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51.
The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.  相似文献   
52.
The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were 87Sr/86Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), 143Nd/144Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and 176Hf/177Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were 206Pb/204Pb = 18.8029 ± 10 (2s, 55 ppm), 207Pb/204Pb = 15.6239 ± 8 (2s, 52 ppm), 208Pb/204Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.  相似文献   
53.
Zircon (U‐Th‐Sm)/He (ZHe) thermochronometry is a powerful tool that has been widely used in geology to constrain the exhumation histories of orogens. In this study, we present an alternative protocol for dissolving zircon grains for determination of parent nuclides. This new alkali fusion procedure developed at the SARM (Service d'Analyse des Roches et des Minéraux) in Nancy, France, is fast (requiring only 2 d, including cleaning steps) and offers several advantages over conventional methods by avoiding: (i) use of HF pressure dissolution and (ii) complete removing of grains from the metal microvials. After dissolution, U, Th and Sm were measured using an ICP‐MS. We tested the new procedure on two different ZHe reference materials, the Fish Canyon Tuff and Buluk Tuff; these provided precision values for ZHe‐age estimations of 9 and 6% (1s), respectively. In addition, using this method, zircons from the Buluk Tuff are shown to be chemically more homogenous and more suitable for assessing the uncertainty of the entire integrated procedure.  相似文献   
54.
The LA‐ICP‐MS U‐(Th‐)Pb geochronology international community has defined new standards for the determination of U‐(Th‐)Pb ages. A new workflow defines the appropriate propagation of uncertainties for these data, identifying random and systematic components. Only data with uncertainties relating to random error should be used in weighted mean calculations of population ages; uncertainty components for systematic errors are propagated after this stage, preventing their erroneous reduction. Following this improved uncertainty propagation protocol, data can be compared at different uncertainty levels to better resolve age differences. New reference values for commonly used zircon, monazite and titanite reference materials are defined (based on ID‐TIMS) after removing corrections for common lead and the effects of excess 230Th. These values more accurately reflect the material sampled during the determination of calibration factors by LA‐ICP‐MS analysis. Recommendations are made to graphically represent data only with uncertainty ellipses at 2s and to submit or cite validation data with sample data when submitting data for publication. New data‐reporting standards are defined to help improve the peer‐review process. With these improvements, LA‐ICP‐MS U‐(Th‐)Pb data can be considered more robust, accurate, better documented and quantified, directly contributing to their improved scientific interpretation.  相似文献   
55.
Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO3 results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF3 precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH4HF2 open vessel digestion and (c) NH4F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF3 and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH4HF2 or NH4F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO3, the white precipitates and the semi‐transparent gels present in the NH4HF2 and NH4F digestion methods could be efficiently dissolved by evaporation with HClO4. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.  相似文献   
56.
Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with 76Se, 78Se, 80Se and 82Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding 78Se/76Se isotope mixtures and 82Se/76Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.  相似文献   
57.
Ilmenite (FeTiO3) is a common accessory mineral and has been used as a powerful petrogenetic indicator in many geological settings. Elemental fractionation and matrix effects in ilmenite (CRN63E‐K) and silicate glass (NIST SRM 610) were investigated using 193 nm ArF excimer nanosecond (ns) laser and 257 nm femtosecond (fs) laser ablation systems coupled to an inductively coupled plasma‐mass spectrometer. The concentration‐normalised 57Fe and 49Ti responses in ilmenite were higher than those in NIST SRM 610 by a factor of 1.8 using fs‐LA. Compared with the 193 nm excimer laser, smaller elemental fractionation was observed using the 257 nm fs laser. When using 193 nm excimer laser ablation, the selected range of the laser energy density had a significant effect on the elemental fractionation in ilmenite. Scanning electron microscopy images of ablation craters and the morphologies of the deposited aerosol materials showed more melting effects and an enlarged particle deposition area around the ablation site of the ns‐LA‐generated crater when compared with those using fs‐LA. The ejected material around the ns crater predominantly consisted of large droplets of resolidified molten material; however, the ejected material around the fs crater consisted of agglomerates of fine particles with ‘rough' shapes. These observations are a result of the different ablation mechanisms for ns‐ and fs‐LAs. Non‐matrix‐matched calibration was applied for the analysis of ilmenite samples using NIST SRM 610 as a reference material for both 193 nm excimer LA‐ICP‐MS and fs‐LA‐ICP‐MS. Similar analytical results for most elements in ilmenite samples were obtained using both 193 nm excimer LA‐ICP‐MS at a high laser energy density of 12.7 J cm?2 and fs‐LA‐ICP‐MS.  相似文献   
58.
LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.  相似文献   
59.
依据IPCC第六次评估报告(AR6)第一工作组报告第四章的内容,对未来全球气候的预估结果进行解读。报告对21世纪全球表面气温、降水、大尺度环流和变率模态、冰冻圈和海洋圈的可能变化进行了系统评估,并对2100年以后的气候变化做了合理估计。评估指出全球平均表面气温将在未来20年内达到或超过1.5℃,平均降水也将增加,但随季节和区域而异,同时变率将增大。大尺度环流和变率模态受内部变率影响较大。到21世纪末,北冰洋可能出现无冰期;全球海洋会继续酸化,平均海平面将持续上升,百年内上升幅度依赖不同排放情景,都在2100年后继续升高。在最新的评估中采用多种约束方法,减小了预估不确定性的范围。AR6对于低排放情景以及“小概率高增暖情节”的关注为应对气候变化提供了更多、更完整的信息。综合报告的评估结果指出,未来需要进一步减小区域,特别是季风区气候预估的不确定性,并从科学研究和模式发展两方面加强我国气候预估能力的建设。  相似文献   
60.
利用国际耦合模式比较计划第六阶段(CMIP6)中18个地球系统模式总初级生产力(GPP)模拟数据,基于传统的多模式集合平均(MME)和可靠集合平均方法(REA),在4个未来情景(SSP1-2.6,SSP2-4.5,SSP3-7.0和SSP5-8.5)下预估了21世纪全球陆地生态系统GPP的变化量,并分析了GPP变化的驱动因子。研究结果表明:在4个未来情景下,基于REA方法预估的全球陆地生态系统年GPP在未来时期(2068—2100年)比历史时期(1982—2014年)分别增长了(14.85±3.32)、(28.43±4.97)、(37.66±7.61)和(45.89±9.21)Pg C,其增量大小和不确定性都明显低于MME方法。在4个情景下,大气CO2浓度增长对GPP变化的贡献最大,基于REA方法计算的贡献占比分别为140%、137%、115%和75%;除SSP5-8.5(24%)外,其他情景下升温均导致全球陆地生态系统GPP降低(-42%、-37%、-16%),部分抵消了CO2施肥效应的正面贡献。温度的影响存在纬度差异:升温在低纬度地区对GPP有负向贡献,在中高纬度地区为正向贡献。降水和辐射变化对GPP变化的贡献相对较小。  相似文献   
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