页岩气赋存动态演化模式及含气性定量评价

与常规天然气相比,页岩气具有特殊的赋存形式,并且吸附、游离和溶解三种赋存形式的含量差别较大。为评价不同沉积环境、不同成熟度下页岩气赋存形式及其含气能力的差异性,选取了鄂尔多斯盆地延长组低成熟页岩和四川盆地龙马溪组高成熟页岩样品进行对比研究。通过对这些样品开展镜质体反射率测定、TOC含量分析、场发射扫描电镜观察、低温氮气吸附、甲烷等温吸附等实验,定性分析了页岩气在孔隙空间中的赋存状态及赋存机理,定量计算了不同赋存状态页岩气的含量,并结合不同页岩的热演化程度、孔隙空间变化特征和含气量变化规律,建立了页岩气赋存形式动态演化模型。研究结果表明,不同热演化阶段,页岩气的赋存形式差异较大。对低成熟的延长组页岩而言,吸附气含量约占58%,游离气占32%,溶解气占10%,具有"吸附气为主,游离气次之,溶解气不可忽略"的特征;而对高过成熟的龙马溪组页岩而言,游离气含量约占51%,吸附气含量占48%,溶解气仅占1%,具有"游离气和吸附气共同主导"的特征。随着热成熟度的增加,生成的页岩气首先满足页岩表面的饱和吸附和部分溶解,再以游离态的形式存在于孔隙之中,最后吸附气和游离气处于动态平衡,该过程分别对应吸附、孔隙充填、裂缝充填和聚集成藏四个赋存演化阶段。结合页岩气藏的生产特征认为,延长组页岩气是吸附气占主导的气藏,总体产气量较低,初始产能较低,随着成熟度增加,稳产时间相对较长;而龙马溪组页岩气是吸附气和游离气共同主导的气藏,总体产气量较高,初始产能大,稳产期相对较长,气藏潜力较大。     

页岩气在孔隙表面的赋存状态及其微观作用机理

吸附态是页岩气的主要赋存状态之一，对吸附气含量的准确评价是页岩气勘探开发中的重要环节.在页岩吸附气含量评价过程中，所选用的等温吸附模型是否遵循页岩气的赋存状态及其微观作用机理，是决定模型适用性的关键所在，也是决定吸附气含量评价准确性的重要因素.因此，需要对页岩气在孔隙表面的赋存状态及其微观作用机理开展深入研究，为科学地优选或建立吸附气评价模型提供理论依据.利用巨正则蒙特卡洛（Grand Canonical Monte Carlo，简称GCMC）法分别模拟甲烷在有机质和伊利石孔隙中的吸附特征并得到分子构型，并进行分子动力学（MD）模拟使体系达到充分平衡.在此基础上，根据气体浓度分布、密度场分布以及分子间相互作用等特征阐明页岩气在孔隙表面的赋存状态及其微观作用机理.研究表明，页岩气在孔隙表面的吸附作用并非单层吸附，吸附相可划分为强吸附层、弱吸附层和二者之间的吸附层波谷.强吸附层主要受到矿物表面的吸附作用；吸附层波谷与弱吸附层既受到矿物表面的吸附作用，又受到不同吸附层之间的吸附作用.Langmiur模型与BET模型的假设条件与此机理不严格相符，可能对模型评价精度造成一定影响.对页岩气在孔隙表面赋存状态及其微观作用机理的研究，有望为吸附模型的优选或建立提供理论依据.      

