鄂尔多斯盆地上三叠统长7段泥页岩储集性能

页岩气的成功勘探开发引发了全球海相页岩研究的热潮, 然而对处于生油窗内的陆相页岩储集性能的研究尚需加强.基于光学薄片、场发射扫描电镜、环境扫描电镜、纳米CT、图像分析、GRI物性、气体吸附等方法对长7段泥页岩储集性能进行系统研究.结果表明: 长7段泥页岩形成于陆相半深湖-深湖环境, 面积为10×104 km2, TOC＞2%, R_o=0.8%~1.0%, HI=124~480 mg/g, 生烃潜力高; 脆性矿物含量为45%~59%, 孔隙度为0.6%~3.8%, 渗透率为0.000 72×10-3~0.002 30×10-3 μm2; 主要发育粒内孔、粒间孔和有机质孔, 以伊蒙混层等粘土矿物粒内孔为主, 有机质孔较少; 孔隙直径为30~200 nm, 孔喉系统连通性中等, 具备储集能力; 伊蒙混层等粘土矿物含量与比孔容相关性优于热演化程度与烃指数等, 表明长7页岩微观孔隙主要受控于成岩作用, 有机质生烃作用对储集空间贡献相对较小; 滞留烃主要以吸附态和游离态存在于黄铁矿晶间孔、伊蒙混层粒内孔、伊利石粒内孔与长石粒间孔.      

Diagenesis of organic matter and fine clay minerals: a comparative study

A geochemical study has been made of fine clay minerals and organic matter in subsurface shale samples from the Canadian Northwest Territories. The mixed layer clays comprise smectite-vermiculite-illite but are transformed during thermal diagenesis to a pseudo-quaternary system (smectitevermiculite-illite-chlorite) by incorporation of amorphous inorganic material. The first clay dehydration occurs prior to hydrocarbon generation and is accompanied by adsorption of K⁺ and substitution of Al³⁺ for Si⁴⁺ in the clay lattice. Vermiculite is an intermediary in the transformation of smectite to illite and in the presence of Ca²⁺ ions delays the second dehydration step to the zone where cracking of liquid hydrocarbons to gas occurs.Hydrocarbon generation commences at a vitrinite reflectance level of ? 0.5% R₀ maximum in both amorphous and woody-herbaceous organic matter but does not reach a significant level in the latter case until reflectance levels of 0.7% R₀ maximum. The pristane to phytane ratio and proportion of n-alkanes and acyclic isoprenoids increase during hydrocarbon generation from woody-herbaceous organic matter. Anomalous hydrocarbon yields from certain samples are attributed to high concentrations of plant resins. Destructions of liquid hydrocarbons by cracking commences at a reflectance level of 1.0% R₀ maximum and is essentially complete by a reflectance level of 1.4% R₀ maximum. The proportion of n-alkanes in the saturates decreases during cracking of the liquid hydrocarbons.     

Low-temperature gas from marine shales: wet gas to dry gas over experimental time

Marine shales exhibit unusual behavior at low temperatures under anoxic gas flow. They generate catalytic gas 300° below thermal cracking temperatures, discontinuously in aperiodic episodes, and lose these properties on exposure to trace amounts of oxygen. Here we report a surprising reversal in hydrocarbon generation. Heavy hydrocarbons are formed before light hydrocarbons resulting in wet gas at the onset of generation grading to dryer gas over time. The effect is moderate under gas flow and substantial in closed reactions. In sequential closed reactions at 100°C, gas from a Cretaceous Mowry shale progresses from predominately heavy hydrocarbons (66% C₅, 2% C₁) to predominantly light hydrocarbons (56% C₁, 8% C₅), the opposite of that expected from desorption of preexisting hydrocarbons. Differences in catalyst substrate composition explain these dynamics. Gas flow should carry heavier hydrocarbons to catalytic sites, in contrast to static conditions where catalytic sites are limited to in-place hydrocarbons. In-place hydrocarbons and their products should become lighter with conversion thus generating lighter hydrocarbon over time, consistent with our experimental results.     

