Major and Trace Element Composition and Homogeneity of Microbeam Reference Material: Basalt Glass USGS BCR-2G

Major and trace element abundances in two different fragments of reference material basalt glass BCR-2G are reported. The data were obtained by ion and electron microprobe and represent both random point and profile analyses. Major and trace element abundances are constant within a few per mil and a few percent, respectively. This overall homogeneity is valid for scales of a few tens of micrometres to a few tens of centimetres. It is shown that the difference in the scatter of apparent element abundances is not due to chemical heterogeneity but reflects analytical uncertainty. Within error, the concentrations of both the major and lithophile trace elements in BCR-2G appear to be identical to the bulk dry weight abundances in BCR-1. Possible exceptions are the alkali metals.     

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.     

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.     

Fitness-for-Purpose of Reference Material Reference Values in Relation to Traceability of Measurement, as Illustrated by USGS BCR-1, NIST SRM 610 and IAEA NBS28

As in all fields of sample analysis, reference materials play a large role in supporting measurements in the geosciences. While a rather large number of materials are in distribution (> 380), not all are equally effective or fit-for-purpose in supporting laboratory data quality and thereby assuring the desired comparability of measurements between laboratories. Equally important, reference values that are not fit-for-purpose cannot be used effectively to establish traceability links between laboratory measurements and national and international standards. The needed fitness-for-purpose is not achieved for reference values either when more than one reference value has been proposed and a consensus does not exist among users as to which should be used by all, or when reference value uncertainties are too large in comparison to those of routine laboratory measurements. The focus of this review will be, first to outline the current reality, and second to suggest ways in which certifications of RMs can be improved to provide reference values that are universally accepted and more fit-for-purpose in general laboratory use. The discussion will be illustrated largely by current uses of USGS BCR-1, NIST SRM 610 and IAEA NBS28, as these three materials are those for which the largest body of newly published data exists, according to recent bibliographies of the geoanalytical literature published annually in Geostandards Newsletter: The Journal of Geostandards and Geoanalysis.     

Fluorine in Twenty-Two International Reference Rock Samples and a Compilation of Fluorine Values for the USGS Reference Samples

Fluorine in 22 international reference samples has been determined with an ion selective electrode following fusion with a Na₂bCO₃-ZnO mixture. To eliminate the effect of fluorine complexes in the solutions, the results presented are means of fluoride determinations from a standard calibration curve and from the method of standard addition. Together with these new determinations an updated compilation of USGS-I reference samples is presented.     

An Inter-Laboratory Assessment of the Thorium Isotopic Composition of Synthetic and Rock Reference Materials

We present a concerted international effort to cross-calibrate five synthetic Th isotope reference materials (UCSC Th "A", OU Th "U", WUN, IRMM-35 and IRMM-36), and six rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2, USGS BHVO-2, LV18) using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We then compare our new values with a compilation of literature mass spectrometric data for these reference materials and derive recommended "consensus"²³⁰Th/²³²Th values for each. We also present isotope dilution U and Th concentration data for four rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2).     

Suitability of AuRM2 as a Reference Material for Trace Element Microanalysis of Native Gold

Microanalysis of native gold specimens has been hampered by the lack of a suitable reference material (RM) known to be sufficiently homogeneous at the scale of microanalytical sampling. The suitability of gold reference material AuRM2 for microanalysis was assessed. This RM was created for bulk analysis of refined gold and was only certified for homogeneity at the bulk scale. However, it contains trace elements in appropriate mass fraction ranges for analysis of native gold. This study was not intended to provide alternative mass fractions from the original certified values, only to assess its suitability for microanalytical methods. Micro‐scale (~ 3.4 μg sample mass) heterogeneity was calculated from measurement repeatability of LA‐ICP‐MS analyses of AuRM2 by factoring in signal (represented by counting statistics) and instrument set‐up‐specific variability (determined using measurement variability of a reference material known to be homogeneous). Elements determined to be homogeneous or to have minor heterogeneity (< 10% calculated heterogeneity RSD) are Mg, Al, Ti, Fe, Ni, Cu, Zn, Se, Rh, Sn, Sb, Pt and Pb. Elements with moderate heterogeneity (10–20% heterogeneity RSD) are: Mn, As, Pd, Te and Bi. Correlation of element mass fractions indicates that micro‐scale inclusions of chalcophile‐rich phases along grain boundaries may be responsible for some of the chemical heterogeneity. However, the level of heterogeneity is statistically negligible compared with the ranges of chemical signatures observed in sample populations of native gold. Therefore, AuRM2 is shown to be sufficiently homogenous at a micro‐scale for use as a RM for microanalysis of native gold.     

