北京市西北城区大气可吸入颗粒物中饱和烃的分布特征

利用气相色谱、气相色谱-质谱分析法从北京市西北城区四个季节大气可吸入颗粒物（PM10）中检测出种类丰富的饱和烃,主要包括正构烷烃、萜烷及甾烷等系列化合物。利用饱和烃的多项参数（如主峰碳数、碳优势指数CPI、藿烷22S/(22S+22R)比值等）对大气PM10中可溶有机物的来源及分布作了探讨。北京市西北城区PM10中正构烷烃的主峰碳数均介于23和27之间,而CPI值介于1和3之间,表明北京市西北城区PM10中的饱和烃均不同程度地受到了高等植物等现代生物和化石燃料（石油、煤等）不完全燃烧产物两种来源的影响,其中在春、夏季以高等植物、花粉、微生物等生物来源占比重较大,而在秋、冬季,尤其在冬季,化石燃料的不完全燃烧造成的污染比较明显。萜烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃来自于石油等化石燃料的不完全燃烧。甾烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃是来自于车辆释放的机油等。     

济阳拗陷特殊生物降解油的初步研究

济阳拗陷草古100平19井奥陶系储层原油,饱和烃馏分均已损失殆尽,仅残余藿烷系列化合物;同时,芳烃馏分化合物也已损失殆尽,仅残余三芳甾烷系列化合物。上述芳烃化合物俱已损失殆尽的蚀变特征,在相关文献中的报道较为少见。原油中不受水洗作用影响的正构烷烃和不受生物降解作用影响的有机硫化合物(苯并噻吩和二苯并噻吩)均已损失殆尽,显然暗示了原油蚀变是遭受水洗作用和生物降解作用共同作用的结果。原油芳烃馏分的“UCM”鼓包幅度明显大于饱和烃馏分的“UCM”鼓包,暗示了芳烃化合物的降解速率平行甚至超过饱和烃的降解速率。原油中低分子量芳烃化合物的快速降解,暗示了油藏可能是在氧化条件下而非在还原条件下发生蚀变的。     

Carbon catalysed hydrogen exchange in petroleum source rocks

Exchange of carbon bound hydrogen has been observed when alkenes, saturated and aromatic hydrocarbons are heated at moderate temperatures on carbonaceous surfaces (activated carbon and coal). Isomerisation of alkenes and the formation of hydrogenated/dehydrogenated products from the saturated and aromatic reactants resulted. A suite of crude oils from the Carnarvon Basin (Western Australia) have been analysed with a view to comparing their relative abundances of structurally similar hydrocarbons. The consistent relationships between hydrocarbons in crude oils that are chemically related via hydrogenation/dehydrogenation reactions suggest that a hydrogen exchange process similar to that demonstrated in laboratory experiments occurs during crude oil formation in sedimentary rocks.     

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.     

Effect of water washing on hydrocarbon compositions of petroleum sandstone reservoir rocks in Tarim Basin, NW China

Gross compositions and distribution of saturated and aromatic hydrocarbons in Carboniferous sandstone reservoire rocks in oil and water zones for Tzhong-10 well of the Zhongyang Uplift in the Tarim Basin were studied in dteail by means of Rock-Eval Pyrolysis,thin-chromatograph-flame ionization detection(TLC-FID),gas chromatography,gas chromatography-mass spectrometry.The results suggest that the gross composition of reservoir hydrocarbons between the oil zone and the water zone show significant differences,Water wahing has a dramatic effect on saturated hydrocarbon blomarkers,especially drimane series compounds,Drimane series compounds in the water zone have been depleted completely.However,the contents of tricyclic iterpanes and pentacyclic triterpanes tend to decrease slightly,but the water-zone reservoir hydrocarbons contian a large amount of gammacerane.This suggests that gammacerane be more resistant to water washing than diterpanes and homohopanes.The contents of pregnane,homopregrane,diasteranes relastively decrease as a result of water washing.Water washing has a noticeable effect on polycyclic aromatic hydrocarbon compounds,especially aromatic sulfur compounds,and the contents of dibenzothiophene series compounds and benzonaplyiothipophene decrease significantly as a result of water washing.However,the conterts of bicyclic and tricyclic aromatic hydrocarbons decrase slightly and those of tetracyclic and pentacyclic aromatic hydrocarbons,especially benzofluoranthene and benzopyrenes,increase markedly owing to adecrease in light aromatie hydrocarbons as a result of water washing.     

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.     

