The F,Cl, Br and I Contents of Reference Glasses BHVO‐2G,BIR‐1G,BCR‐2G,GSD‐1G,GSE‐1G,NIST SRM 610 and NIST SRM 612

Halogen contents for the widely distributed reference glasses BHVO‐2G, BIR‐1G, BCR‐2G, GSD‐1G, GSE‐1G, NIST SRM 610 and NIST SRM 612 were investigated by pyrohydrolysis combined with ion chromatography, total reflection X‐ray fluorescence analysis, instrumental neutron activation analysis, the noble gas method, electron probe microanalysis and laser ablation‐inductively coupled plasma‐mass spectrometry. Glasses BHVO‐2G, GSD‐1G and GSE‐1G have halogen contents that can be reproduced at the 15% level by all bulk techniques and cover a significant range in halogen mass fractions for F (~ 20–300 μg g^?1), Cl (~ 70–1220 μg g^?1) and Br (~ 0.2–285 μg g^?1) and I (~ 9–3560 ng g^?1). The BIR‐1G glass has low F (< 15 μg g^?1), Cl (~ 20 μg g^?1), Br (15 ng g^?1) and I (3 ng g^?1). The halogen contents for the silica‐rich NIST SRM 610 and 612 glasses were poorly reproduced by the different techniques. The relatively high Cl, Br and I abundances in glasses GSD‐1G and GSE‐1G mean that these glasses are well suited for calibrating spatially resolved micro‐analytical studies on silicate glasses, melt and fluid inclusions. Combined EPMA and laser ablation‐inductively coupled plasma‐mass spectrometry data for glass GSE‐1G demonstrate homogeneity at the 10% level for Cl and Br.     

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.     

The Calcium Isotope Composition (δ44/40Ca) of NIST SRM 915b and NIST SRM 1486

The calcium isotopic composition of NIST SRM 915b and 1486 provided by the National Institute of Standards and Technology was analysed. The δ^44/40Ca values of the two reference materials relative to NIST SRM 915a were: NIST SRM 915b =+0.72 ± 0.04‰ and NIST SRM 1486 =?1.01 ± 0.02‰. NIST SRM 1486 did not require any chemical separation prior to measurement.     

Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.     

Measurements of Rare Earth Element and Other Element Mass Fractions in Environmental Reference Materials (NIST SRM 1646a,NIST SRM 1400, IAEA‐395 and IAEA‐450) by INAA,ICP‐AES and ICP‐MS

INAA, ICP‐AES and ICP‐MS were used to elementally characterise four environmental reference materials – NIST SRM 1646a (Estuarine Sediment), NIST SRM 1400 (Bone Ash), IAEA‐395 (Urban Dust) and IAEA‐450 (Algae). An analytical scheme consisting of the three methods was first applied to NIST SRM 1646a to validate the methodology because it has been extensively analysed and has certified values for many elements. With repeated analyses of NIST SRM 1646a, the accuracy and measurement repeatability of the data obtained were evaluated based on two statistical calculations (zeta‐score and Horwitz ratio) and were observed to be good enough for the analytical scheme to be applied to similar sorts of environmental/geochemical samples. Applying the same approach to NIST SRM 1400, IAEA‐395 and IAEA‐450, enabled mass fractions of 29, 38 and 28 elements to be determined, respectively. Among these results, the data for rare earth elements are of particular interest, not only for IAEA‐450 but also for the other three reference samples. The data for Pr, Gd, Dy, Ho, Er and Tm in NIST SRM 1646a are newly reported in this study. By using small test portions (< 100 mg) for NIST SRM 1646a and IAEA‐395, and recommended minimum amounts for NIST SRM 1400 and IAEA‐450, sample homogeneity was evaluated.     

