Second Hydrocarbon—Generation from Organic Matter Trapped in Fluid Inclusions in Carbonate Rocks

The mechanism and significance of second hydrocarbon-generation from organic matter trapped in fluid inclusions in carbonate rocks are discussed.The types of organic matter and the relationship between them are also reviewed.The organic matter trapped in inclusions and crystals,which account for more than 20%of the total organic matter in carbonate rocks,may be of great significance in the generation of hydrocarbons.High-temperature oil resulting from second hydrocarbon-generation should be an important target,in addition to natural gas,in oilgas prospecting in regions of high-maturity carbonate rocks.     

Thermal Evolution of Organic Matter in Source Rocks—Experimental and Scanning Electron Microscopic Studies

Five major froms(lamellar,banded,crack-like,dissceminated and segregated encrustation(of organic matter distribution in sourc rocks have been revealed under scanning electron microscope by using the heavy metal staining technique.The degree of organic impregnation is related to the amount of liquied hydrocarbons in the rocks,and from this relationship a rough estimation of organic matter can be made on the basis of electron microscopic observations.In conjunction with experimental studies it has been found that the distribution forms of organic matter are a function of its maturity in the process of thermal evolution and accordingly some microscopic criteria can be developed for the assessment of source rocks.     

碳酸盐矿物的包裹有机质及其生油意义

Fluorescent slice observations have revealed a considerable amount of organic matter enclosed in carbonate minerals, most of it giving off yellow-brown fluorescence and being zonally distributed in calcite and dolomite. The amount of enclosed organic matter released from the enclosure when treated with HCl is two times higher than that of extractable organic mattes in the same rock sample. In comparison to the extractable organic matter, the enclosed organic matter is possessed of some compositional characters of its own. In terms of the distribution of biological markess, it is suggested that the enclosed organic matter may be low in maturity relative to the extractable organic matter in the same source rock.Results of the simulating experiments under high temperatures and pressures show that this kind of organic matter enclosed in carbonate minerals can be converted into oil-generating substances. Therefore, detailed studies of the enclosed organic matter are of much help to the evaluation of oil-generating potentiality of carbonate source rocks.     

Study of the Factors Affecting the Abundance of Organic Matter in Jurassic Carbonate Rocks in Qiangtang Basin, Tibet

Field and laboratory analyses of carbonate rock samples from the Qiangtang Basin,Tibet, indicate that carbonate source rocks are mainly developed in the Middle Jurassic Xiali Formation and Upper Jurassic Suowa Formation. Comprehensive studies showed that the Suowa Formation carbonate source rocks have a favorable hydrocarbon-generating potential. The abundance of organic matter in the carbonate rocks is controlled mainly by sedimentary environment and inorganic compounds in the rocks, which is higher in the restricted platform facies than in the open platform facies. Organic carbon contents decrease with increasing CaO contents in the source rocks.     

Supercritical Carbon Dioxide Extraction of Organic Matter from Petroleum Source Rocks and Its Implications

Organic matter was experimentally extracted by supercritical fluids(CO2 1% isopropanol)from petroleum source rocks of different thermo-maturities at different buried depths in the same stratigraphic unit in the Dongying Basin.The results show that supercritical fluid extraction(SFE)is more effective than Soxhlet extraction(SE),with higher amounts and greater varieties of hydrocarbons and soluble organic matter becoming extractive.The supercritical CO2 extraction is therefore considered more valuable in evaluation of petroleum source rocks and oil resources,particularly those of immature types.     

A study on hydrocarbon generation potential of deep source rocks and gas sources in Changling Fault Depression,Songliao Basin

Through natural gas exploration in the Changling Fault Depression,abundant natural gas flows were obtained and high-quality source rocks were also reveiled.Based on bulk analyses,organic matter abundance,organic matter type and thermal maturity of the source rocks were studied systematically.At the same time,gas gener-ating intensity and gas generating quantity were quantitatively analyzed by using basin modeling technologies.The results indicated that gas source rocks of the Shahezi Formation are characterized by abundant organic matter and dark mudstone distributions and high-over thermal maturity.They possess high gas generating intensity with the biggest value surpassing 500×108 m3/km2,and large gas generating quantity,accounting from 74.40% of the total amount.The Yingcheng Formation has good gas-source rocks with moderate dark mudstone and relatively high organic matter.It has type-Ⅲ organic matter and low-over thermal maturity.The gas generating intensity is moderate,between 20×108 and 60×108 m3/km2.The gas generating quantity is 13.63% of the total amount.The Huoshiling Formation has relatively good source rocks with limited dark mudstone and low organic matter.It has type-Ⅲ kerogen and over-thermal maturity.The gas generating quantity is 7.10% of the total amount.The Denglouku Formation has poor-gas source rocks,and is characterized by undeveloped dark mudstone and low organic matter abundance.It has type-Ⅲ organic matter and low-high thermal maturity.Hydrocarbon gases in the Changling Fault Depression mainly originated from the Shahezi Formation,and secondarily from the Yingcheng Formation.The contribution of the Huoshiling Formation gas source rocks is relatively small.     

