鄂尔多斯盆地奥陶系碳酸盐岩沥青 A 和沥青 C 的生物标志物特征

摘 要　 研究了鄂尔多斯奥陶系碳酸盐岩中沥青 A 和沥青 C 的生物标志物特征‚表明沥青 A 和沥青 C 之间在生物标志物组成上存在着明显的差异‚产生这些差异的原因主要是氧化还原 环境、成熟度及粘土矿物含量的不同。结合沉积相分析‚探讨了不同沉积环境中沥青 A 与沥 青 C 的分布规律。     

川西北侏罗系沙溪庙组固体沥青包裹烃的释放及其地球化学意义

固体沥青分子结构中可能存在类似于沥青质的吸附包裹现象,其包裹烃组分属于成熟度较低条件下的产物,包含有早期的地球化学信息.选用 H2O2/CH3COOH 作为氧化体系对其进行轻度化学氧化降解释放其中的包裹烃,并结合有机地球化学研究手段对川西北下寺侏罗系沙溪庙组固体沥青进行研究.结果显示,该固体沥青可溶组分中烷烃类包括生物标志物基本未检测到,仅残留一些简单的芳烃化合物,很难提供有用的地球化学信息.而其包裹组分中检测到一系列偶碳数正构-1-链烯、正构烷烃和部分异构烷烃以及生物标志物等.包裹组分中 Ts/(Ts+Tm)比值为0.26, C29甾烷20S/(20S+20R)比值为0.43,均反映了固体沥青低成熟度的特征;规则甾烷相对含量 C29>C27>C28,显示弱的 C29优势,其中(C27+C28)占52.1%, C29占47.9%;正构烷烃的分布呈微弱偶碳数优势;固体沥青总碳同位素值为–21.5‰,显示强烈富集13C 的特征.分析表明,藻类等低等水生生物对源岩母质有重要贡献,但不能确定是否有陆生高等植物的输入,母源可能沉积于弱的还原环境.沙溪庙组固体沥青与该地区其他层位固体沥青、油砂和油苗可能有不同的来源.     

高有机硫煤抽提物中含硫化合物的组成与热演化特征

高有机硫煤是一种十分特殊的煤种,其特点之一是抽提物芳烃馏分中含丰富的含硫化合物。在我国西南地区晚二叠世碳酸盐台地潮坪成因、具不同煤化程度的四种高有机硫煤中均检测出了四种系列的含硫化合物,它们分别为二苯并噻吩系列、苯并萘并噻吩系列、菲并噻吩系列和苯并二苯半噻吩系列。含硫化合物的类型组成虽然相似,但它们的相互比例关系与煤化程度和具体的沉积环境密切相关。分析发现,随煤化程度增加:（1）具三环结构的二苯并噻吩相对于四、五环结构的化合物数量减少;（2）具稳定甲基取代位的含硫化合物数量不断增加,同时还发现含硫化合物与同环数的常规芳烃间的比值可反映碳酸盐台地受局限的程度。     

四川盆地碳酸盐岩储层中固体运移沥青的性质和成因

四川盆地碳酸盐岩储层中固体运移沥青的性质和成因林峰王廷栋代鸿鸣王顺玉黄清德（西南石油学院勘探系,四川南充市６３７００１）关键词固体运移沥青显微结构脱沥青作用四川四川盆地位于扬子准地台西北部,区内碳酸盐岩沉积分布广泛,在碳酸盐岩储层中固体沥青含量极为丰...     

盐湖相低演化烃源岩的生烃机理及生物标志物演化特征——沥青“A”热模拟

柴达木盆地盐湖相低演化烃源岩沥青“A”的热模拟研究表明:在热作用下其排烃高峰在热模拟温度较低区间220~270℃，且以非烃和沥青质相对丰度最高为特征。沥青“A”在由未熟—低熟—成熟的演化过程中，各系列生物标志物的成熟速率不同，表现为正构烷烃＞藿烷＞甾烷。非烃和沥青质中含杂原子的极性化合物在热模拟温度300℃后开始大量发生脱羟基、脱羧基、脱羰基及链断裂反应。沉积有机质在低演化阶段甾烷C29 ββ/(ββ+αα)值异常高表明该地区细菌微生物发育。柴达木盆地低演化烃源岩在较低温度区间大量排烃，是细菌微生物对沉积有机质改造后其活化能大大降低所致。     

TSR对碳酸盐岩中沥青生烃影响的模拟实验

利用地层孔隙热压生排烃模拟仪实验装置,对采自四川盆地西北部广元矿山梁地区下寒武统具高有机质含量、高氢指数和低成熟度特征的固体沥青,开展了模拟地层条件下的"沥青+白云岩+去离子水"(系列A)和"沥青+白云岩+硫酸镁+去离子水"(系列B)生排烃实验。结果表明,这两个系列的气体产率具有较大差异,其中,加入硫酸镁的系列(系列B)发生了热化学硫酸盐还原反应(TSR),使气态烃和非烃气体的产率增大,同时也加速了重烃气体的裂解,导致重烃气体大量裂解的温度降低。     

