Relationships among geochemical indices of coal and carbonaceous materials and implication for hydrocarbon potential evaluation

A worldwide dataset of organic material from 553 samples belonging to coal and carbonaceous materials was used to analyze the evolution of hydrogen index (HI) and bitumen index (BI) with increasing thermal maturity. Basic statistical analyses were applied to detect the boundary lines of HI_max and BI_max in delineating the upper and lower limits of the HI and BI bands for the majority of samples. In addition, cross-plots of HI or BI versus maturity (Ro% and T _max) also provide criteria for defining the HI_max and BI_max boundary lines. The constructed HI and BI bands are broad at low maturities and become narrower with increasing thermal maturities. The petroleum generation potential is completely exhausted at the vitrinite reflectance of 2.0–2.2% or T _max of 510–520°C. An increase in HI implies extra petroleum generation which was related to changes in structure of organic materials. A declining BI means that the oil expulsion window starts to occur at the vitrinite reflectance range of 0.75–1.05%. The petroleum potential can be divided into four different areas based on the cross-plot of HI versus Ro%. The highest petroleum potential area is located in section II with Ro = 0.6–1.0% and HI > 100. The oil generation potential is rapidly exhausted at section III with Ro > 1.0%. This result is also in accordance with the result of curve regression of HI versus Ro% based on 80 samples with Ro = 1.02–3.43% (R ² = 0.72). Overall, the total oil window can be extended up to Ro = ~1.25–1.95%. Finally, in the cross-plots of S1 versus S2, shale or C-shale exhibits a higher and slowly decreased slope, compared with a lower and then sharply increased slope of coal samples, which is attributable to their compositional difference in organic material.     

Relationship between petroleum reservoir rocks and source rocks

A substantial fraction of sandstones containing commercial quantities of oil are proposed to be in contact with source rocks which produce oil. For these situations the quantity of oil collected in a sandstone is proportional to the area of contact with a source rock of relatively low permeability, rather than to the total thickness of the potential source rock. It is inferred that source rocks along the upper or lower faces of a sandstone should produce more oil into the sandstone than source rocks lateral to the sandstone. Semiquantitative estimates of the thickness or width of required source rock are obtained. The arguments and results are based on published statistical studies and the assumption that a degree of geometrical similarity exists among sandstones.     

Inter-element relationships between trace elements in primitive carbonaceous and unequilibrated ordinary chondrites

The results of a search for significant (95 % confidence level) inter-element relationships among 13 trace elements in carbonaceous chondrites and 26 elements and the disequilibrium parameter for silicate phases in unequilibrated ordinary chondrites (UOC) indicate pronounced differences in the formation processes of these two sorts of primitive chondrites. Twenty-six pairs of elements are correlated in carbonaceous chondrites and these correlations lend support to a model involving mixing in different ratios of material differing in thermal history.Comparison of the 26 elements in UOC shows that 39 pairs of elements are significantly related and only very volatile elements are correlated with the disequilibrium parameter. Each of the inter-element relationships can be specifically ascribed to a metal-silicate fractionation in the solar nebula or to a thermal fractionation. These relationships are about equally consistent with the metamorphism, two-component condensation and simultaneous accretion-condensation models for the origin, of the ordinary chondrites, each requiring adoption of specific ad hoc assumptions for complete consistency.     

南祁连盆地热水—默勒地区上三叠统可能烃源岩地球化学特征

应用多项分析测试技术，对南祁连盆地热水－默勒地区上三叠统可能烃源岩进行了有机质丰度，类型、成熟度、有机母源和沉积环境等方面的分析。该区上三叠统可能烃源岩为前三角洲和湖沼相的泥质岩沉积，其有机质丰度较高，有机质类型为腐殖型和混合型，主要处于成熟阶段，有机母质主要为高等植物和一定数量的藻菌类低等水生生物的贡献。综合分析认为该套地层具有一定的生烃能力，其中一些层段生烃潜力较大。     

A contribution to geochemical correlation between crude oils and potential source rocks in the eastern Molasse Basin (Southern Germany)

Nineteen core samples of potential source rocks for crude oils in the Eastern Molasse Basin were investigated with respect to their isotopic composition of stable carbon in organic extracts and kerogens. p] Some of the chemical and isotopic results give positive or negative indications for the relationship between crude oils and the selected core samples. The analytical data point to the clayish sediments of the Rupelian and Sannoisian as probable source rocks, but further sampling and methodological research will be necessary to confirm the preliminary results on these samples which proved to be of low maturity by their elementary composition.     

