Geostandards and Geoanalytical Research最新文献

In this study we determined rubidium isotope ratios in twenty-one commonly used international geological reference materials, including igneous, sedimentary and metamorphic rocks, as well as an IAPSO seawater reference material. All δ⁸⁷Rb results were obtained relative to the NIST SRM 984 reference material. For most reference materials, Rb was purified using a single column loaded with Sr-spec resin. For reference materials containing low Rb but high mass fractions of matrix elements (such as basic rock and seawater), Rb was purified using two-column chromatography, with the first column packed with AGMP-50 resin and the second column packed with Sr-spec resin. Two methods for instrumental mass bias correction, sample-standard bracketing (SSB) mode, and the combined sample-standard bracketing and Zr internal normalisation (C-SSBIN) method, were compared for Rb isotopic measurements by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The long-term reproducibility of Rb isotopic measurements using both methods was similar, better than 0.06‰ (2s, standard deviation) for NIST SRM 984. Significant Rb isotopic fractionation was observed among the reference materials, with an overall variation in δ⁸⁷Rb values of approximately 0.5‰. The δ⁸⁷Rb values of igneous rocks ranged from -0.28‰ to +0.06‰, showing a trend from heavier isotopic compositions in mafic rocks to lighter δ⁸⁷Rb values in the more evolved felsic rocks. The sedimentary and metamorphic rocks had Rb isotope ratios similar to those of igneous rocks. The δ⁸⁷Rb values of the reference materials related to low-temperature geological processes showed a wider range than those of high-temperature processes. Notably, the IAPSO seawater reference material had a δ⁸⁷Rb value of +0.14‰, which deviated from that of igneous rocks, and represents the heaviest reservoir of Rb isotopes found thus far on Earth. The comprehensive dataset presented here has the potential to serve for quality assurance purposes, and provide a framework for interlaboratory comparisons of Rb isotope ratios.

The National Centre for Compositional Characterisation of Materials (NCCCM) / Bhabha Atomic Research Centre (BARC) and National Aluminium Company Limited (NALCO), India have produced an Indian origin bauxite certified reference material (CRM), referred to as BARC-B1201, certified for major (Al₂O₃, Fe₂O₃, SiO₂, TiO₂, loss on ignition - LOI) and trace contents (V₂O₅, MnO, Cr₂O₃, MgO). Characterisation was undertaken by strict adherence to ISO Guides. A method previously developed and validated in our laboratory, using single step bauxite dissolution and subsequent quantitation (of Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃ and MgO) by ICP-AES (SSBD ICP-AES) was used for homogeneity studies and an inter-laboratory comparison exercise (ILCE) of the candidate CRM. LOI was determined by thermo-gravimetric analysis. Property values were assigned after an ILCE with participation from seventeen reputed government and private sector laboratories in India. The CRM was certified for nine property values: Al₂O₃, Fe₂O₃, SiO₂, TiO₂, V₂O_5, MnO, Cr₂O₃, MgO and LOI, which are traceable to SI units.

Although in situ analysis by LA-ICP-MS is considered a rapid technique with minimal sample preparation and data reduction, mapping areas of millimetres in size using a small beam (< 15 μm) can be time consuming (several hours) when a quadrupole ICP-MS is used. In addition, fully quantitative imaging using internal standardisation by LA-ICP-MS is challenging in samples with more than one mineral phase present due to varying ablation rates. A new protocol for the quantification of multiple coexisting phases, mapped at a rate of about 12 mm² h^-1 and a resolution of 12 μm × 12 μm per pixel, is presented. The protocol allows mapping of most atomic masses, ranging from ²³Na to ²³⁸U, using a time-of-flight mass spectrometer (ICP-ToF-MS, TOFWERK) connected to a 193 nm excimer laser. A fast-funnel device was successfully used to increase the aerosol transport speed, reducing the time usually required for mapping by a factor of about ten compared with a quadrupole ICP-MS. The lower limits of detection for mid and heavy masses are in the range 0.1–10 μg g^-1, allowing determination of trace to ultra-trace elements. The presented protocol is intended to be a routine analytical tool that can provide greater access to the spatial distribution of major and trace elements in geological materials.

Laser ablation multi-collector mass spectrometry (LA-MC-ICP-MS) has emerged as the technique of choice for in situ measurements of Sr isotopes in geological minerals. However, the method poses analytical challenges and there is no widely adopted standardised approach to collecting these data or correcting the numerous potential isobaric inferences. Here, we outline practical analytical procedures and data reduction strategies to help establish a consistent framework for collecting and correcting Sr isotope measurements in geological materials by LA-MC-ICP-MS. We characterise a new set of plagioclase reference materials, which are available for distribution to the community, and present a new data reduction scheme for the Iolite software package to correct isobaric interferences for different materials and analytical conditions. Our tests show that a combination of Kr-baseline subtraction, Rb-peak-stripping using βRb derived from a bracketing glass reference material, and a CaCa or CaAr correction for plagioclase and CaCa or CaAr + REE²⁺ correction for rock glasses, yields the most accurate and precise ⁸⁷Sr/⁸⁶Sr measurements for these materials. Using the analytical and correction procedures outlined herein, spot analyses using a beam diameter of 100 μm or rastering with a 50–65 μm diameter beam can readily achieve < 100 ppm 2SE repeatability ("internal") precision for ⁸⁷Sr/⁸⁶Sr measurements for materials with < 1000 μg g^-1 Sr.

