时间谱电阻率法中的剩余电磁效应研究

根据频谱激电（SIP）法或复电阻率（CR）法中研究剩余电磁（REM）效应的思想，通过分析时间谱电阻率（TSR）法中场的基本特征，在TSR法中建立了与SIP（或CR）法中参数Φmax/Φ0max相类似的参数－Emax/E0，用来描述了TSR法中的REM效应。通过对一维可极化大地模型的REM效应的理论计算，验证了用Emax/E0表示的REM异常可用来形象地反映地电断面电阻率的高低。     

Geochemical characteristics and isotopic reversal of natural gases in eastern Kopeh-Dagh,NE Iran

Natural gas samples from two gas fields located in Eastern Kopeh-Dagh area were analyzed for molecular and stable isotope compositions. The gaseous hydrocarbons in both Lower Cretaceous clastic reservoir and Upper Jurassic carbonate reservoir are coal-type gases mainly derived from type III kerogen, however enriched δD values of methane implies presence of type II kerogen related material in the source rock. In comparison Upper Jurassic carbonate reservoir gases show higher dryness coefficient resulted through TSR, while presence of C₁C₅ gases in Lower Cretaceous clastic reservoir exhibit no TSR phenomenon. Carbon isotopic values indicate gas to gas cracking and TSR occurrence in the Upper Jurassic carbonate reservoir, as the result of elevated temperature experienced, prior to the following uplifts in last 33–37 million years. The δ¹³C of carbon dioxide and δ³⁴S of hydrogen sulfide in Upper Jurassic carbonate reservoir do not primarily reflect TSR, as uplift related carbonate rock dissolution by acidic gases and reaction/precipitation of light H₂S have changed these values severely. Gaseous hydrocarbons in both reservoirs exhibit enrichment in C₂ gas member, with the carbonate reservoir having higher values resulted through mixing with highly-mature-completely-reversed shale gases. It is likely that the uplifts have lifted off the pressure on shale gases, therefore facilitated the migration of the gases into overlying horizons. However it appears that the released gases during the first major uplift (33–37 million years ago) have migrated to both reservoirs, while the second migrated gases have only mixed with Upper Jurassic carbonate reservoir gases. The studied data suggesting that economic accumulations of natural gas/shale gases deeper than Upper Jurassic carbonate reservoir would be unlikely.     

Dissolution characteristics of deep?buried dolostone in the Member 5 of Ordovician Majiagou Formation in southern Ordos Basin

The different types of deep-buried dissolution process in the Member 5 of Ordovician Majiagou Formation in the southern Ordos Basin and its influence on the reservoir properties are studied in this paper. It shows that three types of mechanisms include organic acid fluid, hydrothermal fluid and TSR are identified through studies of core observation, thin section analysis, inclusion temperature, trace elements and rare earth elements. It is found that the dissolution of organic acid fluid causes the stratified dissolution pores, film-like asphaltene and ring-like asphaltene, while hydrothermal fluid causes the non-selective dissolution pores without petrofabric, veins of pyrites, massive pyrites and the association of hypothermal minerals. Four occurrence models of dissolution include, (1) the deep-buried dissolution of low-temperature hydrothermal fluid occurs in Zhiluo Period of Middle Jurassic; (2) the deep-buried dissolution of organic acid fluid started from the late Middle Jurassic followed by the first hydrocarbon injection; (3) the deep-buried dissolution of middle-high temperature hydrothermal fluid occurred in the Dongsheng Period of Early Cretaceous; (4) TSR occurred at the end of Early Cretaceous with the second larger hydrocarbon injection. Both organic acid fluid and hydrothermal fluid can improve the porosity and permeability of reservoir, but the hydrothermal fluid is more effective than that of organic acid fluid.     

热化学硫酸盐还原作用对碳酸盐岩气藏的化学改造——以川东北地区长兴组-飞仙关组气藏为例

目前在川东北地区长兴组—飞仙关组已发现普光、渡口河、铁山坡、罗家寨等多个高含H2S的大、中型气田。通过天然气地球化学特征、流体包裹体盐度和岩心及薄片的镜下详细观察后认为,川东北地区长兴组—飞仙关组的大多数气藏遭受了热化学硫酸盐还原作用(TSR)的化学改造,TSR的改造主要表现在3个方面:1使C2 重烃相对于CH4、12C相对于13C优先被消耗,造成天然气干燥系数变大和碳同位素变重;2由于TSR产生的大量淡水的加入,使气藏的原生地层水被稀释,造成地层水盐度降低;3TSR相关流体(烃类和H2S等)与储层岩石之间的相互作用使储层被溶蚀和硬石膏发生蚀变,造成储层孔隙度增大,从而对改善其物性具有重要意义。     