Assessment of Dissolution of Silicate Rock Reference Materials with Ammonium Bifluoride and Nitric Acid in a Microwave Oven

The complete dissolution of representative test portions of powdered rock samples for the determination of the mass fractions of trace elements by ICP‐MS relies either on aggressive and time‐consuming acid digestions or fusion/sintering with appropriate fluxes. Here, we evaluate a microwave oven dissolution method that employs a solution of NH₄HF₂ and HNO₃. The entire procedure occurs in a closed vessel system and takes up to 4 h. In hundreds of digestions, the precipitation of fluorides was never observed. Replicate decomposition of 100 mg of twenty‐one international reference materials (RMs) of igneous rocks, and also one of a shale presented mostly satisfactory recoveries of forty‐one trace elements. Important exceptions were Zr and Hf in G‐2 and GSP‐2 (mean recoveries of ca. 70%), although for four other felsic rock RMs, the digestion was complete. For ultramafic rock RMs, we present Cr results that indicate quantitative dissolution of Cr‐bearing phases. We discuss the findings and conclude that advances in sample preparation of geological materials for instrumental analysis would benefit from a better understanding of how specific characteristics, such as composition and crystallinity of certain minerals, may affect their reactivity.     

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.     

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.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Antarctic Ice‐Core Water (USGS49) – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from ice‐core water from the Amundsen–Scott South Pole Station. This isotopic reference material, designated as USGS49, was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity and measured by dual‐inlet isotope‐ratio mass spectrometry. The δ²H and δ¹⁸O values of USGS49 are ?394.7 ± 0.4 and ?50.55 ± 0.04 mUr (where mUr = 0.001 = ‰), respectively, relative to VSMOW, on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5 mUr. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95% probability of encompassing the true value. This isotopic reference material is intended as one of two isotopic reference waters for daily normalisation of stable hydrogen and oxygen isotopic analysis of water with an isotope‐ratio mass spectrometer or a laser absorption spectrometer. It is available by the case of 144 glass ampoules or as a set of sixteen glass ampoules containing 5 ml of water in each ampoule.     

Comparison of UV and IR Laser Ablation ICP-MS on Silicate Reference Materials and Implementation of Normalisation Factors for Quantitative Measurements

Direct analysis of geological reference materials was performed by LA-ICP-MS using two Nd:YAG laser systems operating at 266 nm and 1064 nm. The aim of this work was to compare UV and IR laser ablation and to assess the potential of the technique for the quantitative bulk analysis of rocks, sediments and soils. The laser sampling process was investigated and the analytical performance of both systems was compared. The influence of the laser operating conditions and the nature of the matrix on ICP-MS response factors calculated for major, minor and trace elements was evaluated. Under consistent laser settings, the response factors appeared to be matrix dependent. For a given matrix, the response factors were also significantly different for the two lasers. Normalisation with a single matrix element was effective only for matrices with similar mineralogy. When operating at 266 nm instead of 1064 nm, matrix effects could be reduced but not overcome. However, variations of the response factors between the different matrices appeared to be similar within distinct groups of elements, reflecting geochemical associations. When using multiple internal standards, matrix effects but also effects of the laser wavelength, could be fully compensated.     

Instrumental Neutron Activation Analysis of Estuarine Sediment as a Proposed Reference Material for Environmental Studies

The International Atomic Energy Agency (IAEA) Marine Environmental Studies Laboratory (MEL) organised an intercomparison exercise, through its Analytical Quality Control Services (AQCS), for the determination of trace elements in estuarine sediment IAEA-405, well suited for the characterisation of sediments. The instrumental neutron activation analysis technique (INAA) was developed using a 27 kW low power research reactor. Forty elements in the sediment were determined with a measurement precision varying from 1.8% to 12.3%. IAEA reference materials SL-1 and SD-M-2/TM were analysed throughout this work as quality assurance samples.     

