The impact of composition on pore throat size and permeability in high maturity shales: Middle and Upper Devonian Horn River Group,northeastern British Columbia,Canada

Shale reservoirs of the Middle and Upper Devonian Horn River Group provide an opportunity to study the influence of rock composition on permeability and pore throat size distribution in high maturity formations. Sedimentological, geochemical and petrophysical analyses reveal relationships between rock composition, pore throat size and matrix permeability.In our sample set, measured matrix permeability ranges between 1.69 and 42.81 nanodarcies and increases with increasing porosity. Total organic carbon (TOC) content positively correlates to permeability and exerts a stronger control on permeability than inorganic composition. A positive correlation between silica content and permeability, and abundant interparticle pores between quartz crystals, suggests that quartz may be another factor enhancing the permeability. Pore throat size distributions are strongly related to TOC content. In organic rich samples, the dominant pore throat size is less than 10 nm, whereas in organic lean samples, pore throat size distribution is dominantly greater than 20 nm. SEM images suggest that in organic rich samples, organic matter pores are the dominant pore type, whereas in quartz rich samples, the dominant type is interparticle pores between quartz grains. In clay rich and carbonate rich samples, the dominant pore type is intraparticle pores, which are fewer and smaller in size.High permeability shales are associated with specific depositional facies. Massive and pyritic mudstones, rich in TOC and quartz, have comparatively high permeability. Laminated mudstone, bioturbated mudstone and carbonate facies, which are relatively enriched in clay or carbonate, have fairly low permeability.     

Jurassic source rocks in the Vienna Basin (Austria): Assessment of conventional and unconventional petroleum potential

The Upper Jurassic marlstones (Mikulov Fm.) and marly limestones (Falkenstein Fm.) are the main source rocks for conventional hydrocarbons in the Vienna Basin in Austria. In addition, the Mikulov Formation has been considered a potential shale gas play. In this paper, organic geochemical, petrographical and mineralogical data from both formations in borehole Staatz 1 are used to determine the source potential and its vertical variability. Additional samples from other boreholes are used to evaluate lateral trends. Deltaic sediments (Lower Quarzarenite Member) and prodelta shales (Lower Shale Member) of the Middle Jurassic Gresten Formation have been discussed as secondary sources for hydrocarbons in the Vienna Basin area and are therefore included in the present study.The Falkenstein and Mikulov formations in Staatz 1 contain up to 2.5 wt%TOC. The organic matter is dominated by algal material. Nevertheless, HI values are relative low (<400 mgHC/gTOC), a result of organic matter degradation in a dysoxic environment. Both formations hold a fair to good petroleum potential. Because of its great thickness (∼1500 m), the source potential index of the Upper Jurrasic interval is high (7.5 tHC/m²). Within the oil window, the Falkenstein and Mikulov formations will produce paraffinic-naphtenic-aromatic low wax oil with low sulfur content. Whereas vertical variations are minor, limited data from the deep overmature samples suggest that original TOC contents may have increased basinwards. Based on TOC contents (typically <2.0 wt%) and the very deep position of the maturity cut-off values for shale oil/gas production (∼4000 and 5000 m, respectively), the potential for economic recovery of unconventional petroleum is limited. The Lower Quarzarenite Member of the Middle Jurassic Gresten Formation hosts a moderate oil potential, while the Lower Shale Member is are poor source rock.     

Properties and shale oil potential of saline lacustrine shales in the Qianjiang Depression,Jianghan Basin,China