Zinc Isotopic Compositions of NIST SRM 683 and Whole‐Rock Reference Materials

In this study the homogeneity of the zinc isotopic composition in the NIST SRM 683 reference material was examined by measuring the Zn isotopic signature in microdrilled sample powders from two metal nuggets. Zinc was purified using AG MP‐1M resin and then measured by MC‐ICP‐MS. Instrumental mass bias was corrected using the “sample‐standard bracketing” method and empirical external normalisation with Cu doping. After evaluating the potential effects of varying acid mass fractions and different matrices, high‐precision Zn isotope data were obtained with an intermediate measurement precision better than ± 0.05‰ (δ⁶⁶Zn, 2s) over a period of 5 months. The δ⁶⁶Zn_JMC‐Lyon mean values of eighty‐four and fourteen drilled powders from two nuggets were 0.11 ± 0.02‰ and 0.12 ± 0.02‰, respectively, indicating that NIST SRM 683 is a good isotopic reference material with homogeneous Zn isotopes. The Zn isotopic compositions of seventeen rock reference materials were also determined, and their δ⁶⁶Zn values were in agreement with most previously published data within 2s. The δ⁶⁶Zn values of most of the rock reference materials analysed were in the range 0.22–0.36‰, except for GSP‐2 (1.07 ± 0.06‰, n = 12), NOD‐A‐1 (0.96 ± 0.03‰, n = 6) and NOD‐P‐1 (0.78 ± 0.03‰, n = 6). These comprehensive data should serve as reference values for quality assurance and interlaboratory calibration exercises.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Determination of Reference Values for NIST SRM 610–617 Glasses Following ISO Guidelines

We present new reference values for the NIST SRM 610–617 glasses following ISO guidelines and the International Association of Geoanalysts’ protocol. Uncertainties at the 95% confidence level (CL) have been determined for bulk‐ and micro‐analytical purposes. In contrast to former compilation procedures, this approach delivers data that consider present‐day requirements of data quality. New analytical data and the nearly complete data set of the GeoReM database were used for this study. Data quality was checked by the application of the Horwitz function and by a careful investigation of analytical procedures. We have determined quantitatively possible element inhomogeneities using different test portion masses of 1, 0.1 and 0.02 μg. Although avoiding the rim region of the glass wafers, we found moderate inhomogeneities of several chalcophile/siderophile elements and gross inhomogeneities of Ni, Se, Pd and Pt at small test portion masses. The extent of inhomogeneity was included in the determination of uncertainties. While the new reference values agree with the NIST certified values with the one exception of Mn in SRM 610, they typically differ by as much as 10% from the Pearce et al. (1997) values in current use. In a few cases (P, S, Cl, Ta, Re) the discrepancies are even higher.     

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.     

Niobium and Tantalum Concentrations in NIST SRM 610 Revisited

Niobium and Ta concentrations in MPI‐DING and USGS (BCR‐2G, BHVO‐2G, BIR‐1G) silicate rock glasses and the NIST SRM 610–614 synthetic soda‐lime glasses were determined by 193 nm ArF excimer laser ablation and quadrupole ICP‐MS. Measured Nb and Ta values of MPI‐DING glasses were found to be consistently lower than the recommended values by about 15% and 25%, respectively, if calibration was undertaken using commonly accepted values of NIST SRM 610 given by Pearce et al. Analytical precision, as given by the 1 s relative standard deviation (% RSD) was less than 10% for Nb and Ta at concentrations higher than 0.1 μg g^?1. A significant negative correlation was found between logarithmic concentration and logarithmic RSD, with correlation coefficients of ‐0.94 for Nb and ‐0.96 for Ta. This trend indicates that the analytical precision follows counting statistics and thus most of the measurement uncertainty was analytical in origin and not due to chemical heterogeneities. Large differences between measured and expected Nb and Ta in glasses GOR128‐G and GOR132‐G are likely to have been caused by the high RSDs associated with their very low concentrations. However, this cannot explain the large differences between measured and expected Nb and Ta in other MPI‐DING glasses, since the differences are normally higher than RSD by a factor of 3. Count rates for Nb and Ta, normalised to Ca sensitivity, for the MPI‐DING, USGS and NIST SRM 612–614 glasses were used to construct calibration curves for determining NIST SRM 610 concentrations at crater diameters ranging from 16 (im to 60 μm. The excellent correlation between the Nb/Ca_1μgg‐1 signal (Nb represents the Nb signal intensity; Ca_{1μg g‐1} represents the Ca sensitivity) and Nb concentration, and between the Ta/Ca_{1μg g‐1} signal (where Ta represents the Ta signal intensity; Ca_{1μg g‐1} represents the Ca sensitivity) and Ta concentration (R²= 0.9992–1.00) in the various glass matrices suggests that matrix‐dependent fractionation for Nb, Ta and Ca was insignificant under the given instrumental conditions. The results confirm that calibration reference values of Nb and Ta in NIST SRM 610 given by Pearce et al. are about 16% and 28% lower, respectively. We thus propose a revision of the preferred value for Nb from 419.4 ± 57.6 μg g^?1 to 485 ± 5 μg g^?1 (1 s) and for Ta from 376.6 ± 77.6 μg g^?1 to 482 ± 4 μg g^?1 (Is) in NIST SRM 610. Using these revised values for external calibration, most of the determined average values of MPI‐DING, USGS and NIST SRM 612–614 reference glasses agree within 3% with the calculated means of reported reference values. Bulk analysis of NIST SRM 610 by standard additions using membrane desolvation ICP‐MS gave Nb = 479 ± 6 μg g^?1 (1 s) and Ta = 468 ± 7 μg g^?1 (1 s), which agree with the above revised values within 3%.     

