON ACTIVATION USING A LOW FLUX REACTOR

Ten U.S. Geological Survey rock standards have been analyzed for trace elements by instrumental neutron activation using a low flux reactor and Ge detectors. Results compare favorably with the current working values for all elements except Mo. REE values that have been determined are generally slightly lower than accepted values. Data obtained for rocks that have very low trace element concentrations (e.g., BIR-1) will aid in refining the working values for these standards.     

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.     

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.     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

玄武岩标准样品铁铜锌同位素组成

报道了三种玄武岩标准样品(BCR-2、BIR-1a和GBW 07105)的铁铜锌同位素数据。实验使用HNO3-HF混合酸消解玄武岩标准样品;AGMP-1阴离子交换树脂分离提纯样品中的铜铁锌,利用多接收等离子体质谱仪(MC-ICPMS)测定铁铜锌同位素比值,分析过程中使用样品-标准-样品交叉法校正仪器的质量分馏。实验得到BCR-2、BIR-1a和GBW 07105标准样品的高精度铁铜锌同位素组成(95%置信水平的不确定度)分别为:δ56FeBCR-2-IRMM014=0.070‰±0.018‰(2SD),δ65 CuBCR-2-SRM976=0.16‰±0.04‰(2SD),δ66 ZnBCR-2-IRMM3702=-0.072‰±0.020‰(2SD);δ56 FeBIR-1a-IRMM014=0.044‰±0.026‰(2SD),δ65CuBIR-1a-SRM976=0.027‰±0.019‰(2SD),δ66 ZnBIR-1a-IRMM3702=0.085‰±0.032‰(2SD);δ56FeGBW 07105-IRMM014=0.126‰±0.039‰(2SD),δ65 CuGBW 07105-SRM976=0.12‰±0.01‰(2SD),δ66ZnGBW 07105-IRMM3702=0.22‰±0.03‰(2SD)。这些数据在误差(不确定度)范围内与国际上已发表的数据是一致的。三个玄武岩标准样品的铁铜锌同位素组成数据的发表为铁铜锌同位素研究提供了统一的标准,使地质样品的铁铜锌同位素数据的质量监控成为可能。     

Low-Level Analysis of Lanthanides in Eleven Silicate Rock Reference Materials by ICP-MS After Group Separation Using Cation-Exchange Chromotography

A simple method is described for the determination of lanthanides in depleted rocks based on acid dissolution, cation-exchange chromatography and ICP-MS analysis using a low flow, microconcentric nebuliser. The potential of the method is evaluated by analysis in triplicate of eleven low-concentration level geochemical reference materials (UB-N, NIM-D, BIR-1, DNC-1, JB-2, JGb-1, JGb-2, NIM-N, NIM-P, FK-N and MA-N). The repeatability of the three dissolutions is between 0.2% and 0.6% relative standard deviation (RSD) for basaltic samples BIR-1 and JB-2, with the exception of La in BIR-1 (2.6% RSD), presumably because of blank or memory effects. The results are more scattered for coarsegrained rocks. A good agreement between the results and working values is observed for most mafic samples and the serpentinite UB-N. Significant deviations observed between the data obtained in this work and working values for some reference materials might reflect heterogeneities of the REE distributions in coarse-grained (especially granitic) rocks at the 10 0 mg sub-sampling scale.