Determination of Total Sulfur Contents in the International Rock Reference Material SY-2 and Other Mafic and Ultramafic Rocks Using an Improved Scheme of Combustion/Iodometric Titration

An extensively modified combustion/iodometric titration method was used for the determination of sulfur in SY-2, a CANMET international rock reference material, in coarse-grained mantle rocks and glassy materials at the microgram level. Replicate analysis (n = 27) of SY-2 demonstrated the potential for this sample to be certified as a reference sample for S. Our mean sulfur concentration (122 ± 3 μg g-1) suggests that the recommended value (0.011% w/w) could underestimate the true value by 10%. The other results compare well with those generated by other more sophisticated techniques such as X-ray fluorescence spectrometry and electron probe microanalysis, whether S is dissolved in glassy materials or occurs as discrete sulfides.     

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.     

应用CH4/N2指标估算塔里木盆地天然气热成熟度

通过对塔里木盆地满加尔凹陷低成熟煤岩在开放在线程序升温体系的热模拟实验,获得煤岩在不同温度点的热分解产物CH4、CO和N2,并对模拟后残留产物进行了镜质体反射率测试,建立了镜质体反射率与对应受热温度之间的关系。煤岩镜质体反射率与热温度之间的二阶关系表达为:Ro=0.0014×T+0.109,r=0.9931(Ro<0.6%);Ro=0.0067×T-1.5855,r=0.9996(Ro>0.6%)。通过上述方程建立CH4/N2值与煤岩镜质体反射率之间的对应关系,并利用CH4/N2值对塔里木盆地库车坳陷天然气热成熟度进行了预测。预测结果与实际地质分析结果相吻合,说明CH4/N2值可以作为塔里木盆地煤成气热成熟度预测指标应用于油气勘探中。     

Role of Carbonic Anhydrase as an Activator in Carbonate Rock Dissolution and Its Implication for Atmospheric CO_2 Sink

The conversion of CO2 into H+ and is a relatively slow reaction. Hence, its kinetics may be rate determiningin carbonate rock dissolution. Carbonic anhydrase (CA), which is widespread in nature, was used to catalyze the CO2 conversion process in dissolution experiments of limestone and dolomite. It was found that the rate of dissolution increases by a factor of about 10 after the addition of CA at a high CO2 partial pressure (Pco2) for limestone and about 3 at low Pcoj for dolomite. This shows that reappraisal is necessary for the importance of chemical weathering (including carbonate rock dissolution and silicate weathering) in the atmospheric CO2 sink and the mysterious missing sink in carbon cycling. It is doubtless that previous studies of weathering underestimated weathering rates due to the ignorance of CA as an activator in weathering, thus the contribution of weathering to the atmospheric CO2 sink is also underestimated. This finding also shows the need to examine the situ distribution and activ     

Rhenium‐Osmium Isotope Measurements of Geological Reference Material BIR‐1a: Evaluation of Homogeneity and Implications for Method Validation and Quality Control

To evaluate the homogeneity of geological reference material BIR‐1a (basalt; United States Geological Survey, USGS) for Re‐Os isotopic studies at the 0.2–1.0 g test portion size level, sixty‐three precise measurement results of Re and Os mass fractions and isotope amount ratios were obtained over an 18‐month period. These data reveal that the reference material has higher Re (0.691 ± 0.022 ng g^?1, 2s, n = 63) and lower Os mass fractions (0.343 ± 0.089 ng g^?1, 2s, n = 63) than UB‐N (serpentinite, CRPG) and is homogeneous in ¹⁸⁷Os/¹⁸⁸Os isotope amount ratio (0.13371 ± 0.00092, 2s, n = 63) at the 0.2–1.0 g test portion size level. The results are essentially consistent with previous views indicating that BIR‐1a gives precise measurement results for Re‐Os isotope amount ratio measurements at the 1 g test portion size level (Ishikawa et al., Chemical Geology, 2014, 384, 27–46; Meisel and Horan, Reviews in Mineralogy and Geochemistry, 2016, 81, 89–106). Based on these new Re‐Os data and previous studies, we propose BIR‐1a as a useful reference material that can be used in method validation and quality control and interlaboratory comparisons for studies dealing with mafic geological samples at test portion sizes of > 0.4 g.