Homogeneity testing of microanalytical reference materials by electron probe microanalysis (EPMA)     

《Chemie der Erde / Geochemistry》2014,74(3):375-384

Homogeneity testing of candidate reference materials requires distinguishing the effects of measurement uncertainty of the analytical method from true compositional variations within the material. Many in situ microanalytical techniques do not allow classical ANOVA homogeneity testing due to the infeasibility of truly replicated analyses on the same analysis volume. This also applies to the analysis of beam-sensitive and light element-bearing materials by electron probe microanalysis (EPMA). This reality has led me to reconsider the homogeneity index approach used in the testing of microanalytical reference materials by EPMA. Based on statistical considerations, I show that the homogeneity index is suitable for statistical significance testing using F and chi-squared statistics and allows estimating the contribution of compositional heterogeneity to the total uncertainty budget of the referenced values. However, there are problems of bias and masking of small compositional variations by measurement uncertainty. This contribution shows the strong impact of the total number of measurements on the resolution of a microanalytical homogeneity study and discusses how to quantify the relative contribution of heterogeneity to the total uncertainty budget. I present an example of EPMA to illustrate this approach and show some pitfalls and limitations in its application.  相似文献   

国际标准物质数据库COMAR及有证标准物质   总被引：2，自引：1，他引：1  

王巧云 《岩矿测试》2014,33(2):155-167

有证标准物质（CRMs）是具有准确量值的测量标准,在分析方法研究和评价、定性和定量分析、矿产勘查、仲裁检验、质量监督检验等领域发挥着重要的作用。20世纪80年代成立的国际标准物质数据库（COMAR）是目前国际上最大的CRMs数据库,收录来自25个成员国274个生产机构提供的CRMs数量超过10200种。本文从CRMs的数量、分类、发展变化等角度全面评述了国际数据库COMAR,阐述了欧盟组织、美国、中国、日本、澳大利亚等成员国的标准物质研究情况。英、美、法、德等国家的标准物质研究开展较早,研究水平高,处于世界领先地位;中国、日本等亚洲国家标准物质的发展虽起步晚,但发展迅速,已成为向COMAR提供CRMs最多的两个国家,分别为1194种和1456种（截至2013年8月）。COMAR建立以来,工业、有色金属和物理特性三大传统应用领域的CRMs占COMA数据库总CRMs的份额一直较大,比例始终保持50%以上,其中工业领域的CRMs数量最多,占19%;有机、生物与临床类CRMs所占份额最少,仅为7%和3%。随着社会需求的增加,生物与临床、生活质量领域标准物质成为未来标准物质发展的热点方向。本文指出,未来标准物质的发展将由过去的钢铁、有色金属、物理特性等传统领域逐渐转向食品安全、环境保护、气候变化、临床医学、制药产业、生物能源等新兴领域,标准物质的研究制备、定值及不确定度将面临新的技术挑战。  相似文献   

中国近海沉积物氮和有机碳标准物质的研制     

白亚之  朱爱美  崔菁菁  施美娟  高晶晶  张俊 《岩矿测试》2014,33(1):74-80

我国海洋沉积物的研究近几年发展较快,但是缺少有定值的氮、有机碳标准物质。本文针对及其匮乏的氮、有机碳国家二级标准物质进行了我国近海沉积物总氮(TN)、总碳(TC)、总有机碳(TOC)含量的分析标准参考物质的研制。研究样品采自"我国近海海洋综合调查与评价"专项提供的表层沉积物,经过冷冻干燥、研磨至74μm,使用元素分析仪和氧化热解-气相色谱法分析总氮和总碳的含量;使用元素分析仪和氧化热解-电位法分析总有机碳的含量,制备了一系列16个有定值的总氮、总碳、总有机碳含量的近海沉积物标准物质。样品在均匀性检验中,F的实测值小于临界值,相对偏差较小,样品的均匀性较好。在稳定性检验方面,两年内多次测定的分析结果无方向性变化,统计计算结果显示稳定性良好。本文研制的这16个近海沉积物标准物质在3家实验室进行了联合定值,按照ISO导则35和国家一级标准物质研制规范,给出了该系列标准物质总氮、总碳、总有机碳含量的标准值和不确定度。这批标准物质分为不同海区,不同海区的标准物质又分为不同的沉积物类型,研制的不同海区不同沉积物类型的标准物质对现有的海洋沉积物标准物质进行了有效的补充。  相似文献   