海相原油沥青质作为特殊气源的生气特征及其地质应用

应用高压封闭体系,对塔里木盆地海相原油中的沥青质组分进行了热裂解模拟实验,从气态烃产率及碳同位素演化、焦沥青的生成等方面,探讨了沥青质作为特殊气源的生气机理。运用Kinetics动力学软件,计算得到沥青质裂解的动力学参数（活化能和指前因子）,在此基础上,将模拟实验结果外推至地质条件下,探讨其动力学模型的实际应用。结果表明,沥青质裂解气在Easy%Ro值0.8左右开始生成,在Easy%Ro值2.65左右其转化率达到1。Easy%Ro为0.9时沥青质裂解进入主生气期（转化率0.1）,Easy%Ro为2.3时主生气期结束（转化率0.9）。研究成果可为中国海相层系裂解气的判识、资源评价及勘探决策等提供实验和理论依据。     

Natural background of hydrocarbon gases (C1–C5) in the waters of the Kara Sea

The distributions of methane and hydrocarbons (HC) C2+ throughout the vertical section of the water mass and sediments of the Kara Sea and the estuaries of the Ob and Yenisei rivers were examine during expeditions aboard the R/V “Akademik Boris Petrov” in 1997–2002. Data obtained during the expeditions and extensive information provided by the complex study of the carbon cycle in the aquatic area were used to analyze the genesis of hydrocarbon gases in marine water. The example of particulate matter was used to demonstrate that hydrocarbon gases of the composition C2–C5 contained in seawater are genetically related to aquatic organic matter (OM), regardless of seawater salinity. The hydrocarbon complex is dominated (80%) by higher C4–C5 homologues. The concentration of C4–C5 hydrocarbons in the estuarine fresh waters is comparable with the high methane concentration (2–3 μl/l), drastically decreases in the zone of water mixing, and then rapidly increases to values several times higher than the methane concentration in seawater outside the outer boundary of the sedimentation depocenter of riverine particulate matter. A direct correlation was established for the concentration of the C4 + C5 homologues with the OM of the water mass, and the leading role was demonstrated to be played by labile OM of the autochthonous biomass (marine phytoplankton) in the genesis of higher hydrocarbon gases (alkenes, alkanes, and isoalkanes) during the early diagenetic stage of OM transformations in water. Along with the biomass of phytoplankton, a significant role in the genesis of C2–C3 hydrocarbons is played by destruction products of terrigenous OM. The destruction of OM and generation of gaseous hydrocarbons, including methane, are restricted to the pycnocline and the water-sediment interface. The absolute predominance of the sum of the C4 + C5 homologues in the hydrocarbon C2+ gases and the presence of unsaturated C2–C4 hydrocarbons are typical of the natural background of hydrocarbons of the Kara Sea water mass.     

含铀物质对有机质生烃的实验研究

采用密闭容器水热模拟实验方法,考察含铀物质对有机质热解生烃过程的影响。对热模拟实验产物分析发现,在暗色泥岩和煤岩样品中加入含铀物质后,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’族组成分析表明,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氧化催化作用。     

铁白云石矿物学特征及原生次生成因机制

长期以来,铁白云石的命名划分标准混乱,一直被当成高温及次生的产物.综述了国内外铁白云石的研究进展,详细探讨了铁白云石的矿物学特征,特别在其成因中加入了微生物因素,运用地质微生物学探讨原生铁白云石的成因机制.研究认为:（1）铁白云石命名划分依据应遵照国际矿物学会的原则,以铁是否替代白云石晶格中半数镁的位置为标准,分为白云石和铁白云石;（2）详述铁白云石矿物学及其晶体特征;（3）铁白云石成因分为原生沉淀及次生两种,微生物介导形成原生白云石的过程中,有助于铁进入到白云石晶格中,增加晶格中铁的含量.      

腐殖煤气态产物演化特征的模拟实验研究

本文较详细地探讨了成熟阶段腐殖煤在加水热模拟过程中气态产物的演化特征。成熟阶段的煤仍具有相当的生烃潜力,其主要生烃阶段仍以生油为主,生气相对较少。生油高峰之后由于液态产物的大量热裂解才开始进入气态烃的大量生成阶段。由于地质条件下煤中的可溶有机质十分丰富,在高演化阶段由可溶有机质进一步裂解是煤成气的重要来源。非烃主要形成于早期阶段。成熟煤生成的气态烃中甲烷为之主要成分,非烃中H₂为主,其次为CO₂,甲烷的碳同位素值明显低于乙烷,而乙烷和丙烷的碳同位素值差别较小,并且随演化程度的增加各气态组分的碳同位素值差别愈来愈小。     

On the Origin of Petroleum Hydrocarbon Gases

The compositional variation of oil-soluble gaseous hydrocarbons in high-pressure in-place oil from more than 40 oil wells in the Northern Jiangsu oil field, China, was studied. Samples in which the effects of the factors of pressure and biodegradation had been got rid of were chosen as the representatives that could really reflect the original composition of hydrocarbon gases. Such samples were compared compositionally with their corresponding hydrocarbons formed by decarboxylation of volatile low-molecular fatty acids. Thus highly correlative regularities were found to exist between them. The numerical values of both are graphically expressed. The two curves on the diagram are very similar. These two sets of values have a simple correlation coefficient of 0.9935, which presents their genetic relation.Based on the study of the formation of gaseous hydrocarbons from decarboxylation of volatile fatty acids, the following regularities of the isomers are revealed:1) n-butyric acid + isobutyric acid = propane:2) 1 2 isopentanoic acid(2-methyl-butyric acid) + n-pentanoic acid = n-butane; and3) 1 2 isopentanoic acid(3-methyl-butyric acid) = isobutane.The thermodynamics of decarboxylation was analysed and the enthalpy change △H, entropy change △S and Gibbs free energy change △G in the following reaction were calculated:CH_3COOH(1)--CH_4(g) + CO_2(g).Thus the author considers that the reaction for the formation of hydrocarbons due to the decarboxylation of fatty acids is an exothermic one with increased entropy and decreased free energy as well as a spontaneous one. According to the CRC rule, the resultant Gibbs free energy change △G is approximately-41.84 kJ/mol, which is well within the range of the energy levels of biophysiological changes.According to the changes in odd-carbon preference in n-alkanes of petroleum and sediments and the analysis of fatty acids and amino acids, it is considered that hydrocarbon gases do not originate from pyrolysis or thermal degradation but from decarboxylation of organisms. But this biological reaction is not ordinary biochemical reaction in the artificial fermentation for generating marsh gas. On the basis of the change tendency of the fatty acid content in the fermentation liquor for marsh gas generation and the change tendency of the carbon isotopes in methane and carbon dioxide in the marsh gas, it can be judged that the biochemical reaction for forming hydrocarbon gases is a special biological one occurring after the fermentation.     

Clay mineralogy, organic carbon burial, and redox evolution in Proterozoic oceans

Clay minerals formed through chemical weathering have long been implicated in the burial of organic matter (OM), but because diagenesis and metamorphism commonly obscure the signature of weathering-derived clays in Precambrian rocks, clay mineralogy and its role in OM burial through much of geologic time remains incompletely understood. Here we have analyzed the mineralogy, geochemistry and total organic carbon (TOC) of organic rich shales deposited in late Archean to early Cambrian sedimentary basins. Across all samples we have quantified the contribution of 1M and 1M_d illite polytypes, clay minerals formed by diagenetic transformation of smectite and/or kaolinite-rich weathering products. This mineralogical signal, together with corrected paleo-weathering indices, indicates that late Archean and Mesoproterozoic samples were moderately to intensely weathered. However, in late Neoproterozoic basins, 2M₁ illite/mica dominates clay mineralogy and paleo-weathering indices sharply decrease, consistent with an influx of chemically immature and relatively unweathered sediment. A late Neoproterozoic switch to micaceous clays is inconsistent with hypotheses for oxygen history that require an increased flux of weathering-derived clays (i.e., smectite or kaolinite) across the Precambrian-Cambrian boundary. Compared to previous studies, our XRD data display the same variation in Schultz Ratio across the late Neoproterozoic, but we show the cause to be micaceous clay and not pedogenic clay; paleo-weathering signals cannot be recovered from bulk mineralogy without this distinction. We find little evidence to support a link between these mineralogical variations and organic carbon in our samples and conclude that modal clay mineralogy cannot by itself explain an Ediacaran increase in atmospheric oxygen driven by enhanced OM burial.     