粘球形藻干酪根热模拟产物中饱和烃生物标志物特征与意义

粘球形藻干酪根热模拟产物中饱和烃生物标志物特征与意义蒲秀刚柳飒郝石生（江汉石油管理局研究院,湖北潜江４３３１２４）（石油大学,北京１０２２００）关键词粘球形藻热模拟生物标志物饱和烃塔里木盆地全球范围内奥陶系生油岩和原油独特的地球化学特征研究表明,这些...     

一价阳离子和水溶性有机质对生物沥浸中次生铁矿物形成的影响

在嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)作用下,污泥生物沥浸体系中常会有次生铁矿物形成,这些矿物对污泥脱水和重金属溶出有重要影响。本研究模拟生物沥浸体系,考察了一价阳离子(K+、NH4+、Na+)和污泥DOM(dissolved organic matter)对次生铁矿物形成的影响。结果表明,一价阳离子生成次生黄铁矾类矿物的能力迥异,其中K+的成矾能力最强,120 mmol/L NH4+和80 mmol/L Na+会抑制体系中黄钾铁矾形成。在1.6 mmol/L K+-120 mmol/L NH4+-40 mmol/L Na+和1.6 mmol/L K+-80 mmol/L NH4+-80 mmol/L Na+两个处理所得矿物的结晶度均低于1.6 mmol/L K+-80 mmol/L NH4+-40 mmol/L Na+处理所得矿物的结晶度。另外,在50 mg/L DOM(以DOC计)存在的生物氧化体系,Fe2+最大氧化速率为4.96 h-1,比没有DOM存在时降低48.1%,矿物结晶度也明显低于后者。可见,过高的一价阳离子和DOM含量会影响A.ferrooxidans菌生理生化活性,降低Fe2+氧化速率,继而影响Fe3+供应,使微环境中的黄铁矾形成动力发生改变,最终在一定程度上影响了次生铁矿物的形成。     

含铀矿物对烃源岩生烃影响的热模拟研究

采用密闭容器加水的热模拟方法,从生烃组成特征、生烃量等方面,探讨了含铀矿物对烃岩热解生烃过程的影响.热模拟实验结果表明,在暗色泥岩和煤岩样品中加入含铀矿物后,气态烃和液态烃的生烃量都有比较明显的增加,其中煤岩的气态烃产量平均增加值为34%,而泥岩样品平均增加值也达到了30%以上.液态烃产率分析表明,含铀矿物也促进了泥岩和煤岩的液态烃产率.从泥岩氯仿沥青'A'族组成分析发现,加入催化剂后泥岩的饱和烃和芳烃在高温阶段具有规律性的明显增大的趋势,反映出非烃和沥青质甚至不溶有机质向相对稳定的饱和烃转化以及芳烃随演化程度增加的高聚合作用.综合以上分析,认为放射性铀对油气生成具有积极的意义.     

The role of minerals in the thermal alteration of organic matter--III. Generation of bitumen in laboratory experiments

A series of pyrolysis experiments, utilizing two different immature kerogens (from the Monterey and Green River Formations) mixed with common sedimentary minerals (calcite, illite, or Na-montmorillonite), was conducted to study the impact of the mineral matrix on the bitumen that was generated. Calcite has no significant influence on the thermal evolution of bitumen and also shows virtually no adsorption capacity for any of the pyrolysate. In contrast, montmorillonite and illite, to a lesser extent, alter bitumen during dry pyrolysis. Montmorillonite and illite also display strong adsorption capacities for the polar constituents of bitumen. By this process, hydrocarbons are substantially concentrated within the pyrolysate that is not strongly adsorbed on the clay matrices. The effects of the clay minerals are significantly reduced during hydrous pyrolysis. The strong adsorption capacities of montmorillonite and illite, as well as their thermocatalytic properties, may in part explain why light oils and gases are generated from certain argillaceous source-rock assemblages, whereas heavy immature oils are often derived from carbonate source rocks.     

A study on microwave dielectric properties of solid bitumen

Microwave complex dielectric constants were measured with the cavity perturbation method for natural bitumens of various degrees of metamorphism as well as for bitumen samples subjected to thermal metamorphism under lab conditions. The results show a positive correlation between microwave complex dielectric constant and metamorphic degree and that the magnitude of variation in this parameter is greater than that of H/C,R _max, free radical concentration,d ₀₀₂ value, back-peak temperature in organic DTA and density. Microwave complex dielectric constant can be used as an indicator of oil-gas-generating threshold. For bitumen from oil- generating areas,ε′<5 andε″<0.070; and for that from oil-pyrolyzed gas areas,ε′=5?15 andε″=0.07?0.03.     

