Crude-oil biodegradation via methanogenesis in subsurface petroleum reservoirs

Biodegradation of crude oil in subsurface petroleum reservoirs has adversely affected the majority of the world's oil, making recovery and refining of that oil more costly. The prevalent occurrence of biodegradation in shallow subsurface petroleum reservoirs has been attributed to aerobic bacterial hydrocarbon degradation stimulated by surface recharge of oxygen-bearing meteoric waters. This hypothesis is empirically supported by the likelihood of encountering biodegraded oils at higher levels of degradation in reservoirs near the surface. More recent findings, however, suggest that anaerobic degradation processes dominate subsurface sedimentary environments, despite slow reaction kinetics and uncertainty as to the actual degradation pathways occurring in oil reservoirs. Here we use laboratory experiments in microcosms monitoring the hydrocarbon composition of degraded oils and generated gases, together with the carbon isotopic compositions of gas and oil samples taken at wellheads and a Rayleigh isotope fractionation box model, to elucidate the probable mechanisms of hydrocarbon degradation in reservoirs. We find that crude-oil hydrocarbon degradation under methanogenic conditions in the laboratory mimics the characteristic sequential removal of compound classes seen in reservoir-degraded petroleum. The initial preferential removal of n-alkanes generates close to stoichiometric amounts of methane, principally by hydrogenotrophic methanogenesis. Our data imply a common methanogenic biodegradation mechanism in subsurface degraded oil reservoirs, resulting in consistent patterns of hydrocarbon alteration, and the common association of dry gas with severely degraded oils observed worldwide. Energy recovery from oilfields in the form of methane, based on accelerating natural methanogenic biodegradation, may offer a route to economic production of difficult-to-recover energy from oilfields.     

Biological activity in the deep subsurface and the origin of heavy oil

At temperatures up to about 80 degrees C, petroleum in subsurface reservoirs is often biologically degraded, over geological timescales, by microorganisms that destroy hydrocarbons and other components to produce altered, denser 'heavy oils'. This temperature threshold for hydrocarbon biodegradation might represent the maximum temperature boundary for life in the deep nutrient-depleted Earth. Most of the world's oil was biodegraded under anaerobic conditions, with methane, a valuable commodity, often being a major by-product, which suggests alternative approaches to recovering the world's vast heavy oil resource that otherwise will remain largely unproduced.     

Biodegradation of oil in uplifted basins prevented by deep-burial sterilization.

Biodegradation of crude oil by bacterial activity--which has occurred in the majority of the Earth's oil reserves--is known to reduce greatly the quality of petroleum in reservoirs. For economically successful prospecting for oil, it is therefore important to understand the processes and conditions in geological formations that lead to oil biodegradation. Although recent studies speculate that bacterial activity can potentially occur up to temperatures as high as 150 degrees C (refs 3, 4), it is generally accepted that effective petroleum biodegradation over geological timescales generally occurs in reservoirs with temperatures below 80 degrees C (ref. 2). This appears, however, to be at odds with the observation that non-degraded oils can still be found in reservoirs below this temperature. Here we compile data regarding the extent of oil biodegradation in several oil reservoirs, and find that the extensive occurrence of non-biodegraded oil in shallow, cool basins is restricted to those that have been uplifted from deeper, hotter regions of the Earth. We suggest that these petroleum reservoirs were sterilized by heating to a temperature around 80-90 degrees C during deep burial, inactivating hydrocarbon-degrading organisms that occur in the deep biosphere. Even when such reservoirs are subsequently uplifted to much cooler regions and filled with oil, degradation does not occur, implying that the sterilized sediments are not recolonized by hydrocarbon-degrading bacteria.     

