The specific carbon isotopic compositions of branched and cyclic hydrocarbons from Fushun oil shale

Various branched and cyclic hydrocarbons are isolated from the Fushun oil shale and their carbon isotopes are determined. The analytical results show that the branched and cyclic hydrocarbons are fully separated from n-alkanes by 5 A molecular-sieve adduction using long time and cold solvent. The branched and cyclic hydrocarbon fraction obtained by this method is able to satisfy the analytic requests of GC-IRMS. The carbon isotopic compositions of these branched and cyclic hydrocarbons obtained from the sample indicate that they are derived from photoautotrophic algae, chemoautotrophic bacteria (-33.4‰— -39.0‰) and methanotrophic bacteria (-38.4‰— -46.3‰). However the long-chain 2-methyl-branched alkanes indicate that their carbon isotopic compositions reflect biological origin from higher plants. The carbon isotopic composition of C30 4-methyl sterane (-22.1‰) is the heaviest in all studied steranes, showing that the carbon source or growth condition for its precursor, dinoflageilate, may be different from that of regular steranes. The variation trend of δ^13C ValUes between isomers of hopanes shows that ^13C-enriched precursors take precedence in process of their epimerization. Methanotrophic hopanes presented reveal the processes of strong transformation of organic matter and cycling of organic carbon in the water column and early diagenesis of oil shale.     

柴达木盆地三湖坳陷气钾1井烃源岩地球化学特征分析

对烃源岩的地球化学特性的研究有助于油气的勘测。柴达木盆地三湖坳陷有丰厚的天然气资源,沉积范围广,厚度较大其厚度整体约2 000~3 200 m。选取三湖地区达布逊湖东部气钾1井的烃源岩样品,通过分析生物标志化合物,研究烃源岩的地球化学特征。实验结果表明:饱和烃的中低碳数分子无明显偶奇碳数优势,反映出微生物的降解作用明显改变了常规生物标志物的分布特征;有机质母质,植烷含量丰富,其碳数值接近于主峰碳数值,呈现弱还原的沉积环境特征;气钾1井中天然气有机母质主要来源于以陆生高等植物为主要母源的湖相沉积环境;伽马蜡烷也出峰明显,说明其沉积的水环境主要为高盐特征;正构烷烃C_(31)/C_(29)的比值表明这一期间的气候条件为寒冷干燥。     

Molecular source of biomarkers by genetic engineering techniques

The mutant lacking ORF469 fragment inSynechocystis sp. PCC 6803 (cyanobacterium) was created by means of DNA recombination. In its genome,ORF ₄₆₉, the key DNA fragment controlling the light-independent pathway of chlorophyll biosynthesis was deleted and replaced by erythromycin resistance cassette. The operation resulted in the fact that the content of chlorophyll in mutant cells was fully controlled by illumination and two kinds of cells were harvested, one is high chlorophyll with concentration of 9.427 μg· mg⁻¹ and the other is low chlorophyll with concentration of 0.695 μg · mg¹. They were subjected to thermal simulation respectively at 300°C for 100 h. The alkanes biomarkers from pyrolysates were analyzed by GC-MS and main difference between high and low chlorophyll cells was found at their contents of isoprenoid hydrocarbons. Pr/nC₁₇ and Ph/nC₁₈ from pyrolysate of low chlorophyll cells were 0.192 and 0.216 respectively, which were about 1/3 and 1/7 of that from high chlorophyll cells. The results provide direct evidence that isoprenoid hydrocarbons such as phytane(Ph) and pristane (Pr) could be derived from chlorophyll. The lipids in algal cells would be the most important contributors to hydrocarbon production in their thermal degradation. The results also indicated that the combination of molecular biology and organic geochemistry would provide a new path to investigate the molecular sources of biomarkers.     

鄂尔多斯盆地姬塬地区长8油源分析

长8油层组是鄂尔多斯盆地姬塬地区最为有利的油气聚集层位之一,本文分析了姬塬地区长8油藏的甾萜烷生物标志化合物特征,探讨了原油成因,并进行油源对比。研究结果表明,原油δ13CPDB值介于-31.11%～-31.57%,与盆地中生界各产层湖相油型油一致。藿烷以C30藿烷占优势,位于北东运聚带上的原油含较高的C29藿烷,18a（H）-30-降新藿烷（C29Ts）次之,重排藿烷和伽马蜡烷含量较低;位于南西运聚区带上的原油C30重排藿烷相对丰度较高,C30重排藿烷与C29降藿烷的比值高（〉1.0）。甾烷中：规则甾烷含量高,含一定量的孕甾烷、升孕甾烷和重排甾烷,aβ和βa构型甾烷丰富,aaa-20R构型甾烷呈不对称＂V＂型分布。油源对比显示,姬塬地区长8油藏的原油形成于弱还原-弱氧化,淡水,微咸水环境,主要来自于长7油层组烃源岩。     