The geochemical and petrographic characteristics of saline lacustrine shales from the Qianjiang Formation, Jianghan Basin were investigated by organic geochemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and low pressure nitrogen adsorption analysis. The results indicate that: the saline lacustrine shales of Eq3 member with high oil content are characterized by type I and type II oil-prone kerogen, variable TOC contents (1.0–10.0 wt%) and an early-maturity stage (R_o ranges between 0.41 and 0.76%). The mineral compositions of Eq3 saline shale show strong heterogeneity: brittle intervals with high contents of quartz and carbonate are frequently alternated with ductile intervals with high glauberite and clay contents. This combination might be beneficial for oil accumulation, but may cause significant challenges for the hydraulic stimulation strategy and long-term production of shale oil. The interparticle pores and intraparticle pores dominate the pore system of Eq3 shale, and organic matter hosted pores are absent. Widely distributed fractures, especially tectonic fractures, might play a key role in hydrocarbon migration and accumulation. The pore network is contributed to by both large size inorganic pores and abundant micro-factures, leading to a relatively high porosity (2.8–30.6%) and permeability (0.045–6.27 md) within the saline shale reservoir, which could enhance the flow ability and storage capacity of oil. The oil content (S₁ × 100/TOC, mg HC/g TOC and S₁, mg HC/g rock) and brittleness data demonstrate that the Eq3^3x section has both great potential for being a producible oil resource and hydraulic fracturing. Considering the hydrocarbon generation efficiency and properties of oil, the mature shale of Eq3 in the subsidence center of the Qianjiang Depression would be the most favorable zone for shale oil exploitation.     

Organic geochemistry of the Silurian Tanezzuft Formation and crude oils,NC115 Concession,Murzuq Basin,southwest Libya

Thirty-six Silurian core and cuttings samples and 10 crude oil samples from Ordovician reservoirs in the NC115 Concession, Murzuq Basin, southwest Libya were studied by organic geochemical methods to determine source rock organic facies, conditions of deposition, thermal maturity and genetic relationships. The Lower Silurian Hot Shale at the base of the Tanezzuft Formation is a high-quality oil/gas-prone source rock that is currently within the early oil maturity window. The overall average TOC content of the Hot Shale is 7.2 wt% with a maximum recorded value of 20.9 wt%. By contrast, the overlying deposits of the Tanezzuft Formation have an average TOC of 0.6 wt% and a maximum value of 1.1 wt%. The organic matter in the Hot Shale consists predominantly of mixed algal and terrigenous Type-II/III kerogen, whereas the rest of the formation is dominated by terrigenous Type-III organic matter with some Type II/III kerogen. Oils from the A-, B- and H-oil fields in the NC115 Concession were almost certainly derived from marine shale source rocks that contained mixed algal and terrigenous organic input reflecting deposition under suboxic to anoxic conditions. The oils are light and sweet, and despite being similar, were almost certainly derived from different facies and maturation levels within mature source rocks. The B-oils were generated from slightly less mature source rocks than the others. Based on hierarchical cluster analysis (HCA), principal component analysis (PCA), selected source-related biomarkers and stable carbon isotope ratios, the NC115 oils can be divided into two genetic families: Family-I oils from Ordovician Mamuniyat reservoirs were probably derived from older Palaeozoic source rocks, whereas Family-II oils from Ordovician Mamuniyat–Hawaz reservoirs were probably charged from a younger Palaeozoic source of relatively high maturity. A third family appears to be a mixture of the two, but is most similar to Family-II oils. These oil families were derived from one proven mature source rock, the Early Silurian, Rhuddanian Hot Shale. There is a good correlation between the Family-II and -III oils and the Hot Shale based on carbon isotope compositions. Saturated and aromatic maturity parameters indicate that these oils were generated from a source rock of considerably higher maturity than the examined rock samples. The results imply that the oils originated from more mature source rocks outside the NC115 Concession and migrated to their current positions after generation.     

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.     

Novel 3D centimetre-to nano-scale quantification of an organic-rich mudstone: The Carboniferous Bowland Shale,Northern England

X-ray computed tomography and serial block face scanning electron microscopy imaging techniques were used to produce 3D images with a resolution spanning three orders of magnitude from ∼7.7 μm to 7 nm for one typical Bowland Shale sample from Northern England, identified as the largest potential shale gas reservoir in the UK. These images were used to quantitatively assess the size, geometry and connectivity of pores and organic matter. The data revealed four types of porosity: intra-organic pores, organic interface pores, intra- and inter-mineral pores. Pore sizes are bimodal, with peaks at 0.2 μm and 0.04 μm corresponding to pores located at organic–mineral interfaces and within organic matter, respectively. These pore-size distributions were validated by nitrogen adsorption data. The multi-scale imaging of the four pore types shows that there is no connected visible porosity at these scales with equivalent diameter of 20 nm or larger in this sample. However, organic matter and clay minerals are connected and so the meso porosity (<20 nm) within these phases provides possible diffusion transport pathways for gas. This work confirms multi-scale 3D imaging as a powerful quantification method for shale reservoir characterisation allowing the representative volumes of pores, organic and mineral phases to be defined to model shale systems. The absence of connected porosity at scales greater than 20 nm indicates the likely importance of the organic matter network, and associated smaller-scale pores, in controlling hydrocarbon transport. . The application of these techniques to shale gas plays more widely should lead to a greater understanding of properties in the low permeability systems.     