包气带土层中重质油的生物可降解性

通过投加高效微生物和半腐熟堆肥材料 ,改善微生物生态环境 ,促进重质油的生物降解。利用 Soxhlet抽提重量法评价重质油污染土层生物修复的进程 ,并探讨了微生物活性与石油污染物生物降解之间的关系。结果表明 ,重质油生物降解的半衰期长 ,经过 90 d,生物降解量仅占总量的2 0 %。微生物计数和脱氢酶活性与石油污染物生物降解之间存在良好的相关性 ,表明了微生物量和脱氢酶活性是油污土层生物可修复性的良好评价指标     

Influence of biodegradation on benzocarbazole distributions in reservoired oils

Partition coefficient difference of benzocarba-zole isomers between oil, water and mineral phase makes them auseful indicator to quantify petroleum migration distance. Because of their nitrogen-heteroatom andannelated aromatic cycles they are generally regarded asbeing more resistant and the effects of biodegradation ontheir concentrations and distributions have not previouslybeen investigated. Reservoir extracts from three wells lo-cated in the Leng43 block of the Liaohe Basin were analyzed to investigate their occurrence and the effect of biodegrada-tion. Both hydrocarbon biomarkers and benzocarbazole isomers show systematical changes with the increase extent of biodegradation in study columns. Carbazole compounds may be biodegraded in a similar way to that observed in aliphatic and aromatic hydrocarbons. The distance from oil water contact is a primary control factor for biodegradation. The concentrations of benzocarbazole isomers show a slight increase in the upper part of the columns then a sharp de-crease towards oil water contact (OWC). Among three iso-mers benzo[a]carbazole seems more susceptible to biode-gradation than other two isomers and benzo[b]carbazole has higher ability to res ist bacterial attack. Benzo[b]carba-zole/benzo- [a]carbazole ratios can sensitively indicate the degree of biodegradation and the benzocarbazole index (BCratio) cannot be directly used as a migration indicator inbiodegraded oils.     

渤南洼陷深层(沙四段)油气成藏模拟实验研究

综合渤南洼陷实际地质资料,认为渤南洼陷深层具备油气成藏条件,并总结出两种深层油气成藏模式,即自生自储型和上生下储型成藏模式,后者主要以侧向供烃方式为主.借助物理模拟实验对油在两种成藏模式中的充注、运聚过程进行了研究.实验表明,储层物性特别是渗透率是影响油能否充注到储层中的关键因素;储层中的含油饱和度主要受充注压力、注油量的影响,并随其增大而增大,但不超过60%;储层物性只对含油饱和度增长速率影响较大,但对其大小的影响不大;储层物性影响油运移过程中的受力情况,从而限制了油在储层中的运移方向,最终影响油的聚集程度———含油饱和度的增长.     

Constraints on the diversity of crude oil types in the Lunnan Oilfield, Tarim Basin, NW China

Hydrocarbons, include heavy oils, normal oils, waxy oils and light oils, condensate oils and gases were all found in Lunnan Oilfield, the occurrences of hydrocarbons with complicated physical properties indicates a complicated distribution of reservoirs. By the drilling data, the distribution pattern had been found that, in plan view, the density of crude oils in the western part is heavier than that of oils in the eastern part in Lunnan region, namely the crude oils were mainly found in the western part while the natural gases were mainly found in the eastern, which shows that an obvious differentiation in the east and west part was presented in the Lunnan region. Furthermore, in vertical view, the light hydrocarbons were mainly found in the Carboniferous reservoir while the heavier hydrocarbons were mainly found in the Ordovician and Triassic reservoirs. By analysis of the semi-logarithm distribution of n-alkanes, biomarker ratios and stable carbon isotopic compositions of crude oils, we have found that two oil families and discontinuous distribution were presented in hydrocarbons in Lunnan Oilfield. This kind of discontinuous distribution of geochemical parameters was not from continuous fractionation in migration process. The biodegraded heavy oil reservoirs in western part belong to the lower matured oil family, while the light or condensate oils reservoirs belong to higher matured oil family. Thus, a mixed filling of hydrocarbons was occurred in the middle part in Lunnan Oilfield and resulted in the occurrence of waxy oil. The mixed filling model may help to explain the distribution pattern of hydrocarbon reservoirs in Lunnan Oilfield, especially can lead to a relatively consistent explanation for all kinds of geochemical data, such as physical properties, pyrrolic nitrogen compounds, biomarker parameters and stable carbon isotopic compositions.     

沉积盆地岩性地层圈闭成藏主控因素分析

随着世界油气勘探技术的发展和理论研究的不断深入,在新发现的油气藏中岩性地层油气藏无论是产量还是储量上都占有重要地位.因此,对这类油藏的理论研究一直是国内外石油地质学家研究的重要内容.本文认为岩性地层圈闭与构造圈闭在成藏条件和成藏机制方面存在一定差别,岩性地层圈闭的形成条件复杂,决定了其成藏主控因素具有自身的特点.提出了岩性地层圈闭成藏“四元主控”观点:即运移通道条件、流体动力条件、储层临界物性特征和砂体封闭条件.这4项主控因素控制和决定了岩性地层油气藏的形成.     

