Geochemical Evaluation of the Permian Ecca Shale in Eastern Cape Province,South Africa: Implications for Shale Gas Potential

Shale gas has been the exploration focus for future energy supply in South Africa in recent time. Specifically, the Permian black shales of the Prince Albert, Whitehill, Collingham, Ripon and Fort Brown Formations are considered to be most prospective rocks for shale gas exploration. In this study,outcrop and core samples from the Ecca Group were analyzed to assess their total organic carbon(TOC), organic matter type, thermal maturity and hydrocarbon generation potential. These rocks have TOC ranging from 0.11 to 7.35 wt%. The genetic potential values vary from 0.09 to 0.53 mg HC/g,suggesting poor hydrocarbon generative potential. Most of the samples have Hydrogen Index(HI) values of less than 50 mg HC/g TOC, thus suggesting Type-Ⅳ kerogen. Tmax values range from 318℃ to601℃, perhaps indicating immature to over-maturity of the samples. The vitrinite reflectance values range from 2.22% to 3.93%, indicating over-maturity of samples. Binary plots of HI against Oxygen Index(OI), and HI versus Tmax show that the shales are of Type II and mixed Type Ⅱ-Ⅲ kerogen.Based on the geochemical data, the potential source rocks are inferred as immature to over-matured and having present-day potential to produce gas.     

Origins of natural gases from marine strata in Northeastern Sichuan Basin (China) from carbon molecular moieties and isotopic data

To determine the origin, maturity, formation mechanism and secondary process of marine natural gases in Northeastern Sichuan area, molecular moieties and carbon isotopic data of the Carboniferous and Triassic gases have been analyzed. Typical samples of marine gas precursors including low-maturity kerogen, dispersed liquid hydrocarbons (DLHs) in source rocks, residual kerogen and oil have been examined in a closed system, and several published geochemical diagrams of gas origins have been calibrated by using laboratory data. Results show that both Carboniferous and Triassic gases in the study area have a thermogenic origin. Migration leads to stronger compositional and weak isotopic fractionation, and is path dependent. Carboniferous gases and low-H₂S gases are mainly formed by secondary cracking of oil, whereas high-H₂S gases are clearly related to the TSR (Thermal Sulfate Reduction) process. Gases in NE Sichuan show a mixture of heavy (¹³C-enriched) methane in comparison to the lower maturated ethane of Triassic gas samples, suggesting a similar source and maturity for ethane and propane of Carboniferous gases, and a mixture of heavy ethane to the propane for Triassic gases. Based on the data plotted in the diagram of Chung et al. (1988), the residual kerogen from Silurian marine shale and palaeo oil reservoirs are the main source for Carboniferous gases, and that the residual kerogen from Silurian and Permian marine rocks and Permian paleao oil reservoirs constitute the principal source of Triassic gases.     

成熟度对陆相烃源岩可溶有机质Pr/Ph比值的影响

Pr/Ph比值一直作为重要的生物标志物参数,其不仅与生源、沉积环境条件有关,而且在一定程度上还受成熟度影响。本论文对取自南海珠江口盆地西部不同有机相的陆相烃源岩样品进行了生排烃热模拟实验,获取了不同温度点的可溶有机质（油）,结合对不同成熟度地质烃源岩样品抽提物的分析,较系统的研究了油/抽提物的Pr/Ph比值随着成熟度的变化规律。研究结果表明,在Ro为0.6%～1.8%阶段,中深湖相Ⅱ型和浅湖相-河沼相Ⅲ型烃源岩生成油的Pr/Ph比值随着成熟度的增高而降低,并且Ⅲ型烃源岩降低的幅度明显大于II型烃源岩,而到高成熟度阶段,两类烃源岩的Pr/Ph比值相近。应用Pr/Ph比值进行油-油对比、油-源对比、判识古沉积环境等,需要充分考虑成熟度对该比值的影响,尤其是对于含有陆相Ⅲ型烃源岩的沉积盆地,应结合其它地球化学参数综合对比分析。     