页岩气的赋存形式研究及其石油地质意义

页岩气是以游离、吸附和溶解状态赋存于暗色泥页岩中的天然气,其赋存形式具有多样性,但以游离态和吸附态为主,溶解态仅少量存在。综述了页岩气的赋存形式及其影响因素,包括页岩气成因、页岩的物质组成(有机碳含量、矿物成分、岩石含水量)、岩石结构(孔隙度、渗透率)和温度、压力等。认识影响不同形式页岩气赋存量的地质因素,有助于利用容积法评估页岩气地质储量的水平,因为游离态页岩气的含量取决于页岩的有效孔隙度和含气饱和度,而吸附态页岩气的含量则受页岩的气体吸附能力影响。认为发展页岩孔隙结构表征技术,研究页岩气在粘土矿物表面和纳米孔隙中的吸附行为,可以进一步了解不同地质条件下页岩气的赋存形式,并为页岩气的资源评价提供更为准确的参数,因此它们将是页岩气下一步研究的重点之一。     

高丰度低演化程度湖相页岩储层特征——以柴达木盆地北缘中侏罗统为例

页岩储层特征对于页岩气的赋存状态、含气量和后期开发均具有重要意义。湖相页岩多处于生油窗阶段,其储层特征与海相页岩区别较大。以柴达木盆地北缘中侏罗统页岩为研究对象,利用岩芯观察、有机地球化学分析、XRD矿物成分分析、低温氮气吸附、FE-SEM以及甲烷等温吸附等手段分析页岩储层的岩石类型、地化、矿物组成、孔隙结构和含气性特征。结果表明,与海相页岩相比,柴达木盆地北缘中侏罗统页岩具有"两高两低两种类型"的特点,即有机碳含量高、黏土矿物含量高,热演化程度低、脆性矿物含量低,有机质类型以Ⅱ、Ⅲ型为主。较低的热演化程度导致样品有机质孔隙发育较少;有机酸的溶蚀作用及矿物的转化作用是次生孔隙形成的主要因素。与海相页岩不同的是,高丰度低演化程度导致该演化阶段以产液态烃为主,且样品中可溶有机质含量较高,它对于样品的孔隙结构和甲烷赋存状态都有影响,表现为随比表面积增大,样品等温吸附实验结果呈现下降的趋势。对于高丰度低演化程度湖相页岩储层特征的研究,不仅为柴达木盆地北缘中侏罗统页岩气的勘探开发提供地质依据,同时也完善了页岩气地质理论。     

基于半封闭体系热模拟实验页岩全岩与粉末样品的排烃效率与孔隙演化差异对比

与传统基于粉末样品的模拟实验相比，基于页岩全岩样品的模拟实验能更好地保存岩石微观结构及孔隙特征，结果更接近地质实际，但有关全岩与粉末样品的排烃效率与微观孔隙差异尚无系统的研究。本文利用半封闭体系热模拟实验获取延长组7段页岩全岩圆柱与粉末样品的排烃效率，并利用低压气体吸附实验表征孔隙特征。当R_o从0.61%升至1.68%时，粉末样品和圆柱样品的排烃效率差值最高达32.47%,随后降至3.98%,粉末样品孔隙分形维数从2.46增加至2.53,而圆柱样品分形维数总体稳定。圆柱样品宏孔体积比例整体随着温度的升高而上升，而中孔体积比例则逐渐下降。与粉末样品相比，页岩全岩样品保留了岩石结构，能反映烃类运移排出过程，孔隙演化更具规律性。本研究最终建立了页岩圆柱、粉末样品生-排烃过程与孔隙演化模型，为研究地质情况下页岩排烃效率与孔隙演化提供了新的思路。     

