Geochemistry,reservoir characterization and hydrocarbon generation potential of lacustrine shales: A case of YQ-1 well in the Yuqia Coalfield,northern Qaidam Basin,NW China

Ever since a breakthrough of marine shales in China, lacustrine shales have been attracting by the policy makers and scientists. Organic-rich shales of the Middle Jurassic strata are widely distributed in the Yuqia Coalfield of northern Qaidam Basin. In this paper, a total of 42 shale samples with a burial depth ranging from 475.5 m to 658.5 m were collected from the Shimengou Formation in the YQ-1 shale gas borehole of the study area, including 16 samples from the Lower Member and 26 samples from the Upper Member. Geochemistry, reservoir characteristics and hydrocarbon generation potential of the lacustrine shales in YQ-1 well were preliminarily investigated using the experiments of vitrinite reflectance measurement, maceral identification, mineralogical composition, carbon stable isotope, low-temperature nitrogen adsorption, methane isothermal adsorption and rock eval pyrolysis. The results show that the Shimengou shales have rich organic carbon (averaged 3.83%), which belong to a low thermal maturity stage with a mean vitrinite reflectance (R_o) of 0.49% and an average pyrolytic temperature of the generated maximum remaining hydrocarbon (T_max) of 432.8 °C. Relative to marine shales, the lacustrine shales show low brittleness index (averaged 34.9) but high clay contents (averaged 55.1%), high total porosities (averaged 13.71%) and great Langmuir volumes (averaged 4.73 cm⁻³ g). Unlike the marine and marine-transitional shales, the quartz contents and brittleness index (BI) values of the lacustrine shales first decrease then increase with the rising TOC contents. The kerogens from the Upper Member shales are dominant by the oil-prone types, whereas the kerogens from the Lower Member shales by the gas-prone types. The sedimentary environment of the shales influences the TOC contents, thus has a close connection with the hydrocarbon potential, mineralogical composition, kerogen types and pore structure. Additionally, in terms of the hydrocarbon generation potential, the Upper Member shales are regarded as very good and excellent rocks whereas the Lower Member shales mainly as poor and fair rocks. In overall, the shales in the top of the Upper Member can be explored for shale oil due to the higher free hydrocarbon amount (S₁), whereas the shales in the Lower Member and the Upper Member, with the depths greater than 1000 m, can be suggested to explore shale gas.     

Organic geochemistry and reservoir characterization of the organic matter-rich calcilutite in the Shulu Sag,Bohai Bay Basin,North China

Although extensive studies have been conducted on unconventional mudstone (shales) reservoirs in recent years, little work has been performed on unconventional tight organic matter-rich, fine-grained carbonate reservoirs. The Shulu Sag is located in the southwestern corner of the Jizhong Depression in the Bohai Bay Basin and filled with 400–1000 m of Eocene lacustrine organic matter-rich carbonates. The study of the organic matter-rich calcilutite in the Shulu Sag will provide a good opportunity to improve our knowledge of unconventional tight oil in North China. The dominant minerals of calcilutite rocks in the Shulu Sag are carbonates (including calcite and dolomite), with an average of 61.5 wt.%. The carbonate particles are predominantly in the clay to silt size range. Three lithofacies were identified: laminated calcilutite, massive calcilutite, and calcisiltite–calcilutite. The calcilutite rocks (including all the three lithofacies) in the third unit of the Shahejie Formation in the Eocene (Es₃) have total organic carbon (TOC) values ranging from 0.12 to 7.97 wt.%, with an average of 1.66 wt.%. Most of the analyzed samples have good, very good or excellent hydrocarbon potential. The organic matter in the Shulu samples is predominantly of Type I to Type II kerogen, with minor amounts of Type III kerogen. The temperature of maximum yield of pyrolysate (T_max) values range from 424 to 452 °C (with an average of 444 °C) indicating most of samples are thermally mature with respect to oil generation. The calcilutite samples have the free hydrocarbons (S₁) values from 0.03 to 2.32 mg HC/g rock, with an average of 0.5 mg HC/g rock, the hydrocarbons cracked from kerogen (S₂) yield values in the range of 0.08–57.08 mg HC/g rock, with an average of 9.06 mg HC/g rock, and hydrogen index (HI) values in the range of 55–749 mg HC/g TOC, with an average of 464 mg HC/g TOC. The organic-rich calcilutite of the Shulu Sag has very good source rock generative potential and have obtained thermal maturity levels equivalent to the oil window. The pores in the Shulu calcilutite are of various types and sizes and were divided into three types: (1) pores within organic matter, (2) interparticle pores between detrital or authigenic particles, and (3) intraparticle pores within detrital grains or crystals. Fractures in the Shulu calcilutite are parallel to bedding, high angle, and vertical, having a significant effect on hydrocarbon migration and production. The organic matter and dolomite contents are the main factors that control calcilutite reservoir quality in the Shulu Sag.     