Anomalous Enrichment of Silver in Organic Matter of the Songxi Shale-hosted Ag-Sb Deposit in Northeastern Guangdong

The silver contents of organic matter in the host rocks of the Songxi shale-hosted Ag-Sb deposit of northeastern Guangdong, South China, have been directly determined using the electron microprobe technique. The silver contents in two types of organic matter, marine vitrinite and solid bitumen, vary in the range from 100×10-6to 350×10-6, which are from tens of times to thousands of times higher than those of the host rocks in the ore deposit. The average silver content of the organic matter is also several times higher than the pay grade of silver for commercial mining of the ore deposit. It is quite obvious that the organic matter of the host rocks in the ore district is characterized by an anomalous enrichment of silver. The results of this study indicate that the silver anomalies in the organic matter have been derived from both the host rocks and the silver-bearing fluids of the Songxi black shale ore source. In the course of sedimentation and later hydrothermal reworking, organic matter was able     

碳酸盐岩生油岩的有机地球化学、岩石学特征

Features of oil-generating carbonate rocks are studied in terms of petrology and organic geochemistry of fluorescent materials in rocks. It is postulated by the authors that the organic carbon content in oil-generatlng carbonate rocks is necessarily lower than that in shales, and the possible cause of this observation is discussed. The quality of oil-ganerating carbonate rocks may be judged by aromatic structure index,amino acid, pigment index, and DTA data on organic matter. However, the application of presently available organic geochemical criteria to non-oil-generating reservoir rocks may always give misleading results. To circumvent this difficulty, it is necessary first to make distinction between primary and secondary organic matter by cxamining the fluorescent materials under a fluorescence microscope. Measurementof radical content of the organic substances and DTA are useful techniques to determine the degree of maturation. The maturation of organic substances proceeds at a lower rate in carbonate rocks than in shales. It is likely, therefore, that some older carbonate strata can also be promising areas for petroleum exploration. Oil-generating carbonate rocks consist mainly of mierite limestones rich in organic matter and are thought to be formed under low-encrgy environment. Consequently, petrological(especially mierolithofacies) studies are very important in evaluating carbonate source rocks.     

Minerogenetic Mechanism of the Songxi Silver—Antimony Deposit of Northeastern Guangdong—Ore—Controlling Role of Organic Matter

Organic geochemistry and comparisons of characteristics of the organic matter in wall rocks of the ore-controlling strata and ores of the Lower Jurassic Songling black shale formation and the related Songxi silver-antimony deposit of northeastern Guangdong have been studied in this paper.The results show that the Lower Jurassic Songling shale formation is a suite of biologic-rich and organic-rich ore-bearing marine sedimentary rocks.Micro-components of the organic matter in the Songling black shale formation consists primarily of algae,amorphous marine kerogen,solid bitument,and pyrobitument.The thermal evolution of organic matter is at the over-maturity stage.There is a general positive correlation between total organic carbon(CO)and metallogenetic elements such as Ag and Sb in the black shale formation.Organic matter in the host rocks in the Songxi ore deposit played a role in controlling the silver-antimony depositing environment during the forming process of the black shale ore-bearing formation.In the absence of vitrinite,the relative level of thermal maturity calculated by solid bitument reflectance indicates that the ore-forming temperatute of the Songxi silver-antimony deposit was about 150-170℃,which was considered as an epithermally reworked ore deposit.The roles of organic matter in the formation of the Sonxi ore deposit are a primitive accumulation of the metallogenetic elements(Ag,Sb) in the sea-water cycle system for ore source and a concentration of metals by ion exchange of chelation as well as reductionn of the oxidzed metals.     

