Helium and argon isotope geochemistry of natural gases in China’s petroliferous basins

The age-accumulation effect of 40Ar in hydrocarbon source rocks was discussed in accordance with the decay law of radioactive elements. In terms of the mean values of 40Ar/36Ar, the old Sinian gas reservoirs (mean values of 40Ar/36Ar: 7009) were definitely distinguished from the Permian gas reservoirs (mean values of 40Ar/36Ar: 1017) in Weiyuan, Sichuan Province, and the gas source of the Permian gas reservoir (mean values of 40Ar/36Ar: 5222) in well Wei-7 with the Weiyuan structure is defined as the Sinian system. Based on the values of 40Ar/36Ar, the coal-type gases (The source rocks are of the C-P system; mean values of 40Ar/36Ar: 1125) are definitely distinguished from the oil-type gases (The source rocks are of the Tertiary system; mean values of 40Ar/36Ar: 590) in the Tertiary reservoirs of the Zhongyuan Oilfield. Besides, 40Ar/36Ar values also have a positive effect on the oil-source correlation of oil reservoirs in ancient hidden mountains. According to the crust-mantle interchange information reflected by 3He/4He values, petroliferous provinces in China can be divided into three major tectonic regions. (1) The eastern active region: The crust-mantle volatile matter exchanges actively, and the 3He/4He values are mainly around 10-6, partly around 10-7. (2) The central stable region: The 3He/4He values are all around 10-8. (3) The western sub-stable region: The 3He/4He values are mainly around 10-8, and around 10-7 on the edges of the basins. Helium contents of some gas wells in China’s eastern petroliferous region reach the industrial abundance (He≈0.05%–0.1%), the 3He/4He values reach 10-6, and the equivalent values for the mantle-source components in helium gas can reach 30%–50%. As viewed from this, a new type of crust-mantle composite helium resources has been proposed. Geneses of some CO2 gas reservoirs in the east of China and some issues concerning mantle-source methane were discussed in the light of the helium and carbon isotopes of CO2 and CH4 in natural gases. In the discussion on helium isotopic characteristics of inclusions in the reservoirs, it was discovered that the 3He/4He values are close to those in natural gases. That is to say, this phenomenon is related to regional tectonism. The 3He/4He, CO2/3He and CH4/3He data were used to discuss the tectonic activities of fault zones in a certain number of regions in China.     

广东三洲矿田构造序列研究及其意义

三洲矿田内主要矿床与燕山期更晚的构造活动腾。燕山期构造活动可分为六个序列：（１）下石炭统与上三叠统不整合面附近和不整合面之上的上三叠统一下侏罗统中的低角度正滑断层及伴生构造,２）泥盆系－石炭及上三叠统一下侏罗统中的纵弯０褶皱北西向逆冲支,４）北东向平移断层,５）第二次北西向逆冲断层,６）伸展性正滑小断层。其中１、４、５三个构造序列是主要控矿构造,第１构造序列控制了长坑金银矿,第４构造序列控制蛘     

Effects of natural attenuation processes on groundwater contamination caused by abandoned waste sites in Berlin

The aim of this research project is to identify, characterize and quantify natural attenuation (NA) processes in groundwater affected by emissions of abandoned waste disposal sites in Berlin-Kladow/Gatow, Germany. It is part of the funding priority called KORA established by the Federal Ministry for Education and Research (BMBF) to explore the extent to which NA can be used for remedial purposes for varied forms of soil and groundwater contamination. Information on the emission behaviour of individual parameters is generated on the basis of hydrogeochemical comparison of 20 years old and new data. Using groundwater-modelling and CFC-analysis, information on the transport and retention of pollutants in groundwater is compiled. The microbial colonization of contaminated aquifers is characterized by molecular biological methods [polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE)] to differentiate between contaminated and not contaminated zones.     

Redox Condition,Nature and Tectono-magmatic Environment of Granitoids and Granite gneisses from the Karbi Anglong Hills,Northeast India: Constraints from Magnetic Susceptibility and Biotite Geochemistry

The Karbi Anglong hills (erstwhile Mikir hills) in northeast India are detached and separated from the Meghalaya plateau by a NW-SE trending Kopili rift. The Karbi Anglong hills granitoids (KAHG) and its granite gneissic variants belong to Cambrian plutons formed during Pan-African orogenic cycle, which commonly intrude the basement granite gneisses and Shillong Group metasediments. The KAHG can be broadly classified into three major granitoid facies viz., coarse grained porphyritic granitoid, medium grained massive non-porphyritic granitoid, and granite gneiss, which share a common mineral assemblage of plagioclase-K-feldspar-quartz-biotite±hornblende-apatite-titanite-zircon-magnetite but differ greatly in mineral proportion and texture. Modal mineralogy of KAHG, granite gneiss and basement granite gneiss largely represents monzogranite and syenogranite. The magnetic susceptibility (MS) of the KAHG, granite gneiss and basement granite gneiss varies widely between 0.11×10^-3 and 43.144×10^-3 SI units, corresponding to ilmenite series (<3×10^-3 SI; reduced type) and magnetite series (>3×10^-3 SI; oxidized type) of granitoids respectively. The observed MS variations are most likely intrinsic to heterogeneous source regions, modal variations of orthomagnetic and ferromagnetic minerals, and tectonothermal and deformational processes that acted upon these rocks. The primary and re-equilibrated compositions of biotites from the KAHG, granite gneiss and basement granite gneiss suggest calcalkaline, metaluminous (I-type) nature of felsic host magma formed in a subduction or post-collisional to peraluminous (S-type) host magma originated in syn-collisional tectonic settings, which were evolved and stabilized between FMQ and NNO buffers typically corresponding to reducing and oxidising magma environments respectively.     

有机酸对长石溶解度影响的热力学研究

为明确认识有机酸（草酸、醋酸）对长石溶解度及储层次生孔隙发育的影响，本文利用热力学方法，计算了不同温度、酸度下钾长石在含有醋酸根0.05mol/L、草酸0.0055mol/L的溶液中的溶解度及草酸和醋酸对溶液酸度的影响，计算的结果表明醒酸根与铝的络合作用只发生在偏酸性的溶液体系中，并且随温度升高要求酸度增加，实际的络合能力降低，醋酸根的络合作用对长石溶解度的增加作用极及有限，最高时不足一倍；但醋酸能有效地缓冲溶液酸度，从而提高长石溶解度。草酸根与铝的络合作用发生在弱碱性至酸性条件下，温度升高，络合能力增加，络合效应对长石溶解度，草酸根上铝的络合作用发生在弱碱性至酸性条件下，温度升高，络合能力增加，络合效应对长石溶出量的增加最多可达2个数量级以上，草酸的浓度太低无法通过缓冲溶液在较高的酸度下来促进长石的溶解，草酸和醒酸能否促进储层次生孔隙的发育取决于盆地流体的酸度及组成流体的缓冲体系。     

SILLS软件在单个萤石流体包裹体LA-ICP-MS微量元素分析数据处理中的应用

近年来激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)应用于单个流体包裹体成分定量分析已成为研究流体包裹体的最佳手段之一。该实验过程和数据处理比较复杂,目前国内外采用的数据分析软件为一款基于MATLAB的SILLS软件,该软件主要是对矿物(锆石)、流体包裹体以及熔体包裹体LA-ICP-MS分析结果进行处理。本文以萤石流体包裹体LA-ICP-MS分析为例,阐述了样品制备与流体包裹体的优选方法,对流体包裹体片厚度以及单个流体包裹体的选取要求作了详细描述,对仪器参数设置、内外标样选取和剥蚀方法等进行了说明。基于SILLS软件采用尖峰消除的方法对待处理数据进行校正,对不同种类型的波峰进行峰宽的选取。在元素比值校正和等效盐度计算过程中,由于被测样品是萤石,Ca元素具有较高的背景值,选择以Na作为流体包裹体的内标元素,以Ca作为寄主矿物的内标元素对寄主矿物浓度进行计算,同时提出以电价平衡代替质量平衡进行等效盐度计算。以上方案提高了LA-ICP-MS分析单个萤石流体包裹体的准确性,有助于解释成矿流体来源和矿床成因等问题。     