Pore characteristic analysis of a lacustrine shale: A case study in the Ordos Basin,NW China

Organic shales deposited in a continental environment are well developed in the Ordos Basin, NW China, which is rich in hydrocarbons. However, previous research concerning shales has predominantly focused on marine shales and barely on continental shales. In this study, geochemical and mineralogical analyses, high-pressure mercury intrusion and low-pressure adsorption were performed on 18 continental shale samples obtained from a currently active shale gas play, the Chang 7 member of Yanchang Formation in the Ordos Basin. A comparison of all these techniques is provided for characterizing the complex pore structure of continental shales.Geochemical analysis reveals total organic carbon (TOC) values ranging from 0.47% to 11.44%, indicating that there is abundant organic matter (OM) in the study area. Kerogen analysis shows vitrinite reflectance (Ro) of 0.68%–1.02%, indicating that kerogen is at a mature oil generation stage. X-ray diffraction mineralogy (XRD) analysis indicates that the dominant mineral constituents of shale samples are clay minerals (which mainly consist of illite, chlorite, kaolinite, and negligible amounts of montmorillonite), quartz and feldspar, followed by low carbonate content. All-scale pore size analysis indicates that the pore size distribution (PSD) of shale pores is mainly from 0.3 to 60 nm. Note that accuracy of all-scale PSD analysis decreases for pores less than 0.3 nm and more than 10 μm. Experimental analysis indicates that mesopores (2–50 nm) are dominant in continental shales, followed by micropores (<2 nm) and macropores (50 nm–10 μm). Mesopores have the largest contribution to pore volume (PV) and specific surface area (SSA). In addition, plate- and sheet-shaped pores are dominant with poor connectivity, followed by hybrid pores. Results of research on factors controlling pore structure development show that it is principally controlled by clay mineral contents and Ro, and this is different from marine systems. This study has important significance in gaining a comprehensive understanding of continental shale pore structure and the shale gas storage–seepage mechanism.     

Enrichment and distribution of shale oil in the Cretaceous Qingshankou Formation,Songliao Basin,Northeast China

The Songliao Basin is a large-scale petroliferous basin in China. With a gradual decline in conventional oil production, the exploration and development of replacement resources in the basin is becoming increasingly important. Previous studies have shown that the Cretaceous Qingshankou Formation (K₂qn) has favorable geological conditions for the formation of shale oil. Thus, shale oil in the Qingshankou Formation represents a promising and practical replacement resource for conventional oil. In this study, geological field surveys, core observation, sample tests, and the analysis of well logs were applied to study the geochemical and reservoir characteristics of shales, identify shale oil beds, build shale oil enrichment models, and classify favorable exploration areas of shale oil from the Cretaceous Qingshankou Formation. The organic matter content is high in shales from the first member of the Cretaceous Qingshankou Formation (K₂qn¹), with average total organic carbon (TOC) content exceeding 2%. The organic matter is mainly derived from lower aquatic organisms in a reducing brackish to fresh water environment, resulting in mostly type I kerogen. The vitrinite reflectance (Ro) and the temperature at which the maximum is release of hydrocarbons from cracking of kerogen occurred during pyrolysis (T_max) respectively range from 0.5% to 1.1% and from 430 °C to 450 °C, indicating that the K₂qn¹ shales are in the low-mature to mature stage (Ro ranges from 0.5% to 1.2%) and currently generating a large amount of oil. The favorable depth for oil generation and expulsion is 1800–2200 m and 1900–2500 m, respectively as determined by basin modeling. The reserving space of the K₂qn¹ shale oil includes micropores and mircofractures. The micropore reservoirs are developed in shales interbedded with siltstones exhibiting high gamma ray (GR), high resistivity (Rt), low density (DEN), and slightly abnormal spontaneous potential (SP) in the well-logging curves. The microfracture reservoirs are mainly thick shales with high Rt, high AC (acoustic transit time), high GR, low DEN, and abnormal SP. Based on the shale distribution, geochemical characteristics, reservoir types, fracture development, and the process of shale oil generation and enrichment, the southern Taikang and northern Da'an are classified as two favorable shale oil exploration areas in the Songliao Basin.     

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.     