河床含水系统对单环芳烃净化特征室内模拟

为了模拟长期排污河流中单环芳烃在地表水-地下水系统迁移转化规律以及不同含水介质和水动力条件对单环芳烃的净化特征, 室内土柱实验采用3种有代表性的天然砂土为研究对象, 以生活污水模拟纳污河流, 实验历时5个月.单环芳烃的自然净化作用主要发生在河床底下0.4m内, 垂直向下单环芳烃各组分浓度呈由高到低的分布特征; 粗砂对苯、甲苯和单环芳烃总量(TBETX) 总净化率分别为32.06%、21.39%和27.13%;中砂1分别为76.26%、81.40%、87.99%;中砂2分别为68.94%、74.41%、81.69%, 这表明, 河流污染初期河床底含水介质完全饱水, 含水介质颗粒尺寸越大, 对单环芳烃的净化率就越低, 单环芳烃容易迁移进入地下水中; 随着时间的延长, 河床底部淤泥层不断增加, 砂层中的水流处于非饱和状态, 淤泥层和含水介质系统对单环芳烃的净化能力较饱水流时大, 单环芳烃不容易迁移进入地下水.      

松粉热解脂肪酸生物标志物的特征及其地球化学意义

现代松粉的温－压热模拟实验中，产出的轻质烃和氯仿抽提物芳烃馏份的GC－MS分析均检出大量偶数碳优势明显的脂肪酸类分子生物标志物，轻烃主要为C16，C18烷酸及其甲，乙酯，芳烃组分相对比较复杂，包括饱和脂肪酸（酯），不饱和脂肪酸（酯）和脂肪酸内酯，前者碳数分布为C15－，C30，C16，C18碳酸（酯）相对丰度占绝对优势为特征，后者碳数分布为C20-C30,以C26，C28和C30脂肪酸内酯为主，在250℃以下样品中检测出相对丰度较高的不饱和C18碳酸（酯），脂肪酸酯化合物在极低的温度条件下便可排出，并分别在200－300℃和300－400℃之间形成两次产出高峰；花粉内质体中的游离态脂肪酸及不饱和脂肪酸形成低温阶段的第一次高峰；花粉壁脂质结构中的脂肪酸及饱和脂肪酸在较高温度阶段形成第二次高峰，原样及低温样品以脂肪酸酯为主，250℃及其以上温度条件下因水解产生较多的脂肪酸，随温率继续升高，脂肪酸酯易发生脱羰反应而生成链烷烃。400℃以后因强烈降解脂肪酸酯含量大大降低，这与350－450℃之间奇数碳优势正构烷烃在轻质烃和饱和烃中的大量产出相吻合，研究表明，植物花粉是沉积有机质中饱和及不饱和C16，C18脂肪酸酯的重要母源之一。     

Geochemical Characteristics and Their Geological Significance of the Sterane in the Crude oil of Chang 2 Oil Group in Yanchang Formation in Xifeng area,Ordos Basin

Xifeng area is a key oil and gas exploration and development area in the Ordos Basin. The Chang 2 oil group of Yanchang Formation is an important replacement oil‐bearing horizon in this area. The sterane compounds in the saturated hydrocarbons of crude oil contain abundant geochemical information and can reflect the source of parent materials and the maturity of crude oil, so they are important information carriers for oil source correlation(Huang et al., 1991; Duan, et al., 2001). In this paper, the crude oil samples were systematically collected from the reservoirs of Chang 2 oil group in 10 production wells in Xifeng area and the group compounds of crude oil were separated. The separated saturated hydrocarbon components were tested by chromatography‐mass spectrometry (GC‐MS) and the sterane compounds were identified and analyzed. The geochemical characteristics of the sterane in the saturated hydrocarbons of crude oil and their geological significance could provide a scientific basis for the oil source correlation of Chang 2 oil group at late stage.     

The genesis of the asphalt in the Dead Sea area

The hydrocarbon occurrences of asphalts, heavy oils and oil shales in the Dead Sea area and the possible genetic relation between them have been studied. The similarity in organochemical characteristics, i.e., the elemental composition of asphaltenes, the distribution pattern of the saturated hydrocarbons and the predominance of V (over Ni)-porphyrins in both the oils and the asphalts indicate a close relation between them. On the other hand, dissimilarities in the same organochemical characteristics in both the asphalts and the oil shale exclude the hypotheses that asphalt was generated and expelled from the oil shales or that the shales were contaminated by oils. Water washing and biodegradation are considered to be the processes through which preferential depletion of hydrocarbons occurred, altering the oils to asphalts. The burial of the degraded asphalt to a relatively great depth resulted in a secondary generation of small amounts of light saturated hydrocarbons in these asphalts. The oils, which are thought to be the precursors of the asphalts, have either been flushed into the Dead Sea depression from the surrounding elevated areas or have seeped upwards from deep local accumulations in the graben.     