页岩气成藏富集主控因素研究及目标优选

中国页岩气勘探取得了显著的成果,并建立了涪陵焦石坝、长宁—威远、昭通和延长4个国家级页岩气示范区。近年来,页岩气钻井近400口,其中探井143口(直井)、评价井130口(水平井),页岩气产量相差巨大,充分反应出对页岩气的富集条件、机理及其主控因素认识依然不够深入,这也从根本上制约了页岩气勘探开发的进程。为此本文采用页岩样品地球化学分析、薄片鉴定、X-射线衍射、N2吸附实验、CO2吸附实验、压汞实验、扫描电镜实验和现场解析等方法,对川东南及其周缘地区龙马溪组、牛蹄塘组页岩开展了与页岩气富集密切相关的页岩岩相、微纳米孔隙结构、页岩气赋存状态及保存条件等方面的研究,以期揭示页岩气成藏富集的主控因素。结果表明:1岩相控制了页岩的有机质丰度和脆性矿物含量。页岩岩相(lithic facies)是一定沉积环境中形成的岩石或岩石组合,它是沉积相的主要组成部分。有机质丰度、矿物组成和岩石力学特征是表征页岩岩相的重要指标。根据有机质丰度和矿物组成可划分出12种页岩岩相,不同页岩岩相在有机质丰度、脆性矿物含量和含气性等方面都具有较大的差异。涪陵地区龙马溪组底部深水陆棚以发育富有机质硅质页岩岩相为主,具有有机碳含量、脆性指数、有效孔隙度和含气量均较高的特征,有机碳含量高使其生烃潜力大,脆性指数高使其可压裂性好,有利于页岩气富集成藏及后期开发压裂。2多尺度孔隙结构控制了页岩气的赋存状态和含气量。涪陵地区龙马溪组和牛蹄塘组页岩主要发育原生和次生孔隙,原生孔隙主要包括原生晶间孔和原生粒间孔,次生孔隙主要有次生晶间孔、溶蚀孔和有机质孔。孔隙以微纳米孔为主,其中有机质对微孔和中孔(50nm)贡献最大,二者对孔比表面积贡献占总孔贡献的90%以上,主要影响页岩气的吸附作用;石英等脆性矿物主要控制宏孔(50nm)的发育,中孔和宏孔贡献了孔体积的90%以上,对页岩中游离气的富集和页岩气的渗流具有决定作用。3不同演化阶段页岩气赋存状态随地质条件改变而发生转变。结合埋藏史及有机质生烃过程,将涪陵和渝东南地区页岩气赋存演化过程划分为早期生物游离气、热解吸附气、热解游离气和晚期游离气吸附4个阶段。不同阶段页岩气赋存状态可发生转化,后期构造抬升幅度决定了页岩气赋存状态和含气量的大小,抬升幅度越大,游离气和总含气量含量越少,深度越大,游离气含量越大。明确页岩气赋存状态对于资源潜力评价、开发方案制定及产能评价均具有重要的作用。4构造保存条件是页岩气有利区块优选关键要素之一。一般盆内抬升幅度小,盆内保存条件好与盆缘。有利于页岩气富集的区域构造样式主要为宽缓向斜和小倾角单斜,裂缝密度低、剥蚀厚度小、单层厚度大和扩散系数低等因素控制着页岩气的保存,进而影响页岩气成藏和富集,页岩气保存条件是南方页岩气有利区块优选的重要指标之一。利用资源潜力指数和地质风险系数双因素对川东南及其周缘地区龙马溪组页岩气进行了评价,优选了游离目标区,成果对指导川东南及其周缘地区龙马溪组勘探开发有重要参考价值。     

川东焦石坝五峰-龙马溪组页岩气赋存机理及其主控因素

页岩气是重要的非常规天然气资源,主要以游离气与吸附气状态赋存于页岩中,研究和阐明其含量、主控因素和演化规律对于揭示页岩气成藏机理具有重要意义.采用不同条件下页岩高温高压等温吸附实验、FE-EM、CO₂吸附、N₂吸附、压汞等实验方法综合研究页岩气藏中的游离气与吸附气的主控因素.结果表明,游离气主要受页岩孔隙类型、孔隙结构、储层温度与压力等条件控制;OC、成熟度和水分影响吸附气含量.基于吸附气体积校正、地质模型和数值计算综合表征,五峰-龙马溪组页岩中以游离气为主,其平均含量约为%,吸附气含量约为4%.在抬升阶段,储层温度和压力发生改变,页岩气赋存形式随之变化,游离气减少,吸附气增加.      