Organic Geochemistry of Sedimentary Rock-hosted Disseminated Gold Deposits in Southwestern Guizhou Province, China

Sedimentary rock-hosted disseminated gold (SRHDG) deposits in the Youjiang-Nanpanjiang Basin,southwestem Guizhou Province are commonly hosted by the same fold crests that commonly contain a remarkable amount of organic material. The total organic carbon (TOC) contents of the ores and host rocks are usually less than 1%. The reflectance of vitrinite and pyrobitumen in the ores and the host rocks ranges from 1.5% to 4.5%, often in the range of 2% to 3%. In the Lannigou deposit, the reflectance of vitrinite and pyrobitumen in the ores is usually somewhat higher than those within the host rocks, indicating a hydrothermal impact on the organic matter in the altered host rocks. On the contrary, the estimated maximum paleotemperatures of the Getang and Zimudang deposits are higher than the homogenization temperatures of the fluid inclusions in the ores, signifying that the organic matter maturation predated Au mineralization. No correlation between the organic matter contents and Au concentrations were recognized in the ores.However, the most striking observation is that there is a positive correlation between the $2 (a parameter of Rock-Eval analysis), Au and As contents of the ores in the Lannigou deposit. Organic matter maturation and migration is apparent from the TOC vs. HCI diagram. Furthermore, group analysis of the dichloromethane extractable organic component of the ores and host rocks shows that the maturation degree of the organic matter in the ores is slightly higher than that of the host rocks in the Lannigou gold deposit. However, the compositions of their alkanes, steranes and terpenes, which serve as biomarkers, are quite similar; this suggests that the organic matter found in the ores and host rocks has a common marine source. Organic matter probably contributed to the preconcentration of Au in the host rocks. Hydrocarbons in the system,on the other hand, clearly contributed to the emplacement of the gold mineralization through thermal sulfate reduction.Organic matter in the solution might have increased the potential of the hydrothermal solution to transport Au.     

A Study on Organic Inclusions in Clastic Reservoir Rocks and Their Application to the Assessment of Oil and Gas Accumulations

Terrigenous clastic reservoir rocks are widespread in China,and nearly all the industrial oil and gas accumulations in eastern China occur in the clastic rocks.The study shows that organic inclusions are mostly distributed in the secondary fissures and pores which were ormed in the process of oil-rock interaction,rather than in the cements or secondary enlargements. The organic inclusions are dominantly organic gas-rich or are composed of pure hydrocarbons.Homogenization temperatures range mainly from 120℃ to 130℃，which shows a relatively high maturity of organic matter.Vertical and horizontal temperature changes provide the grounds for the investigation of basin evolution and thermal fluid-kinetics-model.Fluorescence spectral characteristics o the organic inclusions indicate that oils and gases in the area studied probably have experienced two-stage or two-time migration.Micro-fluorescence rescearch is one of the effective approaches to oil/source correlation and oil migration-stage determination.The abundance and occurrence of organic inclusions is one of the indicators of oil and gas abundance and accumulation in rock layers.With the help of other informatio,organic inclusions can provide the basis for the prospective assessment of oil and gas in clastic reservoir rocks.     

Characteristics of biomarkers in source rocks of the Ganquan Formation in the Dahulishan region, Ejina Banner

Based on gas chromatography and gas chromatography mass spectrometry techniques, the authors examined biomarker characteristics of the Ganquan Formation source rocks in the area of Dahulishan, Ejina, and analyzed the information and petroleum geological significance that were indicated by the source of organic matter, sedimentary environment and maturity and so on. Gas chromatography peak of saturated hydrocarbons from the Ganquan Formation source rocks showed "the former peak" of the single peak distribution, the main peak of carbon being C18 , indicating the main sources of organic matter with marine organic matter. Pr/Ph ranges from 0.3 to 0.6, indicating a strongly reducing sedimentary environment. Biomarker assemblages of the Ganquan Formation source rocks are abundant in tricyclic terpane with long side chains, with a high level of gammacerane, showing dominant distribution of C27 sterane. High contents of gammacerane in organic matter show organic facies of source rocks in the saltwater sedimentary environment. That average hopane/sterane ratio is 0.59, showing that algae have made more contributions to organic matter than bacteria. And the high level of C27 steranes shows that algae are the main source of hydrocarbon precursors. The Ganquan Formation’s methylphenanthrene index, which is an effective molecular parameter index to measure thermal evolution of organic matter, ranges from 0.35 to 0.50, and the conversion of vitrinite reflectance Rc from it is within the range of 2.00-2.09, indicating that the Ganquan Formation source rocks are in the over-mature stage of thermal evolution.     