黏性材料细观与宏观力学参数相关性研究

岩土工程数值模拟技术中参数选取的正确性是反应材料真实力学特性的基本前提。借助于颗粒离散元分析软件PFC2D,对黏性土类材料样本开展了大量的平面双轴压缩试验。通过记录不同围压下样本的轴向应力峰值,并依据摩尔-库仑强度准则对数值试样的剪切强度参数（内摩擦角、黏聚力）进行标定。着重探讨了黏性材料细观参数中颗粒刚度比kn /ks（0.5～10共12组）、颗粒粘结强度SBS（0～50 kPa共12组）、颗粒摩擦系数?（0～6共16组）以及颗粒粘结强度比K（0.1～10共15组）和材料宏观剪切强度参数以及材料剪切特性之间的相关性。研究结果表明：颗粒粘结（法向、切向）强度同对材料黏聚力呈线性相关;颗粒摩擦系数与材料内摩擦角呈近似对数相关;颗粒刚度比大小对材料剪切强度参数变化亦有微弱的影响;此外,K值（切向粘结强度/法向粘结强度）是影响材料的剪切破坏形态的重要因素。最后,采用了两个多元非线性拟合公式,定量地描述了以上各细观参数和材料宏观剪切强度参数的联合关系,并给出了K值的建议取值,为后续的研究提供重要的理论基础。     

Guidelines for assessing the petroleum potential of coaly source rocks using Rock-Eval pyrolysis

Coaly source rocks are sufficiently different from marine and lacustrine source rocks in their organic matter characteristics to warrant separate guidelines for their assessment using Rock-Eval pyrolysis. The rank threshold for oil generation is indicated by the increase in BI (S1/TOC) at Rank(S_r)9–10 (T_max 420–430 °C, R_o 0.55–0.6%), and the threshold for oil expulsion is indicated by the peak in QI ([S1+S2]/TOC) at Rank(S_r)11–12.5 (T_max 430–440 °C, R_o 0.65–0.85%). The pronounced rank-related increase in HI (S2/TOC) prior to oil expulsion renders the use of immature samples inappropriate for source rock characterisation. A more realistic indication of the petroleum generative potential and oil expulsion efficiency of coaly source rocks can be gained from samples near the onset of expulsion. Alternatively, effective HI′ values (i.e. HIs near the onset of expulsion) can be estimated by translating the measured HIs of immature samples along the maturation pathway defined by the New Zealand (or other defined) Coal Band. Coaly source rocks comprise a continuum of coaly lithologies, including coals, shaly coals and coaly mudstones. Determination of the total genetic potential of coaly source rock sequences is best made using lithology-based samples near the onset of expulsion.     

油气化探异常的稳定性及油气地质意义

油气化探利用地球化学方法寻找油气,具有直接、快速、有效、成本低的特点,已在油气勘探实践中取得了较好的效果,并在一定时期得到了较为广泛的应用。但油气化探作为一门新兴学科,在许多方面仍存在不足,其中异常的稳定性与重现性是制约油气化探推广应用的认识障碍。以河南泌阳洼陷（井楼-古城油田）和山东临邑洼陷南斜坡（临南油田）的实际地球化学测量资料为基础,通过已知油气藏上方不同期次（同年）、不同时期的油气化探异常特征的对比,从油气化探指标组合关系、结构特征、剖面显示、油气异常的平面分布等方面证实油气化探异常存在较好的稳定性,表明利用油气化探技术方法寻找油气是可行的,并进一步证实了油气化探在油气勘探中的应用前景。     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

苏里格地区山西组烃源岩地化特征及生烃能力评价

鄂尔多斯盆地苏里格地区上古生界地层为海陆交互及河流-湖泊三角洲相的石炭-二叠系含煤岩系。下二叠统山西组发育煤和暗色泥岩二类烃源岩。根据苏里格及周边地区大量钻井岩芯样品的残余有机碳含量,干酪根同位素,有机质显微组份组成,干酪根镜质体反射率（Ro）等地球化学数据,综合分析了下二叠统山西组烃源岩的有机质丰度,类型和热演化程度。采用有机碳产烃率法,分别计算了煤层和暗色泥岩的生烃强度。在此基础上,结合苏里格地区山西组成藏特征,综合评价认为山西组生烃能力居于中等偏低的级别。     

Changes in gas composition during simulated maturation of sulfur rich type II-S source rock and related petroleum asphaltenes

Asphaltenes extracted from crude oils are proposed to possess structural features of the related source rock kerogen. For the present study micro-scale sealed vessel pyrolysis (MSSV) and combustion isotope ratio mass spectrometry (GC–C–IRMS) were used to compare gas generation from a whole rock (type II-S kerogen) from southern Italy with that from related sulfur rich asphaltenes isolated from a low maturity heavy crude oil. The purpose of was to determine whether experimental pyrolysis of oil asphaltenes can be used to predict the timing and the chemical and isotopic composition of hydrocarbon gases generated from genetically related kerogen in the source rock during burial maturation. The results show that parameters such as (gas to oil ratio) GOR and oil and gas formation timing are very similar for these two sample types, whereas gas composition, product aromaticity and sulfur content are remarkably different. Slight differences in GOR are mainly due to differences in gas formation characteristics at very high levels of thermal alteration. Secondary gas formation from the whole rock covers a much broader temperature range under geological conditions than that from the asphaltene products. However, it is remarkable that both the onset and the maximum temperature are nearly identical under geological conditions. The observed differences in gas generation characteristics are supported by discrepancies in the carbon isotopic characteristics of the gas range compounds and indicate different precursors and/or mechanisms for gas generated from whole rock and asphaltenes.     

Integrated electromagnetic and geochemical surveys for petroleum exploration in West Siberia

Electromagnetic soundings with controlled and natural sources (TEM and MT, respectively) integrated with IP and geochemical surveys have been tested for petroleum exploration in West Siberia. The TEM method, with loop sizes smaller than the depth to the target, provide high resolution, sufficient penetration depth, and data locality. The MT method sounds deeper earth and can place constraints on the Paleozoic basement structure and its electrical properties. The petroleum implications of IP and geochemical data are associated with secondary alteration (mineralization) of rocks over oil traps.     

Microspectrofluorescence measurements of coals and petroleum source rocks

Good, reproducible microspectrofluorescence data, similar to published fluorescence trends, are obtainable from samples of coals and petroleum source rocks (shales). These data are reproducible when measured by different operators, different instruments, or at different times (for example, the remeasurement of samples several months apart). These fluorescence data are used to predict maturity or rank to within about 0.10% R₀ (mean vitrinite reflectance, oil immersion). Commercially available computerized fluorescence equipment, with customized software and specific hardware mod modifications, makes the acquisition of fluorescence data feasible. Fluorescence can be used for measuring low-maturity samples, in which the measurement of vitrinite reflectance is difficult. Source rocks from oil-rich basins frequently do not contain enough particles of vitrinite for a reflectance determination, but they may contain fluorescing particles which can be measured. Although the results from only two different kinds of fluorescence equipment (Zeiss Zonax and Vickers Gamma-Scientific) are discussed, any instrument with equivalent stability and sensitivity can be used to attain reproducible and accurate fluorescence data.We propose the use of the term “R_F” to report fluorescence data in equivalent vitrinite reflectance values. Although the principles and techniques of measuring fluorescence were introduced several years ago, much work remains to establish standardized methods of maesuring as well as data evaluation. The current method of reporting fluorescence data in terms of spectral characteristics (such as the wavelength of maximum intensity or wavelength ratios) is awkward to use and difficult to compare results from various laboratories. R_F values convey rank or maturation meaning and can be easily compared among laboratories.Data from fluorescing grains in both coal and petroleum source rock samples are given in this study. Polished samples of coal, this sections, and kerogen strewn slides of source rocks are measured. Spectral data are evaluated by four parameters: the wavelength of maximum intensity (Peak), the red/green ratio (Q), the coordinates of a metric color system (CIE), and the relative intensity at 490 nm. The measurement of intensity, reported in units of radiance, is possible with the Vickers Gamma-Scientific instrument. Measuring both fluorescent colors (R_F) and intensities may help explain some of the relationships among organic particles, maturation, and hydrocarbon generation.     