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.     

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.     

Effects of composition and pore structure on the reservoir gas capacity of Carboniferous shale from Qaidam Basin,China

Shale adsorption and breakthrough pressure are important indicators of shale gas development and key factors in evaluating the reservoir capacities of shales. In this study, geochemical tests, pore-structure tests, methane adsorption tests, and breakthrough-pressure tests were conducted on shales from the Carboniferous Hurleg Formation in eastern Qaidam Basin. The effects of the shale compositions and pore structures on the adsorption and breakthrough pressures were studied, and the reservoir capacities of the shales were evaluated by analyzing the shale adsorptions and sealing effects. The results indicate that the organic carbon content was only one of factors in affecting the adsorption capacity of the shale samples while the effect of the clay minerals was limited. Based on the positive correlation between the adsorption capacity and specific surface area of the shale, the specific surface area of the micropores can be used as an indicator to determine the adsorption capacity of shale. The micro-fracturing of brittle minerals, such as quartz, create a primary path for shale gas breakthrough, whereas the expansion of clay minerals with water greatly increases the breakthrough pressure in the shale samples. Methane adsorption tests showed that maximum methane adsorption for shale samples Z045 and S039 WAS 0.107 and 0.09655 mmol/g, respectively. The breakthrough pressure was 39.36 MPa for sample S039, maintained for 13 days throughout the experiment; however, no breakthrough was observed in sample Z045 when subjected to an injected pressure of 40 MPa for 26 days. This indicates that sample Z045, corresponding to a depth of 846.24 m, exhibited higher adsorption capacity and a better reservoir-sealing effect than sample S039 (498.4 m depth). This study provides useful information for future studies of Qaidam Basin shale gas exploration and development and for evaluation of shale quality.     

Logging identification and characteristic analysis of marine–continental transitional organic-rich shale in the Carboniferous-Permian strata,Bohai Bay Basin

Currently, global shale gas exploration and exploitation are focused on marine shale. Recently, major shale gas-oil breakthroughs have been made within continental and marine–continental transitional shale in China. This study will show how transitional shale is of great importance. Based on geological field surveys, core observations, thin section analysis, organic geochemistry and X-ray diffraction, we systematically studied the basic geological characteristics (including lithology, mineral composition, and organic geochemistry) of this transitional shale. By comparative analysis of well logging data from 260 wells in the Taiyuan–Shanxi shale, we will show that these methods are effective for identifying organic-rich shale from conventional well logs and determining its thickness distribution in the Carboniferous–Permian strata of the Taiyuan–Shanxi transitional coal-bearing formation.The results indicate that the Taiyuan–Shanxi shale has a high TOC (most 2%–4%) and that the lithology is primarily carbonaceous shale with type Ⅱ₂-Ⅲ kerogens. The high thermal maturation (Ro ≥ 1.1%) favors the generation of gas. The mineral components primarily include clay minerals, quartz, and plagioclase with a moderate brittle mineral content (47 wt.%) and high clay mineral content (51 wt.%) dominated by kaolinite (43%) and mixed-layer illite-smectite (31%). The transitional organic-rich shale on conventional log curves is generally characterized by higher gamma ray (GR), neutron porosity (CNL), acoustic travel time (AC), resistivity (R_t), potassium (K), and uranium (U) readings and a lower density (DEN), photoelectric absorption index (PE) and thorium-uranium ratio (TH/U). After analyzing the log response characteristics of the organic-rich shale, the most sensitive logging curves (such as CNL, AC, DEN, PE and U) were optimized to conduct logging overlays and to construct cross-plots to qualitatively identify organic-rich shale. The identified organic-rich shale amalgamates in the middle-upper member of the Taiyuan Formation and the lower member of the Shanxi Formation consistent with the results of the TOC analysis and practical gas logging. Based on the qualitative evaluation methods of the modified △LogR and a multivariate linear regression model, we calculated the TOC of shale wells in the Taiyuan–Shanxi formation. From this we calculated the characteristic values of organic-rich shale thickness. The results indicate that organic-rich shale in the Taiyuan formation is thicker than that in the Shanxi formation. Additionally, the thickness of organic-rich shale within lagoons and deep reed swamp facies are much thicker (25–35 m and 40–80 m) than other structural profile types, whereas their lateral distribution is less than that of marine shale. The relatively small continuous thickness of the single shale layer and high clay content may have negative effects for developing the shale gas potential.     

