Determination of Radiogenic 87Sr/86Sr and Stable δ88/86SrSRM987 Isotope Values of Thirteen Mineral,Vegetal and Animal Reference Materials by DS‐TIMS

This work presents new ⁸⁷Sr/⁸⁶Sr and δ^88/86Sr_SRM987 isotopic values of thirteen mineral, vegetal and animal reference materials. Except for UB‐N, all our results are consistent with previously published data. Our results highlight intermediate precisions among the best presently published and a non‐significant systematic shift with the calculated δ^88/86Sr_SRM987 mean values for the three most analysed reference materials in the literature (i.e., IAPSO, BCR‐2 and JCp‐1). By comparison with the literature and between two distinct digestions, a significant bias of δ^88/86Sr_SRM987 values was highlighted for two reference materials (UB‐N and GS‐N). It has also been shown that digestion protocols (nitric and multi‐acid) have a moderate impact on the δ^88/86Sr_SRM987 isotopic values for the Jls‐1 reference materials suggesting that a nitric acid digestion of carbonate can be used without significant bias from partial digestion of non‐carbonate impurities. Different δ^88/86Sr_SRM987 values were measured after two independent Sr/matrix separations, according to the same protocol, for a fat‐rich organic reference material (BCR‐380R) and have been related to a potential post‐digestion heterogeneity. Finally, the δ^88/86Sr_SRM987 value differences measured between animal‐vegetal and between coral‐seawater reference materials agree with the previously published results, highlighting an Sr isotopic fractionation along the trophic chain and during carbonate precipitation.     

Copper Isotopic Analysis in Geological and Biological Reference Materials by MC‐ICP‐MS

The characterisation of relative copper isotope amount ratios (δ⁶⁵Cu) helps constrain a variety of geochemical processes occurring in the geosphere, biosphere and hydrosphere. The accurate and precise determination of δ⁶⁵Cu in matrix reference materials is crucial in the effort to validate measurement methods. With the goal of expanding the number and variety of available geological and biological materials, we have characterised the δ⁶⁵Cu values of ten reference materials by MC‐ICP‐MS using C‐SSBIN model for mass bias correction. SGR‐1b (Green River shale), DOLT‐5 (dogfish liver), DORM‐4 (fish protein), TORT‐3 (lobster hepatopancreas), MESS‐4 (marine sediment) and PACS‐3 (marine sediment) have for the first time been characterised for δ⁶⁵Cu. Additionally, four reference materials (with published δ⁶⁵Cu values) have been characterised: BHVO‐1 (Hawaiian basalt), BIR‐1 (Icelandic basalt), W‐2a (diabase) and Seronorm? Trace Elements Serum L‐1 (human serum). The reference materials measured in this study possess complex and varied matrices with copper mass fractions ranging from 1.2 µg g^?1 to 497 µg g^?1 and δ⁶⁵Cu values ranging from ?0.20‰ to 0.52‰ with a mean expanded uncertainty of ± 0.07‰ (U, k = 2), covering much of the natural copper isotope variability observed in the environment.     

First Multi‐Isotopic (Pb‐Nd‐Sr‐Zn‐Cu‐Fe) Characterisation of Dust Reference Materials (ATD and BCR‐723): A Multi‐Column Chromatographic Method Optimised to Trace Mineral and Anthropogenic Dust Sources

Atmospheric dust is an integral component of the Earth system with major implications for the climate, biosphere and public health. In this context, identifying and quantifying the provenance and the processes generating the various types of dust found in the atmosphere is paramount. Isotopic signatures of Pb, Nd, Sr, Zn, Cu and Fe are commonly used as sensitive geochemical tracers. However, their combined use is limited by the lack of (a) a dedicated chromatographic protocol to separate the six elements of interest for low‐mass samples and (b) specific reference materials for dust. Indeed, our work shows that USGS rock reference materials BHVO‐2, AGV‐2 and G‐2 are not applicable as substitute reference materials for dust. We characterised the isotopic signatures of these six elements in dust reference materials ATD and BCR‐723, representatives of natural and urban environments, respectively. To achieve this, we developed a specific procedure for dust, applicable in the 4–25 mg mass range, to separate the six elements using a multi‐column ion‐exchange chromatographic method and MC‐ICP‐MS measurements.     

