Black shales and carbon isotopes in pelagic sediments from the Tethyan Lower Jurassic

Detailed sampling and analysis of Jurassic pelagic limestones and marls from Italy, Hungary and Switzerland have enabled construction of an isotope stratigraphy across the Pliensbachian-Toarcian boundary with resolution to the zonal level. The oxygen-isotope record is unremarkable. The carbon isotopes, however, show two positive excursions: one, relatively minor, during the Pliensbachian, margaritatus Zone, subnodosus Subzone, the other, more major, during the Toarcian. early falciferum Zone, where a maximum δ¹³C value of 4·52%_PDB is attained. These intervals are known to be favoured periods of organic-rich sedimentation in diverse parts of the globe and the isotopic excursions are interpreted as a response to abnormally high rates of storage of organic carbon in the sedimentary record. A comparable phenomenon has been documented from the Cenomanian-Turonian boundary in the Cretaceous where it has been referred to the influence of an ‘Oceanic Anoxic Event’. Some Italian sections spanning this Lower Jurassic interval contain organic-rich shales in the falciferum Zone; the isotopic signatures from their included, locally manganiferous carbonate betray a considerable diagenetic overprint and they cannot therefore be incorporated in a composite isotopic curve. Carbon isotopes from the organic carbon itself are extremely negative, falling to –33δ_PDB and, in one section examined in detail, correlate with the calcium-carbonate content of the shales; they may reflect a partial change to a non-calcified planktonic biota during deposition of this lime-poor interval, possibly responding to upwelling and increased fertility of near-surface waters. The onset of upwelling may have been as early as spinatum-tenuicostatum Zone time, that is, at the Pliensbachian-Toarcian boundary.     

Analysis of the organic matter of oil shales by nuclear magnetic resonance

¹³C NMR spectroscopy was applied in the investigation of the structure of the organic matter in oil shales. By using Proton Enhanced Nuclear Induction Spectroscopy, a fair resolution of aliphatic and aromatic carbon signals was achieved. This method provided information on the relative ratio of aliphatic and aromatic carbons within a given set of samples (Aleksinac, Kimmeridge, Colorado, Australian torbanite and Estonian kukersite).     

Carbon,hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

Solvent extractions were done on the carbonaceous chondrites Murray, Murchison, Orgueil and Renazzo, using CCl₄ and CH₃OH. Between 2 and 10% of the total carbon in these meteorites is extractable by ordinary techniques, most of it in CH₃OH. After demineralization with HF, perhaps as much as 30% of the total carbon in Murray may be extractable with CH₃OH. The extracts from Renazzo have isotopic ratios which suggest that they are mainly terrestrial organic matter, with lesser contributions from indigenous organics. The CH₃OH-soluble organic matter from Murchison and both untreated and HF-treated Murray has δ¹³C values of about +5 to + 10%. and δ¹⁵N values of about +90 to +100%., both of which are significantly higher than the bulk meteorite values. The Orgueil CH₃OH-extract also has a δ¹⁵N value well above the value in residual organic matter. Values for δD of +300 to +500%. are found for the CH₃OH-soluble organic matter. The combined data for C, H and N isotopes makes it highly unlikely that the CH₃OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relationship is suggested between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water-soluble (methanol-soluble) organic compounds. Organic matter soluble in CCl₄ has essentially no nitrogen, and δ³C and δD values are lower than for CH₃OH-soluble phases. Either there are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.     