泥炭的热模拟实验及其在煤层气研究中的应用

采用高温高压多冷阱热解实验装置,在温度和压力分别为336.8~600℃和 50MPa,升温速率为 20℃/h和 2℃/h条件下,对泥炭进行了热解生气的模拟实验,获得了烃类甲烷和C₂-C₅气体以及非烃二氧化碳、氢气和硫化氢气体的产率和体积分数数据,研究了热模拟产物气体的组分特征和热演化过程。结果表明,泥炭高温热解产物气体主要由非烃二氧化碳气体组成,其次为烃类甲烷和C₂-C₅气体。随着实验温度的增高,非烃气体体积分数呈下降趋势,烃类气体体积分数呈上升趋势。不同升温速率实验条件下,泥炭样品热解生气表现出不同的特征,主要体现了时间因素控制着泥炭的生烃过程和生烃量,这符合化学反应动力学时间与温度之间互补的原理。并且与煤岩热解生气特征进行了对比,表明泥炭比煤岩具有更高的产烃气能力。根据热模拟实验研究结果,探讨了煤层气形成方面的地球化学意义。      

Evolution of nC16H34-water–mineral systems in thermal capsules and geological implications for deeply-buried hydrocarbon reservoirs

Organic-inorganic interactions between hydrocarbons and most minerals in deeply buried reservoirs remain unclear. In this study, gold capsules and fused silica capillary capsules (FSCCs) with different combinations of nC₁₆H₃₄, water (distilled water, CaCl₂ water) and minerals (quartz, feldspar, calcite, kaolinite, smectite, and illite) were heated at 340 °C for 3–10 d, to investigate the evolution and reaction pathways of the organic–inorganic interactions in different hot systems.After heating, minerals exhibited little alteration in the anhydrous systems. Mineral alterations, however, occurred obviously in the hydrous systems. Different inorganic components affected nC₁₆H₃₄ degradation differently. Overall, water promoted the free-radical thermal-cracking reaction and step oxidation reaction but suppressed the free-radical cross-linking reaction. The impact of CaCl₂ water on the nC₁₆H₃₄ degradation was weaker than the distilled water as high Ca²⁺ concentration suppressed the formation of free radicals. The presence of different waters also affects the impact of different minerals on nC₁₆H₃₄ degradation, via its impact on mineral alterations. In the anhydrous nC₁₆H₃₄-mineral systems, calcite and clays catalyzed generation of low-molecular-weight (LMW) alkanes, particularly the clays. Quartz, feldspar, and calcite catalyzed generation of high-molecular-weight (HMW) alkanes and PAHs, whereas clays catalyzed the generation of LMW alkanes and mono-bicyclic aromatic hydrocarbons (M-BAHs). In the hydrous nC₁₆H₃₄-distilled water–mineral systems, all minerals but quartz promoted nC₁₆H₃₄ degradation to generate more LMW alkanes, less HMW alkanes and PAHs. In the nC₁₆H₃₄-CaCl₂ water–mineral systems, the promotion impact of minerals was weaker than that in the systems with distilled water.This study demonstrated the generation of different hydrocarbons with different fluorescence colors in the different nC₁₆H₃₄-water–mineral systems after heating for the same time, implying that fluorescence colors need to be interpreted carefully in investigation of hydrocarbon charging histories and oil origins in deeply buried reservoirs. Besides, the organic–inorganic interactions in different nC₁₆H₃₄-water–mineral systems proceeded in different pathways at different rates, which likely led to preservation of liquid hydrocarbons at different depth (temperature). Thus, quantitative investigations of the reaction kinetics in different hydrocarbon-water-rock systems are required to improve the prediction of hydrocarbon evolution in deeply buried hydrocarbon reservoirs.     