福建德化地区东洋浅成热液金矿床成矿作用与成因研究

为揭示福建德化东洋金矿床的成因,进行了矿床地质、流体包裹体和氢-氧、硫、铅同位素的系统研究。结果显示成矿流体接近于大气降水;硫元素具有深源硫的特征;铅同位素表明成矿物质来源于古老下地壳。综合研究结果表明该矿床的初始成矿流体为中高温、低密度、低盐度的岩浆热液,沸腾作用以及大气水混合是成矿物质卸载的主要因素,矿床成因属于与次火山岩岩浆作用有关的浅成热液低硫化型金矿床。     

A simulation experimental study on oxidative kinetics of sphalerite under hypergene condition

The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT     

长江经济带岩盐矿特征与盐穴储库适宜性评价

长江经济带包括上海、江苏、浙江、安徽、江西、湖北、湖南、四川、重庆、云南和贵州11个省(直辖市),是我国重要的经济发展区域,油气资源长期安全可靠的储存对于该区经济可持续发展至关重要。基于长江经济带战略油气储库基地建设规划布局的需求,在充分收集利用前人地质调查和研究成果的基础上,对区内岩盐矿床进行了综合研究和分析,建立了层次结构模型,评价了盐穴油气储库建设的可行性。长江经济带除上海和贵州外,其余9省(直辖市)均发现了大量的岩盐矿床,主要成盐时代为震旦纪、三叠纪、白垩纪和古近纪; 成盐盆地范围0.29~10 000 km²,盐层累计厚度3~1 050 m,矿体埋藏深度40~3 400 m; 矿石中NaCl含量20%~99.86%; 矿体顶底板及夹层岩石主要为泥岩、粉砂质泥岩及泥质粉砂岩。地质调查揭示出区内大部分地下盐穴远离地震活动带,构造稳定,因此可以改造为石油储库。考虑储气库的密闭性及安全性,江苏金坛盆地等6个盐矿埋深适中,建穴地质条件较好,适合建造储气盐穴库; 江苏淮安等14个盆地的局部地区适合建造天然气储库; 重庆垫江等11个盐矿埋深较大,可以建造储气盐穴库,但建造成本较高; 湖南澧县等21个盐矿埋藏偏浅,应选择更深部的盐层空间建造油气储库。建议在江苏金坛、淮安、赵集和丰县,江西清江和会昌,湖北云应、天门小板和潜江等盐矿地区优先开发利用盐穴。     

Chromium speciation in oxide-type compounds: application to minerals,gems, aqueous solutions and silicate glasses

Cr K-edge XANES spectra were obtained for a variety of Cr-bearing model compounds containing Cr(II), Cr(III), Cr(IV), Cr(V) and Cr(VI), in which the Cr-site symmetry is D4h, Oh and Td. The centroid position of the pre-edge feature is a better indicator of the Cr valence than the edge position. In Cr-rich oxides, higher-energy transitions must be excluded in order to refine a robust valence for Cr. The pre-edge for chromates is not unique and varies as a function of the CrO₄ ^2? moiety distortion, which is often related to Cr-polymerization (monochromate vs. dichromate). Both the analogy with the Mn K-pre-edge information and ab initio FEFF calculations of the pre-edge feature for Cr(III) and Cr(VI) confirm the experimental trends. This methodology is applied to the Cr K-edge pre-edge feature collected in gems (emerald, spinel and ruby), the layered minerals fuchsite and kämmererite, two Cr-bearing aqueous solutions and a set of sodo-calcic silicate glasses used for bottling sparkling white wine. In emerald and fuchsite, the Cr-site is differently distorted than its ruby or spinel counterpart. In a Cr(III)-bearing aqueous solution and sodo-calcic glass, no evidence for Cr(III) with Td and C3v symmetry is detected. However, minor amounts of chromate moieties (most likely monomeric) are detected in a glass synthesized in air. Preliminary spectra for the wine bottle glass suggest that only trace amounts of chromates might possibly be present in these glasses.