济阳坳陷孤岛潜山油气充注特征

岩心观察、录井资料和有机地球化学分析表明,孤岛潜山曾有过两期油气充注.早期充注的油藏受到了强烈的生物降解作用改造,绝大多数样品中均存在25-降-17α,21β-藿烷.晚期所充注的油藏未受到生物降解作用的改造.早期和晚期所充注的油藏流体分别来自于沙三段和沙一段烃源岩.已成藏于古潜山中的油藏受到改造和破坏后,先存油藏向上运移聚集到上覆不同层位的储层中,形成多层位充注和上部层位较下部层位油气相对富集的特征,使古潜山中不能形成规模性油气藏.     

轻中度生物降解作用对原油中烷基萘和烷基菲的影响

研究了辽河盆地冷东油田经生物轻中度降解原油族组分布特征,并根据饱和烃生物标志化合物特征对生物降解程度进行了划分.借助于定量GCMS分析技术,分别研究了萘系列和甲基菲异构体的抗生物降解能力.随着萘系列取代基的增多,其抗生物降解能力逐渐增强.在生物降解程度为四级时,甲基菲4个异构体的含量才出现较大的变化:9-MP的抗生物降解能力最强,3-MP、2-MP和1-MP的抗生物降解能力相当.计算了TMNr,TeMNr,MNR,DNR,TNR-2,TNR-1共6个地化参数,并计算出了相对应的成熟度Ro,Ro值要比实际值(0.25%～0.65%)稍偏高,TMNr与TeMNr、MNR与DNR之间的相关性很差,说明经微生物轻中度降解后的原油的地化参数发生了改变,不能用来计算成熟度.探讨了轻中度生物降解程度原油中甲基菲指数(MPI1和MPI2)的变化情况:在降解程度为三级以前该指数没有明显变化,当降解程度超过三级时呈现变小的趋势,所以使用该参数前要考虑原油是否经历过生物改造.     

油气地质二元论与石油工业可持续发展

目的 为了开拓油气勘探的思路，探索油气勘探的新领域。方法 从油气地质二元论的思想出发，论述了陆壳结晶基底的通道．块状结构、无机油气的生成和裂谷盆地的形成过程。结果 中地壳费．托合成反应形成的烃类和盆地中干酪根热解生成的烃类是油气的两种来源；大油气田在平面上受通道．块状结构控制，在剖面上受圈闭控制，即更多的油气富集在超基性岩通道上方的圈闭中。结论 油气地质二元论可成为石油工业可持续发展的理论基础。     

Natural Biological Attenuation of Benzene in Groundwater

IntroductionBenzene is a toxic contaminant often detectedin high concentration above the allowable limits ingroundwater beneath petro- chemical plants.Theprocesses for removing benzene from groundwaterinclude adsorption by activated carbon,airstripping,chemical oxidation,and biologicaldegradation[1] .Pumping the benzene out of theground and treating itexternally is commonly usedbutis expensive and requires long periods of time.The method of in situ biological degradation isthought to be cost- …     

厌氧微生物对新疆六中区稠油的降解特性

厌氧微生物作为油藏中微生物的重要组成部分,受到人们越来越多的关注,但是关于对原油的降解效果和降解机制的研究报道较少.对发酵菌富集培养物和产甲烷菌富集培养物作用前后的原油进行色质联用分析,结果表明:产甲烷菌富集培养物作用后的原油,其原油族组成变化明显,饱和烃和胶质相对含量降低,而芳香烃和沥青质相对含量上升,其中正构烷烃的含量有所增加,尤其是大于C22的正构烷烃的含量增加明显,藿烷及其同系物的含量也都有所上升.而发酵菌富集培养物作用后,饱和烃、芳烃以及胶质含量都略有上升,变化最明显的沥青质作用后下降了2%,发酵菌富集培养物降解了原油中的杂环芳烃二苯并噻吩和二苯并呋喃.同时两种富集培养物对二环芳烃的降解作用明显.产甲烷菌富集培养物和发酵菌富集培养物作用后,新疆六中区原油中短链正构烷烃含量相对增加,而长链正构烷烃含量则相对减少,∑nC21-/∑nC22+值由作用前1.033分别下降到1.023和1.015,Pr/Ph的值基本都保持在0.945左右,但是Pr/nC17和Ph/nC18都有所增大.总的来说,产甲烷菌富集培养物对原油的降解作用更明显,两种不同厌氧微生物的富集培养物对原油的作用表现出了一定的选择性.     