鄂尔多斯盆地能源矿产氯仿沥青Sm-Nd同位素研究

对鄂尔多斯盆地石油、煤、含铀砂岩及其围岩的氯仿沥青进行了Sm-Nd同位素研究。结果表明,盆地流体(包括深部流体)活动具有多期性,且后期的流体活动对铀矿床的形成具有重要作用;赋存于同一套地层中的含铀砂岩沥青、煤沥青及石油沥青,虽然均具有富集地幔特征,但并非同期活动的产物;东胜矿区侏罗系直罗组煤沥青和盆地西南部陈家山矿区侏罗系延安组的煤沥青,源区时代上存在较大差异,伴生沥青并非全部由煤的热演化形成,可能还存在外来流体的加入,且东胜直罗组煤的伴生沥青较延安组煤的伴生沥青来源深度更大;盆地内马岭油田的直罗组石油沥青、陈家山延安组煤层石油沥青及其煤沥青在源区特征上具有内在联系。     

Fractionation of multiple sulfur isotopes during phototrophic oxidation of sulfide and elemental sulfur by a green sulfur bacterium

We present multiple sulfur isotope measurements of sulfur compounds associated with the oxidation of H₂S and S⁰ by the anoxygenic phototrophic S-oxidizing bacterium Chlorobium tepidum. Discrimination between ³⁴S and ³²S was +1.8 ± 0.5‰ during the oxidation of H₂S to S⁰, and −1.9 ± 0.8‰ during the oxidation of S⁰ to , consistent with previous studies. The accompanying Δ³³S and Δ³⁶S values of sulfide, elemental sulfur, and sulfate formed during these experiments were very small, less than 0.1‰ for Δ³³S and 0.9‰ for Δ³⁶S, supporting mass conservation principles. Examination of these isotope effects within a framework of the metabolic pathways for S oxidation suggests that the observed effects are due to the flow of sulfur through the metabolisms, rather than abiotic equilibrium isotope exchange alone, as previously suggested. The metabolic network comparison also indicates that these metabolisms work to express some isotope effects (between sulfide, polysulfides, and elemental sulfur in the periplasm) and suppress others (kinetic isotope effects related to pathways for oxidation of sulfide to sulfate via the same enzymes involved in sulfate reduction acting in reverse). Additionally, utilizing fractionation factors for phototrophic S oxidation calculated from our experiments and for other oxidation processes calculated from the literature (chemotrophic and inorganic S oxidation), we constructed a set of ecosystem-scale sulfur isotope box models to examine the isotopic consequences of including sulfide oxidation pathways in a model system. These models demonstrate how the small δ³⁴S effects associated with S oxidation combined with large δ³⁴S effects associated with sulfate reduction (by SRP) and sulfur disproportionation (by SDP) can produce large (and measurable) effects in the Δ³³S of sulfur reservoirs. Specifically, redistribution of material along the pathways for sulfide oxidation diminishes the net isotope effect of SRP and SDP, and can mask the isotopic signal for sulfur disproportionation if significant recycling of S intermediates occurs. We show that the different sulfide oxidation processes produce different isotopic fields for identical proportions of oxidation, and discuss the ecological implications of these results to interpreting minor S isotope patterns in modern systems and in the geologic record.     

中低煤阶高有机硫煤含硫结构演化特征

采用计算机曲线拟合方法对实验数据进行分峰处理,定量分析了9个中低煤阶高有机硫煤样的红外光谱(FT-IR)数据特征。研究表明,二硫醚与碳碳双键吸收峰面积比值(X₁)、硫醇与碳碳双键吸收峰面积比值(X₂)分别与R_max以及有机硫含量(S_o,d)呈显著的正相关性。煤质参数相近,有机硫含量及其占全硫比例受微环境的影响。同一煤样中,二硫醚、硫醇、二硫化铁三种含硫结构红外参数均依次递减。低煤阶及低-中阶烟煤阶段,以二硫醚、硫醇为代表的有机硫与含氧官能团的红外参数呈现此消彼长关系,且在第二次煤化跃变点附近,参数急剧增大。高有机硫煤样随煤阶升高,脂肪链支链化程度下降,芳构化程度加大,与一般低硫煤结构演化特征相符。     

