不平衡铀系定年的新技术突破——高精度、高灵敏度238U-234U-230Th同位素质谱测定和应用

80年代中期发展起来的高精度、高灵敏度不平衡铀系热电离质谱定年新技术是同位素定年技术的一次革命性突破，并已在古气候、古环境、古海洋、考古学以及近代火山—岩浆作用研究中取得了一系列重要成果，本文介绍了这方面的研究进展。这一新技术已引起越来越广泛的重视，显示出巨大的应用前景。尽快开展不平衡铀系热电离质谱定年技术的应用，对提高我国的高分辩率第四纪年代学分析技术和应用研究水平有重要意义。     

IsoSpike: Improved Double‐Spike Inversion Software

The double‐spike approach for correction of instrumental mass bias in mass spectrometry data is well established. However, there is very little consistency within the scientific community in terms of double‐spike data reduction. Double‐spike solutions require computer calculation, using either geometric or algebraic approaches, and are often performed using spreadsheet calculations that vary from group to group and between isotope systems. Here, we present IsoSpike, a generalised computer procedure for the processing of double‐spike mass spectrometry data, built as an add‐on for the Iolite data‐reduction package ( www.iolite.org.au ). Use of this software permits visualisation of mass spectrometry data in a time window, and rigorous treatment and screening of data. Additionally, IsoSpike uses an integration‐by‐integration approach where the double‐spike calculations are performed on every integration within an analysis, providing straightforward quantification of uncertainties on double‐spike‐corrected isotope ratios. The advantages of this approach over traditional methods are discussed here. Platinum stable isotope data are presented as an example data set, although the procedure is applicable to any double‐spike system. IsoSpike is freely available from www.isospike.org .     

南沙永暑礁表层珊瑚年代结构及其环境记录

南沙群岛永暑礁7个表层礁坪原生块状珊瑚的高精度TIMS U-Th和12个常规^14C测年结果表明,永暑礁表层礁坪形成于现代,与钻探研究结果吻合。全新世永暑礁系从约7300aBP开始,以现代礁坪面以下17m左右的晚更新世礁灰岩为基底连续发育至今,因此,与南海周边地区的珊瑚礁不同,南沙群岛珊瑚礁的表层块状珊瑚不能够提供全新世高海平面的证据。由于现代珊瑚礁的堆积速率大于地壳沉降速率,可能会形成更多的灰沙洲或灰沙岛。     

南海珊瑚TIMS U-Th和14C年代学的对比研究

利用本实验室建立起来的TIMS U-Th 定年方法，测定南海一些全新世珊瑚的TIMS U-Th年龄，并同时测定其14C年龄，建立这两种年龄结果的校正关系，探讨南海全新世珊瑚高精度年代学方法。     

西昆仑山奇台达坂花岗岩锆石TIMS U-Pb测年及热演化历史分析

应用锆石TIMSU-Pb测年获得西昆仑山奇台达坂花岗岩年龄为(202.2士3.4)Ma(MSWD=8.65);利用不同海拔高度获得磷灰石裂变径迹测定年龄为24.8～14.0Ma。通过裂变径迹热史模拟,并结合前人40Ar-39Ar测年数据,得出西昆仑山奇台达坂花岗岩就位以来,至少经历了三快二慢的冷却降温(隆升剥蚀)过程:即202.2～195.6Ma、26～15Ma和5Ma以来3个阶段的快速降温(隆升剥蚀),195.6～26Ma和15～5Ma2个阶段的缓慢冷却降温(隆升剥蚀)。西昆仑山地壳最上部约3km的快速去顶作用主要发生于26～15Ma和5Ma以来,它是印度板块向欧亚板块碰撞的结果。     

A Method to Suppress Isobaric and Polyatomic Interferences for Measurements of Highly Siderophile Elements in Desilicified Geological Samples

Sample decomposition using inverse aqua regia at elevated temperatures and pressures (e.g., Carius tube or high‐pressure asher) is the most common method used to extract highly siderophile elements (HSEs: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) from geological samples. Recently, it has been recognised that additional HF desilicification is necessary to better recover HSEs, potentially contained within silicate or oxide minerals in mafic samples, which cannot be dissolved solely by inverse aqua regia. However, the abundance of interfering elements tends to increase in the eluent when conventional ion‐exchange purification procedures are applied to desilicified samples. In this study, we developed an improved purification method to determine HSEs in desilicified samples. This method enables the reduction of the ratios of isobaric and polyatomic interferences, relative to the measured intensities of HSE isotope masses, to less than a few hundred parts per million. Furthermore, the total procedural blanks are either comparable to or lower than conventional methods. Thus, this method allows accurate and precise HSE measurements in mafic and ultramafic geological samples, without the need for interference corrections. Moreover, the problem of increased interfering elements, such as Zr for Pd and Cr for Ru, is circumvented for the desilicified samples.     

High‐Precision Measurement of Stable Cr Isotopes in Geological Reference Materials by a Double‐Spike TIMS Method

Chromium (Cr) isotopes have been widely used in various fields of Earth and planetary sciences. However, high‐precision measurements of Cr stable isotope ratios are still challenged by difficulties in purifying Cr and organic matter interference from resin using double‐spike thermal ionisation mass spectrometry. In this study, an improved and easily operated two‐column chemical separation procedure using AG50W‐X12 (200–400 mesh) resin is introduced. This resin has a higher cross‐linking density than AG50W‐X8, and this higher density generates better separation efficiency and higher saturation. Organic matter from the resin is a common cause of inhibition of the emission of Cr during analysis by TIMS. Here, perchloric and nitric acids were utilised to eliminate organic matter interference. The Cr isotope ratios of samples with lower Cr contents could be measured precisely by TIMS. The long‐term intermediate measurement precision of δ^53/52Cr_{NIST SRM 979} for BHVO‐2 is better than ± 0.031‰ (2s) over one year. Replicated digestions and measurements of geological reference materials (OKUM, MUH‐1, JP‐1, BHVO‐1, BHVO‐2, AGV‐2 and GSP‐2) yield δ^53/52Cr_{NIST SRM 979} results ranging from ?0.129‰ to ?0.032‰. The Cr isotope ratios of geological reference materials are consistent with the δ^53/52Cr_{NIST SRM 979} values reported by previous studies, and the measurement uncertainty (± 0.031‰, 2s) is significantly improved.     

Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique

A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a ²⁰⁵pb-²⁰⁴pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a ²⁰⁷Pb-²⁰⁴Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g⁻¹ Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of ²⁰⁵pb-²⁰⁴pb, ²³⁰Th and ²³⁵U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions.