胜利油气区有机包裹体研究及其在油气勘探中的应用

应用显生光度术，显微傅立叶红外光谱（Ｍｉｃｒｏ－ＦＴ．ＩＲ）和飞行时间二次离子质谱（ＴＯＦ－ＳＩＭＳ）等原位微分析技术并结合均一温度测量对胜利油气区下第三系沙河街组沙三段中有机包裹体进行了研究，区分出两类有机包裹体，即原生有机包裹体和次生有机包裹体，结果表明两类有机包裹体特征不同，二者物质组成，有机质成分及化学结构，热演化程度差别也较大，结合地质分析表明原生有机包裹体是沙三段烃源岩生成烃类运移产物     

有机包裹体研究方法简介

简介了有机包裹体研究方法,如荧光光谱、ｍｉｃｒｏ－ＦＴ．ＩＲ、ＬＲＭ、ＬＭＰＹ－ＧＣ／ＭＳ和ＴＯＦ－ＳＩＭＳ等原位（Ｉｎ－ｓｉｔｕ）微分析技术,并对它们在有机流体研究中的应用情况作了互相对比。     

有机包裹体显微傅里叶红外光谱和荧光光谱测定及其意义

应用显微光度术、显微傅里叶红外光谱（Ｍｉｃｒｏ－ＦＴ．ＩＲ）结合均一温度测量,对胜利油气区下第三系沙河街组沙三段中有机包裹体进行了研究。区分出两类有机包裹体,即原生有机包裹体和次生有机包裹体。有机包裹体荧光特征和显微傅里叶红餐光谱定量研究表明：（１）原生有机包裹体中含有硫醇化合物,其烃类有机质烷基碳链较长,碳原子数约为１５－１７;次生有机包裹体中除含有硫醇外,还含有一定量的Ｈ２Ｓ,其烃类肯机质烷基     

包裹体研究──盆地流体追踪的有力工具

矿物包裹体在研究碳酸盐岩的成岩作用，恢复盆地的热演化历史，指示油气生成、运移、聚集方面取得了很大进展。矿物包裹体是盆地流体的原始样品，它记录了地质历史中盆地流体的很多信息，有效地测定各期矿物流体包裹体的均一温度，是直接了解盆地热流体活动的重要数据；系统测定各类流体包裹体的初熔温度和冰点温度，能大致判断流体的矿化类型和矿化程度；流体包裹体的ｐ－Ｖ－Ｔ－ｘ研究，是探讨流体温度、压力的依据；荧光显微镜等对有机包裹体的有效鉴别，色谱方法对流体包裹体有机和无机成分的分析能提供流体组成和烃类赋存的多种信息；特别是近年来大力发展的单个包裹体的激光拉曼光谱等探针分析，以及包裹体群的ＧＣ－ＭＳ和δ￣（１３）Ｃ、δＤ、δ￣（１８）Ｏ同位素分析在追踪盆地流体性质、成因及其与油气等矿产的关系方面将发挥愈来愈大的作用。     

流体包裹体成分分析研究

笔者在日本研修期间学习和了解了先进的流体包裹体成分分的方法,其中包括分析群体包裹体液相成分的ＩＣＰ－ＭＳ和ＰＩＸＥ分析方法;分析单个包裹体液相成分的ＬＡ－ＩＣＰ－ＭＳ方法,ＬＲＭ,ＦＴ－ＩＲ单个包裹体气相成分分析方法等。这些方法极大地提高了包裹体成分分析的水平,促进了包裹体研究的发展,本文简要介绍这几种流体包裹体成分分析方法和其它包裹体研究方法及笔者的一些研究成果,以供国内同行借鉴和共同探讨。     

渤海湾盆地石炭纪-二叠纪煤中基质镜质体飞行时间二次离子质谱研究

利用飞行时间二次离子质谱仪（简称ＴＯＦ－ＳＩＭＳ）对渤海湾地区Ｃ－Ｐ太原组和山西组煤中基质镜质体进行了对比研究,结果表明,在接收到的正二次离子中都含有一定的烯基和烷基碎片,这些脂族碎片离子的出现说明它们具有富氢及较好的生烃性质。同时,该仪器的实际应用结果表明,它对研究煤及源岩中有机显微组分的化学成分和结构具有独特的优势。     

海南抱板金矿田流体包裹体地球化学研究

对海南抱板金矿田的外山，抱板和二甲等三个金矿进行的液体包裹体研究表明成矿流体为低盐度（０．１－６ｗｔ％ＮａＣｌ），中低温（２００－２４０℃）热液，处于中低压力（６０－１６０ＭＰａ）下，其ＣＯ２含量较低，探针质谱分析表明流体包裹体中存在Ｈ２Ｓ，结合ＳＯ＾２－４的存在，金在热液中可能是以硫氢络合物的形式迁移的。     

飞行时间二次离子质谱(TOF-SIMS)在矿物包裹体研究中的应用

矿物包裹体的化学成分研究在地质学、矿床学和油气勘探等方面具有重要意义。目前对包裹体化学成分分析的主要分析方法有激光烧蚀电感耦合等离子体质谱(LA-ICP-MS)、电子探针(EPMA)、显微激光拉曼光谱(LRS)、傅里叶变换红外光谱(FTIR)、质子诱发X射线光谱分析(PIXE)、同步辐射X射线荧光光谱(SXRF)和(传统的)二次离子质谱分析(SIMS)等。本文在对上述方法的分析特点进行简单介绍的基础上,重点阐述了对于矿床学样品表征具有广泛应用潜力的飞行时间二次离子质谱(TOF-SIMS)的原理、特点和技术优势,总结了国内外学者应用TOF-SIMS对矿物包裹体化学成分分析的研究进展与存在问题,并做了相关领域的展望。     

离子质谱计测定地质样品中镁同位素组成方法学研究

应用信通公司研制的离子质谱计（ＳＴ－ＩＭＳ），建立了地质样品镁同位素分析的实验流程和误差分析方法，为进一步分析微量地质样品中镁同位素组成和分布奠定了基础。     

地幔橄榄石流体包裹体中的微量元素

本文基于激光探针二次离子质谱对地幔橄榄石中单个CO_2流体包裹体的爆破分析,以及中子活化、超高压透射电镜分析结果,讨论微量不相容元素存在状态对地幔地球化学演化的影响。     

扫描核探针技术及其地学应用进展

扫描核探针技术作为一种重要的微区原位无损痕量分析手段 ,广泛应用于地学与环境、生物与医学、微电子、材料与冶金科学以及艺术与考古学等研究领域。文中简介该技术在仪器装置、分析技术到地学应用方面的新进展 ,并将之与其他微区分析技术的性能特点进行了对比 ,最后讨论了该技术的未来发展和更广泛的地学应用问题。     

安徽铜陵地区中酸性侵入岩及其岩石包体中的矿物包裹体研究

铜陵地区是长江中、下游铁、铜、硫、金成矿带的重要组成部分。笔者对铜陵地区中酸性侵入岩及其岩石包体中的包裹体进行了较系统的岩相学、显微测温和激光拉曼光谱研究。通过岩相学观察发现了 3类包裹体 ,即晶质熔融包裹体、流体熔融包裹体和流体包裹体。显微测温资料表明 ,本区的岩浆流体成矿演化可分为 3个阶段 :岩浆阶段 ( >12 5 0～ 90 0℃± )、过渡岩浆阶段 ( 90 0～ 75 0℃± )和岩浆期后热液阶段 ( <75 0℃ )。部分熔浆的温度之高 (可达 12 5 0℃ ) ,表明其可能是底侵幔源岩浆同熔下地壳形成的。在老庙基岩体、小铜官山岩体、鸡冠石岩体和小陶家岩体中产有晶质熔融包裹体、流体熔融包裹体和流体包裹体这 3种包裹体 ,表明相应的岩浆流体演化具有连续性、继承性和阶段性 ,其对应的成矿溶液以岩浆热液为主 ;与此不同的是 ,在鸡冠山岩体和白芒山岩体中仅产有晶质熔融包裹体和流体包裹体两种类型的包裹体 ,表明相应的岩浆流体演化不具连续性 ,其对应的成矿溶液以天水热液为主。此外 ,在小铜官山岩体和鸡冠石岩体的中酸性侵入岩中 ,发现了不混溶包裹体 ,其可能是在压力释放条件下形成的。     

A Review of Fluid Inclusions in Diagenetic Systems

The study of fluid inclusions can help constrain the conditions at which diagenetic minerals precipitated, leading to a better understanding of the geologic controls and relative timing of changes in porosity and/or mineralising events. Many of the diagenetic minerals are easily deformed and it is important to check for any post-entrapment changes to the inclusions. Possible post-entrapment changes include reaction with the host crystal, necking down, nucleation metastability and thermal re-equilibration. The recommended method of detecting these problems is to examine individual fluid inclusion assemblages (FIAs) and report data for each individual FIA. These studies have been enhanced by the development of new micro-analytical techniques such as micro-fluorescence spectroscopy, micro-infrared spectroscopy, nuclear magnetic resonance, various mass spectrometry techniques and the analysis of individual fluid inclusions using laser ablation/decrepitation methods. Special techniques have been developed for hydrocarbon-bearing inclusions such as the Grains containing Oil Inclusions (GOI), Fluid Inclusion Stratigraphy (FIS), and the Molecular Composition of Inclusions (MCI) techniques. The fluid inclusions that form in some minerals during diagenesis provide the only direct means of examining the fluids present in these systems. They provide useful temperature, pressure, and fluid composition data that cannot be obtained by other means.     

Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) has recently emerged as a powerful in situ microanalytical technique for major to trace elements in heterogeneous samples such as fluid and melt inclusions. Here, a rigorous comparison of melt inclusion (MI) data acquired by electron microprobe (EMP), ion microprobe (the secondary ion mass spectrometry, SIMS) and LA-ICPMS is used to evaluate the applicability and advantages/drawbacks of these approaches. We are specifically interested in determining if LA-ICPMS data on entire, unexposed, crystallized MI that cannot be homogenized in the lab are accurate and of a useful precision.

Quantification of LA-ICPMS MI signals requires the use of an internal standard, i.e., the concentration of one element, or an element ratio, at the time of MI entrapment must be known independently, in order to derive the pure MI composition from the MI plus host mixed signal. Analysis of plagioclase-hosted glassy MI of a mid-ocean ridge basalt (MORB) sample from the East Pacific Rise illustrates that melt inclusion chemistry can be accurately quantified by LA-ICPMS, including the correction for postentrapment sidewall crystallisation of the host mineral without prior reheating in the lab.

The LA-ICPMS data obtained on crystallized MI demonstrate agreement with the EMP and SIMS data on exposed glassy MI at the 1 standard deviation uncertainty level except for a few elements close to their limits of detection. LA-ICPMS data reduction schemes include the quantification of analytical uncertainty on each element of single MI. Therefore, weighted average element concentrations can be obtained for MI assemblages, at precisions that compare well with those of average element concentrations obtained by EMP and SIMS.

Simple sample preparation minimizing inclusion loss through polishing combined with the analytical efficiency of 50 inclusions plus neighbouring host mineral at up to 40 elements per day enable the collection of statistically relevant datasets by LA-ICPMS. These allow to recognize nonrepresentative MI (e.g., heterogeneous entrapment). Application to individual clinopyroxene crystals from the AD79 pumice horizon of Mt. Somma-Vesuvius reveals chemical variability that exceeds the analytical precision on single melt inclusions. This variability was not obvious from the limited data set obtained by SIMS and EMP.