Compositional Heterogeneity in NIST SRM 610-617 Glasses

Extensive compositional heterogeneity is shown to affect at least twenty four of the doped trace elements in the NIST SRM 610-617 glasses.
Compositional profiling and mapping using laser ablation ICP-MS reveals that all NIST SRM 610-617 wafers examined here contain domains that are significantly depleted in Ag, As, Au, B, Bi, Cd, Cr, Cs, Mo, Pb, Re, (Rh), Sb, Se, Te, Tl and W, and antithetically enriched in Cu (and Pt), with large enrichments in Cd, Fe and Mn also being encountered in some cases. These domains are visible in doubly polished wafers by unaided visual inspection and by transmitted light and schlieren microscopy. They occur in close proximity to the wafer perimeters and also as stretched and complexly folded forms within wafer interiors. The chemical and optical properties of these heterogeneous domains are consistent with those of compositional cords, a phenomenon of glass manufacture where glass bulk composition and physical properties are modified by loss of volatile components from the molten glass surface. The NIST SRM 610-617 glasses may be considered reliable reference materials for microanalysis of only between one half and two thirds of the trace elements with which they were doped, including Be, Mg, Sr, Ba, Sc, Y, REE, V, Zr, Hf, Nb, Ta, Th, U, Ga, In, Sn, Co, Ni and Zn. These elements show no evidence of significant heterogeneity, indicating that the original glass constituents and possible residues remaining in the furnace from preceding glass batch fusions were well homogenised during manufacture.     

NIST SRM 610, 611 and SRM 612, 613 Multi-Element Glasses: Constraints from Element Abundance Ratios Measured by Microprobe Techniques

The SRM 600 series of glasses, SRM 611 to SRM 619, which nominally contain 500 (SRM 610, 611), 50 (SRM 612, 613), 1 (SRM 614, 615) and 0.02 (SRM 616, 617) μg g⁻¹ of sixty one elements are now being extensively used as microprobe standards. Recent compilations of the trace element concentrations, which include many new multi-element bulk analyses, do not all give the same value within the stated uncertainty; this observation appears to raise questions about the degree of homogeneity on a microscale reported from probe measurements. The ion microprobe cannot give absolute concentrations, but can accurately measure the abundance ratios between glasses of similar major element chemistry. Recent and new probe measurements show that, although the absolute concentrations are significantly lower than the nominal values, the average dilution factors are 12 : 1 : 0.02 : 0.0004 and close to weighed amounts. The consistency between the ratios of random samples of glasses (SRM 610/SRM 612 and SRM 611/SRM 613) strongly supports a high degree of homogeneity on all scales. The measured abundance ratios between two glasses can, therefore, act as a useful check on bulk measurement accuracy. A clear correlation in the SRM 610, 611/SRM 612, 613 ratios measured by ion probe and SRM 612 trace concentrations measured by bulk techniques demonstrates that SRM 610, 611 has a much more uniform trace content than SRM 612, 613.     

