海洋沉积物的铁和锌同位素测定

介绍海洋沉积物Fe和Zn同位素化学前处理及测定方法,报道南海西部夏季上升流区两个沉积物柱样的Fe和Zn同位素组成。样品采用HF+HNO3+HClO4常压消解,经脱盐后,转化为氯化物形式并经离子交换柱分离纯化后,用多接收器等离子体质谱法测定Fe和Zn同位素比值。该前处理方法可以快捷地实现海洋沉积物的消解、有机质的去除和海盐脱离;结合相关测试流程,可获得较高的δ56Fe(0.10‰,2SD)和δ66Zn分析精度(0.11‰,2SD)。两个沉积物柱样的δ56Fe值(相对于IRMM-014)和δ66Zn值(相对于JMC3-0749C)随深度变化不明显,两柱之间也无明显差异。总体上,南海西部上升流区1～2 ka以来的沉积物δ56Fe值(0.04‰～0.20‰)和δ66Zn值(0.12‰～0.30‰)与已报道的黄土和气溶胶、火成岩以及大部分海洋沉积物接近,明显高于静海相海洋沉积物的δ56Fe值。     

多接收器等离子体质谱精确测定铼含量及其同位素丰度

利用多接收器等离子体质谱建立了快速精确测定铼含量及其同位素丰度的方法。溶液中加入铱元素进行铼同位素的质量分馏校正,在常规的溶液雾化进样条件下,采用同位素稀释法可准确测定纳克级的铼含量。铼标样A的自然同位素丰度的测量结果为185Re(37.437±0.008)%、187Re(62.563±0.008)%(2σ,n=5);铼稀释剂的同位素丰度测量结果为185Re(5.576±0.018)%、187Re(94.424±0.018)%(2σ,n=7);与未进行分馏校正的同位素组成的测量结果相比,精度和准确度均有提高。利用同位素稀释法测得铼标样A的浓度为(516.48±0.35)ng/g(2σ,n=5);测量精度和准确度均优于0.10%;利用反同位素稀释法对铼稀释剂B进行了详细的测量,平均测量结果为(62.74±0.26)ng/g(2σ,n=15),在分析误差范围内与其标定值完全一致;与未进行分馏校正的浓度测量结果相比,铼同位素丰度及铼含量的测量准确度均明显提高。     

Development of high precision Rb-Sr phlogopite and biotite geochronology; an alternative to Ar/Ar tri-octahedral mica dating

Potassium-Ar and Rb-Sr dating of minerals was fundamental in early efforts to date magmatic and metamorphic processes and paved the way for geochronology to become an important discipline within the earth sciences. Although K-Ar and, in particular, ⁴⁰Ar/³⁹Ar dating of micas is still widely applied, Rb-Sr dating of micas has declined in use, even though numerous studies demonstrated that tri-octahedral mica yields geologically realistic, and more reliable and reproducible Rb-Sr ages than the K-Ar or ⁴⁰Ar/³⁹Ar system. Moreover, a reduction of uncertainties typically reported for Rb-Sr ages (ca. 1%) can now be achieved by application of multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) rubidium isotope dilution measurements (<0.3%). Replicate Rb-Sr biotite ages from the Oslo rift, Norway, yield an external reproducibility of ±0.3% (n=4) and an analytical error of ±0.8 Ma for individual ages that vary between 276.9 and 275.5 Ma. Conventional thermal ionisation mass spectrometry (TIMS) Rb analysis on the same mineral separates yields ages between 276.1 and 271.7 Ma, three times the spread compared to Rb MC-ICPMS data. Biotite and phlogopite from the central Nagssugtoqidian orogen, West Greenland, yield ⁴⁰Ar/³⁹Ar plateau ages (ca. 1700 Ma) with a spread of ±150 Ma, while Rb-Sr ages on either biotite or phlogopite separates have a much narrower range of ±10 Ma. This comparison of Rb-Sr and ⁴⁰Ar/³⁹Ar ages demonstrates the robustness of the Rb-Sr system in tri-octahedral micas and cautions against the sole use of ⁴⁰Ar/³⁹Ar tri-octahedral mica ages to date geological events. Analytical errors of 16 Ma for these Rb-Sr mica ages determined by TIMS are reduced to <±5 Ma when the Rb concentration is determined by MC-ICPMS. All the TIMS and MC-ICPMS data from the Nagssugtoqidian orogen agree within assigned analytical uncertainties. However, high precision Rb-Sr dating by MC-ICPMS can resolve geological information obscured by TIMS age determinations. TIMS data for seven phlogopite samples form an isochron age of 1645±6 Ma, and thus, no differentiation in age between the different samples can be made. In contrast, MC-ICPMS Rb measurements on the same samples reveal two distinct populations with ages of 1633±3 or 1652±5 Ma.Combining the mica Rb-Sr geochronological data with the well-constrained thermal history of this ancient orogen, we estimate the closure temperature of the Rb-Sr system in 1-2 mm slowly cooled phlogopite crystals, occurring in a matrix of calcite and plagioclase to be ∼435 °C, and at least 50 °C above that of biotite.     

