Trace Element Analysis of NIST SRM 614 and 616 Glass Reference Materials by Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry

Fifty elements in NIST SRM 614 and 616 glass reference materials were determined by laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS). The values determined for NIST SRM 614 agreed well with the NIST-certified and information values (mean relative difference ± 3.6%), except for B, Sc and Sb. The values determined for NIST SRM 616 agreed with the NIST-certified and information values within a mean relative difference of ± 1.5%, except for B, Sc and Ga. In addition, at an 80 μm sampling scale, NIST SRM 614 and 616 glass discs were homogeneous for trace elements within the observed precisions of 5 and 15% (mean), respectively. Detection limits were in the range 0.01 - 0.3 μg g⁻¹ for elements of lower mass numbers (amu < 80) and 1 - 10 ng g⁻¹ for heavy elements (amu > 80). Detection at the sub ng g⁻¹ level is possible for most of the heavy elements by using an ablation pit size larger than 10 0 μm.     

Determination of Selenium Concentrations in NIST SRM 610, 612, 614 and Geological Glass Reference Materials Using the Electron Probe, LA-ICP-MS and SHRIMP II

A combination of EMPA, sensitive high resolution ion microprobe (SHRIMP II) and/or LA-ICP-MS techniques was used to measure the concentration of selenium (Se) in NIST SRM 610, 612, 614 and a range of reference materials. Our new compiled value for the concentration of Se in NIST SRM 610 is 112 ± 2 μg g⁻¹. The concentration of Se in NIST SRM 612, using NIST SRM 610 for calibration, determined using LA-ICP-MS (confirmed using SHRIMP II) was 15.2 ± 0.2 μg g⁻¹. The concentration of Se in NIST SRM 614, using LA-ICP-MS was 0.394 ± 0.012 μg g⁻¹. LA-ICP-MS determination of Se in synthetic geological glasses BCR-2G, BIR-1G, TB-1G and the MPI-DING glasses showed a range in concentrations from 0.062 to 0.168 μg g⁻¹. Selenium in the natural glass, VG2, was 0.204 ± 0.028 μg g⁻¹.     

Determination of Lithium, Beryllium and Boron at Trace Levels by Laser Ablation-Inductively Coupled Plasma-Sector Field Mass Spectrometry

The analytical capabilities of laser ablation (LA)-ICP-MS in determining Li, Be and B at trace levels in geological samples have been tested on a series of glass reference materials and natural samples. The LA-ICP-MS instrument used consisted of a sector-field ICP-MS coupled with a laser ablation microprobe operating at either 266 or 213 nm wavelength. Reference glasses from NIST (SRM 612, 614 and 616) and MPI-DING (KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, T1-G and ATHO-G) were selected to develop the analytical method and to assess the best instrumental configuration. A series of calcic amphiboles with different Li, Be and B concentrations were also analysed using both LA-ICP-MS and SIMS to test the applicability of the method to natural minerals. Results indicated that with a spot size of 40 μm the agreement between measured and reference values of Li, Be and B is generally better than 10% for NIST SRM 612 and 20% for NIST SRM 614. Average reproducibility at the 2s level was 10% for Li, 20% for Be and 15% for B. Limits of detection were approximately 100 ng g^-1 for Be and B and 200 ng g^-1 for Li. These results were confirmed by analyses carried out on natural amphiboles and compared well in terms of precision and accuracy with those commonly achieved by SIMS.     

Analysis of Re, Au, Pd, Pt and Rh in NIST Glass Certified Reference Materials and Natural Basalt Glasses by Laser Ablation ICP-MS

A new technique for the in situ analysis of Re, Au, Pd, Pt and Rh in natural basalt glass by laser ablation (LA)-ICP-MS is described. The method involves external calibration against NIST SRM 612/613 or 614/615 glass certified reference materials, internal standardisation using Ca, and ablation with a 200 μm wide beam spot and a pulsed laser repetition rate of 50 Hz. Under these conditions, sensitivities for Re, Au, Pd, Pt and Rh analyte ions are ˜ 5000 to 100,000 cps/μg g^-1. This is sufficient to make measurements precise to ˜ 10% at the 2-10 μg g^-1 level, which is well within the range of concentrations expected in many basalts. For LA-ICP-MS calibration and a demonstration of the accuracy of the technique, concentrations of Re, Au, Pd, Pt and Rh in the NIST SRM 610/611 (˜ 1 to 50 μg g^-1), 612/613 (˜ 1 to 7 μg g^-1), 614/615 (˜ 0.2 to 2 μg g^-1) and 616/617 (˜ 0.004 to 2 μg g^-1) glasses were determined by solution-nebulisation (SN)-ICP-MS. Using the 612/613 or 614/615 glasses as calibration standards, LA-ICP-MS measurements of these elements in the other NIST glasses fell within ˜ 15% of those determined by SN-ICP-MS. Replicate LA-ICP-MS analyses of the 612/613 and 614/615 glasses indicate that, apart from certain anomalous domains, the glasses are homogeneous for Re, Au, Pd, Pt and Rh to better than 3.5%. Two LA-ICP-MS analyses of natural, island-arc basalt glasses exhibit large fractionations of Re, Au and Pd relative to Pt and Rh, compared to the relative abundances in the primitive mantle.     