2D and 3D nanopore characterization of gas shale in Longmaxi formation based on FIB-SEM

Studying complex pore structures is the key to understanding the mechanism of shale gas accumulation. FIB-SEM (focused ion beam-scanning electron microscope) is the mainstream and effective instrument for imaging nanopores in gas shales. Based on this technology, 2D and 3D characteristics of shale samples from Lower Silurian Longmaxi formation in southern Sichuan Basin were investigated. 2D experimental results show that the pores in shale are nanometer-sized, and the structure of those nanopores can be classified into three types: organic pores, inorganic pores and micro fractures. Among the three types, organic pores are dominantly developed in the OM (organic matter) with three patterns such as continuous distributed OM, OM between clay minerals and OM between pyrite particles, and the size of organic pores range from 5 nm to 200 nm.Inveresly, inorganic pores and micro fractures are less developed in the Longmaxi shales. 3D digital rocks were reconstructed and segmented by 600 continuous images by FIB cutting and SEM imaging simultaneously. The pore size distribution and porosity can be calculated by this 3D digital core, showing that its average value is 32 nm and porosity is 3.62%.The 3D digital porosity is higher than its helium porosity, which can be regarded as one important parameter for evaluation of shale gas reserves. The 2D and 3D characterized results suggest that the nanometer-sized pores in organic matter take up the fundamental storage space for the Longmaxi shale. These characteristics have contributed to the preservation of shale gas in this complex tectonic area.     

Evaluating the timing of hydrocarbon generation in the Devonian Duvernay Formation: paleomagnetic,rock magnetic and geochemical evidence

The physical and chemical changes associated with the thermal maturation of organic-rich shale have affected the paleomagnetic and rock magnetic characteristics of the Devonian Duvernay Formation in the Western Canada Sedimentary Basin. This formation has several lithofacies that correspond to deposition in platform, slope and deeper water settings under varied redox conditions. Shale, laminated mudstone and some massive mudstone facies show evidence of magnetic changes associated with maturation but wackestone, packstone and some massive mudstone facies appear to be unaffected by the process. Rock magnetic evidence suggests that thermal maturation induces a change in the magnetization carrier from magnetite and hematite to solely magnetite.The packstone and wackestone facies commonly show a reversed characteristic magnetization with a paleopole at 194°E, 70°N (A₉₅=13.2) of Late Cretaceous-age. Shale and laminated mudstone facies in immature areas of the basin have inclination-only characteristic remanent magnetization (ChRM) means that range from 55 to 67 °C, requiring a pre-Cretaceous magnetization age. Shale and laminated mudstone facies in mature areas of the basin have a much steeper ChRM in direction ranging from 77 to 83 °C. Their very steep nature suggests that step demagnetization has not completely removed a drilling-induced remanence in some wells.     