茂名油页岩沉积有机质特征及古气候意义

基于海洋沉积确定的始新世晚期至渐新世早期(约33.5 Ma)的气候过渡期是新生代全球性气候事件,但长期以来相关的陆相沉积记录研究则比较缺乏。本文对形成于始新世晚期至渐新世早期的茂名油柑窝组油页岩样品进行了有机质丰度、烃类组成、单体烃碳同位素组成等分析,以期研究低纬度陆相沉积有机质对古近纪始新世-渐新世气候过渡期(EOT)的响应。研究结果显示,埋藏较浅的上部层位样品正构烷烃碳同位素组成显著正偏,为-19.1‰~-25.9‰,平均值为-22.2‰;而下部层位样品正构烷烃碳同位素组成在-23.7‰~-30.2‰,平均值为-26.3‰。两个样品正构烷烃碳同位素组成之差在1.5‰~8.1‰,平均值之差为4.6‰。正构烷烃碳同位素组成的显著差异指示了EOT低纬度陆相古气候变化引起的陆相有机质响应,而这种响应与当时大气CO2浓度和海洋温度降低导致的气候和植物群落变化密切相关,即可能存在着C3植物向C4植物的转化、C4植物的迅速增加并最终导致沉积有机质碳同位素组成的变化;也可能是由于大气CO2浓度降低导致的大气CO2碳同位素组成整体正偏的结果。很显然,进一步详细的连续剖面分析将对研究古近纪EOT低纬度陆相古气候变化提供重要科学依据。     

Organic matter and deposition conditions of the Kashpir oil shales

The composition of organic matter was investigated in the oil shales and country rocks of the Kashpir deposit. The analysis of the aromatic fraction of bitumen showed the presence of isorenieratene derivatives, which indicates the accumulation of the sequence under anoxic conditions in the bottom waters of a paleobasin. Special attention was given to the composition of organosulfur compounds from the bitumen of rocks and products of kerogen pyrolysis. The concentrations of hydrocarbon structures occurring in the bitumen in a free state and in sulfur-bearing derivatives are comparable. The composition of the pyrolysis products of kerogen depends on the concentration of organic carbon in the rock: carbon-rich rock varieties contain kerogen whose pyrolysis yields relatively high concentrations of organosulfur compounds and low total contents of n-alkanes/n-alkenes-1.     

Regional geology, depositional environment and maturity of organic matter of Early to Middle Jurassic coals, coaly shales, shales and claystones from the Eastern Pontides, NE Turkey

Jurassic coals, coaly shales, shales and claystones from the Eastern Pontides in NE Turkey have been investigated using microscopical, petrophysical and detailed organic geochemical methods in order to determine their catagenetic stage, to reveal the composition of the organic matter and to discuss the depositional environment. The Liassic–Dogger period in the Eastern Pontides was characterised by the presence of a rift system which resulted in rock units of very variable lithology and facies. Coal seams, ranging from a few centimetres to several decimetres and intercalated with shales, claystones and sandstones occur within the basal part (the Aggi Formation) as well as in the uppermost part (the Hamurkesen Formation) of the rift deposits. All coal seams investigated are at a catagenetic maturation stage corresponding to subbituminous B up to low volatile bituminous ranks. They represent a depositional environment of short-lived swamp areas with intense aerobic reworking of the higher plant detritus by heterotrophic bacteria, but with possible anaerobic microenvironments at deeper levels. At least some coal seams were influenced temporarily by marine ingressions. Most samples are impure humic coals with highly variable chemical compositions as indicated by the broad range of their hydrogen contents. This variation in hydrogen content is partly attributed to variable contributions of algal material. On the other side, considering several analytical results, the hydrogen variation is primarily due to bacterial reworking that affected the composition of the organic matter to variable extent and resulted especially in an enrichment of bacterial lipids. Bacterial reworking by an active microbial community within the upper layer of the peat swamp is inferred from elevated concentrations of iso-alkanes even exceeding those of the corresponding n-alkanes in several samples which, to the best of our knowledge, have not been observed with coals before.     

The effect of organic matter type and organic carbon content on Rock-Eval hydrogen index in oil shales and source rocks

The amount of “gas-prone” kerogen (woody, fungal and “inert”) and the organic carbon content (TOC) are the two predominant factors affecting the hydrogen index (HI) in the 226 samples of lacustrine and marine oil shales and source rocks studied. HI decreases as a function of the amount of “gas-prone” kerogen and increases as a function of TOC. In addition, the type of amorphous kerogen influences the hydrogen index, and this can be roughly estimated from the fluorescence intensity of the amorphous kerogen. Nearly eighty percent of the variation in HI in these samples can be accounted for by the percentage of “gas-prone” kerogen, the TOC content, and the fluorescence of the amorphous kerogen in a multiple regression analysis.Hydrogen index increases as a function of TOC up to about 10% TOC (the relationship can be approximated by a quadratic equation) and then levels off. A possible explanation for this is that the capability of a rock to generate and expel hydrocarbons during pyrolysis increases with TOC. When the retention capacity of the rock matrix is saturated (at about 10% TOC) further increases in TOC have no effect on HI. It is also possible that the quality (i.e. oil-proneness) of the amorphous kerogen is poorer in low TOC samples than in high TOC samples.The samples came from the following oil shales and source rocks: Rundle (Queensland Eocene-Miocene), Mae Sot (northwestern Thailand, Eocene-Pliocene), River River (northwestern Colorado, Eocene), Toolebuc (western Queensland, Late Albian), the “Posidonienschiefer” (southwestern Germany, Toarcian), an Argentinian lacustrine deposit (Eocene-Miocene), the Kimmeridgian sections from four North Sea wells (blocks 21, 30, and 210), Monterey Shale (California, Miocene), and sections from six wells from the Alaskan Tertiary (North Slope, North Aleutian Shelf, Navarin Basin, Norton Sound). Most samples appear to be thermally immature (T.A.I. less than 1.8; R_o less than 0.6%) so they should be considered only potential source rocks.The lacustrine oil shales have a higher conversion ratio (yeild/TOC or S₁ + S₂/TOC) than do the marine oil shales in samples with only amorphous and algal kerogen. These, in turn, have a higher conversion ratio than the marine source rocks. These differences are roughly reflected in the fluorescence intensity of the amorphous kerogen. Free hydrocarbons are higher in the marine source rocks than in the marine oil shales, and are lowest in the lacustrine oil shales.     

鄂尔多斯盆地南部侏罗系油砂的发现与成藏模式

本次工作新发现的油砂矿藏位于陕西省铜川市庙湾地区。地层特征和孢粉组合分析表明含油砂地层为侏罗系。野外调查和钻探工作证实渭北隆起的北部单斜构造地表出露大量的侏罗系延安组和直罗组油砂,累计厚度可达29.85 m;钻井油砂累计厚度达11.89 m,最大单层厚度达7.9 m,埋深在70m以浅。油砂主要赋存于中下侏罗统延安组和直罗组河流相辫状河道沉积砂岩孔隙和裂隙之中。该油砂矿藏是在渭北隆起演化的基础上,经燕山晚期构造运动抬升形成,属于抬升运移型成藏模式。经初步资源量估算,研究区油砂油地质资源量为3 232.72万t。     

Investigation of catalytic effects of indigenous minerals in the pyrolysis of Aleksinac oil shale organic matter

The catalytic effect of indigenous minerals in the pyrolysis of Aleksinac (Yugoslavia) oil shale was studied in this paper. The substrates were prepared by gradual removal of the mineral constituents (carbonates, silicates, pyrite) and the free and bound bitumens. The substrates were analyzed by chemical methods, X-ray diffraction, porosimetry, thermal analysis, ¹³C NMR, and standard ASTM Micro Activity Test (MAT) designed for the investigation of cracking catalysts. The liquid pyrolysis products were analyzed by organic geochemical techniques as well. Based on the yields of gaseous and liquid products and the coke, conversion degrees, GC analyses (MAT parameters) and weight losses (TG parameter), the catalytic effect of indigenous mineral components in the pyrolysis of Aleksinac oil shale organic matter was found to be very low. The results suggested that principal organic matter changes should be attributed to thermal rather than to catalytic cracking.     

Comparative studies of organic matter petrography of the late palaeozoic black shales from Southwestern Poland

There are at least two sapropelic units associated with Late Palaeozoic black shales in Central Europe. The older unit, of Late Carboniferous age, is the lower part of the Anthracosia Shales in the Intrasudetic Basin, and the younger one is the well-known Zechstein Kupferschiefer in both the Foresudetic Monocline and the Northsudetic Basin. The first unit is of lacustrine origin, while the second one represents deposition in a shallow marine depositional environment. Both units contain high amounts of organic matter, thus being typical black shales.The organic matter dispersed in these shales was studied petrographically. In general, the vitrinite reflectance of the shales studied indicates variable, but moderate organic matter maturity (0.68–1.25%), equivalent to the oil window. Detailed microscopic studies of the organic material dispersed in the lower unit of the Anthracosia Shales showed that liptinite, especially alginite is the most abundant component. Secondary altered organic matter, i.e. solid hydrocarbons, rarely occurs. Organic components together with mineral matter constitute a lacustrine sapropelic association, a humic (terrestrial) association and an intermediary association. The character and predominance of alginite and lacustrine sapropelic association are indicative of an open-lacustrine depositional environment. In general, this organic composition is typical of type I kerogen.Microscopic analysis of the Kupferschiefer revealed a mixture of liptinite, vitrinite and inertinite macerals, and other organic components such as amorphous sapropelic mass (ASM) and solid bitumens. The most common organic components are liptinite macerals. Bituminite and alginite predominate, and are diagnostic macerals of this unit. The amount of bituminite locally exceeds 85 vol.%. Other liptinite macerals such as sporinite and liptodetrinite, are present in significantly lower amounts, one exception being ASM, which may be present in higher amounts. Humic constituents (vitrinite and inertinite) are rare, present in small amounts in the Kupferschiefer beds. The organic matter composition points to type II kerogen for this unit.     

Pyrite in ammonite-bearing shales from the Jurassic of England and Germany

Pyrite occurs both in normal clays and shales with a benthic fauna (Oxford Clay, England, and Lias ε, Germany) and in highly bituminous shales (Lias ε, Germany). In normal shales it is present in small quantities as early framboids, but more conspicuously as internal moulds of fossils, especially ammonites. The pyrite in these is petrographically varied; several types of internal sediments and chamber linings are described and illustrated by reflected-light and scanning electron microscopy. Most striking are pyrite stalactites, suspended from the roofs of ammonite chambers, which were later filled by calcite or baryte. Pyrite formed in reducing micro-environments, while the sediment generally was not wholly anoxic. Most pyrite pre-dates compaction of sediment, breakage of fossils and solution of shell aragonite. Variable rates and conditions of reduction of sea water sulphate are reflected in δ³⁴S values ranging from ?55 to +44. Stalactites probably started to form when the ammonite chambers were partially gas-filled. In the bituminous Lias ε shales pyrite occurs abundantly as early framboids and micro-nodules. Larger nodules show a variety of forms, some of which post-date compaction of the sediment. Pyrite is not associated with the abundant flattened ammonites. δ³⁴S values in shales are grouped about a mode near ?20. Pyrite formed over a long time-span, and throughout the sediment, not just in protected cavities. Contrasts in pyrite types can be related to differing depositional environments and organic contents of the shales. Pyrite is an important mineral in diagenetic mineral parageneses which can be deduced by studying fossil void-fillings and concretions, and which help define the diagenetic history of a shale.     