河北省铅锌矿源层与地球化学块体

文章以河北省岩石和水系沉积物地球化学调查成果为基础,讨论了省内铅锌矿源层、地球化学块体的空间分布范围以及地球化学块体与矿源层的关系,旨在为研究区内的铅锌矿产勘查提供指导。研究结果表明,以高于该地区表壳岩石铅锌元素丰度的重要矿床的围岩作为铅锌矿源层的判别标志,侏罗纪、白垩纪火山-沉积岩及燕山期侵入岩、遵化岩群、红旗营子岩群等可确定为铅锌矿源层。以25μg/g为异常下限,圈定出水系沉积物铅地球化学块体7处;以100μg/g为异常下限,圈定出水系沉积物锌地球化学块体4处。在铅锌地球化学块体的内部及边缘,有多处大、中型铅锌矿床产出。在丰宁、围场一带出现大范围的铅元素连续成片的岩石高背景分布,锌元素的岩石高背景分布则位于崇礼和围场地区,铅锌高背景区主要分布于侏罗系-白垩系分布区内。侵入岩铅锌高背景区主要集中在乌龙沟-上黄旗岩浆岩带、军都山岩浆岩带及马兰峪复背斜东、西两端。经研究发现,据水系沉积物所圈定出的异常与铅锌矿床分布的一致性要好于据岩石所圈定的异常。在一个地球化学块体分布范围内,存在着多种地质体,而其中对异常形成贡献最大者可能是矿源层和矿床。矿源层与地球化学块体都强调其在成矿作用中是物质的供应源,不同之处在于,前...     

中国浅层油气藏的特征及其资源潜力分析

中国多年来对浅层地区未进行有效的勘探开发和给予应有的重视。对渤海湾盆地等主要大中型盆地浅层油气藏的类型、分布特征和地质特征等的分析表明,中国浅层油气在地质上总体具有埋藏浅、成因复杂、受构造-岩性等复合性影响显著、储量规模与丰度大小不一、油藏类型多且分布广、资源量分布不均等特征,在勘探和开发上具有易勘探、成本低和易出砂出水、稳产难度大等优点和不足。指出中国浅层油气的潜力区域在东部,对浅层油气资源潜力进行了分析,认为浅层油气资源潜力很大,要重视浅层油气资源的勘探开发,重视新理论、新技术、新方法等在浅层隐蔽油气藏勘探开发过程中的应用。     

中国浅层油气藏的特征及其资源潜力分析

中国多年来对浅层地区未进行有效的勘探开发和给予应有的重视。对渤海湾盆地等主要大中型盆地浅层油气藏的类型、分布特征和地质特征等的分析表明,中国浅层油气在地质上总体具有埋藏浅、成因复杂、受构造-岩性等复合性影响显著、储量规模与丰度大小不一、油藏类型多且分布广、资源量分布不均等特征,在勘探和开发上具有易勘探、成本低和易出砂出水、稳产难度大等优点和不足。指出中国浅层油气的潜力区域在东部,对浅层油气资源潜力进行了分析,认为浅层油气资源潜力很大,要重视浅层油气资源的勘探开发,重视新理论、新技术、新方法等在浅层隐蔽油气藏勘探开发过程中的应用。     

Heulandite and mordenite-rich tuffs from Greece: a potential source for pozzolanic materials