川渝地区龙马溪组页岩孔隙结构演化研究

页岩储层孔隙结构是影响页岩气赋存形式和流动行为的关键因素,有关孔隙结构演化的研究受到越来越多的关注.利用低压氮气吸附、脱附实验分析了不同成熟度龙马溪组页岩地质实际样品的孔隙结构特征.结果表明:随着热成熟度的升高,龙马溪组页岩氮气吸附脱附曲线迟滞环形态由H3型向H2型演变,这说明龙马溪组页岩在成熟阶段以黏土矿物有关的狭缝形孔隙为主、有机质孔不发育的孔隙结构,逐渐转变为过成熟阶段由狭缝形孔和圆柱形孔等不同形态和孔径的多种孔隙类型(有机质孔和矿物基质孔)所构成的具复杂网络效应的孔隙结构(墨水瓶结构).有机质孔隙的形成与发育导致不同成熟度的龙马溪组页岩在孔隙体积、比表面积和孔径分布上存在显著的差异,造成孔隙结构的转变.影响页岩孔隙结构的因素包括成熟度、总有机碳(TOC)含量和矿物组成,其中TOC含量和成熟度共同控制页岩孔隙发育,TOC含量控制页岩孔隙发育程度,成熟度决定页岩孔隙发育阶段,矿物组成对孔隙结构的影响居次要位置.基于以上研究,海相Ⅰ～Ⅱ型富有机质页岩孔隙演化可大致划分为三个阶段:原生孔隙压实和次生孔隙开始形成阶段(Ro,V<2.0％)、次生孔隙大量发育阶段(2.0％≤Ro,V<3.6％)和孔隙消亡阶段(Ro,V≥3.6％).     

页岩孔隙空间的形成与演化及孔隙对含气性的影响

虽然页岩气的勘探已经在北美以及中国取得了突破,但是对页岩中孔隙空间的形成与发育仍然存在较大的争议,页岩中是否存在有效的孔隙,这些孔隙与气体的赋存有何联系都需要解答。本文对不同地区、不同岩石类型以及不同热成熟度的页岩进行微观分析,对比前人的研究,同时结合四川盆地龙马溪组页岩的实际分析数据,将页岩划分为富有机质页岩和含粉砂质泥页岩。富有机质页岩中有机质纳米孔是主要的孔隙类型,同时也是气体聚集与吸附的主要空间,有机质孔隙度与有机质含量、热成熟度密切相关;含粉砂质泥页岩中以粒间、粒内溶蚀孔为主,由于有机质含量较少,因而受热成熟影响很小。对页岩的孔隙形成机理分析发现,富有机质页岩孔隙度与有机质含量呈正相关,特别是与初始有机碳含量密切相关,因此恢复初始有机碳的含量是评价页岩含气量与含气性的关键。在热演化程度较低时（Ro < 0.6%）,页岩中有机质孔隙不发育,页岩几乎不含气;随着热演化程度升高（Ro = 0.8%）,页岩微孔隙发育,此时页岩以吸附气为主;随着热演化程度增大（Ro > 1.2%）,微孔逐渐向中孔和宏观孔转化,总的比表面积减小,页岩中游离气含量开始增加,吸附气含量减少。     

