本期文章导读

正117高温高压下元素配分的原位实验与计算模拟研究进展作者:黄圣轩,巫翔*,秦善导读撰文:本刊编辑部高温高压下元素配分行为研究揭示了地球内部物质迁移、富集、分异的动力学过程,有助于解决元素成矿、超临界流体性质、地球及行星演化等基础地质问题,近年来成为地球化学研究热点之一。同步辐射微聚焦X射线荧光光谱结合金刚石压腔技术原位测试方法逐渐取     

地幔矿物与水流体之间元素分配系数的研究及意义

流体是地球内部物质和能量迁移最为活跃的介质，它在造成地幔化学的富集和亏损，产生具有不同地球化学特征的幔源岩浆岩石，以及促进壳幔物质的再循环过程等诸多方面都起了重大作用，高温高压下实验模拟流体与地幔岩石和矿物之间痕量元素分配作用是揭示地幔流体的组成与性质，地幔中不同元素类型之间或内部的分异作用，地幔交代介质的类型与特征，岛孤玄武岩高场强元素亏损原因的一个重要的手段，并对近年来有关高温高压下流体与地幔矿物之间痕量元素分配作用的实验模拟研究进行了评述，分析了制约流体与地幔矿物之间痕量元素分配系数的因素，总结了这些研究的应用。     

同步辐射激光加温DAC技术及在地球深部物质研究中的应用

实验室模拟地球深部的温度和压力环境,研究地球相关材料的物理和化学性质,是解释地震波数据、进一步了解地球内部结构和动力学过程的重要途径。用高功率的红外激光光束,加温金刚石对顶砧压腔(DAC)中的样品,可以获得深部地幔乃至地核的极端温度和压力条件,已广泛地用于地球深部矿物的相变、熔融和状态方程研究。同步辐射微束技术的发展,为激光加温DAC技术的应用开辟了新的领域,也使地幔及地核条件下的矿物研究有了重要的突破。文章介绍激光加温DAC技术的发展;阐述高温高压原位的同步辐射X射线衍射方法;例举激光加温DAC技术在地球深部物质研究中的一些应用;并对一些关键的技术问题加以分析和讨论。     

CaSiO_3-钙钛矿的热力学状态方程

<正>地震学观测对了解地球深内部的结构、物质组成具有重要意义。高温高压矿物学实验为理解地震学观测,确定地球内部的物质组成提供重要的实验依据。我们的研究集中在利用高温高压实验手段,为描绘下地幔的密度和速度结构提供更为准确的实验数据。该项研究的对象是下地幔最为重要的矿物之一——CaSiO3-钙钛矿。CaSiO3-钙钛矿在下地幔的体积分数约为8%。因高温高压原位实验研究的缺乏,致使我们无法准确获取温度对热力学状态方程影响的信息     

实验矿物物理的发展现状与趋势:1.相变和状态方程、电导率、热导率

实验矿物物理是高温高压实验地球科学的重要分支学科之一,它主要是通过高温高压实验模拟地球内部的物理化学环境,并原位测定地球深部物质（矿物、岩石和熔/流体等）的相变和状态方程、电导率、热导率等物理参数,探讨地球内部的圈层结构、物质组成、地球动力学过程等地球物理性质相关的一系列重要科学问题. 综述了实验矿物物理的发展历史、近二十年的研究现状与趋势,并展望了该学科未来发展的方向、关键科学问题与面临的主要挑战.      

实验地球科学的前沿与发展战略

实验地球科学是利用实验装置和技术模拟地球内部的高温高压条件,开展地球内部物质的物理和化学属性与地球内部过程研究. 我国的实验地球科学在过去10年得到了快速发展,已成为国际高温高压实验领域的一支重要研究力量. 主要介绍了实验地球科学的定义与战略价值,简述了我国实验地球科学的发展现状与薄弱环节,提出了未来学科发展的思路和重要举措,并展望了学科未来的优先发展方向.      

