Derivation of Recommended Values: An Opinion*

Two principal approaches are being used currently to develop reference samples used in geochemistry. The first is typified by work at The National Institute of Standards and Technology (NIST) to develop standard reference materials (SRMs) whose elemental concentrations are certified. All data is collected under stringent quality control (QC). Agreement between average results for replicated analyses (6≤n<20) obtained by two or more analysts using either a single, definitive method or independent methods of analysis is required for certification; a large number of laboratory/method average results is not. The United States Geological Survey (USGS), International Working Group (IWG), and others base recommended concentrations on larger sets of compiled data, which may or may not have been collected under similar conditions of QC. The derived recommended concentrations are updated periodically, on the assumption that recommended concentration quality improves as the size of the data base increases. That assumption is examined in this paper, and the general lack of statistically significant difference between original and updated concentration is demonstrated.     

Provisional Elemental Values for Eight New Geochemical Lake Sediment and Stream Sediment Reference Materials LKSD-1, LKSD-2, LKSD-3, LKSD-4, STSD-1, STSD-2, STSD-3 and STSD-4*

The collection and preparation of four lake and four stream sediment reference materials are described. Provisional values related to both total concentrations and concentrations derived from partial extraction procedures are presented for major, minor and trace element constituents. As large amounts of samples (160–200 kg) have been prepared, they should be of interest to soil analysts.     

Sludge Ash Reference Sample

A suldge ash reference sample has been prepared. It has been analyzed by twenty-one independent laboratories. Information is presented on the number of analysts reporting each element, and the various instrumental methods used. Results are reported for twenty-six elemental determinations. Recommended elemental composition of the sample is given for twenty-one elements.     

DETERMINATION OF BROMINE AND IODINE IN FOUR MARINE SEDIMENT REFERENCE SAMPLES BY ENERGY-DISPERSIVE X-RAY FLUORESCENCE SPECTROMETRY

The concentrations of bromine and iodine in the USGS marine mud MAG-1, the NRCC marine sediments BCSS-1 and MESS-1, and the NBS estuarine sediment SRM 1646 have been determined by energy-dispersive x-ray fluorescence spectrometry. Matrix and intermediate thickness effects were overcome by standard additions to constant weights of each sample. 3-sigma detection limits are 6 ppm Br and 24 ppm I. There is a need for many more analysts to report their results before "usable values'can be established for these elements in marine sediment reference malterials.     

Five Robust Indicators of Central Value

The presence of outliers and the statistical noise that affects the data for reference materials have undesirable effects on the mean and on other indicators of the central value. Five robust indicators of the central value, which are resistant to obvious outliers and less obvious contamination (spurious data), were investigated: the dominant cluster mode, the modian, the Gastwirth median, the trimean, and the trimmed mean. The mean and the median were investigated for purposes of comparison.
The results confirm that the mean is very unreliable, and that the Gastwirth median and the dominant cluster mode are strong indicators of the central value.     

A Story of Two Rocks

An attempt is made to assess the impact that the investigation on reference (standard) rocks G-1 and W-1 has had on the geological fraternity. It is pointed out that prior to 1950, most geologists, petrologists, geochemists and the analysts themselves had a false impression of the quality of the data as obtained by classical methods of chemical analysis.
As a result of the G-1 W-1 investigation, numerous other rock standards have been prepared, yet, despite the G-1, W-1 experience and the availability of several other reference rocks, progress on the improvement on data quality is often disappointingly slow.
The G-1, W-1 investigation has had significant consequences for the development of geochemistry and the extra-terrestrial chemistry; one example is given.     