TSR对深部碳酸盐岩储层的溶蚀改造——四川盆地深部碳酸盐岩优质储层形成的重要方式

四川盆地海相层系发现的大气藏部含或高舍硫化氢,都发育一定厚度的优质储层,而且优质储层与硫化氢分布具有密切的关系,即气藏硫化氢含量越高,储层性质越好,气藏产能也越大。研究发现,在 TSR(硫酸盐热化学还原反应)过程中,随着膏质岩类的溶解(为 TSR 反应提供 SO_4~(2-)),使储集孔隙初步得到改善;而 TSR 产生的硫化氢溶于水形成的氢硫酸,具有强烈腐蚀性,加速了储层中白云岩的溶蚀,形成孔隙极其发育的海绵状孔洞体系,并呈层状分布。电镜下可以清晰看到白云石晶面的溶蚀坑及溶孔中 TSR 产生的硫磺晶体。溶孔中自生碳酸盐的碳同位素在-10.3‰～18.2‰,而地层碳酸盐的碳同位素在 3.7‰～ 0.9‰,证实了 TSR 过程中有机-无机的相互作用,即有机成因烃类中的碳转移到次生碳酸盐岩中。包裹体分析表明,次生方解石中的包体富含硫化氢,且均一温度多数在160℃以上,具备 TSR 发生的温度条件;硫化氢和硫磺的硫同位素比地层硫酸盐的硫同位素偏轻8‰左右,是 TSR 作用的证据。因此高含硫化氢气藏的优质储层是在早期埋藏溶蚀作用的基础上,后期发生 TSR 及其形成的酸性流体对深埋碳酸盐岩储层再次进行深刻改造和强烈溶蚀作用的结果;同时可以运用硫化氢来预测碳酸盐岩优质储层的分布。     

The Role of Seal and Source Rocks in Fluid-rock Interactions and their Reservoir Effects within the Carbonate Deep Burial Realm

Discoveries of deep high-quality carbonate reservoirs challenged the general understanding on the evolution of porosity decreasing with depth. New mechanisms of pore generation and preservation in the deep realm require to be proposed. Dolostones in the Feixianguan and Dengying Formations experienced maximum depths in excess of 8000 m, but still retained high porosity. Petrographic observation and homogenization temperatures help to identify products of deep fluid-rock interactions, visual and experimental porosity were used to quantify reservoir effects, the distribution of products finally being plotted to unravel the mechanisms. Th data reveal that thermochemical sulfate reduction (TSR), burial dissolution and quartz cementation are typical deep fluid-rock interactions. The SO42? of residual porewater sourced from the evaporative dolomitizing fluid was supplied for TSR in the hydrocarbon column, the TSR-inducing calcite cements were homogeneously dispersed in the hydrocarbon column. Quartz cementation was caused by the increasing acidity and Si-rich residual porewater in the oil column. Burial dissolution is forced by organic acid and limited in oil–water contact. This study suggests that seal and source rocks not only play important roles in hydrocarbon accumulation, but also have a general control on the deep fluid-rock interactions and porosity evolution in the deep burial realm.     

Origin and quantitative source assessment of deep oils in the Tazhong Uplift,Tarim Basin

A large amount of deep oil has been discovered in the Tazhong Uplift, Tarim Basin whereas the oil source is still controversial. An integrated geochemical approach was utilized to unravel the characteristics, origin and alteration of the deep oils. This study showed that the Lower Cambrian oil from well ZS1C (

_1x) was featured by small or trace amounts of biomarkers, unusually high concentration of dibenzothiophenes (DBTs), high δ³⁴S of DBTs and high δ¹³C value of n-alkanes. These suggest a close genetic relationship with the Cambrian source rocks and TSR alteration. On the contrary, the Middle Cambrian oils from well ZS1 (

_2a) were characterized by low δ¹³C of n-alkanes and relatively high δ³⁴S of individual sulfur compounds and a general “V” shape of steranes, indicating a good genetic affinity with the Middle–Upper Ordovician source rocks. The middle Cambrian salt rock separating the oils was suggested to be one of the factors responsible for the differentiation. It was suggested that most of the deep oils in the Tazhong Uplift were mixed source based on biomarkers and carbon isotope, which contain TSR altered oil in varied degree. The percentage of the oils contributed by the Cambrian–Lower Ordovician was in the range of 19–100% (average 57%) controlled by several geological and geochemical events. Significant variations in the δ³⁴S values for individual compounds in the oils were observed suggesting a combination of different extent of TSR and thermal maturation alterations. The unusually high DBTs concentrations in the Tazhong-4 oilfield suggested as a result of mixing with the ZS1C oil (

_1x) and Lower Ordovician oils based on δ³⁴S values of DBT. This study will enhance our understanding of both deep and shallow oil sources in the Tazhong Uplift and clarify the formation mechanisms of the unusually high DBTs oils in the region.     