东濮凹陷西部斜坡带混合原油地球化学特征

东濮凹陷西部斜坡带原油地球化学特征同凹陷内其他地区原油明显不同,而研究程度相对较低.系统分析了原油饱和烃、芳烃组成及生物标志物,研究结果表明:原油生油母质类型较好,以低等水生生物为主,陆源高等植物占次要地位;原油中伽玛蜡烷含量高,类异戊二烯烃呈植烷优势,表明源岩沉积环境为强还原的半咸化-咸化湖相;原油成熟度参数具有不一致性,表明原油并非是低熟油,应为混合原油,其主要来源于沙三段成熟烃源岩.     

Occurrence and significance of prist-1-ene in kerogen pyrolysates

A SERIES of acylic isoprenoid alkanes, of which pristane and phytane are typical, frequently occurs in crude oils, shales, coals, bitumens and so on. It is generally agreed that the primary source of these compounds is the phytyl side chain of chlorophyll(1,2) although the mechanisms of its incorporation into sediments and its subsequent diagenesis, are not completely understood. At present, little is known about the role of kerogen as a source, or sink, of isoprenoid moieties and we report here that the principal isoprenoid, obtained by the high temperature (600 degrees C) pyrolysis of kerogens has been identified as prist-1-ene.     

三水盆地的构造演化及油气地质特征

三水盆地的构造演化主要经历了裂陷、坳陷、沉陷和抬升四个发展阶段,发育了深湖一浅湖-河流三角洲型沉积层序,以泥岩、砂岩为主的沉积地层,具有良好的油气生、储条件.经野外露头剖面勘察和钻井岩性分析,下第三系布心组发育深湖、半深湖相泥岩、碳质泥岩和泥灰岩,是主要的烃源岩;布心组二段为湖泊极盛时期沉积,以暗色泥岩为主夹碳酸盐岩沉积,是盆地内主力生油岩系.根据烃源岩和地质构造特征,主要的含油气系统为布心组生、布心组和西布组储、布心组和西布组盖的生、储、盖组合,为具有一定勘探潜力和开采价值的含油气盆地.     

Composition of substituents on pyrrole ring of high-carbon-number geoporphyrins and its dealkylation

Geoporphyrins, isolated from source rock, were analyzed on electron ionization mass spectrometry (EIMS) and Tandem mass spectrometry (MS/MS). The spectrum of EIMS shows that the geoporphyrins are mainly composed of two types: DPEP and eito. Most of the porphyrin carbon numbers are greater than C₃₂. The daughter spectra of the molecular ions (C_34-36DPEPs) display the loss of methyl and ethyl groups, which indicate there are ethyl and propyl groups in the mother ions. The average condensed structural formulae, derived from the data of the spectra on MS/MS, have clearly shown the composition of the substituents on the porphyrin pyrrole ring, and the regular changes of the substituents reveal the characteristics of the dealkylation of the porphyrins in the geosphere.     

依兰油页岩分级萃取物分析

为分析油页岩的组成结构,完善其可分离分析方法,在温和条件下使用石油醚、甲苯、二氯甲烷和氯仿四种溶剂对依兰油页岩进行了分级萃取研究。实验结果显示：石油醚萃取物中以C15～C31,正构烷烃为主;甲苯萃取物中除了烷烃之外以苯、萘衍生物为主,其中烷烃中检出了生物标记物姥鲛烷和藿烷;二氯甲烷萃取物中检出的特征化合物为亚油酸、2,2-亚甲基双（4-甲基-6-叔丁基苯酚）和胆固醇;氯仿萃取物中2,2′－亚甲基双（4－甲基－6－叔丁基苯酚）的相对丰度很高。各级萃取物的GC／MS分析表明：采用分级萃取技术可以初步实现油页岩中成分的族分离,有利于萃取物的结构分析,且石油醚对正构烷烃具有良好的选择性、甲苯对芳香族化合物具有较好的选择性。     

油页岩粉尘层着火的理论模型与实验研究

为了解油页岩粉尘着火爆炸危险性,利用化学反应动力学、传热学以及Thomas热自燃理论,建立了稳态条件下粉尘层着火的不对称理论模型.利用热板测试装置测试了我国4大产地油页岩粉尘层的最低着火温度,结果介于503~613 K,最低着火温度随粉尘层厚度的增加而降低,不同产地油页岩粉尘着火温度高低依次为:抚顺桦甸龙口茂名,与油页岩挥发分含量成反相关.利用测试结果确定了油页岩粉尘层燃烧动力学参数值,代入不对称着火理论模型,计算得到相应厚度粉尘层的临界着火温度,和实验结果对比,误差在10%以内,为预测生产过程油页岩着火危险性提供了可行的理论方法.     

内蒙古乌达地区上古生界不同沉积环境煤系烃源岩分子地球化学特征及意义

内蒙古乌达地区上古生界煤系烃源岩主要在海陆过渡相和陆相沉积环境的控制下沉积而成。精选出五种沉积环境下形成的煤系烃源岩样品,深入研究其分子地球化学特征。研究表明,泛滥平原形成的烃源岩以高氧芴、高姥鲛烷、高C29规则甾烷、高C19三环萜烷和高C24四环萜烷为主要特征;河控三角洲除氧芴含量稍低,具有和泛滥平原沉积环境相似的地化特征;潮坪和泻湖相的烃源岩中伽马蜡烷、植烷含量均较高,C26+三环萜烷丰度相对较高,三环萜烷绝对浓度大,规则甾烷以C27占优势,硫芴含量相对较丰富;潮控三角洲除Pr/Ph较高外,其余生物标志物特征与潮坪、泻湖环境下的烃源岩相似。     

东濮凹陷北部沙三段泥页岩岩相特征

东濮凹陷北部沙三段泥页岩厚度大、分布广,具有良好的页岩气生烃潜力;但陆相湖盆泥页岩非均质性强,不同岩相生烃能力和储集性能差异较大。为厘清不同岩相的含油气性特征,通过偏光显微镜、X衍射等手段研究泥页岩微观岩相类型,发现东濮凹陷北部沙三段主要发育块状粉砂质泥岩相、纹层状膏质泥岩相、纹层状灰质泥岩相三种典型岩相及多种过渡岩相。通过对比不同泥页岩相地球化学特征、荧光特征、试油试气数据,发现深湖-半深湖环境中的纹层状灰质泥岩相是页岩油气赋存的优势岩相。     

干酪根热解平行反应模型中表观活化能与视频率因子的关联

本文考察了三种类型干酪根以及抚顺和茂名油页岩热解反应的动力学特性,对由平行反应模型所求得的表观活化能及视频率因子进行了数学关联。关联式表明,视频率因子的对数值与表观活化能成一直线关系。由此关系可以推出,所有平行反应在某一特定温度下具有一个相同的反应速率常数。根据直线的斜率,还可以比较不同类型干酪根热降解反应的难易程度。     

准噶尔盆地陆梁油气田原油的生物降解特征及其成藏意义

准噶尔盆地陆梁油气田原油的生物降解现象具有较强的规律性,白垩系吐谷鲁群原油既表现了轻微-中等的生物降解(饱和烃分布不完整)特征,又表现了严重的生物降解(存在25-降藿烷)特征;侏罗系西山窑组X1段原油同时表现了无生物降解(饱和烃分布完整)和严重生物降解的特征,而X4段原油无任何生物降解.轻微-中等生物降解原油的凝固点和含蜡量明显降低而密度有所增大.严重生物降解原油的生物标记物分布特征表明,Ts,C29重排藿烷和伽马蜡烷具有较强的抗生物降解能力,C27规则甾烷抗生物降解的能力强于C28规则甾烷.根据原油的生物降解特征,推测白垩系和侏罗系油藏都是异地油藏破坏后再运移聚集的结果.     

太湖梅梁湾不同沉积物对3种沉水植物生长的影响

在人工栽培的条件下,研究了太湖重污染区梅梁湾2种不同沉积物（湖泥、岸泥）对苦草（Vallisneria natans （Lour．）Hara）、黑藻（Hydrilla verticillata （Linn．f．）Royle）、马来眼子菜（Potamogeton malaianus Miq．）3种沉水植物生长的影响．在上覆水相同条件下,湖泥中培养的3种沉水植物均生长良好,生物量高,分枝较多,其中苦草最为显著,生长在湖泥中的苦草比岸泥中的植株高,且提前发育成熟至生殖生长阶段;在湖泥中,3种沉水植物的叶绿素含量均较高,苦草在2种不同沉积物中的差别最大,叶色区别明显;在湖泥中,苦草、黑藻的根长及根系活力等指标均高于岸泥,但岸泥中的根较为粗壮,根数相对较多．试验结果表明：苦草、黑藻、马来眼子菜3种沉水植物能够适应梅梁湾湖泥的肥沃底质条件,生长发育正常,可以进行现场引种栽培试验．     