苏北盆地上白垩统—第三系页岩油气成藏层位及有利区带

苏北盆地上白垩统—第三系分布广,地层完整。其中泰州组二段、阜宁组二段和阜宁组四段泥页岩发育,厚度为100～250m,有机质丰富,有机碳一般大于1.0%,演化程度高,并在泥页岩中见到了良好的油气显示,表明苏北盆地具备了泥页岩油气成藏的地质条件。通过对苏北盆地上白垩统—第三系基本石油地质条件分析,指出苏北盆地的金湖凹陷、高邮凹陷、海安凹陷和盐城凹陷的深凹带是泥页岩油气勘探、开发的有利区带。     

大巴山前缘五峰组-龙马溪组干酪根碳同位素特征与有机质类型

大巴山前缘五峰组-龙马溪组有机质类型组成存在较大争议。在万源曹家、城口周溪、巫溪田坝、巫溪白鹿和巴东两河口等地区采集代表性样品进行有机碳含量、成熟度和干酪根碳同位素分析。五峰组-龙马溪组δ¹³C组成分布为-31.1‰~-28.2‰,田坝地区δ¹³C最轻,两河口地区δ¹³C最重。大巴山前缘干酪根类型是碳同位素组成的主要控制因素,有机质成熟度和有机碳含量影响较小。当有机质处于高成熟演化阶段,有机碳含量越高,δ¹³C组成偏轻;有机质处于过成熟演化阶段,有机碳含量越高,δ¹³C组成偏重,变化幅度小于1.2‰。按照干酪根碳同位素组成划分干酪根类型原则,大巴山前缘五峰组-龙马溪组有机质类型为I型(腐泥型)和Ⅱ₁型(腐殖腐泥型)。     

Depositional environments of the Senonian chert, phosphorite and oil shale sequence in Israel as deduced from their organic matter composition

In the Upper Cretaceous sequence of the Negev (southern Israel) the organic matter in phosphorites and cherts differs from that associated with oil shales in its higher content of humic substances and lower kerogen content, and in its more intensive microbial alteration. The n-alkane distribution pattern of the oil shales, phosphorites and cherts indicates that marine biota, probably algae, are the main organic precursors of their organic matter. In some of the oil shales, however, some contribution of terrestrial organic matter is also evident. Similar high phytane/pristane ratios indicate that the organic matter in the oil shales as well as in the phosphorites and cherts accumulated under reducing conditions. The main differences in the organic matter composition are attributed to early diagenetic processes rather than to different biotic precursors or to late modifications due to temperature-induced maturation. The depositional model suggested for the sequence involves upwelling conditions at the boundary between the deep Tethys and the shallow shelf, which induced high organic productivity deep into the inner shelf. Bottom water circulation enabled intensive microbial alteration of the organic matter, followed by a winnowing process leading to phosphorite formation. Since humification is considered an oxygen-consuming reaction, these processes favoured the formation of oxygen-enriched humic substances and the oxidation of humic substances already present. These humic substances are relatively resistant to further alteration and their conversion into kerogen is thus retarded. Subsequently, syndepositional tectonic activity resulted in the introduction of less saline water, restriction of bottom-water circulation and the establishment of a density stratification in the water body. Consequently, aeration of the bottom layer and the sediments was inhibited, microbial alteration was reduced and later winnowing processes were prevented. Such conditions favoured the formation of kerogen directly, rather than through humic substances, and also favoured the preservation of most of the organic matter in the form of oil shale deposits instead of phosphorites.     

柴达木盆地北缘中段侏罗系页岩有机质孔隙演化特征

柴北缘侏罗系页岩的有机碳含量高、厚度大、分布广,但有机质成熟度总体处于未成熟—低成熟阶段,制约了研究区页岩气的表征与评价。通过开放体系下的加热实验,系统刻画了不同温度下的页岩有机质孔隙发育特征及演化过程。分析认为,热模拟温度200~400℃是有机质孔隙发育的优势温度区间,孔隙数量多,从微孔到宏孔都非常发育,孔隙间可形成网状连通。之后随着温度进一步升高,孔隙会出现"塌陷"现象,对页岩气的赋存起到抑制作用。与此同时,有机质的孔隙发育也具有不均一性,不同有机质显微组分孔隙发育能力存在差异,以镜质组、壳质组等为主的有机质显微组分孔隙发育较迟缓,有机质转化不彻底,而以沥青质体、藻类体、无定形体等为主的有机质显微组分孔隙发育时间早、强度大、孔隙之间的连通性好,是页岩气储集空间的主要贡献者。另外,结合能谱分析,认为元素的重量百分比及Ca、Mg等碱土元素的含量也是影响有机质孔隙发育的主要因素。     