地球内部极端条件下流体和物质相互作用:透过金刚石窗口探测地球深部流体

报道关于地球内部极端条件下的流体实验研究的最新进展。使用金刚石压砧结合各种谱学方法及同步辐射光源技术,在高温超高压条件下原位直接测量物质的结构和性质,已经获得分子-原子尺度信息新的实验数据。本项工作使用金刚石压砧对高压(10GPa)和高温高压(800℃,3GPa)条件下的NaCl-H2O进行红外谱原位直测,研究了高压和高温高压下水分子结构,发现水分子的O—H振动特征峰频率随温度向高波数变化,而且,在临界态区域时水分子间的氢键网格被破坏。实验说明:地球内部流体性质由深到浅不断变化,如水的密度、介电常数等物理参数随温度压力而改变,在临界态出现突变。这些变化可以用高压高温的物质的各种谱学特征来表征。水的性质与它的分子结构、分子振动有关。在跨越临界区时水的性质异常涨落是由水分子结构异常变化、分子振动形式变化和氢键网格破坏所导致的。从分子尺度认识地球内部流体在极端条件下的性质和高压原位实验观测有助于我们进一步了解地球深部物质的性质及其相互作用,有助于认识深部过程。     

地幔硫化物的物理化学性质及其地质意义

地幔硫化物是地球亲硫、亲铁元素的重要载体,与硅酸盐矿物有很大的物理性质上差别,它在高温高压条件下的物理化学性质是认识地幔物质组成及其不均一性的重要内容。此外,早期地球、火星、水星和月球幔部来源的硫化物对认识行星演化具有重要意义。地幔硫化物的存在条件、赋存方式以及元素分配系数受到硫化物和硅酸盐体系的化学平衡控制;硫化物在流体介质和固体介质中的迁移可以分别用斯托克斯方程和表面张力模型进行解释。基于目前的天然样品和实验研究结果,本文提出了地幔硫化物物理化学性质研究中尚存在的问题,并作展望：高温高压实验制约分配系数适用的元素含量远高于天然样品,导致亨利定律并不一定适用,要求开展元素含量更低的实验并进行测试;现有的线性或自然对数的经验方程不能准确描述硫化物-硅酸盐体系,机器学习可能揭示其错综复杂的热力学关系;硫化物熔体在深部地幔硅酸盐矿物表面的分布尚不清楚,对极端条件下的静水压力实验提出了需求。     

地球深部物质科学——在静高压大腔体实验研究方面的某些进展

介绍近年来使用静态超高压大腔体实验技术 ,在模拟地球内部的高温高压条件下 ,对地球物质进行的若干物理和化学性质的实验研究。高压同时高温条件下多种岩石样品的弹性波速就位测量揭示出物质的声软化现象和振幅效应 ;高温高压下陨石和岩石的熔融结晶实验发现了陨石硅酸盐相的不混溶现象以及玄武岩熔体结构的变化 ,在玄武岩转变为榴辉岩的实验中观测到了刚玉相 ;在高温高压水的实验中 ,发现了冰 Ⅶ 的亚稳相和熔融前效应以及超临界水及其稀溶液的一些新性质。这些实验结果为探索地球深部物质的性质和状态以及迁移和演化提供了新的依据。     

高温高压和不同氧逸度下二辉橄榄岩电导率实验研究

在一定热力学条件下矿物和岩石电导率的实验室就位测量能够帮助对已有的大地电磁测深结果进行合理解释,从而一方面为人们探索地球内部物质的化学组成、矿物组成和相态组成,地球内部物质的结构构造,以及地球内部的热结构等地球内部物质的组成和性状提供大量信息,另一方面,亦是人们认识地球内部物质的相变、熔融、脱水、扩散、流变、能量传输以及物质间相互作用等过程极为重要的研究手段.     

铌钽精矿标准物质研制

铌钽精矿标准物质在监控选冶样品分析的过程起到重要作用,在选厂及冶金系统有很大的需求,国内外的文献检索均未发现铌钽精矿标准物质的报道;而铌钽矿物的性质决定了铌钽精矿的粉碎粒度及均匀性对铌钽精矿标准物质的研制提出了更高的要求。本文阐述了4个铌钽精矿标准物质的研制过程,铌钽精矿采集于宜春及尼日利亚铌钽选厂,样品经气流粉碎和高铝球磨两次细碎及机械混匀后,随机抽取包装好的样品进行均匀性和稳定性检验及定值。采用电感耦合等离子体发射光谱法与质谱法(ICP-OES/MS)进行均匀性和稳定性检验,结果表明样品的均匀性和稳定性良好。采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的铌钽等12个元素进行定值,给出了各定值元素的认定值和不确定度。4个铌钽精矿标准物质Ta(Nb)_2O_5的含量为9. 89%、20. 55%、40. 79%、53. 69%,形成一个从粗精矿到精矿较为完整的含量体系,可以满足选冶试验各阶段流程样品分析对标准物质的需求。     