Forty‐Nine Major and Trace Element Concentrations Measured in Soil Reference Materials NIST SRM 2586, 2587, 2709a, 2710a and 2711a Using ICP‐MS and Wavelength Dispersive‐XRF

Excellent agreement was noted in the concentration of major and trace elements in five NIST (National Institute for Science and Technology) soil reference materials (NIST SRM 2586, 2587, 2709a, 2710a and 2711a) between measurement results from wavelength dispersive‐XRF and ICP‐MS from two independent laboratories, and NIST certificate of analysis and literature data. We describe the variability in concentrations of up to forty‐nine elements (plus loss on ignition) and provide values for up to twenty‐one elements previously uncharacterised by NIST in these soil RMs. The additional characterisation provided in this investigation can be utilised to reduce the measurement bias of custom calibration routines and improve the quality of control checks developed using these NIST RMs.     

Determination of Thallium in the USGS Glass Reference Materials BIR‐1G,BHVO‐2G and BCR‐2G and Application to Quantitative Tl Concentrations by LA‐ICP‐MS

Here, we present determinations of thallium (Tl) concentrations in the USGS reference materials BIR‐1G, BHVO‐2G and BCR‐2G measured by solution ICP‐MS. The Tl content in these three glasses spans a range of about 2–230 ng g^?1, which is similar to the values published for the respective powder materials. The determined range of Tl concentrations in these three glass reference materials makes them ideal for investigating Tl concentrations in basaltic and andesitic volcanic glasses. We also performed a series of laser ablation ICP‐MS measurements on the three samples, which show that this technique is able to determine Tl concentrations in glass samples with concentrations as low as 2 ng g^?1.     

Determination of Lithium in the NRCC Marine Sediments: MESS-1, BCSS-1, PACS-1 and the NIST River Sediment: SRM 2704

NRCC marine sediment reference materials: MESS-1, BCSS-1, PACS-1 and the NIST river sediment: SRM 2704 have been analyzed in replicate for lithium (Li) by flame atomic absorption spectrophotometry. Precision (% coefficient of variation) for the NRCC SRM's was <1.5%, and the NIST SRM was 4.3%. Results from replicate acid dissolution of the SRM's in Teflon bombs using boiling water and microwave heating showed no difference in Li concentration between the two methods.     

α- and β-diversity Change of Late Ordovician Hirnantia Fauna of Changning, Sichuan, Southwest China

A continuous Ordovician-Silurian boundary section from the upper Wufeng Formation through the Kuanyinchiao Formation to the lower Lungmachi Formation has been carefully measured and collected at Shuanghe of Changning, southern Sichuan Province. For the first time, the temporal changes of α- and β-diversities of the Hirnantia fauna have been discussed in great detail. The general trend of brachiopod diversity change, increasing upward, is consistent with the regional trend of the Yangtze Platform, which had been controlled by both intrinsic and extrinsic factors. However, the sudden drop of diversity for a short period in the upper Kuanyinchiao Formation might have been controlled by environmental factors rather than normal faunal turnover. Synecological analysis using numerical methods recognizes two brachiopod-dominated associations of the Hirnantia fauna, the Dalmanella-Kinnella Association and the Mirorthis Association, both living in an offshore, deeper water environment corresponding to BA3-upper BA4, particularly lower BA3.     

