利用芳烃参数研究煤系烃源岩中重排藿烷成因

研究发现鄂尔多斯盆地部分地区上古生界煤系烃源岩存在较高丰度的17α(H)-重排藿烷和早洗脱重排藿烷,在对重排藿烷分布、组成特征及生标组成特征研究的基础上,应用芳烃参数对高丰度重排藿烷的成因进行了探讨。饱和烃生物标志物组成特征显示,高重排藿烷与陆源高等植物生源关系密切,主要在弱氧化沉积环境下演化形成。具有高-异常高丰度17α(H)-重排藿烷和早洗脱重排藿烷(C₃₀*/C₃₀H>0.2、C₃₀E/C₃₀H>0.1)的烃源岩二环+三环芳烃相对含量一般大于50%,四环、五环芳烃含量相对较低,普遍低于35%,未见芳香甾萜类,研究认为其生源主要为陆生高等植物;甲基菲指数MPI₁、MPI₂和甲基菲比值F1研究结果显示,Pr/Ph>1的弱氧化环境烃源岩17α(H)-重排藿烷和早洗脱重排藿烷在进入成熟阶段后开始大量形成,并随成熟度升高而增大;Pr/Ph<1还原环境下的烃源岩重排藿烷丰度相对较低,但在进入成熟阶段后仍有随成熟度升高而增大的趋势;三芴系列化合物参数表明,沉积环境的弱氧化性质对17α(H)-重排藿烷和早洗脱重排藿烷的形成有较大的影响,沼泽相沉积环境最有利于重排藿烷的形成。     

Thermodynamic stability of various alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers using molecular mechanics calculations

The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C₂₇, C₂₈, C₂₉, C₃₀ and C₃₁ families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C₂₇ compounds, Ts/Tm.     

Origin of hydrocarbons in triassic serpiano oil shales: Hopanoids

The hydrocarbons in the sapropelic Serpiano oil shales have been examined. The hopanoids are the most predominant hydrocarbons present in the bitumen, with hopanes, hopenes, benzohopanes and monoaromatic secohopanoids being detected. The novelty of the Serpiano hopanoid assemblages lies in the occurrence of high concentrations of methylhopanoids. The distributions of the hopanoids and of their corresponding methylhopanoids are remarkably similar. This similarity was also observed for the hopanes and methylhopanes which were generated from the asphaltene and kerogen by hydrous pyrolysis, and is indicative of a common biosynthetic pathway.     

Strenes and triterpenes in brown coals

The method of gas chromatography-mass spectrometry was used to identify rearranged 24-methylcholestenes, 24-ethylcholestenes and isohopene in brown coals. Possible routes and sources of formation of these hydrocarbons in nature are discussed. Mass spectra both of original hydrocarbons and of their saturated analogues are given.     

Relative stabilities of sedimentary rearranged sterenes as calculated by molecular mechanics: a key to unravel further steroid diagenesis

Molecular mechanics calculations of rearranged cholestenes revealed that diacholest-13(17)-enes with 10α stereochemistry are more stable than their 10β counterparts and that a partly rearranged sterene with a Δ⁸ double bond and 10β, 14β stereochemistry (compound 7) is relatively stable at thermodynamic equilibrium. The calculated data are in good agreement with sedimentary and experimental data and thus reinforce recent propositions for early-stage diagenesis of steroids.     

The Biomarkers in the Mesoproterozoic Organic-rich Rocks of North China Craton: Implication for the Precursor and Preservation of Organism in the Prokaryotic Realm

Mesoproterozoic marine organic-rich rocks are widely distributed in the North China Craton,include the Gaoyuzhuang(GYZ),the Hongshuizhuang(HSZ),and the Xiamaling(XML)formations.According to the T;value and isomerisation ratio of C;homohopanes,the XML,HSZ,and GYZ samples were in low mature,mature and high mature stage,respectively.Biomarker distribution in extractable organic matter(EOM)of three Mesoproterozoic organic-rock samples in different maturity were analysed to reveal the organic precursor and preservation pathway of in the Mesoproterozoic Combined with gold-tube pyrolysates of three Mesoproterozoic samples,it could further illuminate the chemical composition of Mesoproterozoic kerogen,given excluding.The results indicated that the three formations were all deposited under reducing condition and their organic precursors mainly were some aquatic organisms.High content of rearranged hopanes was detected in EOM of XML and HSZ samples,whereas they were relatively low in the high mature GYZ sample.Contrast to that in EOM,the relative concentration of rearranged hopanes sharply decreased in the gold-tube pyrolysates of the XML kerogen,then slightly increased but was still significantly lower than the EOM of XML sample,which indicated that catalysis of clay minerals in the early diagenesis only changed the chemical composition of the unstable functional groups of the kerogen during the preservation.Due to the thriving heterotrophic microbes and low sink rate of particulate organic matter during the Mesoproterozoic,primary producers suffered extensive degradation during sinking process,only some resistant biopolymers lacking of lipid compounds survived from heterotrophic degradation,while heterotrophic microbes contained more proportion of organic precursors.Abundant pristane(Pr)and phytane(Ph)were only released in high mature stage because of the protection of the macromolecular structure of resistant biopolymers which prevented biomarkers from being altered by the thermal stress.The absence of 13α(n-alkyl)-tricyclic terpanes in the high matured hydrocarbon products also indicated the different precursors between different parts of Mesoproterozoic kerogen.The evolution of the biomarker composition and content of Mesoproterozoic kerogen showed some special characteristics differing from those of Phanerozoic kerogen.The total concentrations of hopanes displayed with an order of low mature stage>high mature stage>mature stage.Relative content of rearranged hopanes in the hydrocarbon generated in high mature stage was significantly lower than that in the low maturity stage.The ratios of Pr/n-C₁₇ and Ph/n-C₁₈ increased with thermal maturity,and the ratio of nC_21-/nC₂₂₊ decreased in the high maturity stage,thus displaying another order of mature stage>high maturity stage>low maturity stage.The unique preservation pathway of Mesoproterozoic organisms was attributed to the special evolution characteristics of biomarker distributions,which should be considered in the Mesoproterozoic marine environment and biological studies.