胶西北新城金矿床硫同位素地球化学   总被引：8，自引：6，他引：2  

张潮  刘育  刘向东  冯建秋  黄涛  张庆  王旭东 《岩石学报》2014,30(9):2495-2506

新城金矿床是胶西北金矿集区中典型的破碎带蚀变岩型金矿床,其热液成矿作用可划分为四个阶段:黄铁矿-石英-绢云母阶段(I)、石英-黄铁矿阶段(II)、石英-多金属硫化物阶段(III)和石英-方解石阶段(IV),其中金主要赋存于II和III阶段的黄铁矿内。该矿床赋矿围岩为郭家岭岩体,岩性为石英二长岩和二长花岗岩,主要为胶东群变质基底经部分熔融形成。胶东群变粒岩硫同位素较为均一(δ34S值介于6.9‰~9.4‰,均值为8.0‰);郭家岭岩体的δ34S值介于6.0‰~16.0‰,均值为8.6‰,反映了其硫同位素组成总体上继承了变粒岩的硫同位素特征;长英质脉岩的δ34S值变化范围为0.8‰~8.5‰(均值为6.7‰),其中4件样品的δ34S值变化范围为7.4‰~8.5‰,反映了其硫主要源自于郭家岭岩体,变粒岩可能提供了部分硫源;而其中1件样品的δ34S值仅为0.8‰,符合岩浆硫来源特征,表明深部岩浆可能也提供了部分硫源。新城金矿床矿石中硫化物δ34S值变化范围较大(4.3‰~10.6‰,均值为8.3‰),表明矿石硫可能源于郭家岭岩体、变粒岩和长英质脉岩,最终主要来源于胶东群变质基底。I阶段黄铁矿颗粒较小(5~600μm),晶形主要为立方体,反映其处于温度较高(300~350℃)、成矿流体的过饱和度较低、低氧逸度和硫逸度、冷却快速、物质供应不足的成矿环境;黄铁矿δ34S值变化范围为8.4‰~10.6‰,均值为9.7‰,反映了矿石硫可能源自于δ34S值较高的郭家岭岩体和变粒岩。II和III阶段黄铁矿粒径变化较大(3μm~2.5mm),晶形主要为五角十二面体,反映其处于中-低温度(200~300℃)、成矿流体过饱和度高、高氧逸度和硫逸度、缓慢冷却同时物质供应充分的成矿环境。其中,II阶段黄铁矿δ34S值变化范围为7.7‰~9.7‰,均值为8.7‰,表明矿石硫源除郭家岭岩体和变粒岩外,δ34S值较低的长英质脉岩可能也提供了部分硫源。III阶段硫化物δ34S值变化范围较大(4.3‰~9.4‰,均值为7.1‰),闪锌矿-方铅矿硫同位素热力学平衡温度范围为180~282℃,氧逸度约为10-37.3~10-36.8,反映了矿石硫源自于郭家岭岩体、变粒岩和长英质脉岩,硫化物δ34S值变化范围较大可能是硫同位素分馏达到平衡的结果。IV阶段黄铁矿粒径最小(1~5μm),为晶形完好、表面光滑的立方体晶形,表明其处于较低温度(200℃),成矿流体的过饱和度较低、氧逸度和硫逸度较低、物质供应不足的成矿环境。  相似文献   

脉状铅锌（铜、银）多金属热液矿床研究进展   总被引：1，自引：0，他引：1  

贾敬伍  张洪瑞  胡茂德 《岩石矿物学杂志》2014,33(4):726-746

目前在矿床学分类研究中对沉积岩容贱金属矿床的命名和分类尚未统一,其中一类赋矿围岩为沉积岩、矿体受构造(断层、褶皱等)控制呈脉状产出的、成矿金属为铅锌铜银多金属的矿床成为缺失环节,缺少系统的归纳总结。但该类矿床是造山作用的产物,对其进行归纳综合分析,有助于了解造山作用中的矿质迁移和沉淀过程。本文将该类矿床资料收集,对其成矿特征、控矿构造、成矿流体、矿质来源等进行分析总结。研究表明,此类矿床与造山作用或造山带有着紧密的联系。成矿物质表现为多源性,包括基底围岩、岩浆来源以及幔源贡献。成矿流体具有岩浆流体、变质流体、盆地卤水等多种来源,部分矿床的成矿流体受大气水影响。该类型矿床与MVT铅锌矿床有相似之处,但在成矿环境、控矿因素、金属来源以及成矿流体来源等方面有较大差异。  相似文献   

Determination of trace and rare-earth elements in Chinese soil and clay reference materials by ICP-MS   总被引：2，自引：0，他引：2  

Ye Liu  Chunrong Diwu  Yan Zhao  Xiaoming Liu  Honglin Yuan  Jianqi Wang 《中国地球化学学报》2014,33(1):95-102