藏北羌塘盆地羌资1井中侏罗统沥青脉生物标志化合物分布特征及其意义

藏北羌塘盆地羌资1井中侏罗统沥青脉生物标志化合物含有丰富的正烷烃、类异戊二烯烷烃、萜类化合物和甾类化合物。正烷烃图谱形态以单峰形态占优势,主碳峰以nC16、nC17为主,次为nC18、nC20、nC15轻烃组分占有绝对优势,OEP值介于0,69-1．22之间,平均值为0．96,偶碳数优势不明显;Pr／Ph值介于0．35～0．78之间,平均值为0．59,具有明显的植烷优势。萜烷相对丰度表现为五环三萜烷〉三环萜烷〉四环萜烷,γ-蜡烷普遍存在,但相对含量棱低;甾烷主要为规则甾烷,少量孕甾烷,规则甾烷∑（C27＋C28）〉∑C29,∑C27／∑C29介于0．61～2．18之间,平均值为1．06,显示弱的C27甾烷优势或弱的C29甾烷优势。有机质母质构成中,除有丰富的藻类等低等水生生物外,可能还有陆生高等植物输入混合。成熟度参数和镜质体反射率均显示沥青脉中的有机质处于成熟一过成熟阶段。沥青脉形成环境为还原环境。另外,除饱和烃和芳烃含量上有明显差别外,中侏罗统夏里组砂泥岩中的沥青脉与布曲组碳酸盐岩中的沥青脉的生物标志化合物无明显区别。     

Thermal reactions of kerogen with added water, heavy water and pure organic substances

Finely divided samples of the Messel shale that had first been extracted with organic solvents were subjected to pyrolysis at 330°C for 3 days in the presence of excess water or heavy water and also with added pure organic substances. About 8% of the organic carbon was converted into an assemblage of saturated hydrocarbons that closely resembled petroleum hydrocarbons. No olefins were observed in the products. When the reaction was performed in heavy water, extensive deuteration occurred. The extent of substitution and the position of heavy hydrogen in a variety of hydrocarbon structural types were measured by mass spectrometry. A control experiment in which a saturated hydrocarbon was added showed that this deuterium substitution was not due to simple homogeneous exchange.A mechanism for the production of polydeuterated hydrocarbons is advanced, based on a model wherein the molecular fossils that are chemically bonded into kerogen matrix are released as free radicals. During the subsequent chain reactions, migration of olefinic bonds in intermediates and attack by deuterium free radicals result in multiple deuteration with retention of the carbon skeleton of the molecular fossil.     

塔北隆起深层海相油藏中原油及族组分碳同位素组成的纵向分布特征及其地质意义

利用MAT252同位素质谱仪分析了塔里木盆地塔北隆起深层海相油藏中原油及族组分的碳同位素组成。研究表明该区深层海相油藏中原油的全油碳同位素组成主要受生源控制,受热力作用影响较小;而在继承生源的碳同位素组成的基础上,热力作用将对原油族组分的碳同位素组成及其逆转和分馏产生重要影响。总的趋势是随着油藏埋藏深度的增大和热力作用的加强,饱和烃组分的碳同位素组成逐渐变重,而沥青质组分的碳同位素组成不断变轻,族组分碳同位素逆转程度和分馏程度有所加强,并出现饱和烃﹥芳烃﹥非烃﹥沥青质的整体逆转现象。塔北隆起深层海相原油族组分的碳同位素组成的纵向变化特征,可以反映出热力作用对原油稳定性的影响。     

含铀物质对有机质生烃的实验研究

采用密闭容器水热模拟实验方法,考察含铀物质对有机质热解生烃过程的影响。对热模拟实验产物分析发现,在暗色泥岩和煤岩样品中加入含铀物质后,气态烃和液态烃的生烃量都有比较明显的增加。其中煤岩的气态烃产量平均增加值为34%,而泥岩样品平均增加值也达到了30%以上。液态烃产率分析表明,含铀矿物也促进了泥岩和煤岩的液态烃产率。从泥岩氯仿沥青‘A’族组成分析表明,加入催化剂后泥岩的饱和烃和芳烃在高温阶段具有规律性的明显增大的趋势,反映出非烃和沥青质,甚至不溶有机质向相对稳定的饱和烃转化以及芳烃随演化程度增加的高聚合作用。综合以上分析,认为放射性铀对油气生成具有氧化催化作用。     