中国地质标准物质研制进展

地质标准物质是保障地质样品分析结果准确性的重要基准。目前,一级地质标准物质数量居十三大类首位,形成了具有国际影响力的地质标准物质体系。本文依据基体类型和定值特性,将一级地质标准物质划分为基础、矿石、海洋、环境、能源和特殊用途等六类,总结了各类标准物质的研制数量、特点、定值指标、应用范围及意义。针对现阶段数量众多的地质标准物质在应用中还存在研制数量少、系列化不足、基体类型单一、定值指标少等问题,本文分析了不同类型存在的具体问题及产生的原因,探究研制技术成熟的地质标准物质中仍有多种成分难定值以及定值方法单一的可能原因,重点讨论了标准物质研制技术中影响定值水平的细节问题：①阐述了均匀性检验测量方法的优缺点,XRF法以其高精密度的优势应用于均匀性检验值得关注和研究;②提出了考虑元素性质、含量级次兼顾测试技术评定均匀性未检元素的不确定度评定方法;③分析了稳定性不确定度在总不确定度构成中成为主要贡献量的原因是当前的计算方法造成的,有待于进一步研究合理的评定方法;④建议针对不同类型标准物质,制定相对扩展不确定度控制限以获得准确可靠的标准值。结合当前地质标准物质存在的不足和工作需求,本文提出了研制关键金属矿石标准物质、符合“一带一路”沿线国家地质背景的土壤和水系沉积物标准物质、海洋沉积物和海洋矿产与海产品标准物质、生物元素标准物质与有机污染物标准物质的建议。     

冻融岩体力学特性实验研究

岩石的冻融破坏是寒区岩石工程中常遇到的主要病害之一。通过对3种岩石进行冻融循环试验及电镜微观扫描的方法,研究了不同性质的岩石在冻融条件下的劣化损伤机制,分析了其冻融破坏机理; 并针对不同性质的岩石总结提出了2种不同的冻融劣化模式:裂隙扩展劣化模式和颗粒析出劣化模式; 通过不同冻融循环次数后的3种饱和岩石单轴抗压强度试验,得到了不同性质岩石的单轴抗压强度与冻融循环次数的拟合关系表达式,初步量化了循环冻融对寒区岩石强度衰减的影响,具有一定参考价值,为今后岩石冻融劣化研究和寒区工程建设及工程安全运营提供了可靠的依据。     

基于颗粒流方法的堆积层滑坡运动过程模拟

以颗粒流离散元为研究方法对勉县杨家湾十组堆积层滑坡破坏方式与运动过程进行数值模拟研究。通过PFC^2D双轴模拟试验所标定的岩土体宏观模拟参数与室内试验所获取的宏观实测参数进行对比,确定堆积层滑坡所需的颗粒细观参数,然后将标定的细观参数代入堆积层滑坡模型,对滑坡破坏方式及运动过程进行模拟研究。结果表明：滑坡破坏在初始阶段蠕滑变形累积,滑坡体挤压坡脚,直至坡脚产生剪切破坏,并向上牵引发展,使得滑坡整体顺接触面破坏下滑并堆积于坡脚,表现为典型的牵引式渐进破坏,结果与实际情况基本吻合。研究认为,采用颗粒流方法对堆积层滑坡破坏与运动过程的模拟研究具有较高的适用性,对该类滑坡防治具有一定的参考意义。     

Palaeoecology and the origin of the coconut

While botanists, archaeologists, historians and linguists have contributed to the debate on the origin of the coconut pollen analysts have been silent. This article attempts to integrate the results of recent palaeoecological research with findings from the other disciplines.     

Study and Application of Geochemical Reference Materials in the Institute of Geophysical and Geochemical Exploration (IGGE), China