Black shales in Ukraine – A review

As a result of a long-lasting and complex geological history, organic-matter-rich fine-grained rocks (black shales) with widely varying ages can be found on Ukrainian territory. Several of them are proven hydrocarbon source rocks and may hold a significant shale gas potential.Thick Silurian black shales accumulated along the western margin of the East European Craton in a foreland-type basin. By analogy with coeval organic-matter-rich rocks in Poland, high TOC contents and gas window maturity can be expected. However, to date information on organic richness is largely missing and maturity patterns remain to be refined.Visean black shales with TOC contents as high as 8% and a Type III-II kerogen accumulated along the axis of the Dniepr-Donets rift basin (DDB). They are the likely source for conventional oil and gas. Oil-prone Serpukhovian black shales accumulated in the shallow northwestern part of the DDB. Similar black shales probably may be present in the Lviv-Volyn Basin (western Ukraine).Middle Jurassic black shales up to 500 m thick occur beneath the Carpathian Foredeep. They are the likely source for some heavy oil deposits. TOC contents up to 12% (Type II) have been recorded, but additional investigations are needed to study the vertical and lateral variability of organic matter richness and maturity.Lower Cretaceous black shales with a Type III(-II) kerogen (TOC > 2%) are widespread at the base of the Carpathian flysch nappes, but Oligocene black shales (Menilite Fm.) rich in organic matter (4–8% TOC) and containing a Type II kerogen are the main source rock for oil in the Carpathians. Their thermal maturity increases from the external to the internal nappes.Oligocene black shales are also present in Crimea (Maykop Fm.). These rocks typically contain high TOC contents, but data from Ukraine are missing.     

Could the conventionally known Abu Roash “G” reservoir (upper Cenomanian) be a promising active hydrocarbon source in the extreme northwestern part of Egypt? Palynofacies,palaeoenvironmental, and organic geochemical answers

In different areas of the Western Desert of Egypt, the Abu Roash “G” Member exhibits either a reservoir or source affinity. Thus, thirteen cutting samples covering the Abu Roash “G” Member were selected from the Nest-1A well at Matruh Basin to investigate its hydrocarbon source potential. Palynological age dating of the section that is calibrated with foraminifera and ostracodes enabled a proper identification of the “G” Member. Detailed analysis of the vertical distribution of particulate organic matter of this member shows two palynofacies types. PF-1 reflects an outer middle shelf depositional environment of prevailed reducing (suboxic-anoxic) conditions for the organic-rich shales of the lower “G” Member (samples 1–8). While, PF-2 reflects a minor regression that resulted in deposition of another organic-rich shales of the upper “G” Member (samples 9–13) in an inner middle shelf setting under the same prevailing reducing (suboxic-anoxic) conditions.Organic geochemical analysis reveals good to very good potential of the “G” Member as a hydrocarbon source rock (1.8–2.41, avg. 2.15 total organic content wt %). It also shows good to very good petroleum potential (PP: 4.8–11 , avg. 8 mg HC/g rock). Pyrolsis and palynofacies analyses show kerogen type II for the lower “G” Member (samples 1–8), which is characterized by high Hydrogen index (HI: 396 and 329 mg HC/g TOC at depths 1500 and 1560 m) and very high dominance of oil-prone material (amorphous organic matter “AOM”, marine palynomorphs, and sporomorphs) and very rare occurrence of gas-prone material (brown phytoclasts). The upper “G” Member (samples 9–13) shows kerogen type II-III, which is characterized by a lower HI value of 213 mg HC/g TOC at depth 1340 m and it contains fewer amounts of gas-prone material and relatively lower AOM and marine palynomorphs in comparison to the upper “G” Member. Maturation parameters T_max (430–433 °C), production index (PI: 0.1 mg HC/g rock), and thermal alteration index (TAI: 2+) indicate the lower “G” Member has already entered the early oil-window kitchen, and it is expected to produce oil. The upper “G” Member is expected to produce only oil with no gas shows, because it is marginally mature (T_max 426 °C, PI 0.2, TAI 2). The source potential index (SPI: 5.3 t HC/m²) of the “G” Member shows it as currently generating moderate quantities of oil in the area of Nest-1A well.Consequently, the organic-rich shales of the “G” Member are suggested here as a promising, active oil source rock in that extreme northwestern part of the Western Desert of Egypt. However, for commercial oil recovery from the Abu Roash “G” Member, it is highly recommended to explore the depocentre of Matruh Basin at about 150 km east the Nest-1A well.     

