Immature Oils in China and Their Genetic Mechanisms

Immature crude oils are a kind of unconventional petroleum resources. They are generated through early low-temperature biochemical/chemical reactions of some specific organic matter. Their geological reserves explored are as high as several hundred million tons in China. Based on a detailed organic geochemical study, five genetic mechanisms of immature oils have been proposed in this paper for early hydrocarbon generation from suberinite, resinite, bacteria-reworked terrestrial organic matter, biolipids and sulphur-rich macromolecules respectively.

Application of Biomarkers to Quantitative Source Assessment of Oil Pools

Recent detailed organic geochemical and geological investigation indicate that oils of the Bamianhe oilfield, Bohai Bay Basin, East China are the mixture of less mature oils and normal oils derived from the ES4 mudstones and shales with a wide range of thermal maturity from immature to middle-maturity, and most of the oils were proved to be sourced from the depocenter of the Niuzhuang Sag immediately adjacent to the Bamianhe oilfield. Two approaches to quantify the amount of immature oils mixed through quantitative biomarkers were established. One is a relatively simple way only through organic geochemical analysis while the other is to be combined with basin modeling. Selecting biomarkers as proxies is the crucial point in both of them. The results show that the less mature oils mixed in the Bamianhe oilfield is less than 10% and 18% respectively based on the two approaches, which coincide with the results of oil-source rock correlation.

Contentious Petroleum Geochemical Issues in China’s Sedimentary Basins

Petroleum geochemistry contributes to exploration successes by providing key constraints for geological models and critical input to exploration scenarios. One of the most important tasks in a typical exploration program is to identify the most effective source intervals or kitchens in a basin, through oil-source correlation. The results of correlation are valid only if the geochemical parameters used address adequately the genetic characteristics of the source rocks as well as the mass transport and mixing processes of hydrocarbon fluids occurring in the carrier beds and reservoirs. This manuscript discusses four of the major contentious petroleum geochemical issues in China’s sedimentary basins. It is suggested that marine incursions played a significant role in the formation of prolific petroleum source rocks in the gigantic, dominantly freshwater, Songliao Basin. Several models are proposed to account for the occurrence of immature oils in the Cathaysian rift system including the Bohai Bay Basin, thus immature source rocks are considered a mere minor contributor to the known economic immature oil resources. Both geological and geochemical evidence are reviewed to refute a dominantly coaly source for the petroleum discovered in the Turpan Basin. Results of case studies are presented to demonstrate the importance of recognizing petroleum fluid mixing to solve the oil-source correlation issues in the structurally complex Tarim Basin. In addressing the fundamental assumptions and potential flaws of the molecular geochemical parameters commonly used for oil-source correlation, the need of a mass fraction approach is proposed to deal with such contentious issues as marine versus lacustrine, coal versus lacustrine, and mature versus immature oils.

Quantitative Assessment of Hydrocarbon Expulsion of Petroleum Systems in the Niuzhuang Sag, Bohai Bay Basin, East China

Based on a detailed survey of the distribution and organic geochemical characteristics of potential source rocks in the South Slope of the Niuzhuang Sag, Bohai Bay Basin, eastern China, a new approach to assess the amount of hydrocarbons generated and expelled has been developed. The approach is applicable to evaluate hydrocarbons with different genetic mechanisms. The results show that the models for hydrocarbon generation and expulsion vary with potential source rocks, depending on thermal maturity, types of organic matter and paleoenvironment. Hydrocarbons are mostly generated and expelled from source rocks within the normal oil window. It was calculated that the special interval (algal-rich shales of the ES4 member formed in brackish environments) in the South Slope of the Niuzhuang Sag has a much higher potential of immature oil generation than the other intervals in the area. This suggests that hydrocarbons can definitely be generated in early diagenesis, especially under certain special geological settings. The proportion of hydrocarbons generated and expelled from the ES4 shales in the early diagenetic stage is up to 26.75% and 17.36%, respectively. It was also observed that laminated shales have a much higher expulsion efficiency than massive mudstones. In contrast, the special interval of the ES4 shales proposed from previous studies is probably not the whole rock for oil in the South Slope of the Niuzhuang Sag because of the small proportion of the gross volume and corresponding low percentage of hydrocarbons generated and expelled. A much lower expulsion efficiency of the source rock during the early stage relative to that within the normal oil window has been calculated. Our results indicate that the ES4 mudstones rather than the shales deposited in the Niuzhuang and Guangli Sag are the main source rocks for the oil discovered.