Thermogravimetry-differential thermal analysis coupled with chromatography as a thermal simulation experimental method and its application to gaseous hydrocarbons from different source rocks

In this paper a thermogravimetry-differential thermal analysis method coupled with chromatography （TG-DTA-GC） has been adopted to simulate the generation of gaseous hydrocarbons from different hydrocarbon source rocks such as coals, mudstones, and carbonate rocks with different maturities. The temperature programming for thermal simulation experiment is 20℃/min from ambient temperature to 700℃. As viewed from the quantities and composition of generated gaseous hydrocarbons at different temperatures, it is shown that low-mature coal has experienced the strongest exothermic reaction and the highest loss of weight in which the first exothermic peak is relatively low. Low-mature coal samples have stronger capability of generating gaseous hydrocarbons than high-mature samples. The amounts and composition of gaseous hydrocarbons generated are closely related not only to the abundance of organic carbon in source rocks, but also to the type of kerogen in the source rocks, and their thermal maturity. In the present highly mature and over-mature rock samples organic carbon, probably, has already been exhausted, so the production of gaseous hydrocarbons in large amounts is impossible. The contents of heavy components in gaseous hydrocarbons from the source rocks containing type- Ⅰ and - Ⅱ kerogens are generally high ; those of light components such as methane and ethane in gaseous hydrocarbons from the source rocks with Ⅲ-type kerogens are high as well. In the course of thermal simulation of carbonate rock samples, large amounts of gaseous hydrocarbons were produced in a high temperature range.     

Graptolite, Chitinozoan and Scolecodont Reflectances and Their Use as Indicators of Thermal Maturity

Based on studies of the reflectance of Ordovician and Silurian zooclasts from 11 sections around the Huangling Anticline, Hubei, China, combined with determination of the conodont colour alteration indices (CAI) and of infrared spectroscopy of dispersed organic matter from the same or adjacent horizons, it is further proved that reflectances of graptolites, chitinozoans and scolecldonts, like vitrinite and natural bitumen, increase with increasing maturation, but follow different reflectance paths. They may be used, therefore, as thermal maturation indicators. Graptolites display optically strong anisotropy. The maximum reflectance measured from graptolite on polished section cut parallel to the bedding plane is the most suitable for determination of maturation of their host rocks. In polished section chitinozoan and scolecodont show reflectance, but no bireflectance owing to their isotropy. The random reflectance of chitinozoans is higher than that of scolecodonts in the case of the same maturity. By analysing the distribution trends of graptolite, chitionzoan and scolecodont reflectances, the Ordovician and Silurian strata can be subdivided into three areas of maturation in the present region. The potential of oil or gas generation is discussed for each area. The result is basically coincident with the distribution pattern of regional organic maturation presented by CAI and infrared spectroscopic determination of organic matter.     

Analysis of Organic Inclusions Using Fluorescence Microscopy and Micro-FT.IR Techniques

Organic inclusions from the Shahejie Formation of the Eogene period in the Bohai Gulf Basin,eastern China,were examined using micro-FT.IR and fluorescence microscopy in addition to the measurement of their homogenization temperatures(Th).Two populations of organic inclusions were recognized,the primary and the secondary organic inclusions.The primary organic inclusions contain organic materials with relatively long alkyl chains(the carbon atom number is 15 to 17),whereas the secondary organic inclusions contain a certain amount of H2S besides organic materials which have relatively short alkyl chains with the carbon atom number of 5 to 6.The Th values of the primary organic inclusions within the rage of 87-91℃,lower than those of the secondary organic inclusions(Th=98-105℃）,sugesting that the primary organic inclusions experienced a lower degree of thermal evolution than the secondary inclusions.This inference is consistent with the fluorescence spectroscopic characteristics and parameters(Tmax,Q values)of the organic inclusions.Data from the organic inclusions together with the petroleum geology setting revealed that the primary inclusions resulted from the migration of hydrocarbons generated within the strata they are hosted,whereas the secondary organic inclusions were trapped in the process of secondary hydrocarbons expelled out of the source rocks to the locations where they were accumulated.The thermal properties of the organic inclusions are consistent with the maturation of the oil generated from the Shahejie Formation.The abundance of the organic inclusions and their characteristics indicate that the member Es3 of the Shaheije Formation is highly potential for oil accumulation.The results could provide essential coues to petroleum exploration in the Bohai Gulf Basic.     