泥岩埋藏成岩过程中绿泥石的演化途径及意义

粘土矿物是泥质沉积岩重要的组成部分。在温度、压力、阳离子及水/岩比值等多种因素的共同作用下,埋藏成岩过程常常伴随着不同粘土矿物间的相互转化:蒙脱石、伊利石、高岭石和磁绿泥石等矿物均可发生绿泥石化。但各种矿物发生绿泥石化条件及反应机制不同,形成的绿泥石在化学成分及构型方面也有很大差异,通过X-射线衍射(XRD)、电子探针(EMPA)和高分辨率透射电子显微镜(HRTEM)等测试手段可识别出不同类型的绿泥石,区分不同转化序列并分析其转化机制。不同转化序列形成的绿泥石,不仅受温度的控制,还受阳离子类型和浓度的控制,在利用绿泥石作为地温计时需慎重;不同转化序列绿泥石化过程中都有水的参与,并伴有氢离子释放或消耗,这将会对有机质生烃产生影响。因此,关注泥岩埋藏成岩过程中绿泥石演化途径的差异,对拓宽绿泥石化的地质应用领域,特别是粘土矿物—有机质的协同作用具有重要的意义。     

不同类型烃源岩排烃模式对比及差异性探究

烃源岩的排烃是准确预测含油气盆地油气资源必须涉及的一个非常重要的环节,为了得到不同有机质类型烃源岩的排烃效率、排烃机理,选取不同有机质类型烃源岩进行了黄金管模拟实验,总结了不同类型烃源岩在各演化阶段产物的变化特征与排烃效率。结果表明,烃源岩类型对总生成油与残留油中轻重烃的比例影响较大,但是对排出油中轻重烃的比例影响较低,排出油中均表现为在未熟—成熟阶段以重烃为主,在高熟—过熟阶段以轻烃为主。烃源岩的类型对生排油量的影响明显,烃源岩的类型越好,生排油量越高。Ⅰ型烃源岩的生排油量最高,Ⅲ型烃源岩最低。烃源岩类型越好,排油效率越高。Ⅲ型烃源岩排油效率低,与其生成气态烃较多、显微组分中镜质组含量较高有关。      

http://www.sciencedirect.com/science/article/pii/S1674987113001114

The Deccan Syneclise is considered to have significant hydrocarbon potential.However,significant hydrocarbon discoveries,particularly for Mesozoic sequences,have not been established through conventional exploration due to the thick basalt cover over Mesozoic sedimentary rocks.In this study,near-surface geochemical data are used to understand the petroleum system and also investigate type of source for hydrocarbons generation of the study area.Soil samples were collected from favorable areas identified by integrated geophysical studies.The compositional and isotopic signatures of adsorbed gaseous hydrocarbons(methane through butane) were used as surface indicators of petroleum micro-seepages.An analysis of 75 near-surface soil-gas samples was carried out for light hydrocarbons(C1-C4) and their carbon isotopes from the western part of Tapti graben,Deccan Syneclise,India.The geochemical results reveal sites or clusters of sites containing anomalously high concentrations of light hydrocarbon gases.High concentrations of adsorbed thermogenic methane(C_1 = 518 ppb) and ethane plus higher hydrocarbons(ΣC_(2+) = 977 ppb) were observed.Statistical analysis shows that samples from 13% of the samples contain anomalously high concentrations of light hydrocarbons in the soil-gas constituents.This seepage suggests largest magnitude of soil gas anomalies might be generated/source from Mesozoic sedimentary rocks,beneath Deccan Traps.The carbon isotopic composition of methane,ethane and propane ranges are from-22.5‰ to-30.2‰ PDB,-18.0‰to 27.1‰ PDB and 16.9‰-32.1‰ PDB respectively,which are in thermogenic source.Surface soil sample represents the intersection of a migration conduit from the deep subsurface to the surface connected to sub-trappean Mesozoic sedimentary rocks.Prominent hydrocarbon concentrations were associated with dykes,lineaments and presented on thinner basaltic cover in the study area,which probably acts as channel for the micro-seepage of hydrocarbons.     

