Geostandards and Geoanalytical Research最新文献

In situ U-Pb geochronology and hafnium, oxygen and zirconium isotope measurements in zircons using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and ion microprobe techniques can provide essential isotopic data to constrain geological evolutionary histories. Developing reliable zircon reference materials is the cornerstone for in situ zircon chronology and isotopic studies. In this study, the homogeneity of U-Pb ages and Hf-O-Zr isotope ratios in three Sri Lankan zircon megacrysts (SLZA, SLZB and SLZC) were investigated using multiple analytical methods. The obtained U, Th, Pb and Hf mass fractions of the SLZA zircon were 839 ± 56 μg g^-1 (1s), 151 ± 15 μg g^-1 (1s), 198 ± 28 μg g^-1 (1s) and 8635 ± 286 μg g^-1 (1s), respectively. The mass fractions of U, Th, Pb and Hf in the SLZB zircon were 1106 ± 106 μg g^-1 (1s), 331 ± 61 μg g^-1 (1s), 376 ± 57 μg g^-1 (1s) and 9673 ± 976 μg g^-1 (1s), respectively. The U, Th, Pb and Hf mass fractions determined in the SLZC zircon were 551 ± 35 μg g^-1 (1s), 111 ± 8 μg g^-1 (1s), 129 ± 18 μg g^-1 (1s) and 7881 ± 393 μg g^-1 (1s), respectively. The chemical abrasion isotope dilution thermal ionisation mass-spectrometry (CA-ID-TIMS) method yielded a Th-corrected weighted mean ²⁰⁶Pb/²³⁸U age of 556.94 ± 1.29 Ma (95% conf., n = 5) for the SLZA zircon, 552.90 ± 1.29 Ma (95% conf., n = 7) for the SLZB zircon and 560.83 ± 1.29 Ma (95% conf., n = 7) for the SLZC zircon. The obtained Hf isotopic compositions of the SLZA, SLZB and SLZC zircons determined with the solution MC-ICP-MS method were 0.281651 ± 0.000014 (2s, n = 10), 0.281704 ± 0.000008 (2s, n = 10) and 0.281676 ± 0.000006 (2s, n = 10), respectively. The obtained O isotopes of the SLZA and SLZB zircons measured with the laser fluorination method were 12.14 ± 0.56‰ (2s, n = 4) and 11.91 ± 0.30‰ (2s, n = 4), respectively. The Zr isotopes of the SLZA, SLZB and SLZC zircons determined with double spike TIMS analysis yielded mean δ⁹⁴/⁹⁰Zr_SRM3169 values of -0.03 ± 0.06‰ (2s, n = 10), -0.03 ± 0.04‰ (2s, n = 10) and 0.00 ± 0.07‰ (2s, n = 8), respectively. The SLZA zircon can be used as a primary reference or quality control material for microbeam U-Pb, Hf and Zr isotope measurements because of its slight heterogeneity. The U-Pb, Hf and Zr isotopic compositions of the SLZB and SLZC megacrysts were homogeneous. The O isotopic compositions in the SLZA and SLZB zircon were slightly dispersed, indicating that these two megacrysts can only serve as secondary reference materials for microbeam O isotope measurements.

The accuracy and validation of geo- and thermochronological dating hinges on the availability of well-characterised age reference materials. The Mesoproterozoic gabbroic anorthosite FC1 from the Duluth Complex, Minnesota is a reference material for zircon U-Pb and a suggested reference material for apatite fission-track dating. We evaluate FC1 as (U-Th)/He reference material, and determine its apatite U-Pb, and zircon and apatite (U-Th)/He age. Our dating results constrain the thermal history of FC1, showing that fast cooling occurred between ~ 1099 and 1040 Ma from ≥ 600 °C to ~ 200 °C. The zircon (U-Th)/He data from air-abraded grains give a robust isochron age of 1037 ± 25 Ma (2s) without overdispersion. The within-grain homogeneity of U and Th, the availability of FC1 zircon, and the absence of radiation-damage effects on the (U-Th)/He age support its use as reference material. Unabraded zircon grains give lower and more dispersed ages, highlighting the usefulness of air abrasion to control for α-ejection in (U-Th)/He dating. Our apatite (U-Th-Sm)/He single-grain ages vary between 180 and 300 Ma. Their wide dispersion argues against the use of FC1 apatite as (U-Th-Sm)/He reference material and makes the interpretation of their low-temperature thermal history complicated.

