Geostandards and Geoanalytical Research最新文献

Quantification of water content in silicate glasses is of vital significance in understanding magma evolution and metamorphic anataxis. Here we provide a method for the determination of total dissolved water content and water speciation in silicate melts by confocal laser Raman spectrometry based on a set of hydrous rhyolitic glasses. A series of alumino-silicate glasses with water contents from 0.33 to 9.05% m/m were synthesised in a piston cylinder apparatus. Synchrotron-FTIR mapping shows that these glasses have relatively homogeneous distributions of dissolved water. Total water contents of the glasses were precisely measured by TC/EA-MS and FTIR. Both external and internal calibration were established for the quantitative analysis of water content and water speciation in the silicate glasses based on excellent linear correlation between total dissolved water content and integrated area of the water Raman band. Furthermore, by decomposing the total water Raman bands into four Gaussians components, the relative concentration of water speciation (OH groups and molecules H₂O_m) dissolved in the glasses was determined with a similar trend to water speciation data derived from FTIR. We suggest that the relative concentration of water speciation can be estimated in rhyolitic glasses with 4–8% m/m H₂O. Our work provides an accurate method to determine total water content and a potential tool to limit the relative concentration of water speciation dissolved in silicic glasses.

In a reconnaissance study, we investigated the potential of γ-ray induced production of ³⁸Ar_K from ³⁹K for geochronological applications. For this purpose, various age monitors commonly in use for the established ⁴⁰Ar/³⁹Ar-method were co-irradiated for 60 h at 17.6 MeV maximum energy in the ELBE facility, Dresden-Rossendorf, Germany. Because the available energy was low, total production of ³⁸Ar_K was depressed, leading to low J₃₈-values of (2.1–4.1) × 10^-6 and hence resulted in only minor ³⁸Ar excess when compared with atmospheric ³⁸Ar_/³⁶Ar ratios. In spite of these restrictions, ages of younger monitors could be reproduced within error, whereas older age reference materials showed discrepancies due to the low production rate. We observed Ca-derived contributions on ³⁶Ar in analysed CaF₂ reference materials, and calculated a limit for Ca-interference on ³⁸Ar_Ca of (³⁸Ar/³⁶Ar)_Ca = 0.07 ± 0.03 (1s). In addition, we investigated a potential recoil redistribution of ³⁸Ar by stepwise heating experiments, but could not quantify this further because of concurring processes. More work at higher photon energies is necessary to resolve other open issues, in particular the potential of utilising ⁴⁰Ar/³⁷Ar ratios for age determination and the possibility of ⁴²Ar production from ⁴⁴Ca, which would allow correction for Ca-interference reactions on other Ar isotopes. This would be a pre-requisite for dating extra-terrestrial rocks.

The last decade has seen a marked increase in U-Th-Pb petrochronological studies focused on titanite and apatite. This has motivated the need for detailed, phase-specific method development and well-characterised reference materials with a wide variety of ages and chemical compositions. This study presents new U-Th-Pb isotope and major-, minor- and trace-element mass fraction data for ten titanite and five apatite reference materials based on integrated EPMA, LA-ICP-MS and isotope-dilution (ID) multi-collector (MC)-ICP-MS characterisation. Cross-comparison of EPMA and LA-ICP-MS data for the same titanite reference material suite demonstrates that careful selection of EPMA primary reference materials is necessary to minimise inaccuracies. We further identify a significant X-ray interference when measuring low Ce abundances in Ti-bearing phases and outline a method for its correction. New ID-MC-ICP-MS and LA-ICP-MS data suggest tri-concordance (defined as concordant ages for the ²³⁸U-²⁰⁶Pb, ²³⁵U-²⁰⁷Pb and ²³²Th-²⁰⁸Pb decay systems) of the MKED-1 titanite reference material and demonstrate the reproducibility of ²⁰⁸Pb/²³²Th measurements in some secondary titanite reference materials. Integration of ²⁰⁸Pb/²³²Th results with U-Pb geochronology provides a meaningful tool to help interpret complex U-Th-Pb isotopic age spectra. We provide example applications of ²⁰⁸Pb/²³²Th LA-ICP-MS measurements toward interpreting Archaean titanite ages from the Acasta Gneiss Complex, Northwest Territories, Canada.