In order to meet the needs of geochemical mapping and geochemical exploration, 125 geochemical reference materials have been successively prepared by the Institute of Geophysical and Geochemical Exploration (IGGE) since 1978. They include certified reference materials of stream sediments (GSD1-14), soils (GSS1-16; ASA 1–6, for analysis of available elements), various rocks (GSR1-6, GSR13-15), biological material (GSV1-4 and GSB 1–10), synthetic silicates (GSES I 1–11) and limestones (GSES II 1–9 for spectral analysis). They also include geochemical reference materials for ore analysis: Cu-Pb-Zn ores (GSO1-4), Cu-Pb-Zn concentrates (GSO5-7), platinum-group element (PGE) ores (GPt5-6 and GPt9-10), silver ores (GAg1-6) and geochemical reference materials for Au (GAu8-14) and PGE determination (GPt1-4, and GPt7-8). A multi-laboratory collaborative analysis scheme was adopted in the certification procedure of the IGGE. Dozens of competent laboratories with hundreds of senior analysts in China participated in the certification analysis. These samples have been supplied to more than thirty countries and more than 4000 customers from national industrial, agricultural, environmental, scientific and educational fields. Most of the geochemical reference materials are used for the calibration of measuring apparatus, evaluation of analytical methods, certification studies, quality control and laboratory accreditation programmes.     

煤与瓦斯突出预报的模糊聚类相似分析法

影响煤与瓦斯突出的因素多数是定性的或是模糊相似，采用模糊聚类分析方法对煤炭与瓦斯突出程度进行分析，建立模糊模式；应用模糊相似选择原理进行评价，以模糊模式为评价对象，以待预报样本为参考对象，根据模糊模式与以待预报样本的相似程度进行预测预报。哪一模式与预报样本最相近，等待预报样本即属于那一突出类型。采用模糊聚类及模糊相似原理2种方法结合分析预测，不仅克服了模糊聚类单一分析方法的不确定性，使定性预报转为定量预报，而且提高了预报效果的准确程度。实例分析表明，这是预报煤与瓦斯突出危险程度的一种较好的方法。     

固结问题无单元法解的影响因素分析

无单元法是求解比奥固结问题的一种新型数值方法。在采用罚函数法处理本质边界条件的基础上,推导出无单元伽辽金法解固结问题的系统方程。并着重讨论了计算域内结点分布方式、结点影响域的形状和大小、数值积分方案、惩罚因子等因素对结点位移、超孔隙水压力等的计算结果精度的影响。通过比较、分析,分别提供出相应的取值范围,或给出了参考性建议。     

基于二次场二维起伏地形MT有限元数值模拟

通过计算二次场来进行二维大地电磁数值模拟;导出了二维大地电磁二次场的微分方程,利用有限单元法来解微分方程;对矩形网格进行对角线的二次剖分,更容易且真实地模拟起伏地形。对几个典型模型进行了试算,与前人总场法的计算结果做了比较,两者视电阻率曲线一致,证明本文算法是正确的;通过2个简单的算例说明复杂地表下2种极化模式的MT观测资料都有明显的异常,视电阻率在TM模式下比TE模式更易受地形影响,TE模式下视电阻率曲线形态与地形呈"正相关",TM模式下反之。     

黄土地层盾构隧道受力监测与荷载作用模式的反演分析

为探明黄土地层中地铁盾构隧道管片衬砌结构与周围土体的相互作用关系,以西安地铁2号线穿越老黄土地层盾构隧道为研究对象,对实际作用于管片衬砌结构的水压力、土压力及主体结构内力（轴力、弯矩）进行现场动态跟踪测试,分析施工过程中盾构机动态掘进及后期稳定后的土-水压力对管片结构受力的影响。结合利用管片内力的现场实测值,采用正交试验设计分析方法,定义优化分析函数,反演分析黄土地层中盾构隧道管片衬砌结构设计荷载的合理计算参数。通过对比分析表明,运用优化后的设计参数得出的计算内力值与实测值在量值与分布上均较为接近,证实了分析方法的可行性、合理性,其成果可供类似工程设计参考。     