西藏伦坡拉盆地丁青湖组油页岩特征及勘探有利区评价

西藏伦坡拉盆地出露大规模的油页岩。通过研究油页岩的剖面、探槽、钻井及相关实验数据,根据油页岩厚度、分布范围及沉积相特征,结合油页岩品质特征,对蒋日阿错、伦坡日及爬爬3个油页岩分布区进行了评价。研究表明,伦坡拉油页岩总体为高灰分(平均81.76%)、中高含油率(平均7.2%)、特低含硫量(小于1%)型油页岩,其有机碳含量高(平均8.07%),产烃潜量较大,可作为烃源岩为伦坡拉盆地的油藏提供油源。油页岩厚度受沉积相带控制,主要呈北西-南东向断续分布于盆地半深湖-深湖相区。油页岩平均含油率、有机碳含量总体呈北西部低、南东部较高的趋势。综合油页岩厚度及油页岩展布范围,爬爬地区油页岩具有厚度较大、东西向展布最广、平均含油率及有机碳含量高的特征,是最有利的油页岩勘探区,伦坡日、蒋日阿错地区则次之。     

柴达木盆地北缘侏罗系页岩油气成藏条件地质地球化学分析

基于柴达木盆地北缘侏罗系中下统富有机质泥页岩厚度、有机地化特征、物性及泥页岩含油气性等的分析研究,探讨了该地区页岩油气成藏的地质条件,对有利的勘探层段和区带进行了预测。结果表明,柴达木盆地北缘湖西山组和大煤沟组富有机质泥页岩厚度大,有机碳含量多在1.5%以上;有机质类型主要为Ⅱ和Ⅲ型;有机质成熟度从未成熟至过成熟皆有;泥页岩中脆性矿物含量约占50%,孔隙度多在1%~8%之间,孔隙类型多样。湖西山组和大煤沟组泥页岩显示出较强的吸附气体能力,多口钻井在泥页岩段存在明显全烃异常。综上表明,柴达木盆地北缘地区湖西山组、大煤沟组2个层位具备形成页岩油气的地质条件,其中湖西山组中上部泥页岩段为页岩油气有利层段,有利区在冷湖4号-5号构造一带;大煤沟组五段为页岩气有利层段、大煤沟组七段为页岩油有利层段,有利区分布于苏干湖坳陷、鱼卡断陷、红山断陷、欧南凹陷和德令哈断陷东部、南部区。     

Early Jurassic anoxic conditions and organic accumulation in the eastern Tethys

The Bilong Co oil shale, located in the South Qiangtang depression, northern Tibet Plateau, may record the Early Jurassic anoxic event in the eastern Tethys. New geochemical data from the Bilong Co oil shale section are presented in order to determine the mechanism of organic accumulation and to evaluate Early Jurassic anoxia in the eastern Tethys. In organic-rich oil shales, many redox proxies including the relationship of Mo to total organic carbon (TOC), Re/Mo ratios, and pyrite framboid size distribution suggest deposition under euxinic conditions. However, the correlation between TOC and P and Mo contents indicates that organic matter accumulation was controlled mainly by primary productivity. The Sr/Al ratios and clastic influx proxies such as Si, Ti, Th, Zr, and Al concentrations suggest a continuous supply of fresh water from a nearby continent during oil shale deposition. This supply could have initiated stratification of the water so that the upper zone became favourable for marine life. Increased primary productivity could have led to formation of anoxic/sulphidic bottom waters, which enhanced the preservation of organic matter. Deposition of organic-rich oil shales terminated when primary productivity decreased, leading to more oxic bottom water conditions.