基于热模拟实验的页岩孔隙连通性与形状系数演化研究及其地质意义

富有机质页岩的孔隙演化与页岩气赋存富集关系密切,孔隙连通性与形状演化特征对储集空间精细表征和页岩气赋存机理的揭示具有重要意义。本文对山东半岛北部古近系黄县组低成熟富有机质页岩不同热演化阶段的模拟产物开展低温液氮吸附和扫描电镜实验,并辅以数字图像处理技术分析页岩孔隙连通性和形状系数演化过程。结果表明：① 低成熟阶段,有机孔少量发育,无机孔主要为矿物基质孔;随热演化程度增加,大量近圆形有机孔逐渐形成,少量溶蚀孔和黏土矿物层间孔生成;到过成熟阶段,压实作用导致部分孔隙减小或消失;② 随热演化程度增加,有机孔和无机孔孔径均呈先增大后减小的趋势,孔隙形状系数均呈现近“V”型变化趋势;③ 高温高压导致样品孔隙系统第二个优势孔径峰值变大,表明孔隙系统增加了狭长 裂缝型孔隙,有助于沟通其他类型孔隙,提高孔隙系统的连通性;④ 热演化过程中生成的大量近圆形有机孔能为甲烷提供更多吸附位,生成的黏土矿物层间孔等狭缝型无机孔能够提高孔隙连通性,从而有助于提高页岩气的赋存和运移能力。本研究可为页岩气储层表征与页岩气赋存富集研究提供基础。     

The petroleum generation potential and effective oil window of humic coals related to coal composition and age

A worldwide data set of more than 500 humic coals from the major coal-forming geological periods has been used to analyse the evolution in the remaining (Hydrogen Index, HI) and total (Quality Index, QI) generation potentials with increasing thermal maturity and the ‘effective oil window’ (‘oil expulsion window’). All samples describe HI and QI bands that are broad at low maturities and that gradually narrow with increasing maturity. The oil generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2%R_o or T_max of 500–510 °C. The initial large variation in the generation potential is related to the original depositional conditions, particularly the degree of marine influence and the formation of hydrogen-enriched vitrinite, as suggested by increased sulphur and hydrogen contents. During initial thermal maturation the HI increases to a maximum value, HI_max. Similarly, QI increases to a maximum value, QI_max. This increase in HI and QI is related to the formation of an additional generation potential in the coal structure. The decline in QI with further maturation is indicating onset of initial oil expulsion, which precedes efficient expulsion. Liquid petroleum generation from humic coals is thus a complex, three-phase process: (i) onset of petroleum generation, (ii) petroleum build-up in the coal, and (iii) initial oil expulsion followed by efficient oil expulsion (corresponding to the effective oil window). Efficient oil expulsion is indicated by a decline in the Bitumen Index (BI) when plotted against vitrinite reflectance or T_max. This means that in humic coals the vitrinite reflectance or T_max values at which onset of petroleum generation occurs cannot be used to establish the start of the effective oil window. The start of the effective oil window occurs within the vitrinite reflectance range 0.85–1.05%R_o or T_max range 440–455 °C and the oil window extends to 1.5–2.0%R_o or 470–510 °C. For general use, an effective oil window is proposed to occur from 0.85 to 1.7%R_o or from 440 to 490 °C. Specific ranges for HI_max and the effective oil window can be defined for Cenozoic, Jurassic, Permian, and Carboniferous coals. Cenozoic coals reach the highest HI_max values (220–370 mg HC/g TOC), and for the most oil-prone Cenozoic coals the effective oil window may possibly range from 0.65 to 2.0%R_o or 430 to 510 °C. In contrast, the most oil-prone Jurassic, Permian and Carboniferous coals reach the expulsion threshold at a vitrinite reflectance of 0.85–0.9%R_o or T_max of 440–445 °C.     

Stratigraphy, sedimentology and bulk organic geochemistry of black shales from the Proterozoic Vindhyan Supergroup (central India)

Four organic-rich shale units of the Proterozoic Vindhyan sedimentary succession have been scanned to reveal their origin and hydrocarbon potential. The wavy-crinkly nature of the carbonaceous laminae is suggestive of a microbial mat origin of the shales. These shales are thus different from Phanerozoic black shales which typically exhibit planar laminae. The hydrocarbon potential of the black shale units has been evaluated by Rock-Eval pyrolysis. Total organic carbon content of many of the shales exceeds 1%. The meanT _max for the black shales translate to a vitrinite reflectance range of 2.05-2.40% Rm based on standard conversion techniques. These shales have reached the catagenetic stage near the beginning of anthracite formation.     