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.     

Ultra-Trace Element Analysis of NIST SRM 616 and 614 using Laser Ablation Microprobe-Inductively Coupled Plasma-Mass Spectrometry (LAM-ICP-MS): a Comparison with Secondary Ion Mass Spectrometry (SIMS)

The microanalytical capability of laser ablation microprobe-inductively coupled plasma-mass spectrometry (LAM-ICP-MS) to determine ultra trace elemental concentrations has been demonstrated by the analysis of two low concentration glass standard reference materials, NIST SRM 614 and 616. Results for fifty two elements at concentrations in the low ng g^-1 range are compared with those determined using secondary ion mass spectrometry (SIMS). Both techniques provide results at these concentrations that generally agree within 95% confidence limits, demonstrating the accuracy for ultra-trace level of in situ determinations by the two techniques. At concentrations of less than 20 ng g^-1 in NIST SRM 616, an accuracy and precision of better than 10% has been obtained for most mono-isotopic rare earth elements, when a spot size of 50 μm is used. Limits of detection for selected elements were as low as 0.5 ng g^-1.     

Chemical Characterisation of NIST Silicate Glass Certified Reference Material SRM 610 by ICP-MS, TIMS, LIMS, SSMS, INAA, AAS and PIXE

National Institute of Science and Technology (NIST) silicate glass SRM 610 is widely used as a certified reference material for various micro-analytical techniques such as SIMS or laser ablation ICP-MS. SRM 610 has been nominally doped with sixty one trace elements at the 500 μg g⁻¹ level, but certified concentration data exist for only a few of these elements. This study reports concentration data for fifty nine trace elements obtained by ICP-MS, SSMS, LIMS, TIMS, INAA, AAS, and PIXE analyses of two different SRM 610 wafers. Most elements fall within a 10% band around a median value of about 440 μg g⁻¹. The REE concentrations are shown to be constant to 3% (1 σ), thus emphasizing the value of SRM 610 as a reference material for REE analyses.
Comparison of our values with published data suggests that different SRM 610 wafers are, within errors, chemically identical for most elements. Exceptions to this general rule appear to be restricted to elements which were partly lost during the production of the glass, e.g. Ag and Br. On the basis of six independent determinations of Rb concentrations, which are systematically lower by a few percent than the reported NIST value, we argue that the certified Rb concentration may not be representative for all distributed SRM 610 wafers.     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

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.     

Trace Element Analysis of Fused Whole-Rock Glasses by Laser Ablation-ICP-MS and PIXE

The concentrations of fifty trace elements, including relatively volatile elements and transition metal elements, in fused glasses of Geological Survey of Japan rock reference materials GSJ JR-2, JA-1, JA-2, JB-1a, JB-3, JGb-1 and JF-1 were determined by particle (proton) induced X-ray emission (PIXE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The fused glasses were prepared by rapid fusion and subsequent quenching in welded platinum capsules and were found to be homogeneous for major elements and for trace elements with concentrations of more than 1 μg g^-1 within the observed precision (± 10% mean) on a 70 μm sampling scale. The values obtained by PIXE and LA-ICP-MS for the transition elements (Cr, Mn, Fe, Ni and Cu), the relatively volatile elements (Zn, Ga, Rb and Pb) and the refractory elements (Y, Zr, Nb and Th) with concentrations greater than a few μg g^-1 showed good agreement (within 10 % relative difference). The values for almost all the elements detected at concentrations higher than 1 μg g^-1 as determined by LA-ICP-MS also agreed well with the reference values (mean relative difference < ± 10%), except for B and Cu. The good agreement confirmed the appropriateness of the NIST SRM 600 series glass calibration reference material for LA-ICP-MS analysis of glasses with variable major-element compositions for almost all elements. The concentrations of Cu in all the samples were lower than the reference values, which was attributed to adsorption of the transition metals onto the platinum capsule during preparation.     

