流体包裹体成分测定的低温相变和显微拉曼光谱分析技术研究进展

论述了包裹体低温分析技术的原理以及进展。传统的流体包裹体低温分析技术是以显微冷冻测温测定无机盐体系为主,目前已发展到应用低温原位拉曼光谱技术对包裹体中的阳离子和阴离子进行定量-半定量分析。油气包裹体原位低温分析技术也取得了较大的突破,对不同成分油气包裹体低温下的相变过程取得了一定的认识,据此对油气包裹体进行分类,推测其主要成分,为油气包裹体计算提供基础参数。     

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%。     

Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa

Biominerals are natural composite materials comprising organic and inorganic components. Detailed knowledge of the nature and distribution of both components is a crucial requirement in order to advance our understanding of biomineral formation, their material properties and preservation potential as well as the interpretation of environmental data. Detailed chemical data are essential for our understanding of the nature and distribution of such components. Micro-XANES mapping at the sulphur K-edge reveals that, in the brachiopod Terebratulina retusa, the sulphate concentration is higher in the outer (primary) layer than in the calcite fibres of the secondary layer. This is co-incident with a higher magnesium concentration. In contrast, the sheaths surrounding the calcite fibres contain sulphur as thiol, confirming the presence of protein while, the sulphur within the fibres themselves, occurs as sulphate. Micro-XANES analysis of the insoluble organic extract from T. retusa indicates the presence of organic sulphate while Micro-Raman spectroscopy confirms that structurally substituted sulphate (SSS) is also present although semi-quantitative Raman spectroscopy carried out in this spectral region (wavenumbers 900–1200) indicates that the sulphate present is at the threshold of detection by Raman spectroscopy. The distribution of phosphorus in the shell of T. retusa correlates well with that of protein indicating the presence of phosphorylated proteins in the periostracum, the sheaths surrounding the calcite fibres and the interface between the primary and secondary layer.     

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.     

新疆黑英山-查汗沙拉-地那达坂地区锑矿成矿远景评价

我国西天山南段的黑英山-查汗沙拉-地那达坂锑多金属矿化区为中亚南天山成矿带的东延部分,区内广泛分布有泥盆系滨浅海含碳碎屑岩和碳酸盐岩,岩石具有较高的Sb背景场,异常多呈Sb、Au、As、Hg等元素组合异常出现,异常区内已发现有查汗沙拉、阿特达坂和地那达坂等多个锑矿(点)床.区内锑矿化及异常均受近Nw向大型逆冲推覆构造系统控制,具有良好的成矿条件和较大的找矿潜力.     

实验研究不同盐离子对水分子拉曼效应的影响

对流体包裹体中常见的几种盐水溶液进行了拉曼光谱分析.采用了频移参数描述水分子拉曼峰的形变强度,并讨论了频移参数与盐度之间的关系.实验分析结果表明,盐度越大,频移参数越大,水分子拉曼峰形变越大.对频移参数曲线斜率分析显示,盐类对水分子拉曼峰偏移程度影响的强弱顺序为NaCl＞Na2SO4＞NaHCO3＞Na2CO3.讨论了不同阳离子和阴离子对水伸缩振动拉曼峰的影响,结果表明,高价阳离子的影响明显高于低价阳离子;而阴离子对水拉曼峰影响的强弱顺序初步确定为Cl-≈SO2-4-＞HCO-3＞CO2-3≈NO-3.     

辽东湾凝析气田超压成因及侧向传递机制初探

位于辽东湾西部低凸起北端的JZ20-2超压凝析气田,离供烃中心较远,压力系数却达到1.56~1.7,这在我国东部裂谷盆地比较少见。经过综合分析,作者认为JZ20-2凝析气田异常高压的形成与其所处的特殊地质背景紧密相关,辽中凹陷沙河街组三段超压凝析油气沿不整合面、砂体输导通道向辽东湾西部低凸起的运移、充注和能量的侧向传递是JZ20-2凝析气田异常高压形成的根本原因,而上覆东营组二段下亚段-东营组三段巨厚的强超压泥岩封盖和辽西3号边界断层侧向遮挡共同构成的优越封闭环境是超压保存的必要条件。本文分析了该气田超压特征及其远距离超压侧向传递的成因机制,不仅有助于揭示辽东湾西部低凸起超压流体运移聚集的规律和成藏作用,而且可能提供了一个超压远距离侧向传递的典型实例。     

新甘交界红柳河地区二叠纪玄武岩年代学、地球化学及构造意义

新甘交界红柳河地区二叠系剖面中发育有块状和枕状玄武岩,激光ArAr定年确定的玄武岩形成时间在280～300Ma之间;玄武岩SiO_2含量为44.71%～49.27%,Mg~#为42.4～52.4,(~(87)Sr/~(86)Sr)_i为0.703834～0.706819,(~(143)Nd/~(144)Nd)_i为0.518861～0.5121220,ε_(Nd)(t)为-3.01～3.67。玄武岩微量元素、稀土元素和Sr-Nd同位素均显示出与OIB性质相似的特征。其弱富集的不相容元素和轻稀土元素,显示出源区富集的特点。而Zr/Nb(14.63)和Th/U(2.83)则指示岩浆中可能有少量循环原始地幔和亏损地幔物质的加入。综合对比北山南部柳园地区二叠纪玄武岩源区特征,提出红柳河地区早二叠世OIB型玄武岩主要来源于北山地区晚古生代裂谷带下伏已被不同程度改造的富集地幔。     

陕西白河县月儿潭绿松石与次生磷钙铝矾研究

对陕西省白河县月儿潭风化严重的绿松石样品进行了岩石薄片观察、化学成分测试、X射线粉晶衍射和红外吸收光谱分析等研究.结果表明,绿松石风化分解由天蓝色退色成黄绿色,最后变成白色,结构也由致密细腻变得松散多孔,主要原因是发生了硫酸根对磷酸根的交代作用,最终的交代产物主要是磷钙铝矾.     

安徽铜陵朝山金矿床流体包裹体研究

朝山金矿床是狮子山矿田内的热液交代型金矿床,在成因上与燕山期的白芒山辉石闪长岩有关.通过采集发育在不同深度下的含金黄铁矿-石英一方解石脉样品,进行流体包裹体岩相学观察和显微测温发现,石英和方解石中均捕获了富气相、富液相的两相水溶液包裹体和含子晶的三相水溶液包裹体,以上三种类型包裹体的均一温度统计峰值分别出现于315～335℃和255～275℃,盐度的统计峰值出现于17.50%～22.50%NaCl eq.和32.50%～37.50%NaCl eq.之间.激光拉曼探针分析表明,石英中流体包裹体的气相成分以水蒸汽为主,伴有少量CO2,可能含有CH4.流体的H、O同位素组成具确岩浆水特征.上述研究表明.朝山金矿成矿流体经历了相态变化,发生了不均匀捕获.受燕山期岩浆作用影响,狮子山矿田内的铜、金成矿在时空上具有一定联系,成矿流体运移的过程中,主要发生了相分离、气相液化和减压沸腾作用,可能是形威铜、金矿化分带的重要原因.