Organic Pores Research Articles

Influencing factors of coal elastic parameters based on the generalized Gassmann equation: A case study in Yuwang colliery, eastern Yunnan province

AbstractCoal elastic parameters are an important index reflecting the material composition and porosity, which can be used to guide reservoir evaluation and the safe mining of coal and coalbed methane. In this study, coal samples collected from coal seams #2, #3, #7 + 8 and #9 in the Yuwang colliery, eastern Yunnan, were studied, and the influences of organic matter, ash content and porosity on the elastic parameters of coal samples were investigated. The results show that the elastic parameters of coal are negatively correlated with organic matter content and porosity, and positively correlated with ash content. This means that the bulk modulus and primary‐wave velocity of coal decrease with a gradual increase in organic matter content or porosity and increase with a gradual increase in ash content. The main reason for this is that the ash modulus is typically higher than that of coal. When the ash content gradually increases, the contribution of ash to the equivalent modulus of coal increases, whereas the contribution of organic matter and pores decreases. In this study, the primary‐wave velocity of the target coal seam was fitted based on the generalized Gassmann equation. The calculation results were consistent with the observations and the relative error was within 7%. According to the distribution behaviour of elastic parameters, this provides adequate data support for the prediction of gas content in coal mines and ensures safe and green mining of coal resources.

Shale Gas Exploration and Development Potential Analysis of Lower Cambrian Niutitang Formation and Lower Silurian Longmaxi Formation in Northwestern Hunan, South China, Based on Organic Matter Pore Evolution Characteristics

Shale gas production is obviously higher within the Silurian Longmaxi Formation than that of the Cambrian Niutitang Formation according to the drilling test results in the northwest Hunan area. To clarify the reasons behind this variation, core samples from the two sets of shales were studied for a comprehensive comparison and analysis of their organic matter (OM) pore structure. Methods were used, including the total organic carbon content test, the vitrinite reflectance test, X-ray diffraction, and focused ion-beam scanning electron microscopy (FIB-SEM). The results show that these two shales have similar reservoir characteristics, both with abundant organic matter and high content of brittle minerals. However, the Longmaxi shale with 2.3% to 3.0%Ro presents lower thermal maturity than the Niutitang shale with over 3.0%Ro. In the case of pore structure associated with OM, a huge difference exists between the two shales. The OM pore shape of the Longmaxi shale is very regular, being mostly round and oval, while the OM pore shape of the Niutitang shale is irregular, being flat with a thin middle and thick and elongated ends. An important factor affecting OM pore evolution is thermal maturity. In turn, the thermal maturity is controlled by the tectonic evolution process, especially the maximum paleo-burial depth. In conclusion, the paleo-burial depth of the Lower Cambrian Niutitang shale in northwest Hunan is too large, which leads to the excessive evolution of organic matter in the shale, and the physical and chemical properties are similar to graphite, which leads to the disappearance of OM pores. Shale gas has no effective reservoir space and is largely dispersed in geological history. At the same time, due to the insufficient hydrocarbon-generation evolution time of the Lower Silurian Longmaxi Formation shale in this area, the shale could not form enough gaseous hydrocarbons and a large amount of effective reservoir space (OM pores with regular shape and large pore size), and finally failed to become a gas reservoir. Therefore, the exploration and development potential of the marine shale gas of the Lower Cambrian Niutitang Formation and the Lower Silurian Longmaxi Formation in northwest Hunan is poor.

Sedimentary differentiation triggered by the Toarcian Oceanic Anoxic Event and formation of lacustrine shale oil reservoirs: Organic matter accumulation and pore system evolution of the Early Jurassic sedimentary succession, Sichuan Basin, China

Sedimentary differentiation triggered by the Toarcian Oceanic Anoxic Event and formation of lacustrine shale oil reservoirs: Organic matter accumulation and pore system evolution of the Early Jurassic sedimentary succession, Sichuan Basin, China

Tectonic Control on Shale Pore Structure and Gas Content from the Longmaxi Formation Shale in Southern Sichuan Basin, China: Insights from Fractal Analysis and Low-Pressure Gas Adsorption