渤海湾盆地渤中凹陷深埋古潜山天然气成藏主控因素探讨

渤中凹陷钻探的两口科学探索井均在古生界潜山发现天然气流,其中科A2井经测试获日产天然气40.2×10~4m~3,揭示了渤海海域目前埋深最大、温度最高的古潜山天然气藏。根据渤中凹陷渤中21~22古潜山油气成藏条件和实际地质、测井和地震资料的综合解释,对研究区天然气成藏控制要素进行研究。结果表明:古潜山圈闭面积大,且具有完整背斜形态;深层沙四段—东三段发育大量优质高成熟烃源岩,油气源充足;古潜山储集空间为溶蚀孔洞和裂缝,储层物性较好;成藏要素匹配关系好,天然气具有明显的晚期持续充注成藏的特点。该古潜山气藏的发现,不仅是渤中凹陷深埋古潜山天然气勘探的重大突破,也是深埋古潜山油气成藏地质条件认识和勘探工程技术进步的重大成果,能够推动渤海海域乃至整个渤海湾盆地凹中深埋古潜山的油气勘探工作。     

青东凹陷沙河街组稠油成因及影响因素

青东凹陷西部和西南部边缘部位沙河街组广泛存在稠油油藏,目前在这些稠油的成因机制方面未开展深入研究,没有取得明确的认识,影响了研究区资源量评价和油气勘探进程。根据原油物理性质和生物标志物组成特征对研究区稠油的成因进行了综合分析。结果表明,研究区稠油中既存在有原生的低熟油,又分布有由次生作用（生物降解作用）产生的稠油,其中,低熟油主要分布在凹陷西南部的青东5井区;生物降解油主要分布在凹陷西部斜坡带及青东-青南过渡带,原油的降解等级为2~8级。原油的生物降解程度呈现出下轻上重、北轻南重的规律性变化。研究区稠油的形成与分布主要受有机质早期生烃、古地形、构造背景等因素影响。     

Pool-formation and secondary change of biodegraded viscous oils: Case study of reservoir section in the Zhengjia-Wangzhuang Oilfield, Jiyang Depression

It is demonstrated by various geochemical indexes that the Zhengjia-Wangzhuang Oilfield with viscous crude oil in the Jiyang Depression has been sourced from the contribution of matured source rocks in the upper Es4. The principal cause leading to the densification of crude oils would be biodegradation, with the degradation level of crude oils being ranked as 2-8; vertically, the biodegradation level increases from the top to bottom of the oil column, with a distinctive biodegradation gradient occurring. Calculated parameters of sterane, terpane and methyl-phenanthrene have indicated that the source-rock's maturity of crude oils and asphaltic sands ranges from 0.7 to 0.9, and based on the calculation of Easy Ro model, the temperature of hydrocarbon generation in the source rock would be within 120-140℃, which coincides with the measurements of reservoir inclusions. The measured homogenization temperature would represent the generation temperature of the source rock, and be fairly different from that of reservoir while being charged with hydrocarbons, which reflects the hydrocarbon-charging to be a fast process, and the period of pool-formation to be consistent with that of peaked generation. According to the evaluation of generation history, the pool-formation could have been occurring in 7-15 Ma. And the biodegradation of crude oils in the study area would be considered to take place in 4-15 Ma based on the examination of biodegradation order and dynamic calculations.     

Anaerobic benzene oxidation coupled to nitrate reduction in pure culture by two strains of Dechloromonas.