Organic geochemistry and petrography of Lower Cretaceous Wealden black shales of the Lower Saxony Basin: The transition from lacustrine oil shales to gas shales

Ninety-seven Wealden black shale samples from three wells in the Lower Saxony Basin have been studied by organic geochemical and organic petrographical methods to determine their maturity, organic facies and depositional environment. The maturities of the three wells range from early mature (Ex-A), late to postmature (Ex-C) to overmature (Ex-B) as determined by vitrinite reflectance measurements, diamondoid ratios and other geochemical maturity parameters. Ex-C and Ex-B show distinct petrographic features related to oil generation and migration. In particular, the occurrence of dispersed solid bitumen replacing initial type I kerogen suggests a formerly active petroleum system. Structural and textural differences between early mature alginites and solid bitumen in postmature to overmature samples show an alteration of the pore system with increasing maturity. A freshwater depositional environment is indicated by widespread occurrence of botryococcus algae and other small alginite particles predominating in the immature well. These alginites are absent in the more mature gas shales of wells Ex-C and Ex-B. Geochemical evidence of algae and phytoplankton in general is provided by numerous biomarker parameters, while the occurrence of β-carotane in some samples indicates events of increased salinity, although no hypersaline conditions are inferred due to very low gammacerane indices. Increased amounts of vitrinite and inertinite in samples of Ex-B suggest locally significant terrigenous input of organic matter for some periods during Wealden Shale deposition. High sulfur/organic carbon ratios provide evidence for sulfate rich waters and (partly) anoxic bottom water conditions. While the lower mature lacustrine source rocks generate paraffinic/waxy oils, gas and condensates are produced at post-mature stages. Furthermore, maturity distribution maps from 3D numerical petroleum systems modeling reveal substantial differences in respect to petroleum generation.     

Methane adsorption comparison of different thermal maturity kerogens in shale gas system

To determine the effect of thermal maturity on the methane sorption in shale gas system, two different thermal maturity kerogens of type II isolated from Barnett shale of Fort Worth Basin were used to measure the methane adsorption amount under the pressure ranging from 0 to 14 MPa at constant temperatures. One kerogen was called Lee C-5-1 with 0.58% of vitrinite reflectance; the other was called Blakely#1 kerogen with 2.01% of vitrinite reflectance. The results suggested that the methane sorption capacity of kerogen Blakely#1 was higher than the immature kerogen Lee C-5-1, and its Langmuir constant and Langmuir maximum sorption amount, which were reached by fitting the measured data for at least square method, greater than the immature kerogen Lee C-5-1. This may be associated with that nanopores opened up during the degradation of organic matter, and which increased the specific surface area of kerogen. Therefore, the over mature kerogen has greater methane adsorption capacity.     

Characterization of organic carbon in black shales of the Kachchh basin,Gujarat, India

Thirty-three black shale samples from four locations on the onland Kachchh basin, western India were analyzed to characterize organic carbon (OC), thermal maturity and to determine the hydrocarbon potential of the basin. Upper Jurassic black shales from the Jhuran Formation (Dhonsa and Kodki areas) are characterized by the presence of chlorite, halloysite, high \(T_{\mathrm{max}}\), low OC, low hydrogen index and high oxygen index. These parameters indicate the OC as type IV kerogen, formed in a marine environment. The rocks attained thermal maturity possibly during Deccan volcanism. Early Eocene samples of the Naredi Formation (Naliya-Narayan Sarovar Road (NNSR) and the Matanomadh areas) are rich in TOC, smectite, chlorite and framboidal pyrite, but have low \(T_{\mathrm{max}}\). These indicate deposition of sediments in a reducing condition, probably in a lagoonal/marsh/swamp environment. Organic carbon of the Naredi Formation of NNSR may be considered as immature type III to IV kerogen, prone to generate coal. Core samples from the Naredi Formation of the Matanomadh area show two fold distribution in terms of kerogen. Organic carbon of the upper section is immature type III to IV kerogen, but the lower section has type II to III kerogen having potential to generate oil and gas after attaining appropriate thermal maturity.     

