Electron spin resonance of stabilized free radicals in sedimentary organic matter     

Zeev Aizenshtat  Ida Pinsky  Baruch Spiro   《Organic Geochemistry》1986,9(6)

Electron spin resonance (ESR) is evaluated as a method to study the thermal degradation of sedimentary organic matter which consists mainly of kerogen. Whole rock and separated kerogen samples were pyrolysed stepwise (ambient to 700°C at 50°C increments), extracted and analysed for elemental composition and ESR spectra at each step. Whole rock samples give rise to complex spectra which include those of paramagnetic metals and are therefore unsuitable in most cases for this purpose.The ESR parameters g value, ΔH and N_g differ for different types of immature organic matter. An increase in N_g,shift of g value to 2.0026–2.0028 and reduction in h are the main trends during pyrolysis and in natural heating of sedimentary organic matter.The peak generations of liquid and gaseous hydrocarbons coincide with maxima of free radical density. ESR spectroscopy in combination with complementary geochemical characterization of the sedimentary organic matter can serve to indicate maturity with respect to peak oil-gas generation.  相似文献   

The degree of oxidation of iron in synthetic iron-magnesian biotites     

Dr. V. I. Tikhomirova  Dr. A. N. Konilov  Dr. S. K. Koshemchuk 《Mineralogy and Petrology》1989,41(1):41-52

Summary Chemical analytical and pyrolytical methods have been used to study the Fe⁺²/Fe⁺³ ratios and dehydroxylation reactions in synthetic biotites. It has been found for the biotites with Fe/(Fe + Mg) of 20 to 70 mole % that the oxidation degree decreases from 26 to 16% with increasing iron. Based on the measured amounts of water and hydrogen released during pyrolysis it is inferred that the deprotonization is a dominant reaction at low temperatures (T 600°C), accompanied by dehydration as the temperature increases. Depending on the composition, a complete dehydroxylation takes place at T 900 °C, and the measured amount of water corresponds to the iron oxidation degree in the starting samples. The results of this study have important implications with respect to determination of the formation conditions of biotite-bearing rocks, and also for improvement of the techniques for determination of different valence of iron and water.

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Le degré d'oxidation du fer en biotites synthétiques contenants le fer et le magnésium

Résumé Des méthodes chimiques et pyrolitiques ont été utilisées pour l'étude des rapports Fe⁺²/Fe⁺³ et de la réaction de la déhydroxilation en biotites synthétiques. On a trouvé pour les biotites avec Fe/(Fe + Mg) de 20-70 mole % que le degré d'oxidation décroît à partir de 26 jusqu'à 16% pendent que le contenu du fer s'accroît. Sur la base de la quantité d'eau et hydrogène liberée pendant la pyrolyse, on infère que la déprotonisation est une réaction dominante à températures basses (T = 600°C), mais quand la température s'accroît, la déprotonisation est accopagnée de la déhydratation. Dépendant de la composition il y a une déhydroxilation complète à T = 900°C, et la quantité de l'eau mesurée correspond au degré d'oxidation du fer dans les specimens initials. Les résultats de cette étude infuencent la détermination des conditions de formation des roches contenantes biotite et aussi l'amélioration des techniques de la détermination du fer de valences différentes et de l'eau.

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Effect of a dolerite intrusion on triterpane stereochemistry and kerogen in Rundle oil shale,Australia     

Trevor D. Gilbert  Lorraine C. Stephenson  R.Paul Philp 《Organic Geochemistry》1985,8(2):163-169

Stereochemical changes of triterpanes present in extracts from an immature oil shale sequence intruded by a 3-m dolerite sill have been studied by gas chromatography-mass spectrometry (GC-MS). The steric configuration of the hopanes was observed to change from one dominated by the thermally less stable 17β(H), 21β(H) configuration at some distance from the intrusion, to one dominated by the thermally more stable 17α(H), 21β(H) and 17β(H), 21α(H) configurating in the immediate vicinity of the intrusion. In addition, severe alteration of the kerogen appeared to have taken place as a result of the contact metamorphism, and high concentrations of extractable organic matter were observed below the intrusion. Characterization of the kerogens by Curie-point pyrolysis has enabled the effects of the intrusion on the shales to be monitored.  相似文献   

Pyrolysis-GC-MS and NMR studies of dissolved seawater humic substances and isolates of a marine diatom     

Andrew H. Gillam  Michael A. Wilson 《Organic Geochemistry》1985,8(1):15-25

¹³C- and ¹H-NMR spectra were obtained for humic substances isolated from a coastal marine environment and also for the intracellular and extracellular extracts of a marine diatom. Phaeodactylum tricornutum Bohlin. Highly branched alkyl chains constitute a large proportion of the structure of the marine humic material, whereas aromatic components are less important. Carbohydrate-type materials, possibly uronic acids, are also present in appreciable amounts. Furans (derived from carbohydrates). pyrroles and nitriles (derived from proteins, nucleic acids and/or tetrapyrroles) and phenols and methylphenols (non-lignin derived) are pyrolysis products derived from pyrolysis-gas chromatography-mass spectrometry of the extracts. The results indicate the similarities in chemical structure of P. tricornutum exudate and dissolved marine humic material.  相似文献   

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

Zuleika Carreta Correa Da Silva  Chris Cornford   《Organic Geochemistry》1985,8(6):399-411