有机化学物质碳氮稳定同位素系列标准物质研制

实验室和研究人员所使用的碳、氮同位素标准物质一般由国际原子能机构(IAEA)获得,然而近年来,随着碳氮同位素在实验室质量监控、方法评价、仪器校准等方面的广泛应用,市场需求量不断增加, IAEA研制的碳、氮同位素标准物质的种类与数量逐渐不能满足科学研究快速发展的需求。我国急需研制适应当今分析技术水平的有机质碳氮同位素国家标准物质用以进行质量监控、方法评价、仪器校准。为保证量值传递精度,本文研制了4个有机化学物质的碳氮稳定同位素标准物质,其中3个为尿素样品,1个为L-谷氨酸。经检验4种标准物质的均匀性通过F值检验,标准物质的δ~(13)C和δ~(15)N值经过一年的稳定性检验,特征量值变化在测量方法允许的不确定度范围内,由此判定δ~(13)C和δ~(15)N值稳定性良好。由包括研制单位实验室在内的12家实验室协同定值,采用高温燃烧-气体同位素质谱法测定了δ~(13)C和δ~(15)N值,系列标准物质δ~(13)C和δ~(15)N认定值区间呈梯度分布,δ~(13)C值为-40‰～0‰,δ~(15)N值为-10‰～30‰,涵盖了我国天然样品中有机质碳氮稳定同位素组成范围;研制的系列标准物质δ~(13)C的定值扩展不确定度不大于0.08‰,δ~(15)N的定值扩展不确定度不大于0.09‰,定值水平与国际标准物质相当。该系列标准物质已被国家质检总局批准为国家一级标准物质,批准号为GBW04494～GBW04497。可被用于地质、生态、环境等多种样品δ~(13)C和δ~(15)N比值测定时的分析监控、仪器校准、方法评价、质量保证和质量监控。     

低压密闭消解-电感耦合等离子体发射光谱法测定地质样品中的硼

采用酸溶-电感耦合等离子体发射光谱法(ICP-OES)测定地质样品中的全硼量,关键环节在于如何防止样品消解过程中硼元素的损失,降低测量过程中的基体干扰、光谱干扰和记忆效应。基于以上问题,本文采用氢氟酸-硝酸-高氯酸-磷酸在低压密闭溶样罐中消解样品,溶出的硼元素与少量磷酸充分络合,防止硼的挥发损失;以基体及主成分浓度与样品相类似的地质类固体标准物质绘制标准曲线做线性校准,有效匹配和降低样品的基体干扰;采用仪器自带的操作软件,观察分析谱线附近是否存在其他元素的干扰,来确定背景扣除最佳的位置及宽度,降低ICP-OES测量中的光谱干扰;以10%的王水作为进样系统的冲洗液,有效消减测量过程中的记忆效应。当稀释因子为200时,方法的检出限(3SD)为1.2μg/g,定量限(10SD)为4.0μg/g;用岩石、土壤及水系沉积物国家一级标准物质对精密度及准确度进行分析验证,11次测定相对标准偏差为1.8%～7.9%,相对误差为-3.6%～6.3%;以外检分析结果为参考,对硼含量在定量限以上的样品测定,相对误差为-9.3%～12.5%。     

凤太矿集区东塘子铅锌矿床S、Pb同位素组成对成矿物质来源的示踪

东塘子铅锌矿床是秦岭成矿带中典型的铅锌矿床之一,前人对东塘子铅锌矿床成矿作用研究较多,但受限于测试手段及认识的局限性,多年来对其物质来源的认识仍未统一。本文在充分研究东塘子铅锌矿床地质特征的基础上,开展了相关样品的S、Pb同位素分析,分析对象包括了不同类型的铅锌矿石,讨论了该铅锌矿床的成矿物质来源、区内岩浆岩与铅锌成矿的关系等。研究表明:东塘子铅锌矿床矿石硫化物δ34S值变化范围为1.8‰～12.5‰,平均7.50‰,计算获得成矿流体中总硫δ34S∑S为7.7‰,显示海水硫酸盐(蒸发膏岩)与岩浆硫的混合来源特征。矿石铅同位素组成稳定,铅源主要来自富U-Th-Pb的上地壳与深部,可能与深部岩浆活动有关。研究结果表明,东塘子铅锌矿床的成矿过程与南秦岭印支期大规模多阶段构造-岩浆-流体活动密切相关,为下一阶段区内找矿工作提供了新的思路。     