Results for Rarely Determined Elements in MPI-DING, USGS and NIST SRM Glasses Using Laser Ablation ICP-MS

New analytical results are reported for rarely determined elements Be, B, Ge, As, Mo, Rh, Pd, Ag, Cd, In, Sn, Sb, W, Re, Ir, Pt, Au, Tl and Bi in MPI‐DING and USGS (BCR‐2G, BHVO‐2G, BIR‐1G) silicate glasses and the NIST SRM 610‐614 synthetic soda‐lime glasses using 193 nm ArF excimer laser ablation and quadrupole ICP‐MS. The method used involved external calibration against GOR132‐G for Ir and NIST SRM 610 for other elements, internal standardisation using Ca, and ablation with a crater diameter of 160 μm and a pulsed laser repetition rate of 10 Hz. Small amounts of nitrogen (5 ml min^?1) were added to the central channel gas of the plasma to improve the limits of detection for most of these elements by a factor of 1.2–2.5 and to reduce the oxide interference level to 0.02% (ThO⁺/Th⁺). Under these conditions, the LODs for most of these rarely determined elements were within the range 0.1 to 10 ng g^?1. The operating conditions that were required to minimise ICP‐induced fractionation (U⁺/Th⁺≈ 1) in the mode without nitrogen were accompanied by a 50–60% reduction in sensitivity for elements such as Ca, Au and Pt. In contrast, ICP‐induced fractionation could be minimised (U⁺/Th⁺≈ 1) with no loss of analyte sensitivity in the nitrogen mode. Interferences of CuAr⁺, ZnAr⁺, Cd⁺, Pb²⁺ and Sn⁺ on Pd⁺, Rh⁺, Cd⁺ and In⁺ were corrected. Oxide interferences were not considered due to their lower production rate. Analytical precision, as given by one relative standard deviation (% RSD) was less than 15% for most of the elements present at concentrations greater than 0.1 μg g^?1. A significant negative correlation was found between logarithmic concentration and logarithmic RSD, with a correlation coefficient of ?0.76. This trend indicates that possible chemical heterogeneities for most of these elements are smaller than the analytical uncertainty. Our results for Be, B, Ge, Sb and W are generally in good agreement with their reference values. In contrast, other elements in many of the reference glasses have only information values, upper limits or even no values, which restrict any detailed evaluation of the accuracy of the determined values. However, concentrations from multiple isotopes of one element analysed in this study showed excellent agreement, which guarantee the quality of our data to a certain extent.     

SIMS Determination of μg g−1-Level Fluorine in Geological Samples and its Concentration in NIST SRM 610

The fluorine concentration in NIST SRM 610 was determined by SIMS to be 295 16 μg g⁻¹ (5.40% relative standard deviation). Accuracy of the measurement was determined from a calibration involving the synthesis of glass calibration samples doped with varying concentrations of fluorine and characterized by electron microprobe analysis and SIMS. The calibration was accurate to about 5%. Multiple analyses of the calibration samples and SRM 610 in three different analytical sessions combine to produce a low relative standard deviation of the mean (0.23% RSD) in the mean fluorine value for SRM 610. Analytical uncertainty in the fluorine value was 5.40% (RSD), originating from a combination of calibration and ion counting uncertainties as determined from multiple analyses. Evaluation of the SIMS technique using the new fluorine value in SRM 610 shows that this element can be determined with a precision and accuracy superior to that of EPMA. Measurements of fluorine in igneous and hydrothermal zircon suggest that F-ligands may have been responsible for Zr transportation in hydrothermal fluids also responsible for W-Au mineralisation. Other applications for low-level fluorine determinations may include melt inclusions and nominally anhydrous mineral phases, particularly mantle phases.     

Strontium, Neodymium and Lead Isotope Analyses of NIST Glass Certified Reference Materials: SRM 610, 612, 614

The NIST glass certified reference materials, SRM 610-617, have been widely adopted by the geological community as calibration samples for a variety of in situ trace element analytical techniques. There is now an urgent requirement for similar reference materials for in situ isotopic analytical techniques. We have analysed SRM 610, 612 and 614 for their Pb, Sr and Nd isotopic compositions using thermal ionisation mass spectrometry. Large differences in isotopic composition were observed between each CRM, suggesting a significant trace element content in the initial starting material (base glass). As a result, isotopic compositions for one CRM cannot be extrapolated to another, and each must be calibrated for use independently. We present the first compilation of working values for these glasses.