Permeability measurements in mudrocks using gas-expansion methods on plug and crushed-rock samples

Permeability is an important parameter relative to the production of hydrocarbons in shale oil/gas plays; however, the measurement of permeability in these nano-to microdarcy rocks remains a challenge. Results from different methods or from different laboratories are not consistent, and reasons are not fully understood. In the present study, permeability is measured for both plug and crushed-rock samples with different plug diameter or crushed-sample particle size to systematically investigate the permeability measurement to better understand and apply the measured results. A modified gas-expansion (MGE) method, which can measure permeability for plug samples under confining pressures, was established and applied to several Eagle Ford and Barnett Shale (mudrock) samples. Permeability results from this method are in fair agreement with those from the pulse-decay method. The traditional Gas Research Institute (GRI) method was applied to crushed-rock Eagle Ford Shale samples. The results were comparable to reported permeability for an Eagle Ford Shale sample. Particle or plug size has significant influence on permeability measurement. In general, permeability increases with increasing particle or plug size. For crushed sample with GRI method, the reason of increasing permeability is related to the limitation of the GRI technique and the data analysis method. Estimate of the permeability based on Kozeny–Carman Equation was conducted, and the results were used to evaluate the GRI permeability measurement. Particle size of 2–4 mm (5–10 meshes) is considered as an appropriate size for GRI permeability measurement. For plug sample, larger permeability with larger plug diameter is most likely caused by the artificial fractures. Higher confining pressure can reduce the influence of the fractures, but cannot fully remove it. A range of permeability, defined by the GRI permeability with 2–4 mm particles as the lower boundary and permeability of 1-in plug under high confining pressure (>5000 psi) as the upper boundary, can be a more reliable measures to represent the shale matrix permeability. The range of the permeability also highlights the uncertainty in matrix permeability measurement for shale.     

Pore structure of the graptolite-derived OM in the Longmaxi Shale,southeastern Upper Yangtze Region,China

The Lower Silurian Longmaxi Shale in the southeastern Upper Yangtze Region, which has been the main target for shale gas exploration and production in China, is black marine organic-rich shale and rich in graptolites. Graptolites, usually only periderms preserved in shales, are important organic component of the Longmaxi Shale. However, the pore structure of graptolite periderms and its contribution to gas storage has not yet been studied before. A combination of optical microscopy for identification and “mark” of graptolite and scanning electron microscope (SEM) for pore observations were conducted for the Longamxi Shale samples. Results show that pores are anisotropic developed in the Longmaxi graptolite periderms and greatly associated with their fine structure. Micrometer-sized fractures and spindle-shaped pores between cortical fibrils in the cortical bandage are greatly developed at section parallel to the bedding, while they are rare at section perpendicular to the bedding. Besides, numerous sapropel detritus rich in nanometer-sized pores are discretely distributed in the shale. Though graptolite periderms are low porosity from SEM image analysis, microfractures and elongated pores along the graptolite periderm wall may still make the graptolite an interconnected system. Together with the discrete porous sapropel detritus in shale, these graptolite-derived Organic Matter (OM) may form an interconnected organic pore system in the shale. The difference of pore development observed in graptolite periderms and sapropel detritus also give us new insight for the organic pore heterogeneity study. The OM composition, their fine structure and orientation in the rock may be important factors controlling OM pore development. The combination of identifying OM type under optical microscopy and pores observation under SEM for may be an effective method to study the OM pore development especially in shale that contain more OM.     

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.     

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.     

Evolution of porosity and pore types in organic-rich,calcareous, Lower Toarcian Posidonia Shale