福山凹陷西部地区原油地化特征与油源对比

福山凹陷是北部湾盆地的重要含油气单元,是一个“小而肥”的富生烃凹陷.充分利用烃源岩和原油的有机地球化学等分析测试数据,针对凹陷内研究较少的西部地区的原油进行地化特征分析,进而研究该区油气藏的油源.研究结果显示凹陷西部原油主要为轻质油,族组分以高饱和烃和芳烃含量、低非烃+沥青质含量为特点.凹陷西部的原油生油母质为陆源高等植物和低等水生生物的混合来源,为陆相湖盆混合型母质特征,不同区块不同层段原油的生油母质具有一定的差别.研究区生油母质沉积环境为偏淡水氧化沉积环境的湖沼相,结合原油成熟度,可将研究区原油划分为3类:(1) 美台-红光流三上段原油,具有“中等成熟度,低奥利烷含量”特征;(2) 永安流一上段原油,具有“高成熟度,高奥利烷含量”特征;(3) 朝阳流一上段原油,具有“低成熟度,中等奥利烷含量”特征.进一步油源对比结果显示,美台-红光地区流三段原油来自流三段和流二下段烃源岩,而永安地区的流一段烃源岩为永安地区的原油提供油源.      

An organic geochemical investigation on organic rich sediments from two Neogene formations in the Klias Peninsula area,West Sabah,Malaysia

Twenty organic rich outcrop samples from the Belait and Setap Shale formations in the Klias Peninsula area, West Sabah, were analysed by means of organic petrology and geochemical techniques. The aims of this study are to assess the type of organic matter, thermal maturity and established source rock characterization based primarily on Rock-Eval pyrolysis data. The shales of the Setap Shale Formation have TOC values varying from 0.6 wt%–1.54 wt% with a mean hydrogen index (HI) of 60.1 mg/g, whereas the shal...     

Trace element characterisation of Cretaceous Orange Basin hydrocarbon source rocks

Trace elements in the kerogen fraction of hydrocarbon source rock samples from two wells obtained from the Cretaceous units of the Orange Basin, South Africa were determined using X-ray fluorescence spectrometry, in order to determine their distribution and geochemical significances. The concentrations of the elements (As, Ce, Co, Cu, Fe, Mo, Ni, Pb and V) determined ranged from 0.64 to 47,300 ppm for the samples analysed. The total organic carbon (TOC) values indicate that the samples are organic rich but did not show any trend with the distribution of the trace metals except Ce, Mo and Pb. Dendrogram cluster analysis discriminated the samples into three groups on the basis of their level of thermal maturity. Thermal maturity has a significant effect on the distribution of the trace metals. Cobalt/Ni and V/Ni ratios and cross plots of the absolute values of V and Ni indicate that the samples had significant marine organic matter input. The V and Ni contents and V/(V + Ni) ratio indicate that the organic matter of the source rocks had been deposited in reducing conditions. Despite the similarities in the organic matter source input and depositional environment of the organic matter of the samples from the two well, cross plots of Co/Ni versus V/Ni and Mo/Ni versus Co/Ni were able to reveal subtle differences. Cluster analysis of the samples was also able to reveal the subtle thermal maturity differences of the samples.     

海相碳酸盐岩烃源岩热解动力学研究:全岩和干酪根的对比

我国海相碳酸盐岩地层分布广泛,厚度巨大,经历的地质历史较长,特点是有机质丰度低,多处于高过成熟阶段.碳酸盐岩烃源岩评价对我国的油气资源评价与勘探至关重要.用生烃动力学方法来研究碳酸盐岩生油气过程是一个值得探索的研究方向.本文通过生烃动力学热模拟实验,求取了碳酸盐岩全岩和其干酪根不同烃类组分(甲烷、 C2～ C5气态烃)的生成动力学参数并进行对比.结果表明,在生烃动力学热解实验中,全岩和其干酪根具有相似的动力学参数,采用烃源岩应该比干酪根更符合实际,但是干酪根样品可以测得更为详细的实验数据,因此可以根据样品的情况,选择合理且易行的实验条件.在此基础上,以本文得到的参数作为参照指标,用动力学方法外推到地质实际中,可准确地提出适合我国的碳酸盐岩生烃定量模型,能为碳酸盐岩的资源评估等方面给出定量数值,从而为有效烃源岩的定量评价提供一种新的方法和途径.     