干法灰化和湿法消解植物样品的铜锌铁同位素测定对比研究

测定有机样品中元素含量和同位素时,处理样品常用的方法有干灰化法和湿法两种.目前,测定样品中Cu、Zn、Fe同位素时,多采用湿法处理样品.相对于湿法处理样品,干灰化法溶样迅速、耗酸量少,适合处理大量样品,但高温灼烧过程可能会导致样品中Cu、Zn、Fe同位素的分馏.本研究利用海州香薷植株,以湿法为基础,对干灰化法和湿法处理...     

Early diagenetic imprints and U–Th isotope systematics of fossil land snail shells from the Chinese Loess Plateau

The loess-paleosol sequence on the Chinese Loess Plateau provides a unique archive that records climate change in East Asia in the Quaternary, yet absolute dating of the loess deposits is challenging due to the lack of directly datable materials. Fossil land snail shells, which are made from aragonite, are widely preserved in the loess deposits and have long been used to reconstruct past environmental changes. U-series dating of fossil land snail shells has the potential to provide a route for absolute dating of the loess deposits but remains largely unexplored. In this study, we present the first systematic investigation on the U-series isotope geochemistry as well as the early diagenetic imprints of fossil land snail shells (Cathaica sp.) from the Mangshan loess-paleosol sequence in Henan province, central China. Several geochemical techniques, including Raman microscopy, SEM, LA-ICPMS, LA-MC-ICPMS, solution-MC-ICPMS, and AMS ¹⁴C dating, were employed to investigate the mineralogy, chemical and isotopic compositions of both modern and fossil snail shells to micrometer level. Our results show that the fossil Cathaica sp. shells are overall characterized by a higher degree of porosity and elevated contents of organic matter compared to live-collected shells of the same species. The layers with higher porosity and organic matter content in the fossil Cathaica sp. shell are also found to be enriched in Na, Mg, Mn, Ba, and U, indicating diffusion and adsorption of these elements by specific surface binding sites of either aragonitic lattice or organic compounds of the fossil shell. Combining in-situ measurements using LA-MC-ICPMS with solution U-series determination, we further demonstrate that fossil Cathaica sp. shell is relatively homogeneous regrading both [²³⁴U/²³⁸U] and [²³⁰Th/²³⁸U] values although the distribution of U in the fossil shell is sample-specific. The comparison of different dating results suggests that the calculated apparent closed system U–Th ages are all systematically younger (∼6000 to 13,000 years) than the corresponding shell ¹⁴C ages and quartz SAR (single-aliquot regenerative-dose) ages from the Mangshan section. We suggest that the underestimation of U–Th ages of fossil Cathaica sp. shells is very likely caused by diagenetic uptake of U that started immediately after the burial of the shell and effectively ceased when the fossil shell was isolated from the pore waters due to persistent deposition of eolian dust at the Mangshan section. Our work on both modern and fossil Cathaica sp. shells thus provides detailed morphological and geochemical characterization for the diagenetic alteration of fossil snail shells and suggests that U-series dating of fossil land snail shells may provide age constraints for dust deposits in the semi-arid region although the timing of early diagenetic U-uptake by the fossil shells need to be better quantified for reliable age determination.