水系沉积物标准物质研制

为满足区域地球化学调查及矿产勘查的需要,新研制了15个水系沉积物标准物质,其中6个样品是原有水系沉积物标准物质的复制,9个新研制的样品主要采自中国北方的森林沼泽和干旱荒漠特殊景观区。样品粒度依据区域地球化学调查规范的要求,森林沼泽区采样粒级为2.0～0.22 mm,干旱荒漠区采样粒级为4.76～0.90 mm,山区和丘陵地区的采样粒级为小于0.22 mm。样品在室内晾干后在110℃烘24 h,置于大型高铝瓷球磨机粉碎并混匀,使样品中小于0.074 mm的部分大于99%以上。样品采用波长色散X射线荧光光谱进行进行均匀性检验,方差检验的F值小于临界值,所有元素的RSD均小于4%,大部分元素的RSD小于3%,P、Mn、Ti、Fe2O3、K2O等元素的RSD小于1%,证明样品均匀性良好。经2年内4次分析,检验结果表明对所检验的元素和成分均未发现统计学意义的明显变化,证明样品的稳定性良好。采用多家家实验室用不同原理的方法联合定值,邀请全国15家有资质的实验室采用准确度较高的方法分析测试约72种组分,根据ISO导则35和国家一级标准物质研制规范的要求,计算15种水系沉积物标准物质中72种元素和组分的标准值(部分组分给出参考值)和不确定度,这些新研制的标准物质是原有水系沉积物标准物质的一个补充。     

Comprehensive evaluation of regional flood frequency analysis by L- and LH-moments. I. A re-visit to regional homogeneity

As part I of a sequence of two papers, previously developed L-moments by Hosking (J R Stat Soc Ser B Methodol 52(2):105–124, 1990), and the LH-moments by Wang (Water Resour Res 33(12):2841–2848, 1997) are re-visited. New relationships are developed for regional homogeneity analysis by the LH-moments, and further establishment of regional homogeneity is investigated. Previous works of Hosking (J R Stat Soc Ser B Methodol 52(2):105–124, 1990) and Wang (Water Resour Res 33(12):2841–2848, 1997) on L-moments and LH-moments for the generalized extreme value (GEV) distribution are extended to the generalized Pareto (GPA) and the generalized logistic (GLO) distributions. The Karkhe watershed, located in western Iran is used as a case study area. Regional homogeneity was investigated by first assuming the entire study area as one regional cluster. Then the entire study area was designated “homogeneous” by the L-moments (L); and was designated “heterogeneous” by all four levels of the LH-moments (L₁ to L₄). The k-means method was used to investigate the case of two regional clusters. All levels of the L- and LH-moments designated the upper watershed (region A), “homogeneous”, and the lower watershed (region B) “possibly-homogeneous”. The L₃ level of the GPA and the L₄ level of the GLO were selected for regions A and B, respectively. Wang (Water Resour Res 33(12):2841–2848, 1997) identified a reversing trend in improved performance of the GEV distribution at the LH-moments level of L₃ (during the goodness-of-fit test). Similar results were also obtained in this research for the GEV distribution. However, for the case of the GPA distribution the reversing trend started at L₄ for region A; and at L₂ for region B. As for the case of the GLO, an improved performance was observed for all levels (moving from L to L₄); for both regions.     

Isotope Dilution Determinations of Lu,Hf, Zr,Ta and W,and Hf Isotope Compositions of NIST SRM 610 and 612 Glass Wafers

Isotope dilution determinations of Lu, Hf, Zr, Ta and W are reported for nine test portions (five for W) of NIST SRM 610 and 612 glass wafers. Additionally, all test portions were analysed for their Hf isotope compositions. In general, high field strength elemental (HFSE) distributions in NIST SRM 610 and 612 were reproducible to ～± 1%, except for Zr (± 5%) in NIST SRM 612, and absolute reported concentrations agreed with previously published values, but with higher precision. The slightly worse reproducibility of Zr in NIST SRM 612 compared to other HFSE is interpreted to result from analytical scatter, rather than sample inhomogeneity. The analyses demonstrated elemental homogeneity for both glass wafers for samples of 1–2 mg with respect to the precision of the method, i.e., ± 1% or better. Average Hf isotope compositions for both glass wafers agreed within uncertainty and the weighted average of all determinations yielded a mean ¹⁷⁶Hf/¹⁷⁷Hf ratio of 0.282111 ± 0.000009 (95% confidence level). However, although mean values for NIST SRM 610 and 612 agreed within analytical limits, NIST SRM 610 test portions showed a tendency of systematically elevated isotope composition of ～ 0.5 _?Hf units when compared to NIST SRM 612, which may indicate a slightly more radiogenic Hf isotope composition of NIST SRM 610. The results of this study suggest that NIST SRM 610 and 612 are valuable calibrators for HFSE in situ analyses within the given uncertainties.     

宁夏年气温资料的均一性检验研究

选取宁夏24个气象站从建站到2006年年平均气温资料,采用Potter检验法对年气温资料进行均一性检验.结果表明:宁夏有9个测站年气温资料存在间断点,有15个测站无间断点;间断点主要集中在2001-2006年,共有7个,占总数的77.8%,其中有6个测站是因为站址迁移造成的;20世纪50年代测站的迁移最频繁,迁移次数不是造成年平均气温序列非均一性的直接原因,迁移前后测站环境的显著改变是主要因素,测站未迁移但测站环境城镇化变化也是因素之一.     