Biomarker analysis of the upper Jurassic Naokelekan and Barsarin formations in the Miran Well-2, Miran oil field,Kurdistan region,Iraq

The Miran oilfield is one of the new oil fields in Kurdistan region, northern Iraq, located in the Sulaimani Governorate. Twelve Cuttings samples from the Upper Jurassic Naokelekan and Barsarin formations in well Miran-2 were selected for detailed organic geochemical investigations. All the samples were subjected to bitumen extraction in order to study any biomarkers present using gas chromatography-mass spectrometry. The dominance of low-molecular-weight n-alkanes and other calculated parameters indicate a marine source for the organic matter derived from planktonic algal and bacterial precursors deposited under anoxic conditions. The isoprenoids/n-alkanes ratios indicate type II and mixed II/III kerogen for both formations. The type II/III kerogen is characteristic of transitional environment under anoxic to dysoxic conditions as also indicated by the homohopane index for studied samples. More argillaceous carbonate rocks were deposited when reducing conditions were prevalent. Medium to high gammacerane index values in the rock extracts probably indicate a stratified water column during deposition of both formations. The studied samples from both formations have entered peak oil window maturity as reflected from the biomarker ratios from both aliphatic and aromatic fractions of the extracts.     

Source Rock Characterization and Petroleum Systems in North Ghadames Basin,Southern Tunisia

This paper presents geochemical analysis of drilled cutting samples from the OMZ‐2 oil well located in southern Tunisia. A total of 35 drill‐cutting samples were analyzed for Rock‐Eval pyrolysis, total organic carbon (TOC), bitumens extraction and liquid chromatography. Most of the Ordovician, Silurian and Triassic samples contained high TOC contents, ranging from 1.00 to 4.75% with an average value of 2.07%. The amount of hydrocarbon yield (pyrolysable hydrocarbon: S2b) expelled during pyrolysis indicates a good generative potential of the source rocks. The plot of TOC versus S2b, indicates a good to very good generative potential for organic matter in the Ordovician, Silurian and Lower Triassic. However, the Upper Triassic and the Lower Jurassic samples indicate fair to good generative potential. From the Vankrevelen diagram, the organic matter in the Ordovician, Silurian and Lower Triassic samples is mainly of type II kerogen and the organic matter from the Upper Triassic and the Lower Jurassic is dominantly type III kerogen with minor contributions from Type I. The thermal maturity of the organic matter in the analyzed samples is also evaluated based on the T_max of the S2b peak. The Ordovician and Lower Silurian formations are thermally matured. The Upper Silurian and Triassic deposits are early matured to matured. However, Jurassic formations are low in thermal maturity. The total bitumen extracts increase with depth from the interval 1800–3000 m. This enrichment indicates that the trapping in situ in the source rocks and relatively short distance vertical migration can be envisaged in the overlying reservoirs. During the vertical migration from source rocks to the reservoirs, these hydrocarbons are probably affected by natural choromatography and in lower proportion by biodegradation.     

利用双金刚烷指标研究济阳坳陷凝析油的成熟度和类型

根据济阳坳陷烃源岩中的双金刚烷指标与镜质组反射率实测值,建立了它们之间的数值对应关系,根据这种关系确定了济阳坳陷凝析油的成熟度,它们均属成熟—高成熟阶段的演化产物,Ro值在1.26%以上。利用二甲基双金刚烷类型判识指标,判识出济阳坳陷凝析油为煤成和湖相混合有机质生成两种类型。     