Thermal alteration of coal in the Khasyn coalfield, Magadan region, Russia

The Early Cretaceous coal deposits of the Khasyn coalfield are intruded by Palaeogene diabase dikes. The coal has vitrinite reflectance values of 2.0–2.5% R_o, and characteristics of normal anthracite at some distance from the dikes, but at direct contact with the dike two morphological coal varieties occur: coal inclusions in the diabase dike and dispersed carbonaceous matter within the dike rock. Both types of coaly matter have properties typical of anthracites: strong anisotropy, altered internal structure and high vitrinite reflectance values ranging from 3.8 to 5.5% R_o. The X-ray diffraction measurements of the interplanar spacing d(002) and the crystallite sizes Lc and La show rather similar values for coal inclusions in the dike and dispersed carbonaceous matter. The additional reflection at 3.37 Å, corresponding to semi-graphite admixture, occurs in the coal and carbonaceous matter inside the dike and is absent in the natural coal outside the dike.     

Optical parameters of maturity of organic matter dispersed in sediments: first results from the Central Apennines (Italy)

Levels of organic maturity of Mesozoic and Tertiary sequences outcropping in the Central Apennines have been established, using vitrinite reflectance techniques, the Thermal Alteration Index and fluorescence colours of organic matter dispersed in sediments. These results provide new constraints throughout the Meso-Cenozoic evolution of this crustal sector. In exploration geology, vitrinite reflectance provides data on hydrocarbon maturation by constraining organic matter maturity. In sedimentary basin modelling, it is adopted to define the palaeothermal regime. Vitrinite reflectance (R_o) also provides information on the burial history of sedimentary basins and may be employed to estimate tectonic uplift and erosion rates. Thermal Alteration Index (TAI) and fluorescence colour values can be correlated with R_o and may be used to estimate the degree of maturation when vitrinite is absent. Samples derived from the Sabini and Tiburtini Mts, in slope facies between the Latium–Abruzzi carbonate Platform and the Umbria–Marche pelagic Basin; from the Simbruini and Ernici Mts, in carbonate Platform facies, and from upper Miocene turbiditic deposits outcropping between the Olevano–Antrodoco Une, towards the West, and the Marsica slope facies, towards the East. Both the pre-terrigenous Meso-Cenozoic sequences show a low grade of organic maturity: the Sabini and Tiburtini Mts show R_o values that are less than 0.4%, and the Simbruini–Ernici Range show R_o values that range between 0.5% and 0.65%. Field analysis indicates that the cause of these low maturity levels is that thick sequences of turbidites were never deposited during the Neogene evolution of the Apennine thrust belt. Moreover, Upper Miocene turbiditic deposits also show low maturity levels, with R_o values that are less than 0.5%, indicating that these deposits were never overthrusted by huge volumes of rocks, during the chain building. The slight increase in the maturity level recorded in the Marsica area may be related to local heating along shear zones in areas of strike-slip tectonics.     

Thermal maturity and organic composition of Pennsylvanian coals and carbonaceous shales, north-central Texas: Implications for coalbed gas potential

Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600 m; 2000 ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (R_o) values between about 0.4 and 0.8%. This range of R_o values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100 m; 300 ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar R_o values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650 m; 5400 ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher R_o values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1 m; 3.3 ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.     