原油生物降解模拟实验及其定量化评价

利用筛选到的优势烃降解复合菌(I菌)对大庆油田3口不同油井的油(西5-P10、三元后和G1131-262)进行不同时间的降解实验和全油GC-MS定量分析,探讨饱和烃、芳烃化合物分布情况变化。实验研究表明I菌为高效烃降解菌;相同微生物对此3种不同原油的降解能力存在明显的差异,所以烃污染现场生物修复试验需要根据不同原油性质选择不同的高效降解菌;对于饱和烃和芳烃生物降解的顺序既有对过去结论的验证又提出新的看法。藿烷的降解在重排甾烷之后,萘比菲先开始降解,三甲基萘比三甲基菲更早开始遭受生物降解,三甲基和四甲基萘在深度生物降解后会达到一个平衡,之后的降解速度减慢。当生物降解到一定阶段,抗生物降解能力强的多环芳烃富集会加重对环境的毒害,因此,多环芳烃降解菌或萘、菲降解菌等特效菌是未来烃污染环境修复工作的重点。     

Saturated and aromatic diterpenoids and triterpenoids in Eocene coals and mudstones from China

Several series of saturated, diaromatic, triaromatic C-ring cleaved and triaromatic diterpenoids and triterpenoids have been detected in 4 immature coal and mudstone samples. A number of these compounds appear to represent intermediates in a series of postulated pathways for progressive aromatization of biogenic diterpenoids and triterpenoids. Diagenetic pathways for the formation of tricyclic aromatic hydrocarbons from abietane and pimarane type diterpenoid precursors and for the formation of diaromatic, triaromatic C-cleaved and triaromatic hydrocarbons from β-amyrin and other triterpenoid precursors are proposed. Saturated and aromatized abietanes, pimaranes and phyllocladanes, which are the most abundant compounds in all 4 samples, indicate a predominant higher plant input which can be related to the Coniferales group but not to individual plant families. β-Amyrin and other triterpenoid-derived triaromatic and triaromatic C-ring cleaved hydrocarbons with triterpenoid structures are thought to be characteristic for angiosperms. The relative concentrations of the triaromatic and triaromatic C-ring cleaved hydrocarbons are higher in samples 9602 (mudstone) and 9603 (coal) than samples 9601 (coal) and 9604 (mudstone) indicating samples 9602 (mudstone) and 9603 (coal) contain relatively more angiosperm derived organic matter than samples 9601 (coal) and 9604 (mudstone). The distribution patterns and the relative concentrations of saturated and aromatic diterpenoids and triterpenoids thus are valuable markers for the determination of the relative contents of biological sources of organic material in geological samples.     

Stable hydrogen isotope measurement of archaeal ether-bound hydrocarbons

Compound-specific hydrogen isotope analysis of ether-bound isoprenoid hydrocarbons from archaeal membranes has been developed using chemical degradation and gas chromatography/pyrolysis/isotope ratio mass spectrometry. The ether-bound hydrocarbons are quantitatively converted to saturated hydrocarbons by cleavage of ether bonds with HI followed by H₂ reduction in the presence of PtO₂. The δD value of ether-bound hydrocarbon moieties are corrected by way of isotopic mass balance calculation for the hydrogen incorporated during the hydrogenation. The method was successfully applied to determination of the δD values of biphytane moieties in glycerol dialkyl glycerol tetraethers (GDGTs) from a Sulfolobus sp. culture and a marine sediment.     

ASE3OO与快速索氏抽提仪处理沉积岩样品的地化参数对比

本文对加速溶剂萃取仪(ASE300)和快速索氏抽提仪提取的氯仿沥青“A”及由其分离出的饱和烃、芳烃、胶质和沥青质组分做了详细对比.结果表明:多数情况下ASE300抽提出的氯仿沥青“A”的量比快速索氏抽提仪抽提出的量略多,主要是胶质和沥青质量的增加;不同抽提装置得到的饱和烃和芳烃组分的色谱-质谱谱图高度一致,定量结果的相对偏差在5％以内.各组分的稳定碳同位素分析精度±0.5‰.所有的地化参数表明ASE300完全可以替代快速索氏抽提仪,从而降低消耗、提高分析效率.     

Mathematical models for petroleum-forming processes: n-paraffins and isoprenoid hydrocarbons

Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.