Source rock characteristics and hydrocarbon generation modelling of Upper Cretaceous Mukalla Formation in the Jiza-Qamar Basin,Eastern Yemen

The Upper Cretaceous Mukalla coals and other organic-rich sediments which are widely exposed in the Jiza-Qamar Basin and believed to be a major source rocks, were analysed using organic geochemistry and petrology. The total organic carbon (TOC) contents of the Mukalla source rocks range from 0.72 to 79.90% with an average TOC value of 21.50%. The coals and coaly shale sediments are relatively higher in organic richness, consistent with source rocks generative potential. The samples analysed have vitrinite reflectance in the range of 0.84–1.10 %Ro and pyrolysis T_max in the range of 432–454 °C indicate that the Mukalla source rocks contain mature to late mature organic matter. Good oil-generating potential is anticipated from the coals and coaly shale sediments with high hydrogen indices (250–449 mg HC/g TOC). This is supported by their significant amounts of oil-liptinite macerals are present in these coals and coaly shale sediments and Py-GC (S₂) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀. The shales are dominated by Type III kerogen (HI < 200 mg HC/g TOC), and are thus considered to be gas-prone.One-dimensional basin modelling was performed to analysis the hydrocarbon generation and expulsion history of the Mukalla source rocks in the Jiza-Qamar Basin based on the reconstruction of the burial/thermal maturity histories in order to improve our understanding of the of hydrocarbon generation potential of the Mukalla source rocks. Calibration of the model with measured vitrinite reflectance (Ro) and borehole temperature data indicates that the present-day heat flow in the Jiza-Qamar Basin varies from 45.0 mW/m² to 70.0 mW/m² and the paleo-heat flow increased from 80 Ma to 25 Ma, reached a peak heat-flow values of approximately 70.0 mW/m² at 25 Ma and then decreased exponentially from 25 Ma to present-day. The peak paleo-heat flow is explained by the Gulf of Aden and Red Sea Tertiary rifting during Oligocene-Middle Miocene, which has a considerable influence on the thermal maturity of the Mukalla source rocks. The source rocks of the Mukalla Formation are presently in a stage of oil and condensate generation with maturity from 0.50% to 1.10% Ro. Oil generation (0.5% Ro) in the Mukalla source rocks began from about 61 Ma to 54 Ma and the peak hydrocarbon generation (1.0% Ro) occurred approximately from 25 Ma to 20 Ma. The modelled hydrocarbon expulsion evolution suggested that the timing of hydrocarbon expulsion from the Mukalla source rocks began from 15 Ma to present-day.     

The origin,type and preservation of organic matter of the Barremian–Aptian organic-rich shales in the Muglad Basin,Southern Sudan,and their relation to paleoenvironmental and paleoclimate conditions

Barremian–Aptian organic-rich shales from Abu Gabra Formation in the Muglad Basin were analysed using geochemical and petrographic analyses. These analyses were used to define the origin, type of organic matters and the influencing factors of diagenesis, including organic matter input and preservation, and their relation to paleoenvironmental and paleoclimate conditions. The bulk geochemical characteristics indicated that the organic-rich shales were deposited in a lacustrine environment with seawater influence under suboxic conditions. Their pyrolysis hydrogen index (HI) data provide evidence for a major contribution by Type I/II kerogen with HI values of >400 mg HC/g TOC and a minor Type II/III contribution with HI values <400 mg HC/g TOC. This is confirmed by kerogen microscopy, whereby the kerogen is characterized by large amounts of structured algae (Botryococcus) and structureless (amorphous) with a minor terrigenous organic matter input. An enhanced biological productivity within the photic zone of the water columns is also detected. The increased biological productivity in the organic-rich shales may be related to enhanced semi-arid/humid to humid-warm climate conditions. Therefore, a high bio-productivity in combination with good organic matter preservation favoured by enhanced algae sizes are suggested as the OM enrichment mechanisms within the studied basin.     

Petroleum source rock potential of the Silurian Dadaş shales in the Hazro and Korudağ regions of Southeast Anatolia,Turkey

Shales of the Silurian Dadaş Formation exposed in the southeast Anatolia were investigated by organic geochemical methods. The TOC contents range from 0.24 to 1.48 wt% for the Hazro samples and 0.19 to 3.58 wt% for the Korudağ samples. Tmax values between 438 and 440 °C in the Hazro samples indicate thermal maturity; Tmax values ranging from 456 to 541 °C in the Korudağ samples indicate late to over-maturity. Based on the calculated vitrinite reflectance and measured vitrinite equivalent reflectance values, the Korudağ samples have a maximum of 1.91%R_(g-v), in the gas generation window, while a maximum value of 0.79%R_(amor-v) of one sample from the Hazro section is in the oil generation window. Illite crystallinity (IC) values of all samples are consistent with maturity results.Pr/Ph ratios ranging from 1.32 to 2.28 and C₂₉/C₃₀ hopane ratios > 1.0 indicate an anoxic to sub-oxic marine-carbonate depositional environment.The Hazro shales do not have any shale oil or shale gas potential because of their low oil saturation index values and early to moderate thermal maturation. At first glance, the Korudağ shales can be considered a shale gas formation because of their organic richness, thickness and thermal over-maturity. However, the low silica content and brittle index values of these shales are preventing their suitability as shale gas resource systems.     

