The kerogen type, depositional environment and maturity, of the Irati Shale, Upper Permian of Paraná Basin, Southern Brazil

Two samples from the upper and lower horizons of the Irati oil shale of the Paraná Basin, Brazil were sampled in a single borehole, and analysed using organic petrography and geochemistry. The results are interpreted in terms of the kerogen type, maturity and depositional environment of the two horizons.Organic petrography shows the oil-shales to be composed of a mineral groundmass, mainly clay minerals, carbonate and pyrite, associated, and sometimes impregnated, with fluorescing organic material and disseminated phytoclasts. Humic material is fairly rare and mostly present as very small particles. The liptinitic particles are mostly alginite (A and B), sporinite and more rarely resinite. Reflectance measurements (upper seam = 0.34% R₀; lower seam = 0.40% R₀) indicate an equivalent rank of lignite/sub-bituminous coal (ASTM), i.e. immature with respect to oil and gas generation. Different organic geochemical methods (Rock-Eval pyrolysis, solvent extraction, GC and GC-MS) demonstrate both samples to be immature, rich oil-shales (100–114 kg/ton) containing Type I kerogen, of a dominantly bacterially-degraded algal origin deposited in a lacustrine environment. The presence of Botryococcus suggests deposition under fresh/brackish water conditions.A tentative interpretation of the extract and vitrinite reflectance data suggests a maximum paleo-burial of between 1.3 and 2.8 km for the analysed section of the Irati Formation.     

Organic geochemical characterization of the New Albany Shale group in the Illinois Basin

Benzene extractable aliphatic hydrocarbons from the New Albany Shale in the Illinois Basin were characterized by gas chromatography and mass spectrometry, and the total organic matter of the shale was characterized by solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance. Core samples from a northwest-trending cross-section of the Illinois Basin were studied. Gas chromatography (GC) and gas chromatography-mass spectrometric analysis (GC/MS) data indicate a regional variation of the aliphatic composition of the shale extracts. A positive, linear relationship between the two ratios, pristane/n-C₁₇ and phytane/n-C₁₈, is indicated. The NMR results indicated that organic matter deposited in northwestern Illinois shale is relatively high in aliphatic hydrocarbon content while, in contrast, organic matter found in southeastern Illinois shale is relatively low in aliphatic hydrocarbon content. Our findings suggest that the organic variation of the shale is mainly due to the differences in thermal maturity of the shale organic matter and the use of pristane/n-C₁₇ ratio as a thermal parameter in the study of oil may be extended to the study of the ancient sediments.     

Distribution of carbazole derivatives in petroleum

Carbazole, its alkyl derivatives and higher benzologs have been selectively isolated from six different crude oils. In all samples, benzocarbazoles are major constituents of a series which may extend up to dibenzocarbazole derivatives. The distribution includes unsubstituted parent compounds and shows a maximum content of methyl and dimethyl substituted species. Sixteen individual constituents have been identified by means of comparison with reference compounds using gas chromatography, mass spectrometry and high resolution spectrofluorimetry. So far, no generally acceptable explanation has been given for the origin of these compounds, which presumably are the most stable ones in their respective series of aromaticity. Thus, carbazole derivatives may result from a complex sequence of reactions during kerogen formation, not allowing the recognition of precursing molecules. The geochemical significance of this series of nitrogen compounds needs to be clarified, requiring further studies.     

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.     

陕北高挥发分烟煤煤质特征与应用研究

通过煤质分析、煤岩分析与葛-金干馏试验等对比实验，研究了陕北横山、神府矿区等地侏罗纪不粘-弱粘煤及其配煤的煤炭特性、低温干馏特性以及单种煤与配煤低温干馏性能差异和变化规律。结果表明，陕北侏罗纪煤具有较高的焦油产率，配煤在降低煤中含硫量的同时，有利于低温干馏过程的进行和产品质量的提高；此外，在掌握原煤显微组成和低温干馏特性的情况下，可以预测配煤低温干馏产品的相关参数。     

Occurrence of Highly Mature Organic Matter in Marine Black Shale Petroleum Source Rocks of Basal Cambrian from Northern Tarim Basin, China