Mineralogy of gouge in north-northeast-striking faults,Sydney region,New South Wales

Gouges formed in north-northeast-striking fault zones of the Sydney region and associated host-rocks were investigated by XRD, SEM, TEM and optical microscopy in order to determine their mineralogy. XRD studies reveal that illite, illite–smectite, kaolinite, quartz and dickite are present in varying proportions. Kübler Indices (0.54–0.71) and low smectite contents in illite–smectite (<10% smectite) in most gouges and host-rocks, indicate the assemblages formed at temperatures between 120 and 150°C. Those at the Heathcote Road, Lucas Heights location formed at lower temperatures (<100°C). SEM images of the clays in host sublitharenites and gouges show a variety of sizes and habits that reflect variations in fluid temperature and rate of crystallisation. SEM studies also reveal that detrital quartz grains exhibit overgrowths and etch pits of varying density, size and shape that are more strongly developed in the gouges than in the host-rocks. These features are thought to be related to higher fluid/rock ratios brought about by major ingress of fluids into the fault zones. The mineral assemblage present and the features exhibited are believed to have formed in response to a thermal event associated with the early stages of the breakup of Gondwana.     

Hydrocarbon Generation Kinetic Characteristics from Different Types of Organic Matter

In order to contrast the hydrocarbon generation kinetic characteristics from different types of organic matter (OM), 18 samples from different basins were pyrolyzed using Rock-Eval-II apparatus under the open system. From the experimental results, the curve of hydrocarbon generation rate vs. temperature can be easily obtained, which usually can be used to optimize kinetic parameters (A, E, F) of the hydrocarbon generation model. In this paper, the parallel first-order reaction with a single frequency factor model is selected to describe the hydrocarbon generation kinetic characteristics. The hydrocarbon generation kinetic parameters reveal that the types of compound structures and chemical bonds of the lacustrine facies type I OM are relatively homogeneous, with one dominating activation energy. The types of chemical bonds of the lacustrine facies type II2 OM and the terrestrial facies type III OM are relative complex, with a broad activation energy distribution, and the reaction fraction of the preponderant activation energy drops with the decrease of hydrogen index. The impact of the activation energy distribution spaces on the geological extrapolation of kinetic parameters is also investigated. The results show that it has little effect on the hydrocarbon transformation ratio (TR) and therefore, the parallel first-order reaction model with proper number of activation energies can be better used to describe the hydrocarbon generation process. The geological extrapolation results of 18 samples of kinetic parameters show that the distribution range of the hydrocarbon generation rate of the type I OM is relatively narrow and the hydrocarbon generation curve is smooth. In comparison, the distribution range of the hydrocarbon generation for type II1 and type II2-III OM are quite wide, and the hydrocarbon generation curves have fluctuation phenomena. The distribution range of the hydrocarbon generation rate and the fluctuation phenomena are related to the kinetic parameters of OM; the narrower the activation energy distribution, the narrower the hydrocarbon generation rate distribution, and the smoother the hydrocarbon generation curve, and vice versa.     

Hydrothermal pyrolysis of organic matter in Riphean mudstone

The catagenesis of organic matter (OM) was modeled by the hydrothermal pyrolysis of a source rock (Riphean mudstone from eastern Siberia). Isothermal experiments 72-h long were carried out in an aqueous environment in autoclaves at temperatures of 300, 310, 320,..., 370°. The pyrolysis products were analyzed for yield of extract, organic carbon, and parameters of Rock-Eval pyrolysis. The amount of the generated liquid hydrocarbon (HC) compounds increased to a temperature of 340°C and then decreased. The experimental trend of the hydrogen index (HI) dependence on the T _Max temperature generally coincided with that for natural OM maturation. The carbon isotopic composition of the insoluble (in organic solvents) OM remained practically unchanged in the course of the experiments. The carbon structure of the solid remnants of the experimental samples was ordered (after the experiments) with the origin of turbostratic graphite with a spacing of d ₀₀₂≈3.5 A°. We also conducted pyrolysis in a diamond anvil cell equipped with a digital camera in order to obtain additional qualitative and quantitative information on oil generation and emigration in the source rock and isolated kerogen. Chemical kinetic parameters of kerogen cracking were calculated for pyrolysis in an open system. The extrapolation of the high-temperature experimental results is discussed with reference to natural OM maturation.     