The largest source of nonquantifiable error for EMP and SIMS data stems from the requirement of reheating the melt inclusions in the lab in order to reverse postentrapment crystallisation onto inclusion walls or growth of crystallites. For LA-ICPMS analysis of unexposed MI, the reliability with which the internal standard (IS) element concentration is known determines the quality of the data. LA-ICPMS, however, cannot analyse H₂O, F, S and Cl reliably, has higher limits of detection (LODs) than SIMS for some elements for MI below 25 μm, has lower spatial resolution than both EMP and SIMS and consumes much more sample per analysis. Therefore, EMP, SIMS and LA-ICPMS are complementary in MI research, and the type of application will determine the analytical method or methods of choice.     

庐山星子群变质流体的包裹体研究

庐山星子群沉积变质岩中发育平行区域片理的石英脉和长英质脉体,这些脉体的石英晶体内富含原生的流体包裹体,包括低盐度的含液体ＣＯ２包裹体、液体包裹体、纯ＣＯ２包裹体和高盐度含子矿物包裹体。它们与中生代伟晶岩脉体中包裹体在均一温度、盐度和ＣＯ２密度等方面的明显差异和变质脉体中含液体ＣＯ２包裹体的等容线位置,表明变质脉体石英中的流体包裹体是在变质作用期间被捕获的部分变质流体,进一步证实了脉体是与变质作用同     

Mineral associations and character of isotopically anomalous organic material in the Tagish Lake carbonaceous chondrite

We report a coordinated analytical study of matrix material in the Tagish Lake carbonaceous chondrite in which the same small (?20 μm) fragments were measured by secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), electron energy-loss spectroscopy (EELS), and X-ray absorption near-edge spectroscopy (XANES). SIMS analysis reveals H and N isotopic anomalies (hotspots), ranging from hundreds to thousands of nanometers in size, which are present throughout the fragments. Although the differences in spatial resolution of the SIMS techniques we have used introduce some uncertainty into the exact location of the hotspots, in general, the H and N isotopic anomalies are spatially correlated with C enrichments, suggesting an organic carrier. TEM analysis, enabled by site-specific extraction using a focused-ion-beam scanning-electron microscope, shows that the hotspots contain an amorphous component, Fe-Ni sulfides, serpentine, and mixed-cation carbonates. TEM imaging reveals that the amorphous component occurs in solid and porous forms, EDS indicates that it contains abundant C, and EELS and XANES at the C K edge reveal that it is largely aromatic. This amorphous component is probably macromolecular C, likely the carrier of the isotopic anomalies, and similar to the material extracted from bulk samples as insoluble organic matter. However, given the large sizes of some of the hotspots, the disparity in spatial resolution among the various techniques employed in our study, and the phases with which they are associated, we cannot entirely rule out that some of the isotopic anomalies are carried by inorganic material, e.g., sheet silicates. The isotopic composition of the organic matter points to an initially primitive origin, quite possibly within cold interstellar clouds or the outer reaches of the solar protoplanetary disk. The association of organic material with secondary phases, e.g., serpentine and carbonates, suggests that the organic matter was susceptible to parent-body processing, and thus, isotopic dilution.     

流体包裹体在油气地质地球化学中的应用

流体包裹体研究是油气形成和成藏定量化研究的重要手段。本文总结了油气藏中流体包裹体的地质地球化学意义及其在石油、天然气研究中的应用,探讨了烃源岩和储层流体包裹体在确定源岩演化、沉积环境、有机母质类型、成熟度、油气运移充填期次等方面的应用,指出目前流体包裹体油气地球化学研究应关注的几个前沿方向：①在流体包裹体分析实验技术中,单个包裹体分析技术在油气地质定量化研究中具有重要的作用;②通过有机包裹体自然剖面与模拟实验对比研究烃类流体运移分馏,为建立油气成藏过程地球化学示踪指标提供基础参数;③通过储层中不同期次有机包裹体的化学组成、同位素组成、生物标志化合物与圈闭中已经聚集成藏的油气地球化学特征的对比研究,确定圈闭中油气的成因、来源和充填过程;④有机包裹体成烃作用研究为碳酸盐岩生烃和深层油气成因理论提供依据;这些方向的研究成果为深化油气理论、提高勘探水平具有重要意义。     