Distribution and Significance of Methyl Steranes in Bohai Bay Basin, East China

31 samples of shales and mudstones developed in reducing hypersaline andfreshwater setting and 20 oil samples of Bamianhe oilfield, Bohai Bay basin were collected for adetailed study of petroleum system. Composition and distribution, especially significance ofsteroids, are discussed as a part of those. Abundant steroidal biomarkers, including C_(27-29)regular Steranes, C_(28-30) 4-methyl steranes, di-nosteranes and aromatic steranes, were detected.Results show that the composition and distribution of the steroids in samples studied are functionsof thermal maturity, organic source, paleoenvironment and lithology of potential source rocks.Alga-rich Es_4 shales (brackish water) developed in the south slope of depocenter (Niuzhuang sag)were found particularly rich in steroidal biomarkers including C_(30) 4-methyl steranes anddinosteranes. Es_3 mudstones (fresh water) were found devoid of dinosteranes. Distribution patternsof regular steranes are completely different from methyl steranes indicating different origins ofthe specific compounds of the fractioa Diagnostic distribution of steranes in rock extracts ofdiverse intervals makes the compounds to be essential indictors of source-rock tracing. Methylsteranes prove to be much more useful in oil-source rock correlation than regular steranes. Resultsalso show that alga-rich Es_4 shales located in the south slope are not likely the primary sourcerock responsible for the oils discovered based on the composition and distribution of steroids.

Existence and implications of hop-17(21)-enes in the lower Cretaceous of the Saihantala Sag, Erlian Basin, China

C31- to C35-hop-17（21）-enes are identified by gas chromatography-mass spectrometry （GC-MS） analysis to exist as double isomers in most samples of the Aershan Formation and members 1 and 2 of the Tenggeer Formation from well SH3. Comprehensive organic geochemistry and organic petrology study indicates that algae and bacteria are the main biological source of lower Cretaceous sediments in the Saihantala Sag, and this is in accordance with the existence of hop-17（21）-enes. The similar distributions of hop-17（21）-enes and hopanes of these samples indicate that hop-17（21）-enes were transformed into hopanes through hydrogenation during diagenesis processes. The existence of hop-17（21）-enes means that not only the formation of organic matter is related to an anoxic environment and a biological source of algae and bacteria, but also hop-17（21）-enes are direct indicators of hydrocarbon rock at an immature to low-maturity stage. High hydrocarbon conversion ratio, algae and bacteria source and a high abundance of organic matter suggest that the Saihantala Sag has the potential to generate immature to low-maturity oil, which may be of great significance for oil exploration in the Erlian Basin.

Catalytic decarboxylations of fatty acids in immature oil source rocks

Catalytic decarboxylations of fatty acids in immature oil source rock samples were examined in this study. The rock samples were obtained from seven oil fields in China. In order to clarify the effect of each mineral matter in the rock samples, both the Fe M?ssbauer effect and the X-ray diffraction (XRD) were used to determine the relative content of each mineral in the rock samples, and the catalytic activities of several minerals like clays, carbonates and pyrite were determined. The Fe M?ssbauer effect and the XRD studies show that clays are the main mineral components in the rock samples except for the samples from Biyang and Jianghan in which the main mineral component is ankerite. The other mineral components include calcite, plagioclase, quartz, feldspar, siderite, aragonite, pyrite, analcime, pyroxene and anhydrite. The studies of the catalytic decarboxylations of fatty acids suggest that carbonates and pyrite can make much greater contributions to the catalytic activities of the rock samples than clays. It is found that the overall catalytic activities of the rock samples are well related to the relative contents and the catalytic activities of clays, carbonates and pyrite in the rock samples.

GEOCHEMICAL CHARACTERISTICS OF SUPERGENE ORGANIC MATTER IN HYPERSALINE ENVIRONMENT

The source rocks and crude oils from the Qianjiang Formation (Eocene) in the Jiangban basin have been systematically studied in the present work. Supergene hydrocarboholds are characterized by (ⅰ) high alteration ratio of soluble organic matter over organic carbon and middle ratio of hydrocarbon over organic carbon; (ⅱ) high content of non-hydrocarbon plus asphahene in extracts or crude oils; (ⅲ) sulfur-rich crude oils being an important immature crude oil; (ⅳ) alkane showing high content of phytane, gammacerane and marked even-carbon predominance or odd-carbon predominance; (ⅴ) aromatic biomarkers being distinctly classified into four groups; (ⅵ) pronounced evencarbon predominance in alkyl henzenes. In combination of all geochemical data. it is extrapolated that exploration of immature crude oil in hypersaline environment should be noticed.