High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

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.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

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.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

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 δ^82/76Se 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.     

渤海湾海岸带地区~(137)Cs参考剖面——意义、方法及初步结果

海岸带地区近百年来的现代地质过程重建必须以精确的年代学研究为基础,~(137)Cs时标法和~(210)Pb_(exc)测年法是目前广泛应用的方法。由于易受到河流沉积物供给变化、潮位状况、极端天气事件等的影响,海岸带现代过程的定量研究一直是高分辨率研究的瓶颈。区域性参考剖面可以提升现代沉积物测年方法在海岸带应用中的可靠性。因此,建立区域性的~(210)Pb_(exc)和~(137)Cs比活度-深度参考剖面,将改善对海岸带及邻近海区实测数据的解释。以渤海湾海岸带为研究区,选取沉积环境相对稳定、水平搬运作用较小的地区,采用人工探坑、Eijkelkamp槽型取样器获取了2个柱状岩心,通过γ能谱仪对样品进行~(210)Pb、~(226)Ra及~(137)Cs比活度测试,绘制剖面图,结合研究区已有数据,总结出6类海岸带常见的~(210)Pb_(exc)和~(137)Cs比活度-深度剖面类型,并重建了渤海湾海岸带~(137)Cs区域性参考剖面。结果显示,~(137)Cs在渤海湾地区的最大峰值指示1963年,可以作为区域性主要参考时标。但是,最大峰值上部的次峰在不同区域指示不同的时标,S4和S5两个站位该峰值指示的并非1986年时标。     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.     

基于不同邻近标签数选择的LANDMARC定位算法研究

对于基于射频识别的LANDMARC室内定位算法而言,该系统采用"k近邻"算法,通过选取k个与待测标签相邻且符合特定条件的参考标签,最后根据这些标签的位置结合权值估算出待测标签的坐标信息.但是在实际的操作过程中,最近邻参考标签数的选取无指导原则,具有一定的盲目性.针对这一问题,通过选取与待定位参考点最近邻的参考节点作为未知点,通过搜索法获得最优的邻近标签数k,在随后的未知节点的定位过程中,选取k个邻近标签进行定位.经过多次实验,最终得出结论,使用改进后的LANDMARC算法的性能要优于原来经典的LANDMARC算法,精确度提升了10%左右,同时避免了k值选取的盲目性.     

Sensitivity of penman-monteith reference crop evapotranspiration in Tao’er River Basin of northeastern China

A non-dimensional relative sensitivity coefficient was employed to predict the responses of reference crop evapotranspiration （ET0） to perturbation of four climate variables in Tao＇er River Basin of the northeastern China. Mean monthly ET0 and yearly ET0 from 1961 to 2005 were estimated with the FAO-56 Penman-Monteith Equation. A 45-year historical dataset of average monthly maximum/minimum air temperature, mean air temperature, wind speed, sunshine hours and relative humidity from 15 meteorological stations was used in the analysis. Results show that： 1） Sensitivity coefficients of wind speed, air temperature and sunshine hours were positive except for those of air temperature of Arxan Meteorological Station, while those of relative humidity were all negative. Relative humidity was the most sensitive variable in general for the Tao＇er River Basin, followed by sunshine hours, wind speed and air temperature. 2） Similar to climate variable, monthly sensitivity coefficients exhibit large annual fluctuations. 3） Sensitivity coefficients for four climate variables all showed significant trends in seasonal/yearly series. Also, sensitivity coefficients of air temperature, sunshine hours and wind speed all showed significant trends in spring. 4） Among all sensitivity coefficients, the average yearly sensitivity coefficient of relative humidity was highest throughout the basin and showed largest spatial variability. Longitudinal distribution of sensitivity coefficients for air temperature, relative humidity and sunshine hours was also found, which was similar to the distribution of the three climate variables.     

浙江省地质遗迹保护工作现状与面临的任务

本文以浙江省地质遗迹的展布特点 ,根据目前地质遗迹保护工作现状和存在的主要问题 ,提出了我省地质遗迹保护工作的任务与拟建地质遗迹保护区参考名录     

实时卫星钟差基准精化方法

在基于精密单点定位(PPP)的授时方法中,卫星钟差产品的高精度时间基准至关重要.针对实时卫星钟差产品时间基准不够稳定的问题,本文采用一组具有原子钟外部输入的国际全球卫星导航系统(GNSS)服务(IGS)跟踪站建立了顾及原子钟变化特性的基准精化方法.该方法首先采用阿伦方差对不同的IGS跟踪站外接原子钟进行稳定度分析,挑选出一组稳定度高的原子钟用以精化时间基准.在此基础上,利用阿伦方差分析各台原子钟的噪声参数特征,并确定不同原子钟之间的权比关系.最终,建立时间基准改正量的随机模型,并计算出精化后的时间基准.通过实例验证表明:与IGS事后精密钟差产品定义的时间基准比较,改正后的实时钟差基准单天内的标准差(STD)优于0.1 ns,相比于改正前最高提升了93%.同时,基准改正后的天内万秒稳达到10^-15量级,实现了一个量级的提高.此外,通过相对钟差精度的分析,表明钟差基准修正不影响PPP的定位精度.     

利用奇异谱分析提高极移中长期预报精度

由于空间大地观测数据传输耗时及处理过程复杂, 导致极移测量值的获取存在时延, 无法满足对高精度的极移预报值有重大需求的应用领域. 针对极移复杂的时变特性, 提出一种基于奇异谱分析(singular spectrum analysis, SSA)的预报方法. 首先用SSA分离提取极移时序中的高频组分与低频组分; 其次建立最小二乘(least square, LS)外推与自回归(AutoreGressive, AR)模型对极移高频和低频组分进行组合预报. 结果表明, SSA方法能够准确地分离和提取极移低频和高频组分, 对低频和高频组分组合预报可以显著改善极移的中长期(30--365d)预报精度, 与国际地球自转和参考系服务局(International Earth Rotation and Reference Systems Service, IERS)提供的A公报中的极移预报值相比, SSA方法对极移PMX分量(本初子午线方向)和PMY分量(西90$^\circ$子午线方向)的中长期预报精度改进最高分别可达45.97%和62.44%. 研究结果验证了SSA方法对极移中长期预报改进的有效性.