Flotation Separation of Trace Elements from Alkaline-Earth Matrices by Co(III) Hexamethylenedithiocarbamate before ICP-AES Determination

A method for the selective separation of Ag, Cd, Cr, Cu, Ni, Pb and Zn in traces from solutions of calcite (CaCO₃), dolomite (CaMg(CO₃)₂) and gypsum (CaSO₄.2H₂O) before their determination by inductively coupled plasma-atomic emission spectrometry (ICP-AES) is presented. The expected interferences of Ca and Mg on intensities of trace analytes were removed by collecting the elements of interest with cobalt(III) hexamethylenedithiocar-bamate, Co(HMDTC)₃. The flotation of aqueous solutions (1 l) of calcite, dolomite and gypsum was performed at pH 6.0, by 1.5 mg l⁻¹ Co and 0.6 mmol l⁻¹ HMDTC⁻. To minimise the effect of the reaction between Ca/Mg, which restrains the function of the surfactant, careful selection of the most suitable foaming reagent was necessary. The accuracy of the method was established by analysing natural alkaline-earth minerals by the standard addition method as well as using the dolomite reference materials GBW 07114 and GSJ JDo-1. The ICP-AES limits of detection following flotation on different minerals were found to be 0.080 μg g⁻¹ for Cd, 0.105 μg g⁻¹ for Ag, 0.142 μg g⁻¹ for Cu, 0.195 μg g⁻¹ for Cr, 0.212 μg g⁻¹ for Ni, 0.235 μg g⁻¹ for Zn and 0.450 μg g⁻¹ for Pb.     

Determination of Multiple Trace Element Compositions in Thin (> 30 μm) Layers of NIST SRM 614 and 616 Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS)

To understand and/or avoid small-scale chemical heterogeneities within geological materials prepared as normal thin sections, in situ multiple trace element determination coupled with the simultaneous microscopic observation of the sample during analysis is preferable. We have examined fifty trace elements in thin (< 30 μm) layers of the NIST SRM 614 and 616 glass reference materials by LA-ICP-MS using different pit diameters and internal standard elements (Ca and Si). Compositional heterogeneities of Tl, Bi, As and Cd were found in NIST SRM 614 and 616 at the spatial resolution of ca. 10 0 μm. Except for these elements, the RSDs of six determinations for most elements were better than 10% in NIST SRM 614 when ablation diameters were < 50 μm. The measured concentrations for most elements in NIST SRM 614 and 616 agree with previous values in the literature at the 95% confidence level with the exception of W and Bi. New LA-ICP-MS data for K, As and Cd are also reported. The results support the view that the latest LA-ICP-MS is a powerful and flexible analytical technique for the determination of multiple ultra-trace element compositions in geological materials prepared as normal thin sections of the type that has been used for polarising optical microscopic observations since the end of the 19th century.     

Simultaneous Determination of Total Carbon, Nitrogen, Hydrogen and Sulfur in Twenty-seven Geological Reference Materials by Elemental Analyser

The contents of total carbon, hydrogen, nitrogen and sulfur in twenty-seven geological reference materials, issued by five producer organisations (USGS, CCRMP, ANRT, NIST and GSJ) were determined using an automated simultaneous elemental analyser following combustion. In order to complete gasification of C and N in some geological materials, the combustion temperature needed to be greater than 1150 °C. The calibrator prepared from known amounts of reagent material was not adopted for more than 1.2% m/m of H. Unrealistically high values in certain materials supposed to contain less than 1000 μg g⁻¹ S may be due mainly to memory effects. The limit of detection was 50 μg g⁻¹ for C and N, 500 μg g⁻¹ for H and 1000 μg g⁻¹ for S. Although the blank value of C and N was always stable and less than one third of the detection limit, it had a slightly higher value for N and S. By repeating long-term analysis, high reproducibility for each of the four elements was verified. The method has been applied satisfactorily to a variety of geological reference materials, and recommended values for C, H and N for most of the reference materials studied have been tabulated.     

Boron Isotopic Composition and Concentration of Ten Geological Reference Materials

We present boron isotope and concentration data from magmatic (komatiitic to rhyolitic) and sedimentary geological silicate and artificial glass reference materials that cover a wide spectrum of boron isotope compositions and boron concentrations. Boron isotope compositions were determined by TIMS (Cs₂BO₂⁺ -graphite and BO₂^- method) and boron concentrations by ICP-AES. Boron concentrations ranged from 7 to 159μ g^-1 and agree within 14% with published values. Based on replicate analyses of individually prepared sample aliquots an overall external reproducibility of better than 10% was determined. The obtained δ¹¹B values ranged from -12.6 to +13.6% and were reproducible within 1.1 % (2 RSD; excluding NTIMS) on the basis of individually prepared sample aliquots. The δ¹¹B values of JA-1 (+5.3%), JB-3 (+5.9%) and JR-2 (+2.9%) overlap the published data within analytical uncertainty. For the first time δ¹¹B values for the TB (-12.6%) and the MPI-DING glasses GOR-128-G (+13.6%), GOR-132-G (+7.1 %) and StHs6/80-G (-4.5%) are reported. The δ¹¹B values obtained by the Cs₂BO₂⁺ -graphite and the BO₂^- method as well as the majority of δ¹¹B values obtained using different sample preparation methods agree within analytical uncertainty. Therefore, we conclude that none of these analytical methods introduce any systematic error on the obtained δ¹¹B values.     

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%.     

Boron and Oxygen Isotope Composition of Certified Reference Materials NIST SRM 610/612 and Reference Materials JB-2 and JR-2

We present data on the concentration, the isotope composition and the homogeneity of boron in NIST silicate glass reference materials SRM 610 and SRM 612, and in powders and glasses of geological reference materials JB-2 (basalt) and JR-2 (rhyolite). Our data are intended to serve as references for both microanalytical and wet-chemical techniques. The δ¹¹ B compositions determined by N-TIMS and P-TIMS agree within 0.5% and compare with SIMS data within 2.5%. SIMS profiles demonstrate boron isotope homogeneity to better than δ¹¹ B = 2% for both NIST glasses, however a slight boron depletion was detected towards the outermost 200 μm of the rim of each sample wafer. The boron isotope compositions of SRM 610 and SRM 612 were indistinguishable. Glasses produced in this study by fusing JB-2 and JR-2 powder also showed good boron isotope homogeneity, both within and between different glass fragments. Their major element abundance as well as boron isotope compositions and concentrations were identical to those of the starting composition. Hence, reference materials (glasses) for the in situ measurement of boron isotopes can be produced from already well-studied volcanic samples without significant isotope fractionation. Oxygen isotope ratios, both within and between wafers, of NIST reference glasses SRM 610 and SRM 612 are uniform. In contrast to boron, significant differences in oxygen isotope compositions were found between the two glasses, which may be due to the different amounts of trace element oxides added at ten-fold different concentration levels to the silicate matrix.     

U-Pb Zircon Geochronology with an Integrated LA-ICP-MS Microanalytical Workstation: Achievements in Precision and Accuracy

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is a microanalytical tool especially suitable for providing fast and precise U-Pb geochronological results on zircon grains. A new 193 nm excimer laser adapted to a micromachining workstation, equipped with a newly designed two-volume ablation cell and coupled with a quadrupole ICP-MS, is presented here. The system was tuned routinely to achieve sensitivities in the range of 3000 cps/μg g⁻¹ for ²³⁸U (< 2% RSD), with a 34 μm spot size, at 5 Hz and ∼ 8 J cm⁻², while ablating the NIST SRM 612 glass reference material. The system was capable of providing fast (< 1.5 minutes each analysis) and precise (generally < 1.5% 1s errors) ²⁰⁶Pb/²³⁸U zircon ages. The ages of widely used reference material zircons (Plesovice, 337 Ma; Temora, 416 Ma; R33, 418 Ma; Sri Lanka, 564 Ma; 91500, 1065 Ma) could be precisely matched, with an accuracy on isotopic ratios that ranged from ∼ 2 to ∼ 6%, depending on the homogeneity of the natural reference materials.     

Preparation of a Synthetic Titanite Glass Calibration Material for In Situ Microanalysis by Direct Fusion in Graphite Electrodes: A Preliminary Characterisation by EPMA and LA-ICP-MS

This paper describes a technique for the preparation of a titanite (CaTiSiO₅) glass calibration material for use in in situ microanalysis of major, minor, and trace elements in geological materials. The starting composition was a titanite matrix doped with minor and trace elements at ∼ 200 μg g^-1. The elements Sc, Y, REEs, Th and U were added in the form of nitrates in solution, and the elements V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Hf and W were added as solid oxides. The synthetic titanite glass was produced by direct fusion by resistance heating in graphite electrodes at 1600-1700 °C, and quenched in air. Backscattered electron images indicate good homogeneity, with no signs of separate phases or vesicles, and analysis of the major elements Ca, Ti and Si by electron microprobe showed relative standard deviations between 0.5 and 0.7%, based on six independent measurements. Deviations from nominal concentrations for Ca, Si and Ti were measured to -1.2, -3.3 and -0.8%, respectively. The homogeneity of the trace elements in the glass was assessed by LA-ICP-MS analyses, using NIST SRM 610, 612 and 616 as external calibrators, and Ca as the internal standard element. Determinations were made both with a quadrupole mass spectrometer and a sector field instrument, and both raster and spot modes of analysis were used. For the majority of doped elements, precision was better than 10%, and relative deviations from nominal values were, with few exceptions, between 5 and 10%.     

Determination of Molybdenum in Fifty Three Geochemical Reference Materials by Flameless Atomic Absorption Spectrometry

The molybdenum (Mo) contents of fifty three geochemical reference materials issued by ANRT, GIT-IWG, NIST and GSJ, have been determined by atomic absorption spectrometry, using a graphite furnace atomiser, after extraction of Mo dithiol with isoamyl acetate. Detection limits for this method (0.01 μg g⁻¹) are ten times smaller than for most classical methods. The agreement between the present results and published data is satisfactory.