More and more evidence indicates that organic matter (OM) in immature organicrich sediments and sedimentary rocks is chemically adsorbed onto the outer surfaces of minerals and into interlayer (inner) surfaces of smectitic clay minerals in the form of amorphous molecular-scale carbon. But there have been few reports about the occurrence of highly mature OM in marine black shales ( petroleum source rocks ). The occurrence of highly mature OM in the black shales of basal Cambrian from northern Tarim Basin is studied in this paper. Based on the comprehensive analyses of total organic carbon contents (TOC) , maximum thermolysis tempera tures ( Tmax ) of OM, mineral surface areas (MSA) ,and scanning electronic microscopic (SEM) and transmission electronic microscopic (TEM) observations of the black shales, it is concluded that the highly mature OM in the marine black shales of the basal Cambrian from northern Tarim Basin occurs in particulates ranging in size from 1 to 5 μm in diameter. Through the contrast of the occurrence of the highly mature OM in the black shales with that of the immature ones in modern marine continental margin sediments, some scientific problems are proposed, which are worth to study further in detail.     

Enzymatic and Microbial Degradation of Organic Matter in Lake Hongfeng, Guizhou Province, China

1IntroductionEnzymaticandmicrobialdegradationoforganicmatterhasabearingnotonlyonearlydiagene sis,butalsoonelementcyclingandmicrobedistributioninlakesediments.Somereportsshowedtheabundancevariationsoforganicmatterinsediments (BurdigeandGardner,1998;ArthurandDean ,1998;WanGuojiangetal.,2 0 0 0 ) .However,duetothecomplexchemicalcompositionoforganicmatter,mechanismsofenzymaticandmicrobialdegradationandvariationsofeachchemicalcomponentneedtobestudiedfurther.Underanoxiccondition ,SO2 -4 isanimpo…     

森林沼泽区富含有机质样品中金的存在形式及对分析的影响

为探讨中国东北森林沼泽地区富含有机质样品中金偏低的原因,采用了王水溶矿法和四酸溶矿法的AAS分析来测定样品中的Au。用四酸溶矿法驱除硅胶,明显地提高金的测定值,特别是对含量大于10-9的样品,2种分析方法的差别更大。通过以上研究发现,在森林沼泽区的富含有机质样品中,金除以有机质结合形式存在于介质中,还可能以胶体或纳米形式存在于样品中,并被SiO₂胶体所包裹,在高浓度有机酸的保护下,金能在水溶液中呈活动形式做长距离迁移;但用王水溶矿法不能测定出这种被SiO₂胶体包裹形式的金。     

TOC changes in the process of thermal evolution of source rock and its controls

Through geological observation, simulation in laboratory and numerical modeling, the factors that control the changes in total organic content (TOC) of source rock have been studied. When the formula DTOC=(TOC0-TOC)/TOC0 (original organic carbon content in the rock) is used to measure the TOC (total organic carbon content) changes in the source rock through geological time, the degrees and directions of such changes are determined by losses and relative amounts both of organic and inorganic matter in the source rock. The DTOC equation, which is used to calculate the loss rate in the process of maturation for the source rock, is therefore obtained by analyzing the mass balance relations. For a certain type of source rock with a certain maturation history, the changes of its TOC respond only to the rates of hydrocarbon generation and expulsion. In actual cases of geological entities, DTOC generally ranges from -0.05 to 0.2, while the calculated reconversion coefficient (k) for organic carbon content remains between 0.90 and 1.25. Only in an ideal situation where there are extremely high rates of hydrocarbon generation and expulsion can the DTOC value experience significant changes, with k reaching up to 2.5. It is concluded, therefore, that the criterion for carbonates source rock assessment, based on reconverting the TOC to the value of its original state, may have overestimated the course of the "carbon-reduction", which is likely in many cases to make a poor source rock sound better.     

Study on the threshold value of organic enrichment of carbonate as gas source rocks

In this paper, calculations have been performed about gas quantity of generation, adsorption, dissolving in oil, dissolving in water, diffusion of unit area carbonate rocks at different geologic conditions in the Tarim basin. According to the material balance principle, the corresponding organic carbon content when gas started expelling from source rocks with separate phases has been worked out. We regard it as the theoretical threshold value (TOCmin) of gas source rocks under the same geologic condition. Based on the simulating calculation, a fact has been discovered that TOCmin decreases with the increasing source rocks thickness, decreases at the beginning and then increases with the increasing maturity and decreases with the better type of organic matter. TOCmin evaluation table of carbonate gas source rocks in the Tarim basin has been established. Investigations indicate that the TOCmin of carbonate gas source rocks varies greatly with the differences of geologic conditions, and gas source rocks cannot be evaluated with a unified TOC threshold value. And we also establish a preliminary evaluation table of TOC industrial threshold value, TOCgy, of carbonate gas source rocks in the Tarim basin.