Available contents of potentially toxic elements in soils from the Eastern Amazon

Background Values of potentially toxic elements (PTEs) in soils are typically obtained from total or pseudo-total contents, but not represent the fraction of these elements available for plant uptake due to the predominance of the stable forms. Available contents to plants, in turn, tend to be positively correlated with the potential risk of contamination of PTEs. In this study, we determined the available contents, extracted with Mehlich-III solution, of Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn in Oxisols and Ultisols in the state of Pará, Eastern Amazon, Brazil. Available contents ranged from low to very low when compared to soils from other Brazilian regions and from other countries. Contents of PTE were higher in Oxisols than in Ultisols, except for Cu and Ni. In the Oxisols, PTEs were positively correlated with clay content. However, PTEs were not correlated with soil pH, organic matter and cation exchange capacity. In the Ultisols, Ba, Cu, Pb, and Mn contents were significantly correlated with pH, while Ni contents were correlated with the contents of silt.     

Natural background levels and threshold values for groundwater in fluvial Pleistocene and Tertiary marine aquifers in Flanders,Belgium

Aquifers from the same typology can have strongly different groundwater chemistry. Deducing the groundwater quality of less well-characterized aquifers from well-documented aquifers belonging to the same typology should be done with great reserve, and can only be considered as a preliminary approach. In the EU’s 6th FP BRIDGE project “Background cRiteria for the IDentification of Groundwater thrEsholds”, a methodology for the derivation of threshold values (TV) for groundwater bodies is proposed. This methodology is tested on four aquifers in Flanders of the sand and gravel typology. The methodology works well for all but the Ledo-Paniselian aquifer, where the subdivision into a fresh and saline part is disproved, as a gradual natural transition from fresh to saline conditions in the aquifer is observed. The 90 percentile is proposed as natural background level (NBL) for the unconfined Pleistocene deposits, ascribing the outliers to possible influence of pollution. For the Tertiary aquifers, high values for different parameters have a natural origin and the 97.7 percentile is preferred as NBL. The methodology leads to high TVs for parameters presenting low NBL, when compared to the standard used as a reference. This would allow for substantial anthropogenic inputs of these parameters.     

SERMIN1 and VIDAC18: Two Proposed Reference Materials for Rare Earth Element Determination in Groundwater

In this work, homogeneous samples of two Portuguese mineral waters, SERMIN1 and VIDAC18, have been analysed for their REE contents. The participation of twenty international laboratories made it possible to evaluate the data by robust statistical procedures. Eighty-one percent of the participants used ICP-QMS for REE determination in these two candidate reference materials. Assigned values are reported for SERMIN1, covering the fourteen naturally occurring lanthanides (La-Lu). For VIDAC18, assigned values are presented only for ten REE, since accurate assigned values for La, Ce, Tb and Eu need further analytical work to improve data quality.     

Geostatistical integration of MT and borehole data for RMR evaluation

The geostatistical approach was applied to integrate MT (Magneto-telluric) resistivity data and borehole information for the spatial RMR (Rock Mass Rating) evaluation. Generally, resistivity of the subsurface is believed to be positively related to the RMR, thus the resistivity and borehole RMR information was combined in a geostatistical approach. To relate the two different sets of data, the MT resistivity data were used as secondary information and the RMR mean values were estimated at unsampled points by identification of the resistivity to the borehole data. Two types of approach are performed for the estimation of RMR mean values. Then the residuals of the RMR values around the borehole sites are geostatistically modeled to infer the spatial structure of difference between real RMR values and estimated mean values. Finally, this geostatistical estimation is added to the previous means. The result applied to a real situation shows prominent improvements to reflect the subsurface structure and spatial resolution of RMR information.     