Mineralogical characteristics of upper Jurassic Mikulov Marls,the Czech Republic,in relation to their thermal maturity

The Upper Jurassic Marls of Mikulov present a formation that is considered to be the most promising strata to produce hydrocarbons in the Vienna basin. The marls are composed of dark pelagic marlstones that frequently contain layers of limestone with thickness reaching several hundreds of meters. Twenty-seven core samples from selected wells located in the south-eastern portion of the Czech Republic representing depths ranging from 2300 to 4500 m were analyzed by x-ray diffraction to assess bulk mineralogy and the progress of smectite illitization.Bulk mineralogy of the Mikulov Marls comprises carbonates (mean value = 54.4 mass%), clay minerals (26.6 mass%), quartz (15.0 mass%), and feldspar (1.6 mean%). In the decreasing order, the clay mineral fraction is composed of illite/mica, kaolinite, illite-smectite, and chlorite. The amount of smectite in illite-smectite decreases with depth from 70% to 28%. There is a change from random to ordered interstratification at the depth of 3300 m. The transition from short-range ordering (R1) to long-range ordering (R3) occurs at depths greater than 4,500 m.There was a good correspondence between thermal maturity parameters: the percentage of smectite in illite-smectite structures and vitrinite reflectance as a parameter of organic matter. The increase of the metamorphic grade was compared in respect to the geothermal gradient with adjacent basins.     

Studying of liquid thermolysis products of various types of immature kerogen in sedimentary lacustrine rocks from the valjevo-Mionica basin,Serbia, and the effect of Pt<Superscript>4+</Superscript> and Ru<Superscript>3+</Superscript> ions on their yield and the hydrocarbon composition

Liquid thermolysis products of various types of immature kerogen from sedimentary lacustrine rocks from the Valjevo-Mionica basin in Serbia were studied to evaluate the generation potential of kerogen contained in the organic matter (OM) of the rocks, determine the composition of the biomarkers and alkylaromatics in the liquid thermolysis products, and elucidate the effect of Pt⁴⁺ and Ru³⁺ ions (which were added in the form of inorganic salts) on the yield and hydrocarbon composition of the liquid thermolysis products. For this purpose, representative bitumen-free samples A and B of the sedimentary rocks were subjected to thermolysis under various conditions. Rock A contains high amount of immature organic matter, which is dominated by kerogen type I/II and was generated under strongly reduced sedimentation conditions at a high salinity. Sample B is poorer in immature OM than sample A, and the OM of the former contains kerogen type II/III and was generated predominantly in a reduced environment. The content of the liquid products and the concentrations of hydrocarbons obtained in the course of thermolysis of bitumen-free sample A and the typical oil distribution of the biomarkers and alkylaromatics in the thermolysis products confirm a high generation potential of OM in this rock. In all of our experiments on the thermolysis of bitumen-free sample B, the yield of liquid products and hydrocarbons is low. According to the kerogen type, the thermolysis of this rock generates much gases. The Pt⁴⁺ and Ru³⁺ ions (added in the form of simple inorganic salts) increased the yield of liquid (kerogen type I/II) and gaseous (kerogen type II/III) products. During the thermolysis of various type of immature kerogen in the lacustrine sedimentary rocks at a temperature of 400°C, the OM attained maturation corresponding to the early catagenesis level. Saturated biomarkers and alkylaomatics in the thermolysis products of both samples display typical oil distributions. The type of the source OM most strongly affects the composition of n-alkanes and alkylnaphthalenes. The metal ions used in this research served as catalysts for the methylation process during the thermolysis of immature kerogen, regardless of its type. The effect of the Pt⁴⁺ and Ru³⁺ ions on other transformations of the hydrocarbons, for example, the destruction of high-molecular n-alkanes to low-molecular ones and on isomerization reactions in molecules of polycyclic biomarkers and alkylaromatics to thermodynamically more stable isomers in the thermolysis products is controlled, first of all, by the type of the source OM.