碱消解-高效液相色谱-电感耦合等离子体质谱法测定生物样品中的甲基汞和乙基汞

建立了碱消解-高效液相色谱-电感耦合等离子体质谱联用系统测定生物样品中甲基汞(MeHg)与乙基汞(EtHg)的分析方法。为提高灵敏度,选用微流量的PFA雾化器,在优化的检测条件下,MeHg及EtHg检出限可达到0.036μg/L和0.03μg/L;线性范围达到4个数量级,两条工作曲线线性相关系数为1。对1.78μg/L MeHg、1.65μg/L EtHg的混合标准溶液重复测定7次,色谱峰面积的相对标准偏差(RSD)分别为1.79%和1.44%。对标准物质BCR 464(金枪鱼)的分析结果表明,测定值与标准值基本吻合,但略低于标准值;甲基汞和乙基汞的加标回收率分别为85.9%和84.5%。高效液相色谱与质谱联用技术的高灵敏度和低检出限能够满足生物样品中汞形态定量分析的要求。     

徐州土壤多环芳烃的环境地球化学迁移特征

选择江苏徐州黄棕壤进行不同深度层位多环芳烃含量的定量分析,研究并探讨了多环芳烃在土壤深度剖面中的地球化学迁移特征。研究结果显示,多环芳烃在徐州土壤剖面中主要集中在地表0~20 cm内。其中低环多环芳烃化合物的迁移能力较强,4~6环等高环化合物相对较难迁移,主要残留于地表生态系统环境中。     

XEPOS型偏振能量色散X射线荧光光谱仪分析蒙古铁矿石

以熔融玻璃片和粉末压片制样,采用XEPOS型偏振能量色散X射线荧光光谱仪,建立了铁矿石中总铁、氧化钙、氧化镁、二氧化硅、三氧化二铝、硫、磷、铜等组分的快速分析方法。着重讨论硫、磷两元素测定的可行性和Lucas-Tooth、Price数学校正模型的适应性和改善方法的途径。     

等离子体质谱法测定玄武岩中微量元素三种样品预处理方法的比较

在测定玄武岩的微量元素时,为了保证得到的微量元素结果反映源区特征,需经预处理去除玄武岩的孔洞中充填的碳酸盐等物质。选取雷州半岛新生代玄武岩三个样品,每一个样品用三种预处理方法进行预处理,等离子体质谱法测定其中的微量元素。分析结果表明,用稀硝酸浸泡样品,会导致玄武岩中大多数微量元素严重丢失,得到的数据失真;而用稀盐酸浸泡去除碳酸盐的方法基本不改变玄武岩中微量元素的含量。     

激光拉曼光谱法分析多种显微组分荧光变化及其应用

利用激发488 nm激光的氩离子激光器作为RENISHAW inVia型激光拉曼光谱仪的光源,建立了多种显微组分荧光变化(FAMM)分析方法,并对镜质体反射率明显抑制的东营凹陷有效烃源岩进行了测定。结果表明,东营凹陷有效烃源岩的有机质类型越好,镜质体反射率抑制程度越高,有效烃源岩的真实成熟度应主要处于0.64%~1.30%,而不是实测镜质体反射率所反映的0.37%~1.10%。     

青海南部熔积岩的发现:对寻找VMS型矿床的重要启示

熔积岩指的是侵入、混合到未固结或弱固结的湿沉积物中的熔浆分解、原位形成的一类特殊岩石。正确地认识该类岩石,有利于增进人们对岩浆-水(沉积物)相互作用过程的理解,恢复古环境。在青海南部沱沱河地区发现了一套角砾为撕片状、锯齿状及浑圆状的安山岩,胶结物为铁硅质组合的特殊熔积岩。研究表明,该熔积岩的角砾为岩浆遇水后快速淬火、裂解的产物,铁硅质组合为海底喷气沉积形成的含铁建造;且安山岩与含铁建造发生混合时,含铁建造尚未固结。该套熔积岩的发现,改变了长期以来对开心岭铁矿为火山热液交代安山岩而形成的认识,对于在矿区寻找VMS型矿床、区域内寻找海底热水喷流沉积型矿床具有重要的启示意义。     

高、低煤阶煤层气藏地质特征及控气作用差异性研究

高、低煤阶煤层气地质特征及控气作用差异性是研究煤层气富集成藏的重要组成部分,是煤层气勘探开发理论研究过程中重要的基础性研究领域之一。本文以中国沁水、阜新盆地和美国粉河盆地等典型的含气盆地为例,探讨了高、低煤阶煤层气的储层物性差异,分析了构造控气和水文地质控气作用的差异性。研究表明,高煤阶气藏含气量高,CH4百分含量高,δ13C1值大于-38.75‰,储层渗透率变化小,储层改造难,构造热事件对煤层气的生成、富集贡献大,持续的水动力使气藏遭到破坏,且破坏幅度大,现今地下水格局对气藏的形成具有一定的影响;低煤阶气藏含气量低,CH4百分含量低,δ13C1值大于-49.11‰,储层渗透率变化大,储层易改造,煤热演化史及煤阶影响着煤层气的生成、富集,在煤层气生成过程中活跃的水动力是甲烷生成的主要的水文地质条件之一,但持续的水动力使气藏遭到破坏,且破坏幅度小,而合适的地层水矿化度则是低煤阶煤层气生成的重要条件,地下水格局对气藏的调整和改造起到决定性的影响。     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

Delineation of groundwater protection zones by the backward particle tracking method: theoretical background and GIS-based stochastic analysis

The backward particle tracking method, an effective and powerful tool that can be used to delineate groundwater protection zones, is presented. The theoretical background and insights on the applicability of this method are provided. Moreover, the present work enriches the backward particle tracking method with an uncertainty analysis concerning the porosity values, applying a Monte Carlo (MC) approach, coupled with the use of geographical information systems (GIS). As an application example, a wellfield in the Komotini area, Greece, is investigated. The present study may serve as a potential guideline for wellfield delineation, particularly in areas like Greece where lack of data related to the hydrogeological system is often a problem.     

The largest karst cave discovered in a tunnel during motorway construction in Slovenia’s Classical Karst (Kras)

Karst researchers of the Karst Research Institute ZRC SAZU are regularly consulted during the planning of Slovenia’s motorways and invited to observe and monitor construction in the karst areas. More than 350 caves have been discovered in the course of building 60 km of new motorways over the past decade. Access to the most important caves is preserved by concrete tubes closed with metal covers at the roadside. The largest cave system in a tunnel, named LC-S647, is almost entirely preserved. The protection of this cave will serve as a good example for the preservation of natural heritage in the future. Construction work for the motorway uncovered a high degree of karstification. In particular, the discovery of this cave in the Kastelec tunnel LC-S647 showed the existence of a major cave system in the geological and speleological past. A number of unconnected passages have also been found. Caves discovered during highway construction have brought new knowledge about the cavernosity and the geological history of this part of the karst.