Physical and chemical environments of abnormal vitrinite reflectance evolution in the sedimentary basins

Based on the tested data of pressure and vitrinite reflectance of some wells in sedimentary basins, abnormal high pressure is regarded as not the only factor to retard the increase of vitrinite reflectance (R _o). Apart from the types of the organic matter, the physical environment (temperature and pressure) and chemical environment (fluid composition and inorganic elements) will result in the abnormal vitrinite reflectance values in the sedimentary basins. This paper tested trace elements and vitrinite reflectance data from the the abnormal high pressure and normal pressure strata profiles, respectively, and found that the acidic and lower salinity starta are favorable for the increase of R _o. By discussing the corresponding relationship between the contents of some trace elements in the mudstone and the vitrinite reflectance values, the typical trace elements were found to suppress and/or catalyze the vitrinite reflectance of organic matter, while the elements of Ca, Mn, Sr, B, Ba and P may result in the retardation of R _o. However, elements of Fe, Co, Zn, Ni and Rb may catalyze the organic matter maturation. This study is conductive to the organic maturation correction, oil and gas assessment and thermal history reconstruction by the paleothermometry. Translated from Acta Geologica Sinica, 2006, 80(11): 1760–1769 [译自: 地质学报]     

Organic petrographic investigations of the Kupferschiefer in northern Germany

Results of an organic petrographic study of the Kupferschiefer (Zechstein, Upper Permian) in northern Germany are presented. Because vitrinite occurs only sporadically in this black shale, the random reflectance (R_r) of a relatively high reflecting, vitrinite-like variety of bituminite was measured as a maturity parameter and the problems connected with this procedure were investigated.The main organic component is bituminite, generally with an abundance of more than 90%. Sporomorphs and algae are relatively scarce, inertinite is usually a trace component, and vitrinite is present only in some samples taken close to the coast of the Zechstein sea. Migrabitumen also occurs in small amounts in a few samples. The range of the bituminite reflectance values is often considerable and depends on rank, anisotropy, particle size, porosity, and shearing. Interpretation of the reflectance values is made difficult by differences of up to 0.4% R_r between layers within the Kupferschiefer. Hydrothermal alteration may also be present. The difference between the reflectance of the light and normal varieties of bituminite disappears between 0.9 and 1.2% R_r.Bituminite behaves in a way very similarly to vitrinite during coalification. Their reflectance is identical between 2 and 4% R_r. Below 2% R_r, the reflectance of bituminite is lower than that of vitrinite. Linear regression curves valid up to 4% R_r were calculated for R_max versus R_r and for R_r versus R_max. Taking certain limitations into consideration, bituminite reflectance may be used as a coalification parameter.     

Lower palaeozoic and precambrian petroleum source rocks and the coalification path of alginite

Organic-rich samples derived from a Middle Cambrian Formation in the Georgina Basin, and from the Middle Proterozoic of the McArthur Basin in northern and central Australia, yielded alginite ranging from immature oil shale material to overmature residue. A maturation scale has been developed based on the thermal evolution of alginite as determined from reflectance and fluorescence. The coalification path of alginite is marked by jumps in contrast to the linear path of wood-derived vitrinite. Six zones have been recognised, ranging from undermature (zone I), through the mature (zones II/III), followed by a stable stage of no change (zone IV) to the overmature (zones V and VI). The onset of oil generation in alginite as evident from the present study is at 0.3% R_{o Alg.} and is expressed in a change of fluorescence from yellow to brown, and a coalification jump from 0.3 to 0.6% R_o of Alg. In many boreholes zone III can be distinguished between 0.6 and 0.8% R_o of Alg. where subsequent oil generation occurs. Zones II and III represent the oil window.A zone of little or no change designated zone IV, at of alginite follows zones II/III. A marked coalification jump characterises zone V, where a pronounced change in reflectance occurs to >1.0% R_{o Alg.}, signifying peak gas generation. The border of oil preservation lies at the transition of zone V and VI, at 1.6% R_{o Alg.} In zone VI gas generation only occurs.Comparison of reflectance results with experimental and geochemical pyrolysis data supports high activation energies for hydrocarbon generation from alginite, and therefore a later onset of oil generation than other liptinite macerals (i.e. cutinite, exinite, resinite) as well as a narrow oil window.Transmission electron microscopy (TEM) confirms that alginite does not go through a distinct intermediate stage but that the percentage of unreacted organic matter decreases as maturation proceeds. A clear distinction can be made in TEM between immature alginite, alginite after oil generation, and alginite residue following gas generation. Alginite beyond 1.6% R_o acquires very high densities and the appearance of inertinite in TEM.Bitumens/pyrobitumens make a pronounced contribution to the organic matter throughout the basins and have been shown to effect pyrolysis results by suppressing T_max. The bitumens/pyrobitumens have been divided into four groups, based on their reflectance and morphology, which in turn appears to be an expression of their genetic history. Their significance is in aiding the understanding of the basins' thermal history, and the timing of oil and gas generation.     