The Cr isotope ratios of terrestrial and extra-terrestrial materials are emerging as one of the most important tracers in geosciences. Previous studies on Cr isotopic measurements using TIMS have found that there is residual Cr isotopic fractionation between the mass-fractionation-corrected ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios, which may cause an offset of obtained ratios from the reference values. The residual fractionation was thought to be caused by the evaporation of Cr-oxide species during thermal ionisation, but the mechanism by which this residual fractionation could be reduced remained unclear. Here we revisit the issue of residual fractionation and propose that this problem can be alleviated by utilising W filaments instead of conventionally used Re filaments for Cr ionisation. Using W filaments, the formation of CrO⁺ was suppressed during heating as the filament temperature was ~ 100 °C lower than when Re filaments were used. In repeated measurement of a carbonaceous chondrite, the intermediate precisions of ⁵³Cr/⁵²Cr and ⁵⁴Cr/⁵²Cr ratios in the W filament runs were two to three times better than those of the Re filament runs. Therefore, the new finding of this study will be of key importance for future studies of Cr isotopes for terrestrial and extra-terrestrial materials.

U-Pb dating of andradite-grossular garnet (grandite) and rutile by LA-ICP-MS can be used to constrain various metamorphic, metasomatic and igneous geological processes. In this study, we examine and compare the impact of different analytical conditions (fluence, pulse width, laser beam size and ablation frequency) on the ablation crater morphology, ablation rates, down-hole fractionation and U-Pb ages of grandite and rutile samples of different compositions. The shapes of grandite ablation craters suggest the mineral ablates by classical evaporation with significant melting that cannot be eliminated even at fluences just above the ablation threshold. Grandite garnets with higher andradite proportions have faster ablation rates. The overall low U contents of grandite require using large laser beam sizes to obtain acceptable precision of U-Pb ages. At such conditions and crater depths < 10 μm, fluences of 2.1 and 3.5 J cm^-2, laser pulse width of 5 ns and 20 ns, and ablation frequencies between 3.5 and 6.5 Hz, obtain similar and reproducible ages when the proportion of grossular is < 35%. Rutile ablation crater morphology shows evidence of melt splashing and thermal stress cracking. They have significant crater bottom features, which increase in relief with lower fluences and a higher number of laser shots, indicating the features are probably energy-related and making higher fluences, such as 5 J cm^-2, necessary for uniform ablation when using 193 nm excimer lasers. The slow ablation rate at low fluences and then steep increase at around 2.0 J cm^-2 suggests a transition in the ablation mechanism from exfoliation to classical vaporisation. Crater bottom features and other ablation behaviour vary between samples, which could be related to their difference in colour. Although the down-hole fractionation patterns of the samples are similar at 5 J cm^-2, the U-Pb ages of some samples vary significantly with different analytical conditions and/or measurement sessions, particularly when using laser beam sizes of 30 μm, suggesting differences in mass bias and more variable ablation behaviour. A laser beam size of at least 60 μm is recommended for reproducible U-Pb dating of rutile.

Twelve apatite samples have been tested as secondary ion mass spectrometry (SIMS) reference materials. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis shows that the SLAP, NUAN and GR40 apatite gems are internally homogeneous, with most trace element mass fractions having 2 standard deviations (2s) ≤ 2.0%. BR2, BR5, OL2, AFG2 and AFB1, which have U > 63 μg g^-1, ²⁰⁶Pb/²⁰⁴Pb > 283, and homogeneous SIMS U-Pb data, have respective isotope dilution thermal ionisation mass spectrometry (ID-TIMS) ages of 2053.83 ± 0.21 Ma, 2040.34 ± 0.09 Ma, 868.87 ± 0.25 Ma, 478.71 ± 0.22 Ma and 473.25 ± 0.09 Ma. Minor U-Pb heterogeneity exists and accurate SIMS results require correction with the 3D Concordia-constrained common Pb composition. Among the studied samples, AFG2 and BR5 are the most homogeneous U-Pb reference materials. The SIMS sulfur isotopic compositions of eight of the apatites shows they are homogeneous, with 2s for both 10³δ³⁴S and 10³δ³³S < 0.55‰. One apatite, BR96, has Δ³³S = -0.36 ± 0.2‰. The apatite samples have ID-TIMS ⁸⁷Sr/⁸⁶Sr between 0.704214 ± 0.000030 and 0.723134 ± 0.000035.