Benzene contamination is a significant problem. It is used in a wide range of manufacturing processes and is a primary component of petroleum-based fuels. Benzene is a hydrocarbon that is soluble, mobile, toxic and stable, especially in ground and surface waters. It is poorly biodegraded in the absence of oxygen. However, anaerobic benzene biodegradation has been documented under various conditions. Although benzene biomineralization has been demonstrated with nitrate, Fe(III), sulphate or CO2 as alternative electron acceptors, these studies were based on sediments or microbial enrichments. Until now there were no organisms in pure culture that degraded benzene anaerobically. Here we report two Dechloromonas strains, RCB and JJ, that can completely mineralize various mono-aromatic compounds including benzene to CO2 in the absence of O2 with nitrate as the electron acceptor. This is the first example, to our knowledge, of an organism of any type that can oxidize benzene anaerobically, and we demonstrate the potential applicability of these organisms to the treatment of contaminated environments.     

层序地层特征与油气成藏关系——以塔中4油田为例

 将层序地层学理论与油气成藏理论相结合,从层序特征、沉积体系和油气成藏条件等方面探讨了塔中4油田CI油组层序地层特征与油气成藏模式。综合利用地震、测井及岩心资料,开展塔中4油田CI油组层序地层学研究,将其划分为2个三级层序、5个准层序组、9个准层序。在层序地层格架内进行沉积特征研究,确立研究区发育潮坪和三角洲两类沉积体系。在层序及沉积特征研究基础上,对油气成藏的要素进行分析,确立沿断输导它源成藏模式。CI油组本身烃源岩不发育,油气主要来源于下覆奥陶和寒武统烃源岩。储集层主要分布在SQ1及SQ2的海侵体系域。油气从烃源岩中沿着大断裂向上运移到CI油组成藏,发育有岩性、断层-岩性及微背斜3种类型油气藏。     

芦苇修复新疆石油污染土壤效果

考察芦苇对新疆污染土壤石油烃的处理效能、石油烃对芦苇生长的影响及不同石油污染度条件下芦苇根际微生物数量的变化。研究结果表明:经过123 d的芦苇修复,石油烃去除率可到41.21%～62.14%,明显高于空白样(19.75%～37.92%),其中饱和烃去除效果最好,可达60.52%～73.11%;芦苇对原油污染具有较好的耐受性,在土壤石油污染率低于1.25%情况下能够有效促进土壤中石油烃的去除;芦苇根际土壤中微生物数量与原油降解率呈正相关关系,芦苇根际效应促进原油降解菌数量的增加和活性的增强;芦苇的修复以根际效应为主,芦苇根际恰当的微生物类群为土壤原油降解提供有利保障。     

Anaerobic oxidation of short-chain hydrocarbons by marine sulphate-reducing bacteria

The short-chain hydrocarbons ethane, propane and butane are constituents of natural gas. They are usually assumed to be of thermochemical origin, but biological formation of ethane and propane has been also observed. Microbial utilization of short-chain hydrocarbons has been shown in some aerobic species but not in anaerobic species of bacteria. On the other hand, anaerobic utilization of short-chain hydrocarbons would in principle be expected because various anaerobic bacteria grow with higher homologues (> or =C(6)). Indeed, chemical analyses of hydrocarbon-rich habitats with limited or no access of oxygen indicated in situ biodegradation of short-chain hydrocarbons. Here we report the enrichment of sulphate-reducing bacteria (SRB) with such capacity from marine hydrocarbon seep areas. Propane or n-butane as the sole growth substrate led to sediment-free sulphate-reducing enrichment cultures growing at 12, 28 or 60 degrees C. With ethane, a slower enrichment with residual sediment was obtained at 12 degrees C. Isolation experiments resulted in a mesophilic pure culture (strain BuS5) that used only propane and n-butane (methane, isobutane, alcohols or carboxylic acids did not support growth). Complete hydrocarbon oxidation to CO2 and the preferential oxidation of 12C-enriched alkanes were observed with strain BuS5 and other cultures. Metabolites of propane included iso- and n-propylsuccinate, indicating a subterminal as well as an unprecedented terminal alkane activation with involvement of fumarate. According to 16S ribosomal RNA analyses, strain BuS5 affiliates with Desulfosarcina/Desulfococcus, a cluster of widespread marine SRB. An enrichment culture with propane growing at 60 degrees C was dominated by Desulfotomaculum-like SRB. Our results suggest that diverse SRB are able to thrive in seep areas and gas reservoirs on propane and butane, thus altering the gas composition and contributing to sulphide production.