Pore characterization of organic-rich Lower Cambrian shales in Qiannan Depression of Guizhou Province,Southwestern China

Nine organic-rich shale samples of Lower Cambrian black shales were collected from a recently drilled well in the Qiannan Depression, Guizhou Province where they are widely distributed with shallower burial depth than in Sichuan Basin, and their geochemistry and pore characterization were investigated. The results show that the Lower Cambrian shales in Qiannan Depression are organic rich with TOC content ranging from 2.81% to 12.9%, thermally overmature with equivalent vitrinite reflectance values in the range of 2.92–3.25%, and clay contents are high and range from 32.4% to 53.2%. The samples have a total helium porosity ranging from 2.46% to 4.13% and total surface area in the range of 9.08–37.19 m²/g. The estimated porosity in organic matters (defined as the ratio of organic pores to the volume of total organic matters) based on the plot of TOC vs helium porosity is about 10% for the Lower Cambrian shales in Qiannan Depression and is far lower than that of the Lower Silurian shales (36%) in and around Sichan Basin. This indicates that either the organic pores in the Lower Cambrian shale samples have been more severely compacted than or they did not develop organic pores as abundantly as the Lower Silurian shales. Our studies also reveal that the micropore volumes determined by Dubinin–Radushkevich (DR) equation is usually overestimated and this overestimation is closely related to the non-micropore surface area of shales (i.e. the surface area of meso- and macro-pores). However, the modified BET equation can remove this overestimation and be conveniently used to evaluate the micropore volumes/surface area and the non-micropore surface areas of micropore-rich shales.     

Mineral types and organic matters of the Ordovician-Silurian Wufeng and Longmaxi Shale in the Sichuan Basin,China: Implications for pore systems,diagenetic pathways,and reservoir quality in fine-grained sedimentary rocks

Mineral types (detrital and authigenic) and organic-matter components of the Ordovician-Silurian Wufeng and Longmaxi Shale (siliceous, silty, argillaceous, and calcareous/dolomitic shales) in the Sichuan Basin, China are used as a case study to understand the control of grain assemblages and organic matter on pores systems, diagenetic pathway, and reservoir quality in fine-grained sedimentary rocks. This study has been achieved using a combination of petrographic, geochemical, and mercury intrusion methods. The results reveal that siliceous shale comprises an abundant amount of diagenetic quartz (40–60% by volume), and authigenic microcrystalline quartz aggregates inhibit compaction and preserve internal primary pores as rigid framework for oil filling during oil window. Although silty shale contains a large number of detrital silt-size grains (30–50% by volume), which is beneficial to preserve interparticle pores, the volumetric contribution of interparticle pores (mainly macropores) is small. Argillaceous shale with abundant extrabasinal clay minerals (>50% by volume) undergoes mechanical and chemical compactions during burial, leading to a near-absence of primary interparticle pores, while pores preserved between clay platelets are dominant with more than 10 nm in pore size. Pore-filling calcite and dolomite precipitated during early diagenesis inhibit later compaction in calcareous/dolomitic shale, but the cementation significantly reduces the primary interparticle pores. Pore-throat size distributions of dolomitic shale show a similar trend with silty shale. Besides argillaceous shale, all of the other lithofacies are dominated by OM pores, which contribute more micropores and mesopores and is positively related to TOC and quartz contents. The relationship between pore-throat size and pore volume shows that most pore volumes are provided by pore throats with diameters <50 nm, with a proportion in the order of siliceous (80.3%) > calcareous/dolomitic (78.4%) > silty (74.9%) > argillaceous (61.3%) shales. In addition, development degree and pore size of OM pores in different diagenetic pathway with the same OM type and maturity show an obvious difference. Therefore, we suggest that the development of OM pores should take OM occurrence into account, which is related to physical interaction between OM and inorganic minerals during burial diagenesis. Migrated OM in siliceous shale with its large connected networks is beneficial for forming more and larger pores during gas window. The result of the present work implies that the study of mineral types (detrital and authigenic) and organic matter-pores are better understanding the reservoir quality in fine-grained sedimentary rocks.     

Experimental investigation of thermal maturation on shale reservoir properties from hydrous pyrolysis of Chang 7 shale,Ordos Basin

Thermal maturity has a significant impact on hydrocarbon generation and the storage capacity within shales, but explicit and quantitative characterization of that impact on continental shales is scarce. To better understand how thermal maturation affects the organic and inorganic changes of the continental shale reservoirs, hydrous pyrolysis was performed to simulate the maturation process. TOC, Rock-Eval and adsorption isotherms tests were used to obtain various geochemical parameters of the shale solid residues. The results indicate that with pyrolysis temperature increasing from ambient temperature to 550 °C, the vitrinite reflectance increases from 0.5% to 2.5% Ro and the TOC (total organic carbon) loss weight reaches 25%. Regarding porosity, the fraction of micro-to meso-pores in the shale increases with an increase in the pyrolysis temperature, whereas the macro-pores do not change significantly. The total amount of gas adsorption does not necessarily increase as the TOC is consumed, but the gas adsorption capacity per unit of TOC increases with increasing thermal maturity. Our finding provides theoretical modelling for identifying shale gas development prospective zones according to thermal maturity mapping and for predicting quantitatively the geochemical and inorganic changes that occur with thermal evolution.     