Low and high resolution petrographic studies have been combined with mineralogical, TOC, RockEval and porosity data to investigate controls on the evolution of porosity in stratigraphically equivalent immature, oil-window and gas-window samples from the Lower Toarcian Posidonia Shale formation. A series of 26 samples from three boreholes (Wickensen, Harderode and Haddessen) in the Hils syncline was investigated. The main primary components of the shales are microfossiferous calcite (30–50%), clay minerals (20–30%) and Type II organic matter (TOC = 7–15%, HI = 630–720 mg/gC in immature samples). Characteristic sub-centimetric light and dark lamination reflects rapid changes in the relative supply of these components. Total porosities decrease from 10 to 14% at Ro = 0.5% to 3–5% at Ro = 0.9% and then increase to 9–12% at Ro = 1.45%. These maturity-related porosity changes can be explained by (a) the primary composition of the shales, (b) carbonate diagenesis, (c) compaction and (d) the maturation, micro-migration, local trapping and gasification of heterogeneous organic phases. Calcite undergoes dissolution and reprecipitation reactions throughout the maturation sequence. Pores quantifiable in SEM (>ca. 50 nm) account for 14–25% of total porosity. At Ro = 0.5%, SEM-visible macropores¹ are associated mainly with biogenic calcite. At this maturity, clays and organic matter are not visibly porous but nevertheless hold most of the shale porosity. Porosity loss into the oil window reflects (a) compaction, (b) carbonate cementation and (c) perhaps the swelling of kerogen by retained oil. In addition, porosity is occluded by a range of bituminous phases, especially in microfossil macropores and microfractures. In the gas window, mineral-hosted porosity is still the primary form of macroporosity, most commonly observed at the organic-inorganic interface. Increasing porosity into the gas window also coincides with the formation of isolated, spongy and complex meso- and macropores within organic particles, related to thermal cracking and gas generation. This intraorganic porosity is highly heterogeneous: point-counted macroporosity of individual organic particles ranges from 0 to 40%, with 65% of organic particles containing no macropores. We suggest that this reflects the physicochemical heterogeneity of the organic phases plus the variable mechanical protection afforded by the mineral matrix to allow macroporosity to be retained. The development of organic macroporosity cannot alone account for the porosity increase observed from oil to gas window; major contributions also come from the increased volume of organic micro- and meso-porosity, and perhaps by kerogen shrinkage.     

Lower Cretaceous black shales of the Western Carpathians,Czech Republic: Palynofacies indication of depositional environment and source potential for hydrocarbons

Uppermost Jurassic and Lower Cretaceous strata of the Silesian Nappe of the Outer Western Carpathians contain large amounts of shale, which can, under favourable conditions, become source rocks for hydrocarbons. This study analysed 45 samples from the area of Czech Republic by the means of palynofacies analysis, thermal alteration index (TAI) of palynomorphs and total organic carbon (TOC) content to determine the kerogen type, hydrocarbon source rock potential, and to interpret the depositional environment. Uppermost Jurassic Vendryně Formation and Lower Cretaceous Formations (Těšín Limestone, Hradiště and Lhoty) reveal variable amount of mostly gas prone type III kerogen. Aptian Veřovice Formation has higher organic matter content (over 3 wt.%) and oil-prone type II kerogen. Organic matter is mature to overmature and hydrocarbon potential predisposes it as a source of gas. Aptian black claystones of the Veřovice Fm. are correlatable with oceanic anoxic event 1 (OAE1).     

Experimental mechanical compaction of reconstituted shale and mudstone aggregates: Investigation of petrophysical and acoustic properties of SW Barents Sea cap rock sequences

This study investigates petrophysical and acoustic properties of experimentally compacted reconstituted samples of seal sequences from the southwestern Barents Sea. The aggregates were collected from drill cuttings of mudstone and shale formations of two exploration wells, 7220/10-1 (Salina discovery) and 7122/7-3 (Goliat field). The washed and freeze-dried samples were characterized for grain size distributions, geochemical analyses, and mineralogical compositions. A total of 25 compaction tests (12 dry and 13 brine-saturated) were performed with a maximum effective vertical stress of 50 MPa. The laboratory measurements demonstrated that petrophysical and acoustic properties of argillaceous sediments can change within a sedimentary basin and even within a given formation. The results show that the collected aggregates from Goliat field are compacted more compared to Salina discovery. The maximum and minimum compaction are measured in samples collected from Snadd and Fuglen formations, respectively. The final porosity of brine-saturated specimens varies between 5% and 22%. The ultrasonic velocity measurements depict that samples with the same porosity values can have a broad range of velocity values. The resulting compaction trends in this study were compared to published compaction curves for synthetic mixtures of quartz and clay. All compaction trends show higher porosity reduction than the silt fraction with 100% quartz. Comparison of experimental compaction result of each mudstone and shale aggregate with its corresponding acquired well log data helps to delineate the burial history and exhumation in the study area. A net exhumation of 950 m and 800 m is estimated at Salina and Goliat wells, respectively. The outcomes of this study can provide insights for hydrocarbon prospect discovery in a pre-mature sedimentary basin in terms of exploration and production, and also for geological CO₂ storage sites. The experimental results may provide information for well log and seismic interpretation, basin modeling and seal integrity of investigated horizons.