Organic Geochemical Microanalysis by Time‐of‐Flight Secondary Ion Mass Spectrometry (ToF‐SIMS)

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) is a powerful method for the chemical analysis of solid surfaces. In this paper, the capabilities and limitations of this technique and the potential for its use in geochemical research are outlined. Using ToF‐SIMS, the chemical composition of sample structures down to 10–100 μm can be determined, without the need for pre‐selection or labelling of the analysed substances. In addition, the lateral distribution of organic and inorganic compounds can be mapped in geochemical samples at a resolution in the micrometre range. The capabilities of the technique in geochemistry are illustrated by two examples. In the first example, it is shown that ToF‐SIMS can be used to detect biomarkers in oil samples, making it a promising method for the analysis of biomarkers in fluid inclusions. In the second example, a number of specific lipid biomarkers were identified and mapped on the surface of a microbial mat cryosection surface. Post‐measurement optical microscopy correlated the localisation of the lipids with the presence of methanotrophic archaea in the microbial mat.     

川西呷村黑矿型多金属矿床热液体系稀土元素组成特征

本文首次测定了呷村黑矿矿石中流体包裹体的ＲＥＥ组成,计算了与含矿流纹岩系熔体平衡的岩浆热液ＲＥＥ含量。主成矿期流体具有轻稀土富集、Ｅｕ明显正异常的特点,但岩浆热液却具有明显的Ｅｕ负异常特征,结合热液体系氧同位素及稀土元素交换反应模拟,表明岩浆热液不是直接的成矿热液。蚀变围岩具显著的Ｅｕ正异常,其它稀土元素出现亏损。蚀变反应水／岩比值较大,蚀变岩中的ＲＥＥ组成反映了成矿热液ＲＥＥ的特点,且ＲＥＥ亏损     

In Situ Multi-Element Analysis of the Mount Pinatubo Quartz-Hosted Melt Inclusions by NIR Femtosecond Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Microscopic melt inclusions found in magmatic minerals are undoubtedly one of the most important sources of information on the chemical composition of melts. This paper reports on the successful application of near-infrared (NIR) femtosecond laser ablation (LA) - inductively coupled plasma-mass spectrometry to in situ determination of incompatible trace elements (Li, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Ta, Th, U) and ore metals (As, Mo, Pb) in individual melt inclusions hosted in quartz from the Mount Pinatubo dacites, Philippines. The determined elements cover a concentration range of five orders of magnitude. Femtosecond LA-ICP-MS analyses of twenty-eight individual melt inclusions demonstrate the efficiency of the microanalytical technique and suggests a spectacular homogeneity of the entrapped melt, at least with respect to the following incompatible trace elements: Rb, Sr, Nb, Cs, Ba, La, Ce, Pr, Nd, Pb, Th. The analytical precision (1s) for Na, Ca, Rb, Sr, Y, Nb, Ba and LREE ranged from 3 to 20%. Comparison of trace element concentrations in Mt. Pinatubo melt inclusions determined by femtosecond LA-ICP-MS with those of melt inclusions previously analysed by secondary ion mass spectrometry analysis (SIMS) and those of matrix glasses previously determined by nanosecond LA-ICP-MS showed an agreement typically within 30–40%. The homogeneity of trace element concentrations of the Mt. Pinatubo melt inclusions and the matrix glasses is consistent with the melt inclusion origin as homogeneous rhyolitic melt that was trapped in quartz phenocrysts at the final crystallisation stages of the host adakite (dacite) magma.