Heavy minerals and the evolution of the modern Nile

Heavy mineral analysis is a useful tool in tracing the changes in the hydrographic setting of the Nile through time. Analyses by the writer and others are presented to differentiate between a former Nilotic system, a Proto-Nile, and the modern Nile system, and to demonstrate the changes undergone by the modern Nile.The Proto-Nile was almost totally dependent upon discharge from equatorial and sub-equatorial tributaries in East Africa and from local Sudano-Egyptian affluents. The modern Nile system, in contrast, is dominated by contributions from the Blue Nile and the Atbara River, which drain the Ethiopian Plateau. The discharge of these rivers is governed by the monsoonal rains which are responsible for the summer floods in the Lower Nile Basin. It has been generally believed that this riverine system is very recent, perhaps not much older than 20,000 years. The evidence presented in this paper indicates that the Modern Nile system was well established by the later part of the Middle Pleistocene. In its early stage, the modern Nile was characterized by greater contributions from the non-Ethiopian East African and Sudano-Egyptian tributaries than at present.     

The elemental and isotopic composition of sulfur and nitrogen in Chinese coals

Coal combustion is an important atmospheric pollution source in most Chinese cities, so systematic studies on sulfur and nitrogen in Chinese coals are needed. The sulfur contents in Chinese coals average 0.9 ± 1.0%, indicating that most Chinese coals are low in sulfur. A nearly constant mean δ³⁴S value is observed in low sulfur (TS < 1) Chinese coals of different ages (D, P₁, T₃ and J₃). High sulfur Chinese coals (OS > 0.8%), often found at late Carboniferous (C₃) and late Permian (P₂) in southern China, had two main sulfur sources (original plant sulfur and secondary sulfur). The wide variety of δ³⁴S values of Chinese coals (−15‰ to +50‰) is a result of a complex sulfur origin. The δ¹⁵N values of Chinese coals ranged from −6‰ to +4‰, showing a lack of correlation with coal ages, whereas nitrogen contents are higher in Paleozoic coals than in Mesozoic coals. This may be related to their original precursor plant species: high nitrogen pteridophytes for the Paleozoic coals and low nitrogen gymnosperms for the Mesozoic coals. Different to δ³⁴S values, Chinese coals showed higher δ¹⁵N values in marine environments than in freshwater environments.     

Restoration of the elemental and stable-isotopic compositions of diffusionally altered minerals in slowly cooled rocks

 In polymineralic plutonic igneous and metamorphic rocks, slowly cooled crystals seldom retain their initial chemical compositions. This paper introduces a new, simple and widely applicable material-balance method that recovers the former compositions of minerals – regenerating in many rock types their chemical memory of the environment in which they formed – without a priori knowledge of temperature or pressure or diffusion kinetics. Restored stable-isotopic, trace-element, and/or major-element compositions provide a basis for interpretations of petrogenetic processes and conditions, including recovery of peak temperature and pressure, depth, and average diffusion distance during re-equilibration. Case studies illustrate applications of the mineral-restoration technique to regional crustal dynamics, ore metallogeny, and igneous fluid dynamics and petrogenesis. The first illustrative case addresses the controversial origin of decimetre-thick, modally graded rock layers in the Skaergaard intrusion. Layer-wide mineral-chemistry gradients that previously were ascribed a primary origin are here shown to be due to sub-solidus diffusive re-equilibration amongst minerals that initially were chemically uniform. This finding redefines the constraints to be satisfied by fluid-dynamic models of chemical differentiation processes in the magma chamber, and eliminates the basis of prior interpretations of the modally graded layers as products of in situ crystallization on the magma chamber's floor. In another case, lower crustal olivine-chromite cumulates underwent a long two-stage history of mineral-composition readjustment spanning >500° C. The technique introduced here removes the effects of the second-stage solid-state diffusion, recovering mineral compositions that represent the igneous solidus temperature at the termination of the metasomatic stage. The third example removes effects of retrograde diffusive ion-exchange from garnet, hornblende, and clinopyroxene in order to restore the rock's chemical memory of its pressure and depth of crystallization. The depth corresponds to a measure of extreme Cenozoic uplift and erosion (∼58 km) along the Main Mantle Thrust, which juxtaposes the underthrusting Indian Plate and the over-riding Kohistan island-arc terrain in the Pakistani Himalayas. Received: 28 March 1995 / Accepted: 11 April 1996     

川东北地区长兴组-飞仙关组固体沥青的形貌特征与成因分析

利用扫描电镜观察川东北某地区上二叠统、下三叠统储层固体沥青时,发现固体沥青与显微镜下的无定形、它形充填构造不同,按其外形可分为皮壳状、葡萄状、瘤状、蠕虫状和柿饼状5种类型。其中皮壳状、葡萄状沥青分布在飞仙关组,瘤状、蠕虫状和柿饼状沥青分布在长兴组。根据固体沥青内部鳞片状结构和球粒中间相结构推测其已达高演化阶段。