Natural gas potential of Neoproterozoic and lower Palaeozoic marine shales in the Upper Yangtze Platform,South China: geological and organic geochemical characterization

In this article, we describe the geological features of the Ediacaran (upper Sinian), lower Cambrian and lower Silurian shale intervals in the Upper Yangtze Platform, South China, and report on the gas potential of 53 samples from these major marine shale formations. Reflected light microscopy, total organic carbon (TOC) measurement, Rock-Eval, carbon isotope ratio analysis, thermovaporization gas chromatography (Tvap-GC), and open pyrolysis gas chromatography (open py-GC) were used to characterize the organic matter. Measured TOC in this research is normally >2% and averages 5%. TOC contents are roughly positively correlated with increasing geological age, i.e. lower Silurian shales exhibit generally lower TOC contents than lower Cambrian shales, which in turn commonly have lower TOC contents than Ediacaran shales. Kerogen has evolved to the metagenesis stage, which was demonstrated by the abundant pyrobitumen on microphotographs, the high calculated vitrinite reflectance (R_o = 3%) via bitumen reflectance (R_b), as well as δ¹³ C of gas (methane) inclusions. Pyrolysates from Tvap-GC and open py-GC are quantitatively low and only light hydrocarbons were detected. The lower Silurian shale generally exhibits higher generation of hydrocarbon than the lower Cambrian and Ediacaran shale. Cooles’ method and Claypool’s equations were used to reconstruct the original TOC and Rock-Eval parameters of these overmature samples. Excellent original hydrocarbon generation was revealed in that the original TOC (TOC_o) is between 5% and 23%, and original S1+S2 (S1_o+S2_o) is ranging from 29 to 215 mg HC/g rock.     

四川盆地五峰-龙马溪组页岩成熟度研究

上奥陶统五峰组-下志留统龙马溪组海相页岩是四川盆地下古生界主要的烃源岩和页岩气勘探目标,有机质成熟度不仅是油气生成评价的关键,也是页岩品质评价的重要指标之一.下古生界页岩有机质成熟度一直以来是有机岩石学研究的难点与热点问题.由于下古生界缺乏镜质体,先前的研究多是采用沥青反射率转换为等效镜质体反射率的方法,并且由于沥青的局限性和不确定性,使得五峰-龙马溪组页岩的成熟度缺乏统一的认识和系统研究.通过采集四川盆地及其周缘的岩心和露头样品,系统分析了页岩有机显微组分光学反射率特征.结果表明笔石和固体沥青是最主要的两类有机显微组分.根据固体沥青的显微结构形态和光性特征,将固体沥青大体上分为两类:（1）颗粒状-棱角状的充填在孔隙和微裂缝中高反射率焦沥青;（2）以细小不规则表面的有机质颗粒大量分散于粘土矿物基质中的低反射率基质固体沥青.焦沥青与笔石随机反射率均可以表征下古生界页岩有机质成熟度.但焦沥青反射率略低于笔石反射率,并且随着成熟度的增高,笔石反射率的增速大于焦沥青,各向异性也显著增强.相对于固体沥青反射率,笔石随机反射率分布更为集中,更适合作为含笔石页岩有机质成熟度指标.但是笔石反射率与等效镜质体反射率在过成熟阶段的换算关系需要进一步研究.