傅里叶变换离子回旋共振质谱的地球化学意义及其在油气勘探中的应用前景

NSO杂原子化合物在烃源岩和原油中通常只占很小的一部分,但其包含重要的地质地球化学信息。由于组成复杂且难以分离,对该类化合物的组成研究相对薄弱。电喷雾电离源（ESI）结合傅里叶变换离子回旋共振质谱（FT-ICR MS）是一种新型检测石油组分的手段,具有选择性电离、超高质谱分辨率和质量精度等特征,非常适合检测石油复杂基质中微量NSO极性杂原子化合物分子组成,近年来开始应用于油气勘探领域。结合对塔里木盆地海相油与陆相油、辽河稠油等样品的FT-ICR MS分析,发现原油中NSO化合物受母源岩与油气成因类型、成熟度、油气运移示踪及硫酸盐热化学还原反应（TSR）控制,可提供相关的识别与评价信息,显示FT-ICR MS在油气地球化学理论研究和油气勘探中具有潜在的应用价值。     

Origin of CO_2 in natural gas from the Triassic Feixianguan Formation of Northeast Sichuan Basin

The natural gas from the Triassic Feixianguan Formation of Northeast Sichuan Basin contains high H2S whereas relatively low CO2 concentrations and the CO2 display high δ13C values (ranging from -5.81‰ to 3.3‰ (PDB)). This seems to contradict the conventional wisdom that TSR should be a primary source of CO2 in natural gas from the Feixianguan Formation. In contrast, many authigenic calcite samples from these sites display very low δ13C values (ranging from -18.4‰ to -10.3‰ (PDB)). This suggests that the carbon from TSR source dominated the formation of calcite whereas the carbon from inorganic source came into CO2 in natural gas. In order to assess the origin of CO2 from these H2S-rich sites, we have calculated the relative contributions of organic and inorganic carbon sources to the CO2 and authigenic calcite. The organic carbon source possibly originated from TSR, whereas the inorganic one might be generated from marine carbonates dissolution. This calculation is based on the carbon isotopic compositions of CO2 and authigenic calcite as well as an isotopic mass balance. The results show that the contribution of organic carbon source to the CO2 is only 2%, whereas that to authigenic calcite is as high as 43% on average. Such results combined with thermodynamic evidence indicate that the isotopically light CO2 produced by TSR process may contribute to authigenic calcite precipitation during burial diagenesis. Distinguishable from Ordovician reservoir of Tarim Basin, Feixianguan reservoir of Northeast Sichuan Basin experienced rapid tectonic uplift due to Yanshanian movement after TSR occurred. Such tectonic event could induce temperature decrease and further promote carbonates dissolution. During these processes, secondary porosity has developed in Feixianguan carbonate reservoirs. Therefore, much attention should be paid to the structural highs in search of high quality carbonate reservoirs.     

CaSO4-C-H2O体系研究：模拟实验与热力学探讨

传统认为TSR成因的固态沥青(焦沥青)属于热化学反应的终端产物,不会对TSR的反应进程起到重要作用.本文以活性炭作为固态沥青(焦沥青)的模型化合物,开展了CaSO4-C-H2O体系的热模拟实验研究,探讨了CaSO4-C-H2O体系发生TSR的热力学特征.实验结果表明,CaSO4-C-H2O体系在300℃时即可启动TSR,主要生成CaCO3、H2S和CO2等产物.这一TSR门限温度要远低于以往室内利用气态或液态烃类进行的TSR模拟实验温度范围,与热力学计算结果一致.利用HSC Chemistry 5.0软件进行TSR过程模拟,发现25～200℃时CaSO4-C-H2O体系发生的TSR完全受动力学控制,在温度保持不变情况下,压力增大不利于CaSO4-C-H2O体系发生TSR.较少的含水量对TSR有一定促进作用,而含水量过多则可能抑制TSR的进行,含水量对TSR的影响可能与CaSO4在水中的饱和浓度有关.在一定的温度下,当体系pH≤2时,随着pH逐渐降低,CaSO4的量呈线性递减,但在沉积盆地地层水pH范围内(pH＞4),pH对TSR的作用可以忽略不计.CaSO4-C-H2O体系发生的TSR反应是一个放热过程,并且随着温度升高,反应热逐渐增大.在25～200℃范围内,TSR反应热为12.9～133 J/molCaSO4.热力学计算以及模拟实验结果均暗示,固态沥青(焦沥青)可能比烃类更容易参与TSR.