氧气反应模式-电感耦合等离子体串联质谱法测定土壤中的镉

应用电感耦合等离子体质谱法(ICP-MS)分析土壤中的镉元素时,锆的氢氧化物、钼的氧化物、锡的同位素会对镉造成严重的干扰,导致准确测定土壤中镉的难度较大。本文采用电感耦合等离子体串接质谱法(ICP-MS/MS),选取无同质异位素干扰的111Cd为分析谱线,在MS/MS模式下碰撞反应池中通入的氧气可以与94Zr16O1H+、95Mo16O+进行电子转移、去氢、加氧等反应,抑制这些多原子离子对111Cd的重叠干扰。结果表明：氧气流量越大,去除多原子离子的效果越好,当氧气流量在0.45mL/min时,溶液中2000μg/L以下的锆、1000μg/L以下的钼在111Cd处形成的多原子重叠干扰小于0.005μg/L。实验在石墨消解仪中采用氢氟酸-硝酸-高氯酸消解样品,盐酸复溶,溶液定容稀释至1000倍测定,方法检出限(3δ)达到0.003μg/g;本方法经过国家土壤一级标准物质验证,11个国家土壤一级标准物质的测量值和认定值的相对误差在±7%以内,3个国家土壤一级标准物质的精密度(RSD,n=12)小于5%。本方法可以作为土壤样品中痕量镉元素的分析方法。     

Preparation and Characterisation of Two Geochemical Reference Materials: DG‐H (Granite) and AM‐H (Amphibolite) from the Himalayan Orogenic Belt

Two geochemical reference materials of Himalayan origin named DG‐H (a granite) and AM‐H (an amphibolite) prepared by the Wadia Institute of Himalayan Geology Dehradun are described. Both samples were collected from the NW Himachal Himalaya in India. With the participation of analysts from more than forty international laboratories, element determination data collected during the past 10 years for characterisation of the samples was processed to assign working values using statistical procedures in use for this purpose. Earlier work published on these samples is incorporated in the present communication making it an updated document. The typical chemical and petrological characteristics of these two samples may prove useful for method validation and calibration of analytical instruments used for analysing similar rock types, and for widening the analytical range of several analytical methods used for geochemical analysis.     

模糊可变集合方法在降雨相似性分析中的应用

基于特定流域场次降雨具有的相似性,应用考虑区间值模糊可变的模糊可变集合方法进行场次降雨相似性分析。通过计算各场次降雨隶属于各降雨级别的特征值及与目标场次降雨之间的相似距离,从而获得流域场次降雨相似性排序,有效解决了场次降雨相似分析中的模糊性和不确定性问题。找出与实时阶段场次降雨相似的历史场次降雨,预估水库实时阶段面临的洪水过程及量级,可为水库防洪调度提供信息参考。     

土壤生态地球化学基准值及其研究方法探讨

从土壤生态地球化学基准值概念的涵义及其研究意义入手，对国内外相关研究的现状和方法进行了系统的分析和评述，从中发现，与土壤生态地球化学基准值研究的要求相比，已有的研究方法都不能满足实际科研工作的需要。中尝试应用土壤中矿物组成和化学元素间固有的相关关系来确定土壤生态地球化学基准值，取得了预期的效果。     

Geochemical baseline of trace elements in the sediment in Dexing area,South China

A baseline might be used as a point of reference to monitor change from some specific data without concern for whether the baseline determination is natural or has been changed by human activity. We selected 326 sediment samples from Dexing area, South China, and analyzed for 17 chemical elements. The geochemical baseline was predicted with the method of the normalization procedure combined with the relative cumulative frequency curve. The results indicate Al was the best reference element for the normalization procedure among four potential reference elements (Al, Fe, Ti, and Mn). The baseline value range obtained from the normalization procedure method included both the regional geochemical background of the sediment and the median value of the measured contents. The median value of baselines obtained from relative cumulative frequency method was lower than that obtained from normalization procedure method. In contrast to the geochemical patterns of heavy metals in 1987, the spatial distribution of anomalies sprawled in 2004 in study area, especially for Cu, Pb, Zn, Cd, As, Fe, and Cr.