Source rock potential of selected Cretaceous shales,Orange Basin,South Africa

Twenty Cretaceous shale samples from two wells in the Orange Basin of South Africa were evaluated for their source rock potential. They were sampled from within a 1400 m-thick sequence in boreholes drilled through Lower to Upper Cretaceous sediments. The samples exhibit total organic carbon (TOC) content of 1.06–2.17%; Rock-Eval S2 values of 0.08–2.27 mg HC/g; and petroleum source potential (SP), which is the sum of S1 and S2, of 0.10–2.61 mg HC/g, all indicating the presence of poor to fair hydrocarbon generative potential. Hydrogen index (HI) values vary from 7 to 128 mg HC/g organic carbon and oxygen index (OI) ranges from 37 to 195 mg CO₂/g organic carbon, indicating predominantly Type III kerogen with perhaps minor amounts of Type IV kerogen. The maturity of the samples, as indicated by T _max values of 428–446°C, ranges from immature to thermally mature with respect to oil generation. Measured vitrinite reflectance values (%Ro) of representative samples indicate that these samples vary from immature to mature, consistent with the thermal alteration index (TAI) (spore colour) and fluorescence data for these samples. Organic petrographic analysis also shows that amorphous organic matter is dominant in these samples. Framboidal pyrite is abundant and may be indicative of a marine influence during deposition. Although our Rock-Eval pyrolysis data indicate that gas-prone source rocks are prevalent in this part of the Orange Basin, the geochemical characteristics of samples from an Aptian unit at 3318 m in one of the wells suggest that better quality source rocks may exist deeper, in more distal depositional parts of the basin.     

Geochemical Investigation of the Cretaceous Crude Oil Reservoirs and Source Rock Samples in One of the Abadan Plain Oilfields, SW Iran

Crude oil and source rock samples from one of the main oilfields of the Abadan Plain, Zagros, Iran were analyzed geochemically. Rock-Eval pyrolysis was conducted on Kazhdumi (Upper Cretaceous) and Gadvan (Lower Cretaceous) formations, which are the probable source rocks for the oil in the region. The results indicated that the Kazhdumi Formation can be classified as a fair-to-excellent source rock, while the Gadvan Formation can be identified as having poor-to-good source rock in the basin. Based on the cross-plots of HI versus OI and S2 versus TOC, types II and III kerogen were identified from studied source samples in the area. Determination of the main fraction percentages of the Sarvak and Fahliyan crude oils represented that the oils from the Sarvak reservoir are paraffinic-naphthenic and aromatic-intermediate, whilst that from the Fahliyan reservoir is paraffinic and paraffinic-naphthenic. Biomarker ratios of the saturated fractions of oil from both reservoirs indicate that the source rocks formed in reducing marine environments with carbonate-shale lithology. Furthermore, biomarker data helped to distinguish the degree of biodegradation in the studied oils. According to geochemical analysis, oil samples from the Fahliyan reservoir were generated at a higher thermal maturity than the Sarvak reservoir samples.     

The hydrocarbon potential, thermal maturity, sequence stratigraphic setting and depositional palaeoenvironment of carbonaceous shale and lignite successions of Panandhro, northwestern Kutch Basin, Gujarat, Western India

The objective of the present paper is to provide geochemical and palynological data to characterize lignites and carbonaceous shales from Panandhro, northwestern Kutch Basin, Gujarat, Western India, in terms of their hydrocarbon potential, thermal maturity, sequence stratigraphic settings and depositional palaeoenvironment. The samples, collected in Panandhro lignite mine, belong to Naredi Formation of Late Paleocene-Early Eocene age. The geochemical results are based on proximate analysis, ultimate analysis, X-ray diffraction and Rock-Eval py-rolysis analyses, whereas palynological data include palynofossil composition and thermal alteration index (TAI). The TOC, hydrogen index (HI), cracked hydrocarbon (S2), bitumen index (BI), quality index (QI), and the total genetic potential (S1+S2) values indicate that the studied lignites and carbonaceous shales have good source rock potential. The organic matter is predominantly of type II and type II/III kerogen, which has potential to generate oil as well as gas. Thermal maturity determined from thermal alteration index (TAI), T _max and production index (PI) indicates that the organic matter is immature, and in the diagenesis stage of organic matter transformation. The deposition of the studied carbonaceous shales and lignites took place in palaeoenvironments varying from brackish mangrove to freshwater swamp. This study indicates that the proportion of ferns, palms, volatile matter content, S/C, H/C ratios, as well as the presence of siderite and quartz can be used as an indicator of accommodation trends in the coal depositional system. The Panandhro carbonaceous shales and lignites were deposited during the lowstand systems tract with many cycles of small magnitude trangressive-regressive phases. Thus, the geochemistry and ecological palynology are useful not only for the investigation of coal quality and origin, but also to infer accommodation space settings of the mire. This can be gainfully utilized in the coal industry for coal mine planning, development and exploitation, because of the predictive ability to infer changes in stratigraphy and coal quality.     