Nano-scale pore structure and fractal dimension of organic-rich Wufeng-Longmaxi shale from Jiaoshiba area,Sichuan Basin: Investigations using FE-SEM,gas adsorption and helium pycnometry

Much attention have been recently paid to the upper Ordovician Wufeng shale (O₃w) and lower Silurian Longmaxi shale (S₁l) in the Jiaoshiba area of Sichuan Basin, which is now the largest producing shale gas field in China. Field emission scanning electron microscopy (FE-SEM), low pressure gas (N₂ and CO₂) adsorption, helium pycnometry, X-ray diffraction and geochemical analyses were performed to investigate the pore structure and fractal dimension of the pores in O₃w-S₁l shale formation in the Jiaoshiba area. FE-SEM images show that organic matter (OM) pores are dominant in the organic-rich samples and these pores are often irregular, bubble-like, elliptical and faveolate in shape, while in organic-poor samples, limited and isolated interparticle (interP), intraparticle (intraP) and OM pores are observed. Reversed S-shaped isotherms obtained from nitrogen adsorption are type Ⅱ, and hysteresis loops indicate that the shape of micropore in the samples is slit-or plate-like. BET surface areas and total pore volume vary from 12.2 to 27.1 m²/g and from 1.8 × 10⁻² to 2.9 × 10⁻² cm³/g, with an average of 19.5 m²/g and 2.3 × 10⁻² cm³/g, respectively. Adsorption volume from both N₂ and CO₂ adsorption increases with respect to TOC contents. Porosities obtained from helium porosimetry are comparable with these from gas (CO₂ and N₂) adsorption in O₃w-S₁l shale. However, porosity determined by quantitative FE-SEM analysis is much smaller, which is mainly related to limited resolution and the small areas of investigation.Based on the Frenkel-Halsey-Hill (FHH) model of low-pressure N₂ adsorption, fractal dimensions of the pores varied from 2.737 to 2.823. Relationships between pore structure parameters and TOC content, mineral composition and fractal dimension reveal that the fractal dimension is mainly associated with micropores. Samples with higher TOC content, higher quartz content and lower clay content tend to contain more heterogeneous micropores, resulting in higher fractal dimensions and more complicated pore structure in shales. Therefore, fractal dimension is an effective parameter to reflect the complexity of pore structure and the degree of micropore development in O₃w-S₁l shale.     

Geochemical characteristics of the Paleogene shales in the Dongying depression,eastern China

Fluctuations in lacustrine sedimentary environments significantly affect distributions of organic matter (OM), uranium, and other elements in shales. In this study a high-resolution geochemical record of fluctuations in the paleo-depositional environment of a terrestrial lake basin is provided on the basis of extensive samples collected from the Member 3 of the Paleogene Shahejie Formation (Es₃) of the Niu-38 well in the Dongying Depression, Eastern China. These samples were tested for total organic carbon (TOC), element concentrations, and biomarkers to study the evolution and fluctuation in the depositional environments of an ancient lake basin and associated geochemical response. The evolution and fluctuation of the sedimentary environment from a deep lake to a semi-deep lake and then to a shallow lake delta were indicated by geochemical response. During this evolution, the values of TOC, S₁, S₂, Sr, and Ts/(Ts + Tm) remarkably decreased, whereas those of Co, Ni, Rb, Na, Fe/Mn, Fe/(Ca + Mg), and C₂₉ mortane/C₂₉ hopane significantly increased. The deep lake basin shows depositional fluctuations, as indicated by rock lithofacies and their geochemical parameters. A close interrelationship was observed among U concentration, TOC content, and inorganic element content. Uranium concentrations are positively correlated with TOC contents, Ca and Sr concentrations, and Sr/Ba and Ca/Mg ratios but negatively with K, Na, Ba, and Rb contents and Fe/(Ca + Mg) and Fe/Mn ratios. The observed increase in U concentration in the lower Es₃ section is closely related to surface adsorption by clay minerals and OM, together with some replacements of Ca and Sr by U in the shales.     

