Geostandards and Geoanalytical Research最新文献

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.

The isotopic composition of cadmium in nuclear debris was measured by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). Mass-independent perturbations due to fission product decay on the isotopes of Cd were observed. Relative fission yields for masses 111, 112, 114 and 116 were determined in each sample of nuclear debris and compared with reported values found in irradiated plutonium and uranium fuels. Mass spectrometry measurements of the valley fission product endpoints are extremely challenging due to the low cumulative fission yields and small amounts of each isotope that are produced. To overcome these challenges, a new purification method for Cd was developed and validated by examination of a number of geological reference materials.

U-Pb Saturn is new freeware for U-Pb LA-ICP-MS data reduction. It has been developed to provide easy interaction with and visualisation of LA-ICP-MS U-Pb datasets, and allows fast and reliable data reduction of hundreds of data-points. Saturn offers dynamic graphic interfaces to quickly view, evaluate, and plot U-Pb and Pb-Pb isotope data. It operates online (or offline), giving the freedom to change parameters and reprocess data at any stage of data acquisition. The main interface allows the user to: (1) choose the best statistics for drift correction, (2) include/exclude offset factors and (3) apply (or not) Pb_c corrections in different modes. Signal intensities are displayed in a separate graphic interface that allows users to interact with the time-resolved signal of individual spot analyses. All graphic windows are interactive; any modification to data treatment (e.g., inclusion or exclusion of analyses of reference material, or modification of the time-resolved signal windows) is instantaneously updated on the data tables. Saturn is particularly attractive for beginners in LA-ICP-MS U-Pb geochronology as it is non-commercial, easy to install, and very interactive. Coding information and a version of the software can be accessed at http://www.air.ufop.br.