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 Role of Organic Matter During Metal Enrichment in Permian Kupferschiefer of the Rudna Mine,Southwest Poland

The bulk composition of organic matter and saturated and aromatic hydrocarbons extracted from 16 samples collected from two Kuperschiefer profiles in the Rudna mine,Southwest Poland has been analyzed to study the role of organic matter during base metal enrichment in the Kupferschiefer shale.The results indicated that the extract yields and saturated hydrocarbon yields decreased with increasing base metal contents.GC and GC/MS analyses indicated that n -alkanes and alkylated aromatic compounds were depleted and may have served as hydrogen donators for thermochemical sulfate reduction.The enrichment of base metal is closely connected with the destruction of hydrocarbons.     

Geochemistry and geological significance of the Upper Paleozoic and Mesozoic source rocks in the Lower Yangtze region

The Lower Yangtze region is one of the important marine sedimentation areas of oil and gas distribution in southern China,for its favorable source rocks,reservoirs and covers.However,the intense tectonic movements and complex hydrocarbon generation process made it highly impossible to form large-sized oil and gas reservoirs.So it was divided to different hydrocarbon-bearing preservation units in oil-gas exploration.Recent study shows that the Permian and Lower Triassic source rocks in the Lower Yangtze region are complicated in lithology.The hydrocarbon generation potential of limestone there is low while argillaceous source rocks are overall of high abundance with excellent organic types,now in the process of hydrocarbon generation,so differences in high maturity influence the evaluation of organic matter abundance and type.Biomarker characteristics indicate a reductive environment.n-alkanes are marked by a single peak,with no odd-even predominance.The composition and distribution of the carbon numbers of n-alkanes,and the high abundance of long-chain tricyclic terpanes are indicative of marine sedi-mentation.The high contents of pregnane,homopregnane,rearranged hopane suggest that the source rocks are of high maturity.There is a good linear correlation between methylphenanthrene index and vitrinite reflectance.The correlation of oil-source rocks indicated that the oil of Well HT-3 may come from the Permian Longtan Formation in the Huangqiao area,the oil of Wells Rong-2 and Juping-1 came from the Lower Triassic Qinglong Formation in the Jurong area.The exploration here is promising in those different source rocks which all have great potential in hy-drocarbon generating,and oil and gas were produced in the late stage of hydrocarbon generation.     

碳酸岩生油岩中沥青变质程度和沥青热变质实验

Natural asphalts from carbonate rocks in South China have been studied by using microscopy, X-ray diffraction, ESR and C^-, H^- analysis and subjeeted to thermal alteration experiments under 250℃/1000 atm--500℃/1000atm. It is shown that asphalt and vitriolic behave differently under conditions of thermal alteration. In compariseu with vitriuite, asphalt is of higher reflectivity, more apparemt anisotropy,lower values of d002 and H/C ratio above 350℃. The mierostructure and charaeter of protoasphalt disseminated in carbonate rocks and diagenetic asphalt reflect the thermal history and the maximum paleotemperature to which they haxt been subjected. Reflectivity, H/C ratio, d002 etc. of the asphalts in carbonate rocks may be used as indicators for the extent of maturity of earbenate source rocks. Based on measurements carried on asphalts of pertinent occurrences. R^0=1.65.H/C=0.75, d002=3.53 A are suggested as creteria for the distinction between Oil and natural gas field in carbonate terrains in China.     

Characterization of soil humin by acid hydrolysis

Studies were conducted to characterize soil humin by acid hydrolysis.Two humin samples collected from two different types of soil,namely chernozem and laterite,which are widespread over a vast area from the north to south of China,were hyrolyzed under reflux with 0.5M H2SO4or 3M H2SO4for 4h.The results showed that 25%-29% of organic carbon and 46%-54%of organic nitrogen could be hydrolyzed by 0.5M H2SO4;36%-40%of organic carbon and 93%-97% of organic nitrogen hydrolyzed by 3M H2SO4.The C/N ration in hydrolyzed organic matter is lower than that in soil humin and that in organic matter hydrolyzed by 3M H2SO4 is lower than that in organic matter hydrolyzed by 0.5M H2SO4.The proportion of nitrogen hydrolyzed from humin is markedly larger than that from the original soil and also markedly larger than that from humic acid fraction.Only 3%-7% of nitrogen in humin exists in a relatively stable from,which is not easy to hydrolyze.There in little nitrogen that occurs in the form of heterocyclic rings in humin.Incubation experiments showed that the newly formed organic matter can be hydrolyzed more easily.