Composition of Kerogen in Kupferschiefer from Southwest Poland

Thirty-seven Kupferschiefer samples from southwestern Poland were analyzed by microscopy, Rock-Eval approach and instrumental neutron activation analysis to understand the geochemical and morphological characteristics of kerogen present in the samples. The analytical results indicate that there are two different types of kerogens. One type was only subjected to thermal alteration processes, and the other was further oxidized after deposition of the sediment.In the oxidized samples migrabitumen was transformed into pyrobitumen. Rock-Eval analyses show a significant decrease in HI values in the oxidized samples and an increase in OI values in relation to the samples that were not influenced by oxidation. Variations in S2 versus Corg contents indicate a change in kerogen from Type II to Type III with progressing oxidation. The presence of pyrobitumen and the depletion of hydrogen in the altered kerogen allow one to conclude that the kerogen was used as hydrogen donor for thermochemical sulfate reduction(TSR).     

下古生界海相碳酸盐岩干酪根成熟度研究方法

中国下古生界海相碳酸盐岩干酪根成熟度研究是目前在油气勘探过程中讨论的热点和难点问题之一 ,如何认识下古生界烃源岩中有机质热演化始终是一个悬而未决的问题。通过对以往常规成熟度指标的探讨 ,以及深入研究下古生界海相碳酸盐岩干酪根的特殊性 ,笔者提出了 3种最新方法 :(1)利用干酪根固体13 CNMR所测算的干酪根结构参数芳核平均结构尺寸Xb 较准确地反映碳酸盐岩的热成熟度 ;(2 )双金刚烷指标XMD作为高—过成熟碳酸盐烃源岩成熟度衡量标尺 ;(3)海相镜质组反射率能很好地反映缺乏陆源镜质体的下古生界碳酸盐岩的成熟度。利用这些成果对华北地区下古生界成熟度进行了测定 ,与地质背景甚为吻合 ,效果很好。证明它们确是评价下古生界海相碳酸盐岩干酪根成熟度行之有效的新方法。     

甘肃西成铅—锌矿田干酪根的特征

本文对西成矿田中泥盆统内含有机碳岩石中干酪根分析，认为该区内的干酪根主要由镜质体，壳质体，藻质体，惰质体，惰质组和矿物质组成，属于腐植型干酪根，颜色从淡黄到黑色，从西向东颜色加深，Ｒ０值也有同样的趋势，说明在矿区内成熟度不一致，热解分析发现Ｓ２峰有分叉现象，经过氯仿抽提后分叉消失，从可溶有机质的色谱分析中发现有大量氮硫氧化合物，证明分叉现象可能是由氮硫氧化合物引起。Ｒ０值越大，反映出干酪根的再改造     

Source rock potential (TOC + hydrogen index) evaluation by integrating well log and geochemical data

Evaluation of source rock potential using well log data alone, e.g. density or sonic log, is limited to the assessment of total organic carbon (TOC) content. Well logs that directly measure the most important source quality parameter, the hydrogen content of the kerogen, do not exist. Therefore, a method is proposed that combines log-derived TOC data with calibration schemes relating TOC content to Hydrogen Index and maturity for individual source rock sets. The method has been applied to the compositionally heterogeneous Kimmeridge Clay Formation of the North Sea and the homogeneous Lower Toarcian Shale of N.-Germany. The combination of well log and geochemical data greatly improves the accuracy with which the lateral and vertical distribution of source rocks and their potential can be predicted on a basin and prospect level.