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.  相似文献   

生油煤形成的环境制约   总被引：4，自引：1，他引：4  

孙永革  朱进  徐华  盛国英  傅家谟 《地球化学》2002,31(1):8-14

通过对不同沉积环境下形成煤系源岩生烃潜力的对比研究，揭示出成煤古环境对煤成烃生成具有控制作用，并根据煤系源岩中赋存大分子有机质裂解产物分子的组成特征，提出了识别有利成烃煤相的分子有机地球化学方法——氢指数-苯酚/辛烷图解判识法。结果表明，沼泽环境覆水越深，煤中有机质富氢程度越高，生油气性能越好，裂解产物表现为正构烷烃和正构烯烃相对含量增加，以低本酚/辛烷值和高氢指数为特征；反之，沼泽环境覆水越浅，煤中有机质氢含量越低，裂解产物以高含量酚类化合物和芳香烃为特征，生油气性能关。由此表明，覆水型沼泽应是煤在烃，特别是煤成油生成的有利相带。  相似文献   

利用干酪根热解动力学模拟实验研究塔里木盆地下古生界古地温   总被引：9，自引：0，他引：9  

解启求  周中毅 《地球科学》2002,27(6):767-769

通过热解动力学模拟实验，对塔里木盆地塔参1井奥陶系干酪根的热演化过程进行了模拟，以此基础上利用KINETICS软件求取干酪根镜质体反射率（R0）的生成动力学参数，并结合塔参1井的沉积埋藏史，计算塔参1井寒武－奥陶系的古地温，这对于研究塔里木盆地下古生界高过成熟烃源岩的古地温是一种新方法。  相似文献   

Lead and Zinc Stabilization of Soil Using Sewage Sludge Biochar: Optimization through Response Surface Methodology   总被引：1，自引：0，他引：1       下载免费PDF全文

Azin Fathianpour  Masoud Taheriyoun  Mohsen Soleimani 《洁净——土壤、空气、水》2018,46(5)

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沥青成因及反映的油气成藏过程     

王兆云  马超  龚德瑜  姜华 《地质学报》2020,94(11):3436-3448

地质体中沥青按沉积有机质的不同演化路径分为原生和次生沥青,次生沥青由于经历的地质作用不同,又分为生物降解水洗氧化和热裂解成因两种类型,本文重点讨论热裂解成因沥青。热裂解成因沥青是干酪根在生油窗阶段生成的原油,进一步深埋温度增高,达到原油裂解的热动力学条件,裂解生成天然气后的残余物。干酪根热降解生成的原油有聚集型、源内分散型、源外分散型三种赋存方式,裂解分别对应形成三种赋存状态的沥青。通过四川盆地13口井60余块岩芯样品热裂解成因沥青从宏观到微观不同尺度的研究,沥青体积含量0. 1%~15%,形态有条带状、片状、块状、粉末状;赋存方式有裂缝(区域沟通油源的断层)、层理面、微裂隙、原生、次生溶蚀孔、洞等;赋存岩石有粗晶、中—细晶白云岩。伴生的包裹体发育丰富,可区分出孔洞方解石早期和晚期充填、白云石次生加大边、孔洞方解石微裂隙等方式,还有富沥青质的包裹体。颜色透明无色—淡褐色、无色—灰色、深灰色、深褐色等。常量和微量元素含量及不同比值反映了沥青的氧化还原特征。含烃包裹体均一温度从90~220℃,综合记录了油气生成演化的整个过程,以及经历的异常热作用;同一样品加大边中包裹体温度分布范围普遍比较宽,反映碳酸盐岩溶解重结晶作用频繁。基于沥青及其储集空间特征、有机、无机地球化学分析、包裹体研究,以及埋藏史、热史、油气运聚过程分析,四川盆地古老碳酸盐岩主力生烃层系筇竹寺组、灯影组一、三段烃源岩志留纪末进入生油门限,中二叠世大量生油,晚二叠世进入油裂解气门槛,晚三叠世油大量裂解生气;油气具有从北向南运移的特征,沥青大量形成期的分布与古构造叠合图是二次成藏的关键。  相似文献   

Geochemical characterization of soil organic matter and variability of a postglacial detrital organic supply (chaillexon lake,france)     

Christian di-Giovanni  Jean Robert Disnar  Vincent Bichet  Michel Campy  Bernard Guillet 《地球表面变化过程与地形》1998,23(12):1057-1069

Geochemical analysis of sedimentary organic matter in recent lacustrine sediments appears to be a useful tool in providing information concerning past environmental conditions. However, such analysis is often made without knowing the geochemical characteristics of the organic matter derived from the watershed and, more explicitly, its soils. The present work deals with (i) a geochemical investigation (Rock-Eval pyrolysis) of soil organic matter sampled in a lake watershed, and (ii) the study of the sedimentary organic matter trapped in the lake deposits. The research was conducted on Chaillexon Lake which was created by a rock collapse that dammed the palaeovalley of the Doubs River about 12 000 years ago. Since this event, the sediment trap provides a continuous palaeoclimatic record for the Postglacial period. Results obtained lead to two main conclusions. First, the variability of Rock-Eval pyrolysis values observed in soils modifies the common interpretation given to these parameters in the characterization of sedimentary organic matter. Indeed, variations in these parameters point not only to varying proportions of terrestrial and lacustrine organic matter in a lacustrine infilling but also to variations of the terrestrial supply linked with the evolution of vegetal cover in the catchment. The second conclusion is that the story of the Chaillexon lacustrine system is marked by a rather sudden soil and forest development at the Preboreal–Boreal transition (9000 BP ). Copyright © 1998 John Wiley & Sons, Ltd.  相似文献