Inductively coupled plasma mass spectrometry(ICP-MS) has become a powerful tool for providing reliable analytical results in many laboratories around the word. In this study, the mixture of HF and HNO3 acids in high-temperature and high-pressure closed-vessel digestion technique were used to decompose some Chinese reference materials, and thirty seven elements were determined by ICP-MS. Most of the results for Chinese soil reference materials were found to be in reasonable agreement with the reference values, except Cs, Ta, Li, Ge, Zn, Nd, Tb and Ta whose values need to be revised. Their precisions were typically lower than 5% RSD. However, the Precisions of Chinese clay reference materials, especially for GBW03102 and GBW03102a, were significantly different with reference values, probably reflecting the existence of a coarser-grained fraction(70 μm) in samples, and the formation of fluorides in Al-rich samples during sample decomposition by using the mixture of HF and HNO3 acids. Moreover, thirty-seven trace elements covering the mass range from Li to U in four Chinese clay reference materials were firstly provided with good precision and accuracy in this study.  相似文献   

分层岸滩侧蚀坍塌过程及其水动力响应模拟          下载免费PDF全文

假冬冬  黑鹏飞  邵学军  张幸农 《水科学进展》2014,25(1):83-89

非均质岸滩广泛分布于冲积河流中,其侧蚀过程沿垂向具有分层特点。基于全三维水沙模型及河岸侧蚀坍塌力学模式,提出动态网格跟踪技术,构建了非均质岸滩侧蚀沿垂向差异的三维动力学模拟方法。以连续弯道概化水槽为例,模拟分析了非均质河岸侧蚀过程中三维水流结构的响应特征。研究结果表明:坡脚冲刷后,底部主流向凹岸偏移,在已有弯道环流的基础上,于坡脚处出现一反向次生流;上部粘性土层坍塌后,崩塌土体堆积于坡脚处,上部主流明显左偏,下部次生流消失;随着坡脚堆积体的冲刷搬运,下部主流进一步向凹岸偏移;如此循环,主流不断向凹岸偏移,致使岸坡持续崩退、河道摆动。  相似文献   

Estimation of poromechanical and thermal conductivity properties of unsaturated isotropically microcracked cement pastes     

Benoît Bary 《国际地质力学数值与分析法杂志》2011,35(14):1560-1586

  相似文献   

A virtual experiment technique on the elementary behaviour of granular materials with discrete element method     

Xia Li  Hai‐Sui Yu  Xiang‐Song Li 《国际地质力学数值与分析法杂志》2013,37(1):75-96

Multi‐scale investigations aided by the discrete element method (DEM) play a vital role for current state‐of‐the‐art research on the elementary behaviour of granular materials. Similar to laboratory tests, there are three important aspects to be considered carefully, which are the proper stress/strain definition and measurement, the application of target loading paths and the designed experiment setup, to be addressed in the present paper. Considering the volume sensitive characteristics of granular materials, in the proposed technique, the deformation of the tested specimen is controlled and measured by deformation gradient tensor involving both the undeformed configuration and the current configuration. Definitions of Biot strain and Cauchy stress are adopted. The expressions of them in terms of contact forces and particle displacements, respectively, are derived. The boundary of the tested specimen consists of rigid massless planar units. It is suggested that the representative element uses a convex polyhedral (polygonal) shape to minimize possible boundary arching effects. General loading paths are described by directly specifying the changes in the stress/strain invariants or directions. Loading can be applied in the strain‐controlled mode by specifying the translations and rotations of the boundary units, or in the stress‐controlled mode by using a servo‐control mechanism, or in the combination of the two methods to realize mixed boundary conditions. Taking the simulation results as the natural consequences originated from a complex system, virtual experiments provide particle‐scale information database to conduct multi‐scale investigations for better understanding in granular material behaviours and possible development of the constitutive theories provided the qualitative similarity between the simulation results from virtual experiments and observations on real material behaviour. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

Effective block diagonal preconditioners for Biot's consolidation equations in piled‐raft foundations     

K. B. Chaudhary  K. K. Phoon  K. C. Toh 《国际地质力学数值与分析法杂志》2013,37(8):871-892

The finite element (FE) simulation of large‐scale soil–structure interaction problems (e.g. piled‐raft, tunnelling, and excavation) typically involves structural and geomaterials with significant differences in stiffness and permeability. The symmetric quasi‐minimal residual solver coupled with recently developed generalized Jacobi, modified symmetric successive over‐relaxation (MSSOR), or standard incomplete LU factorization (ILU) preconditioners can be ineffective for this class of problems. Inexact block diagonal preconditioners that are inexpensive approximations of the theoretical form are systematically evaluated for mitigating the coupled adverse effects because of such heterogeneous material properties (stiffness and permeability) and because of the percentage of the structural component in the system in piled‐raft foundations. Such mitigation led the proposed preconditioners to offer a significant saving in runtime (up to more than 10 times faster) in comparison with generalized Jacobi, modified symmetric successive over‐relaxation, and ILU preconditioners in simulating piled‐raft foundations. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献