The microcystalline mass of the Pliocene tuffs of Santorini and Polyegos islands, in the South Aegean Volcanic Arc, Greece, is very rich in zeolite minerals, more specifically heulandite type 3, i.e. clinoptilolite, and mordenite. In Santorini, clinoptilolite is the dominant authigenic phase and it was formed in a semi-closed system, by the activity of interstitial water within the volcaniclastic sequence. In Polyegos, mordenite dominates and it was formed by hydrothermal alteration of pyroclastics. Experiments described in this work show that the presence of the zeolite minerals has created materials with excellent pozzolanic properties. Tuffs from the two areas were calcined at 760 °C and for 12 h and then mixed with lime in a constant ratio of 1 part lime to 3 parts calcined tuff. As a result, the free lime content of the lime-calcined tuff mixtures was reduced from 25% to 2.05% (Santorini) and 1.31 % (Polyegos). Compressive strength tests were carried out on concrete cubes made with 100% Portland cement as the cementitious agent, to be used as reference cubes, and concrete cubes in which the Portland cement has been replaced in 4% and 7% proportions by the calcined tuff as pozzolans. The free lime estimation and the compressive strength tests were all carried out in accordance with the British Standards Institution (BS 4550 and BS 1881) guidelines. Early stage measurements of the compressive strength showed that pozzolan-bearing concrete cubes reached values as high as 140% of the reference cubes. The pozzolan-bearing concrete cubes maintained this superior strength throughout the entire one year period of the experiments. After 360 days, they finally maintained 107% of the compressive strength of the reference cubes.     

Geochemistry and metal potential of triassic carbonaceous silicites in Sikhote Alin

In the Triassic siliceous formation of Sikhote Alin, carbonaceous silicites occur in the late Olenekian-middle Anisian member (4–20 m) of alternating cherts and clayey cherts (“phtanite member”) near the section base. The silicites are represented by radiolarian and spicule-radiolarian cherts alternating with clayey cherts. They contain up to 8.5% C_org. In the majority of sections, the rocks underwent structural and mineral transformation at the mesocatagenetic stage. The slightly oxidized organic (primarily, marine sapropelic) matter contains quinones, methyl, methylene, and ether groups. The content of neutral bitumens in rocks shows a wide variation range. The carbon isotopic composition in phtanites and clayey phtanites (δ¹³C from ?27.3 to ?30.2‰) is identical to that in many Paleozoic-Mesozoic bitumens and oils. As compared with other Mesozoic sedimentary rocks of Sikhote Alin, the carbonaceous silicites are enriched in V, B, Mo, Ni, Cu, and Ag. Anomalously high concentrations of Ba are recorded in phtanite rock sections at the Gornaya and Khor rivers and in the vicinity of Khabarovsk. Modal value of the Au content in phtanites and clayey phtanites is three or four times higher than the clarke value in carbonaceous silicites and reaches anomalous values in some sections (e.g., Ogorodnaya River section). Carbonaceous silicites of this section are also enriched in Pt. Positive Au-C_org correlation is recorded in clayey phtanites of the Ogorodnaya River section containing more than 0.5% C_org. In organic fractions, Au and Ag are concentrated in alcohol and alcohol-benzene bitumens, asphalt acids, and asphaltenes. Migration of bitumens from high-carbonaceous clayey phtanites to the pore-fissure space of cherts and phtanites also fostered the concentration of these metals in some low-carbonaceous layers of the member.     

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.     

渤中凹陷典型富油气区油源断层差异活动与油气富集关系

以渤中凹陷典型富油气区为研究对象,探讨了该富油凹陷油源断层差异活动与油气富集和分布之间的关系。结果表明:研究区不同构造带内油气主要沿油源断层分布,由凸起带向斜坡带方向,油气富集层位逐渐由新近系向古近系及前古近系潜山过渡,且断层平均活动强度逐渐降低;新生代以来断层活动速率整体表现出强-弱--强的演化规律,新近系油气主要富集于油源断层差异活动系数 1. 8且晚期断层活动速率33 m/Ma的断层附近;凸起带边界油源断层长期活动,有利于新近系油气的富集,倾末端油源断层在烃源岩排烃期早、中期活动较强且晚期活动较弱,控制了深、浅层多层系的油气富集,斜坡带油源断层较少且在烃源岩排烃晚期活动强烈,油气主要富集于古近系及前古近系潜山。