Lead isotopes are a powerful and versatile tool to elucidate fundamental geological problems related to the formation and evolution of continental crust. K-feldspar is a popular target for Pb isotope measurement as it is prevalent in many rock types and tends to capture the initial Pb isotope composition of its parental magma. We present data for a new Pb isotope reference material: Albany K-feldspar; as well as updated data for Shap K-feldspar. Results of Pb double-spike TIMS for Albany K-feldspar are ²⁰⁶Pb/²⁰⁴Pb = 16.7872 ± 0.0062, ²⁰⁷Pb/²⁰⁴Pb = 15.5640 ± 0.0056, and ²⁰⁸Pb/²⁰⁴Pb = 36.6600 ± 0.0168 (2s). TIMS measurement results for Shap K-feldspar indicate two isotopically distinct Pb populations. LA-MC-ICP-MS, with a spatial resolution as high as 15 μm, indicates a homogeneous Pb isotopic composition in Albany K-feldspar. In accord with previous studies, our results show that scatter in the measured Pb isotope ratios, related to the low natural isotopic abundance of ²⁰⁴Pb, along with the effect of isobaric ²⁰⁴Hg-²⁰⁴Pb interference, increases at lower count rates. However, the mean Pb isotope ratios measured via LA-MC-ICP-MS using a range of spot sizes are in excellent agreement with TIMS results thus highlighting the feasibility of Pb isotope determination via LA-MC-ICP-MS to access geological information preserved in small crystals, including mineral inclusions.

Simultaneous analysis of carbon and nitrogen isotope ratios by SIMS was applied for the first-time to a natural diamond from the Kelsey Lake kimberlite, State Line Distinct, Colorado (UWD-1). This in situ procedure is faster, reduces sample size for analysis, and measures both isotope ratios from a single ~ 10 μm diameter pit, a critical advantage for zoned diamonds. The carbon isotope ratio (expressed as δ¹³C_VPDB) of the bulk UWD-1 crystal, determined by the conventional combustion method in the present study, is -5.9‰ ± 0.2‰ (VPDB, 2s). Nitrogen mass fraction ([N]) and isotope ratio (expressed as δ¹⁵N_Air) were determined by stepwise combustion and gas-source mass-spectrometry, resulting in 553 ± 64 μg g^-1 and -6.7‰ ± 1.1‰ (Air, 2s), respectively. Secondary ions of ¹²C₂^-, ¹²C¹³C^-, ¹²C¹⁴N^-, and ¹²C¹⁵N^- were simultaneously measured by SIMS using three Faraday cups and one electron multiplier. The spot-to-spot reproducibility of δ¹³C and δ¹⁵N values for the UWD-1 (178 spots on sixteen chips, 10 μm spots), were 0.3‰ and 1.6‰, respectively (2s). While ¹²C¹⁴N^-/¹²C₂^- ratios, which are an indicator for [N], varied up to 12% among these sixteen chips, such variation did not correlate with either δ¹³C or δ¹⁵N values. We propose that UWD-1 is a suitable reference sample for microscale in situ analysis of δ¹³C and δ¹⁵N values in diamond samples.

The amphiboles from Kakanui and Arenal are two natural minerals that have been used worldwide as microanalytical reference materials, but their compositions and crystal structures are still poorly constrained. In this paper, we report new data on H₂O and trace element mass fractions and single-crystal structural refinement of these two amphiboles. H₂O mass fractions of the Kakanui and Arenal amphiboles determined via Karl-Fischer titration are 0.92 ± 0.18 (2s) and 1.56 ± 0.22% m/m (2s), respectively; these values estimated based on crystal-structure refinement are 0.86 and 1.46% m/m, respectively. Trace element mass fractions measured via LA-ICP-MS in two laboratories are in good agreement, and spots from five fragments for both Kakanui and Arenal amphiboles are generally consistent within reproducibility precision (2s). Our measurements indicate a better homogeneity for the amphiboles from Kakanui than that from Arenal. According to the latest scheme for amphibole classification and nomenclature (Hawthorne et al. 2012), the sample from Arenal is a (partially dehydrogenated) pargasite, and that from Kakanui is a kaersutite. The significant amount of oxo-component and that ^CTi⁴⁺ content is strongly ordered at the M(1) site for both amphiboles indicate crystallisation under high fO₂ conditions.

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.