Gem quality andradite-rich garnet (IUC-1), obtained from the Miocene trachyte dome near Ankara city (Turkey), has been identified as a potential natural secondary reference material for U-Pb dating. In this study, U-Pb dating was performed in five different laboratories using isotope dilution TIMS and laser ablation ICP-MS to determine the homogeneity of euhedral garnet crystals. The U-Pb ID-TIMS data for IUC-1 yielded ²⁰⁷Pb/²³⁵U and ²⁰⁶Pb/²³⁸U ages of 20.9 ± 0.4 and 20.6 ± 0.8 Ma respectively, and these values are consistent with U-Pb LA-ICP-MS analyses, in which different garnet crystals yielded ages of 20.8 ± 0.1, 20.7 ± 0.1, 20.7 ± 0.2 and 20.2 ± 0.1 Ma. An andradite (IUC-2) from the Serçeören wollastonite skarn (Turkey) can be used as a secondary reference material provided detailed imaging of the crystals is undertaken. ID-TIMS data yielded ²⁰⁷Pb/²³⁵U and ²⁰⁶Pb/²³⁸U ages of 20.4 ± 0.4 and 20.9 ± 1.0 Ma respectively, and yielded U-Pb ages on different grains of 20.5 ± 0.1, 20.7 ± 1.0, 20.8 ± 1.7 and 20.9 ± 1.6 Ma. The assigned weighted mean age of IUC-1 (20.4 ± 0.5 Ma, 2s) is proposed as a 2023 reference value. IUC-1 garnet is expected to contribute significantly to rapidly developing garnet geochronology in the near future.

The isotopic composition of lithium (Li) in clinopyroxene (Cpx), determined via in situ micro-analysis, has been employed as a potential geochemical tool for studying various geological processes such as crust-mantle recycling, silicate weathering and fluid-rock interaction. To obtain precise and accurate Li isotopic compositions in Cpx by LA-MC-ICP-MS, synthetic Cpx matrix-matched reference materials (RMs) were prepared in this study. Six Cpx-matrix RMs were prepared by mixing metallic oxides with GSP-2 (granodiorite) or pure L-SVEC solution and melting them into glasses (GSP-2 + oxide; L-SVEC + oxide). Two representative synthetic glasses, CPXA01 and CPXB01, were subjected to a series of analyses to investigate the possible qualification of the RMs for in situ Li isotope measurement by LA-MC-ICP-MS, including elemental homogeneity analysis (elemental mapping analysis and spot analysis), Li isotopic homogeneity analysis and accurate Li isotopic determination. The applicability of the synthetic Cpx-matrix RMs was highlighted by comparing the δ⁷Li values of three natural Cpx calibrated against the synthetic Cpx-matrix RMs and other commonly used RMs with different matrices (NIST SRM 612, BCR-2G, GOR128-G, StHs6/80-G, KL2-G and T1-G), respectively. Additionally, CPXB01-05 RMs with the same matrix but different Li contents were prepared to explore the Li content mismatch effect, which is significant for accurate determination of in situ Li isotopic composition by LA-MC-ICP-MS. The results of the cross-calibration of Li isotopes in CPXA01 and CPXB01 suggested no obvious Li isotopic fractionation between the two types of glasses (GSP-2 + oxide; L-SVEC + oxide). Thus, the two methods of producing Cpx-matrix RMs are suitable for preparing the matrix-matched RMs for in situ microanalysis for Li isotopes.

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.