Effect of pore structure on shale oil accumulation in the lower third member of the Shahejie formation,Zhanhua Sag,eastern China: Evidence from gas adsorption and nuclear magnetic resonance

As shale oil occurs primarily in micro–nano pores and fractures, research about the effect of pore structure on shale oil accumulation has great significance for shale oil exploration and development. The effect of pore structure on shale oil accumulation in the lower third member of the Shahejie formation (Es₃^l), Zhanhua Sag, eastern China was investigated using gas adsorption, soxhlet extraction, nuclear magnetic resonance (NMR) analysis, and field emission scanning electron microscope (FE-SEM) observation. The results indicated that the samples contained a larger amount of ink-bottle-shaped and slit-shaped pores after extraction than before extraction. The pore volume and specific surface area of the samples were approximately 2.5 times larger after extraction than before extraction. Residual hydrocarbon occurred primarily in the free-state form in pores with diameters of 10–1000 nm, which can provide sufficient pore volume for free hydrocarbon accumulation. Therefore, pores with diameters of 10–1000 nm were regarded as “oil-enriched pores”, which are effective pores for shale oil exploration, whereas pores with diameters smaller than 10 nm were regarded as “oil-ineffective pores”. Samples with only well-developed small pores with diameters smaller than 1000 nm showed high oil saturation, whereas samples with both small pores and also relatively large pores and micro-fractures presented low oil saturation. As the minimum pore size allowing fluid expulsion is 1000 nm, pores with diameters greater than 1000 nm were considered as “oil-percolated pores”. Large pores and micro-fractures are generally interconnected and may even form a complex fracture mesh, which greatly improves the permeability of shale reservoirs and is beneficial to fluid discharge.     

Modeling free gas content of the Lower Paleozoic shales in the Weiyuan area of the Sichuan Basin,China

Two sets of Lower Paleozoic organic-rich shales develop well in the Weiyuan area of the Sichuan Basin: the Lower Cambrian Jiulaodong shale and the Lower Silurian Longmaxi shale. The Weiyuan area underwent a strong subsidence during the Triassic to Early Cretaceous and followed by an extensive uplifting and erosion after the Late Cretaceous. This has brought about great changes to the temperature and pressure conditions of the shales, which is vitally important for the accumulation and preservation of shale gas. Based on the burial and thermal history, averaged TOC and porosity data, geological and geochemical models for the two sets of shales were established. Within each of the shale units, gas generation was modeled and the evolution of the free gas content was calculated using the PVTSim software. Results show that the free gas content in the Lower Cambrian and Lower Silurian shales in the studied area reached the maxima of 1.98–2.93 m³/t and 3.29–4.91 m³/t, respectively (under a pressure coefficient of 1.0–2.0) at their maximum burial. Subsequently, the free gas content continuously decreased as the shale was uplifted. At present, the free gas content in the two sets of shales is 1.52–2.43 m³/t and 1.94–3.42 m³/t, respectively (under a current pressure coefficient of 1.0–2.0). The results are roughly coincident with the gas content data obtained from in situ measurements in the Weiyuan area. We proposed that the Lower Cambrian and Lower Silurian shales have a shale gas potential, even though they have experienced a strong uplifting.     

Petroleum source rock characterisation and hydrocarbon generation modeling of the Cretaceous sediments in the Jiza sub-basin,eastern Yemen

Cretaceous sedimentary rocks of the Mukalla, Harshiyat and Qishn formations from three wells in the Jiza sub-basin were studied to describe source rock characteristics, providing information on organic matter type, paleoenvironment of deposition and hydrocarbon generation potential. This study is based on organic geochemical and petrographic analyses performed on cuttings samples. The results were then incorporated into basin models in order to understand the burial and thermal histories and timing of hydrocarbon generation and expulsion.The bulk geochemical results show that the Cretaceous rocks are highly variable with respect to their genetic petroleum generation potential. The total organic carbon (TOC) contents and petroleum potential yield (S₁ + S₂) of the Cretaceous source rocks range from 0.43 to 6.11% and 0.58–31.14 mg HC/g rock, respectively indicating non-source to very good source rock potential. Hydrogen index values for the Early to Late Cretaceous Harshiyat and Qishn formations vary between 77 and 695 mg HC/g TOC, consistent with Type I/II, II-III and III kerogens, indicating oil and gas generation potential. In contrast, the Late Cretaceous Mukalla Formation is dominated by Type III kerogen (HI < 200 mg HC/g TOC), and is thus considered to be gas-prone. The analysed Cretaceous source rock samples have vitrinite reflectance values in the range of 0.37–0.95 Ro% (immature to peak-maturity for oil generation).A variety of biomarkers including n-alkanes, regular isoprenoids, terpanes and steranes suggest that the Cretaceous source rocks were deposited in marine to deltaic environments. The biomarkers also indicate that the Cretaceous source rocks contain a mixture of aquatic organic matter (planktonic/bacterial) and terrigenous organic matter, with increasing terrigenous influence in the Late Cretaceous (Mukalla Formation).The burial and thermal history models indicate that the Mukalla and Harshiyat formations are immature to early mature. The models also indicate that the onset of oil-generation in the Qishn source rock began during the Late Cretaceous at 83 Ma and peak-oil generation was reached during the Late Cretaceous to Miocene (65–21 Ma). The modeled hydrocarbon expulsion evolution suggests that the timing of oil expulsion from the Qishn source rock began during the Miocene (>21 Ma) and persisted to present-day. Therefore, the Qishn Formation can act as an effective oil-source but only limited quantities of oil can be expected to have been generated and expelled in the Jiza sub-basin.     