Uncovering the Neoproterozoic carbon cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter. Neoproterozoic carbonate records contain unusual and large negative isotopic anomalies within long periods (10-100 million years) characterized by δ(13)C in carbonate (δ(13)C(carb)) enriched to more than +5 per mil. Classically, δ(13)C(carb) is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments, which can be linked to oxygen accumulation through the stoichiometry of primary production. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of δ(13)C(carb) and δ(13)C in organic carbon (δ(13)C(org)) will covary, offset by the fractionation imparted by primary production. The documentation of several Neoproterozoic δ(13)C(carb) excursions that are decoupled from δ(13)C(org), however, indicates that other mechanisms may account for these excursions. Here we present δ(13)C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple δ(13)C(carb) excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret δ(13)C(carb) anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals.     

Thermal cracking of n-octodecane and its geochemical significance

The mechanism of carbon isotopic fractionation for gaseous hydrocarbons is revealed by investigating the residual liquid hydrocarbons in laboratory pyrolysates of n-octodecane. The results indicate that cracking and polymerization in the relatively low temperatures and dispropor-tionation reactions leading to light hydrocarbons and pol-yaromatic hydrocarbons at high temperatures are probably causes for the carbon isotope reversal of gaseous hydrocarbons that is commonly observed in pyrolysis experiments. This study provides significant insight for quantitative modeling of natural gas δ13C values and aid in the identification and assessment of natural gases derived from oil cracking.     

抚顺煤田始新统沉积演化及其对煤和油页岩发育的控制

通过野外露头测量、沉积特征分析、沉积相恢复、孢粉组合和地球化学数据对比,对抚顺煤田始新统沉积演化过程及其对煤和油页岩发育的控制作用进行研究。结果表明:抚顺煤田始新统从古城子组扇三角洲和沼泽环境开始,经历了计军屯组浅湖和半深-深湖环境,最终演化为西露天组旋回性沉积;古城子组煤层主要在气候温暖潮湿、河流输入持续增加的淡水沼泽环境中沉积;计军屯组油页岩主要在气候向寒冷干燥条件转化、河流输入减少、水体变咸的半深-深湖环境中沉积;贫矿油页岩作为煤到富矿油页岩的过渡层位显示了高等植物和水生有机质双重输入的特征;煤和油页岩沉积条件的不同造成有机质母质来源的差异和水介质条件的改变,引起与油页岩共生煤系的"富氢化"和生油潜力的增大。     

MnO_4~－／MnO_4~（2－）间接电氧化油页岩制取有机羧酸

用ＭｎＯ４－／ＭｎＯ４１２－间接电氧化体系对黄县油页岩的氧化条件及产物进行了研究。实验结果表明此过程可在室温下进行，并大大节省了ＫＭｎＯ４的消耗。氧化产物中的水溶酸主要由Ｃ６～Ｃ２８的饱和脂肪族二元酸和Ｃ８～Ｃ３１的饱和脂肪族一元酸组成。氧化过程中固体燃料残渣的ＦＴ－ＩＲ分析表明，油页岩有机质的脂肪族结构优先被氧化。     

铜川地区油页岩地层电性断面特征及勘查

为了研究电阻率测深方法在油页岩地区的适用性及分辨率,在鄂尔多斯盆地南缘铜川地区开展了电阻率测深
工作。结合钻孔录井和见矿情况,分析了油页岩地段两种勘查方法获得的电阻率断面特征,在电性断面上圈定了油页
岩层的特定部位。油页岩层厚度相对埋深而言属薄层、高阻目标体,其厚度与埋深纵向比小,在获得的电阻率测深断
面上,高阻电性的油页岩层在电阻率测深断面上分辨率不清晰,其层位与电阻率等值线梯度变化带对应较好,从而间
接指示了油页岩层位置。同时,通过岩性与测井参数综合分析,认为测深断面上这种电阻率值随深度的渐变特征,从
电性角度描述了油页岩层由浅湖沉积环境到半深湖环境的变迁过程,提出电阻率测深方法可以达到勘查油页岩层之
目的。