水中系列氢氧同位素标准物质的研制

我国氢氧同位素国家一级标准物质经过二十余年的使用,现已不能满足需求,急需研制代表当今分析技术水平的新的氢氧同位素国家标准物质。本文研制了系列(4个)水中氢氧同位素标准物质,其中三个采自天然水样,一个为人工配制的贫氘水,三种天然水样基本涵盖了我国境内天然水的氢氧同位素组成范围。每种标准物质随机抽取30瓶的均匀性子样,每份子样做双份分析,进行均匀性检验,四种标准物质的均匀性检验得到的F值都小于相应的自由度的临界值,显示四种标准物质的均匀性良好。标准物质的δ¹⁸O和δD值经过2年的稳定性检验,特征量值变化在不确定度范围,由此判定δD、δ¹⁸O值稳定性良好。采用国际间实验室采用不同原理的方法协同定值,11家国内外实验室分别采用Cr还原法、激光法、H₂-H₂O平衡法、高温热转换元素分析法进行水中氢同位素定值,采用CO₂-H₂O平衡法进行氧同位素定值;定值不确定度显著降低,δ¹⁸O的扩展不确定度小于0.08‰,δD的扩展不确定度小于0.9‰。该标准物质已被国家质检总局批准确为国家一级标准物质,批准号为GBW 04458~GBW 04461。     

高温高盐高黏油藏缔合聚合物-表面活性剂二元驱技术

针对大港油田孔南地区高温、高盐、中低渗、稠油等制约化学驱提高采收率的瓶颈技术问题,以官109 1断块枣Ⅴ油组为目标油藏,在优选适合缔合聚合物和表面活性剂基础上,进行聚合物-表面活性剂二元驱技术室内实验和现场应用研究。通过室内实验优选,缔合聚合物AP P7和表面活性剂BHS 01二元体系溶液与常规体系相比,具有较好的耐温抗盐性,拓展了常规二元驱适用油藏的温度和矿化度范围;缔合聚合物经过岩心剪切后仍能够有效建立阻力系数和残余阻力系数;通过岩心驱替实验,体系能有效提高稠油油藏的采收率,拓宽了聚合物驱适用的原油黏度范围;矿场单井试注后,注入井注入压力和启动压力升高,纵向吸水剖面得到改善,说明该体系在高温高盐条件下仍能保持较高黏度,能够有效改善水油流度比,效果明显。     

Mixture models and atypical values

The resolution of a mixture of two or more populations into its component distributions may be markedly influenced by one or a few atypical values. The maximum likelihood solution effectively assigns (part of) each observation to one or another of the components via the posterior probabilities, even though the observation may be widely discrepant from all components. This paper presents a modification of the mixture problem, in which the typicality of each observation is considered, as well as the posterior probabilities, with the contribution of atypical observations being downweighted. The extension to the multivariate case is discussed.     

Geological prognosis of potential zinc and lead resources for Triassic formations in the Silesian-Cracow region in southern Poland

Geological prognosis of zinc and lead potential resources for Triassic formations was carried out for the Olkusz district in the southeast part of Silesian-Cracow region. Known deposits, typical phenomena in surrounding rocks, and quantitative methods for metallic ores for the perspective region or formation were a basis for the models. Statistical analysis of zinc and lead distributions and their interpretation were used to distinguish between the populations of background, anomalies, and ore bodies. Estimated values of the thresholds in the Triassic formations, i.e., 0.5 (anomalies) and 1.1 (ore bodies) wt. % of Zn, and 0.3 and 0.7 wt. % of Pb, respectively, represent the natural limits of concentration for both metals. Similar values of the thresholds obtained by other authors for other districts indicate regional regularities of zinc and lead concentration in the Triassic formations in the whole Silesian-Cracow region. Using these threshold values, the perspective zones of metals concentration can be proposed in the poorly explored areas of this region. In known deposits, the natural limit of zinc used as a cut-off value increase the reserves by about 30–40%.     

锗矿石和铟矿石化学成分分析标准物质研制

目前国内外没有以稀散元素锗、铟为特征元素的矿石标准物质,为了满足我国地质找矿的需求,本文采集广东省韶关凡口铅锌矿作为锗矿石候选物,广西南丹铜坑铅锌矿作为铟矿石候选物,依据国家一级标准物质技术规范,由10家实验室采用化学分析方法和现代仪器分析方法协作定值,研制了1种锗矿石标准物质(GBW07831)和1种铟矿石标准物质(GBW07833)。锗矿石标准物质定值组分为45项,铟矿石标准物质定值组分为47项,包括特征元素、共存元素、稀土元素(15项)、造岩元素和痕量元素,其中锗矿石中锗含量为21.6×10-6,铟矿石中铟含量为39.7×10-6。研制的2种标准物质丰富了我国矿石标准物质的种类,可用于锗、铟矿石化学成分分析测试的量值标准和日常质量监控。