Thermal maturity,source rock potential and kinetics of hydrocarbon generation in Permian shales from the Damodar Valley basin,Eastern India

This study investigates the source rock characteristics of Permian shales from the Jharia sub-basin of Damodar Valley in Eastern India. Borehole shales from the Raniganj, Barren Measure and Barakar Formations were subjected to bulk and quantitative pyrolysis, carbon isotope measurements, mineral identification and organic petrography. The results obtained were used to predict the abundance, source and maturity of kerogen, along with kinetic parameters for its thermal breakdown into simpler hydrocarbons.The shales are characterized by a high TOC (>3.4%), mature to post-mature, heterogeneous Type II–III kerogen. Raniganj and Barren Measure shales are in mature, late oil generation stage (Rr%_Raniganj = 0.99–1.22; Rr%_{Barren Measure} = 1.1–1.41). Vitrinite is the dominant maceral in these shales. Barakar shows a post-mature kerogen in gas generation stage (Rr%_Barakar = 1.11–2.0) and consist mainly of inertinite and vitrinite. The δ¹³C_org value of kerogen concentrate from Barren Measure shale indicates a lacustrine/marine origin (−24.6–−30.84‰ vs. VPDB) and that of Raniganj and Barakar (−22.72–−25.03‰ vs. VPDB) show the organic provenance to be continental. The δ¹³C ratio of thermo-labile hydrocarbons (C₁–C₃) in Barren Measure suggests a thermogenic source.Discrete bulk kinetic parameters indicate that Raniganj has lower activation energies (ΔE = 42–62 kcal/mol) compared to Barren Measure and Barakar (ΔE = 44–68 kcal/mol). Temperature for onset (10%), middle (50%) and end (90%) of kerogen transformation is least for Raniganj, followed by Barren Measure and Barakar. Mineral content is dominated by quartz (42–63%), siderite (9–15%) and clay (14–29%). Permian shales, in particular the Barren Measure, as inferred from the results of our study, demonstrate excellent properties of a potential shale gas system.     

Pore structure and fractal characteristics of organic-rich shales: A case study of the lower Silurian Longmaxi shales in the Sichuan Basin,SW China

Shales from the Lower Silurian Longmaxi Formation in the Sichuan Basin are among the most important shale gas reservoirs in China, and have been investigated because of their great shale gas potential. To understand the pore structure and fractal characteristics of the shales, a series of experiments was conducted on core samples from the Lower Silurian Longmaxi Formation in the Sichuan Basin of China, including X-ray diffraction (XRD), total organic carbon (TOC) content and vitrinite reflectance (Ro) analysis, field emission-environmental scanning electron microscope (FE-ESEM) observation, and low-pressure N₂ adsorption-desorption experiments. Frenkel-Halsey-Hill (FHH) method was applied to calculate fractal dimensions. In addition, the pore genesis, the relationships between composition and thermal maturity, the pore structure parameters, and the fractal dimensions are discussed. FE-ESEM observation results show that the Longmaxi Formation shales are dominated by organic-matter (OM) pores along with interparticle (interP) pores, intraparticle (intraP) pores and fracture pores. This study identified the fractal dimensions at relative pressures of 0–0.45 and 0.45–1 as D₁ and D₂ respectively. D₁ ranged from 2.60 to 2.71 and D₂ ranged from 2.71 to 2.82. D₁ was typically smaller than D₂, indicating that the smaller pores in shales were more homogeneous than the larger ones. The formation of these OM pores is owing to kerogen deformation during the thermal maturation, which results in a large number of nanopores. The pore structure of the Longmaxi Formation shales is primarily controlled by TOC content and thermal maturity. TOC content is a controlling factor on the fractal dimensions as it exhibited positive correlations with D₁ and D₂. Fractal dimensions are useful for the characterization of the pore structures complexity of the Longmaxi Formation shales because D₁ and D₂ correlate well with pore structure parameters as they both increase with the increase of surface area and the decrease of average pore diameter.