用于实验室间比对的铀矿地质样品制备及铀含量均匀性检验

为进行核地质分析实验室间比对,采集了南方硬岩和北方砂岩铀矿石样本,按照标准物质制备方法制备了2种铀矿地质样品(编号分别为Albriug-09、Albriug-10),其粒度为小于60μm,铀含量分别为497mg·kg~(-1)和935mg·kg~(-1)。对用于样品均匀性检验的时间分辨紫外脉冲光诱导荧光分析法(TRLIF)进行了分析性能有效性评价。TRLIF测定铀的检出限为0.09mg·kg~(-1),测定范围为0.27~1250mg·kg~(-1);当铀含量范围在4.6~514mg·kg~(-1)之间时,其精密度(RSD%)在9.6%~3.43%之间;当铀含量范围在1.7~514mg·kg~(-1)之间时,其正确度(RE%)在±16.3%~±0.2%之间。应用TRLIF对制备的样品进行了铀含量均匀性测试并采用单因子方差分析法进行了统计检验,其统计量F分别为0.61和0.76,均小于临界值F0.05(9,10)(3.02),表明制备的样品均匀性好,符合实验室间比对测定要求。     

多种均一性检验方法比较研究

气候资料的均一性检验对气候观测及变化研究有着重要作用。本文从四川省160个台站近50年气温资料中,选取具有连续观测记录的站点105个,综合SNHT(标准正态均一性检验)、Buishand检验、Pettitt检验、MASH(均一性序列多元分析)、TPR(二位相回归检验)和von Neumann比率法,对该省年平均气温进行均一性检验。结果表明有42个台站存在序列间断点,占40%;而不均一台站中,因迁站导致的有29个,更换仪器引起的有19个。对气温序列分年代统计发现不均一台站数目有增加的趋势,其中20世纪60—70和80—90年代不均一性均由台站迁移所致。评估不同检验方法的敏感度和适用性,发现SNHT法与Buishand法、Pettitt法检验结果相符率为48.6%,TPR法与其他方法相符率偏低,但该法不涉及邻近站是否均一,在分析中可做补充判断。参考四川省地形特征分析,SNHT法在盆地及山地台站的断点显露率最高,分别为67.6%和57.1%,漏检和误判较少;高原地区SNHT法和Buishand法显露率较高,其中Buishand法漏检和误判率最低。鉴于减小对元数据依赖度的均一化检验思路,应采用多种检验方法综合,有助于气候资料在区域气候变化研究中的有效利用。     

RHtest方法对我国降水资料的均一性检验试验

应用RHtest方法结合台站元数据信息对我国1725个气象台站1961-2009年月降水资料进行了均一性检验试验和订正,并以波密站、元阳站和巢湖站为例介绍了检验过程.结果表明:该方法能够适用于对我国降水资料均一性检验且具有较高的应用前景.2400台站高密度月降水资料的使用更加有益于参考序列的选取,采用数理统计分析和结合元数据主观判断的方式来对序列进行均一性检验更加合理.检验出存在非均一性断点的台站仅占2.1％,表明我国降水资料序列均一性情况良好,台站较大距离的迁移是造成部分降水序列非均一的重要原因之一.对检验出存在断点的降水序列采用RHtest提供的订正方法进行了订正和趋势分析,发现订正后降水序列的年变化趋势具有明显的改变,均一性也有很大改善.     

PMFT方法对我国年平均风速的均一性检验

利用惩罚最大F检验(PMFT)方法并结合详尽的台站历史沿革信息对我国701个气象观测台站年平均风速资料进行了均一性检验,结果表明该检验方法能够应用于对年平均风速资料进行均一性检验,我国年平均风速资料的不连续点主要集中在1～2个,已检验的701个台站中有61.3%的台站年平均风速序列是均一的,表明我国大部分台站风速资料均一性情况良好。仪器变化和台站迁移是引起年平均风速序列非均一性的主要原因,而仪器变化中的仪器换型是造成年平均风速序列非均一性的最重要原因。     

Spatial variation of cone tip resistance for the clay site at Texas A&M University

The cone tip resistance data available for the clay site at Texas A&M University, USA (one of the National Geotechnical Experimentation Sites) are used to show how the spatial variation of a soil property can be quantified. It is suggested that the first step in quantifying the spatial variation of a soil property should be the identification or selection of the statistically homogeneous soil layers. A new simple procedure is suggested to identify statistically homogeneous layers in a soil profile. Through examples it is shown that the procedure works extremely well in identifying the statistically homogeneous layers. For the chosen statistically homogeneous layers, the spatial variation of cone tip resistance with depth is quantified in terms of a constant mean or a mean trend, variance/standard deviation/coefficient of variation or a variance around the mean trend, and a correlation or variogram function. Correlation distances in the depth direction were found to be between 0.1 and 0.5m for the two soil layers investigated. It was shown that the correlation distance decreases in the presence of a global mean trend for the soil property. In such cases, it is important to note that a part of the correlation is automatically included in the mean trend function.