Kainsaz(CO3)陨石中两个富Al球粒的氧同位素组成特征与形成演化

富Al球粒是原始球粒陨石中一种矿物岩石学特征介于富钙铝包体(CAIs)和镁铁质硅酸盐球粒之间的特殊集合体,所以常常认为富Al球粒在认识CAIs和镁铁质硅酸盐球粒形成演化过程中的相互联系具有特殊意义。然而,对富Al球粒的初始物质组成以及形成演化过程一直存在较多争议,而氧同位素组成研究能够对球粒演化和早期星云环境等提供重要的信息。在本文中我们报导了来自Kainsaz(1937年降落于俄罗斯,CO3型)碳质球粒陨石中的2个富Al球粒(编号K1-CH1和K2-CH2)的矿物岩石学和氧同位素组成特征。K1-CH1的矿物组成主要为橄榄石、低钙辉石和富钙长石,K2-CH2为橄榄石和富钙长石。2个球粒中的矿物均具有贫~(16)O同位素组成特征。K1-CH1中矿物的△~(17)O组成基本上位于2个区间:-11.1‰～-8.7‰和-3.9‰～0.4‰;而K2-CH2的△~(17)O介于-6.6‰～-0.6‰之间,且具有从中部至边部升高的趋势。矿物岩石学和氧同位素特征表明,这2个富Al球粒的初始物质组成为富CAIs和镁铁质硅酸盐。在球粒熔融结晶过程中,与贫~(16)O同位素组成(△~(17)O:-8.7‰～-7.8‰)的星云发生了氧同位素交换。球粒形成后,发生迁移进入陨石母体,在相对更贫~(16)O同位素组成(△~(17)O:-0.6‰～0.4‰)的母体中(流体参与)发生变质作用,并再次发生了氧同位素交换。     

Mechanism for the instability of slopes composed of granular materials

The mechanism of instability of slopes composed of granular materials was examined through a tilting-box experiment using an assembly of aluminium rods and direct shear tests. A detailed observation of the experiment and the simple physical model led to the following conclusion. Avalanching of granular materials is triggered by rotation of rods at the slope surface. The force inducing the rotation was caused by the weight of the particles transmitted through contact points. Therefore, the mechanism of avalanching of granular materials was not comparable to the shear mechanism that has been considered to be responsible for the instability of slopes made of granular materials. © 1997 by John Wiley & Sons, Ltd.     

Seismic responses of postyield hardening single–degree-of-freedom systems incorporating high-strength elastic material

It is widely accepted that ductility design improves the seismic capacity of structures worldwide. Nevertheless, inelastic deformation allows serious damage to occur in structures. Previous studies have shown that a certain level of postyield stiffness may reduce both the peak displacement and residual deformation of a structure. In recent years, several high-strength elastic materials, such as fiber-reinforced polymer (FRP) and high-strength steel bars, have been developed. Application of these materials can easily provide a structure with a much higher and more stable postyield stiffness. Many materials, members, and structures that incorporate both high-strength elastic materials and conventional materials show significant postyield hardening (PYH) behaviors. The significant postyield stiffness of PYH structures can help effectively reduce both peak and residual deformations, providing a choice when designing resilient structures. However, the findings of previous studies of structures with elastic-perfectly plastic (EPP) behavior or small postyield stiffness may not be accurate for PYH structures. The postyield stiffness of a structure must be considered an important primary structural parameter, in addition to initial stiffness, yielding strength, and ductility. In this paper, extensive time history and statistical analyses are carried out for PYH single–degree-of-freedom (SDOF) systems. The mean values and coefficients of variation of the peak displacement and residual deformation are obtained and discussed. A new R-μ_p-T-α relationship and damage index for PYH structures are proposed. A theoretical model for the calculation of residual deformation is also established. These models provide a basis for developing the appropriate seismic design and performance evaluation procedures for PYH structures.     

堆石料三维形状量化及其对颗粒破碎的影响

筑坝堆石料由于尺寸较大,必须对其按一定比例缩尺后才能用来开展室内三轴试验。但缩尺前后颗粒形状难免会有差异,如何评价颗粒形状变化对堆石料变形特性的影响是十分重要的。引入了高精度的三维激光扫描技术对紫坪铺面板坝筑坝堆石料2.5～5、5～10、10～20 mm以及20～40 mm 4个粒径组的颗粒进行了空间形状分析,在此基础上进一步开展了单一粒组的三轴试验,研究了4个粒组的颗粒形状指标与颗粒破碎率的相关性。试验表明,紫坪铺堆石料颗粒破碎率随着其平均球度的增加而减小,并且呈近似半对数线性关系;随着围压的增加,颗粒形状对颗粒破碎的影响逐渐减弱,颗粒强度的影响逐渐增大。紫坪铺堆石料的颗粒强度随着颗粒尺寸的增加逐渐减小,但其破碎率反而随着颗粒尺寸的增加而逐渐减小,主要是因为试验所采用的紫坪铺堆石料颗粒尺寸越小时,其形状越不规则。因此,研究缩尺效应对颗粒破碎率的影响时,要同时考虑颗粒尺寸和颗粒形状。