Tectonic deformation of different intensities significantly controls shale pore structure, seepage channels, and gas content. The Longmaxi Formation shales in the southern Sichuan Basin have experienced multi-stage tectonic movements, resulting in a diverse fracture system and tectonic deformation. This study focuses on three representative tectonic morphologies: deeply buried strongly deformed (DBSD), deeply buried weakly deformed (DBWD) and shallowly buried weakly deformed (LBWD). We investigated the pore structure characteristics and heterogeneity of these shales under various tectonic conditions using total organic carbon (TOC) content, X-ray diffraction (XRD), scanning electron microscopy (SEM), a low-pressure N2/CO2 adsorption experiment (LP-N2/CO2 GA), and multi-scale fractal theory. The results reveal that strong tectonic compression and deformation conditions lead to the compression and flattening of organic pores by brittle minerals, resulting in long, oriented OM pores. Fracturing of brittle pore creates multiple internal fracture systems linked to dissolution pores, forming a complex micro-fracture–pore network. With intense tectonic deformation, mesopores tend to be compressed, increasing micropore pore volume (PV) and surface area (SA). The DBSD shale exhibits the highest micropore heterogeneity, while the LBWD shale shows the lowest heterogeneity. Fractal analysis indicates a significant decrease in micropore fractal dimension (Df) with increasing burial depth. In contrast, the surface and matrix fractal dimensions (Ds and Dm) of low-buried shale micropores and meso-macropores align vertically. Shale reservoirs in tectonically stable regions exhibit more favourable gas-bearing characteristics than strongly tectonically deformed areas. The LBWD has stable tectonic conditions that are favourable for shale gas preservation. Conversely, slip faults under deep burial conditions lead to extrusion and deformation of shale pore space, ultimately compromising the original reservoir capacity and hindering shale gas enrichment. These findings contribute significantly to our understanding of pore structure and heterogeneity in tectonically deformed shale reservoirs, providing invaluable guidance for the exploration, development, and prediction of shale gas resources.

Factors Controlling the Pore Development of Low-Mature Marine–Continental Transitional Shale: A Case Study of the Upper Permian Longtan Shale, Western Guizhou, South China

The Upper Permian Longtan Shale is a significant reservoir in western Guizhou. To clarify the main factors controlling the low-mature marine–continental transitional shale pore development in western Guizhou, pore types were classified with scanning electron microscopy (SEM), and the pore developmental stages and morphological structures were quantitatively characterized by nitrogen adsorption isotherm analyses. Additionally, the qualitative or semi-quantitative relationships between the pore developmental stages and the main controlling factors were established via geochemical analysis. The results showed that the Longtan Shale pores include intergranular pores, intragranular pores, organic pores, and microfractures. The intergranular pore structures were categorized into ink-bottle, slit, layered, and irregular types. The intragranular pores were found to be of the elliptical, nearly circular, ink-bottle, and irregular varieties. The organic pores were categorized into elliptical, bubble-like, and irregular polygonal variants. The microfractures were only of the elongated type. The clay-mineral-related intergranular pores were the predominant pore type. The organic pores were found to be poorly developed. The mesopores were predominant, followed by macropores. The shale pore diameters ranged between 1 nm and 100 nm, and they are characterized by multiple peaks. The specific surface area (SSA) was primarily provided by nanopores in the range of 5 nm to 10 nm, such that the smaller pores provided a greater contribution to the SSA, and they are more conducive to shale gas adsorption and accumulation. Clay mineral content was the dominant internal factor controlling pore development and the SSA, with the illite–smectite mixed layer being the most obvious controlling factor. While too low or too high clay mineral content is adverse to macropore development, brittle mineral content, carbonate mineral content, and total organic carbon (TOC) content are adverse to pore development and the SSA. Thermal maturity has no remarkable control effect on pore volume and the SSA of non-organic pores.

Gas generation potential and pore characteristics of Jurassic lacustrine shale containing type Ⅱ kerogen: A case study of the Yabulai Basin, northwestern China

Jurassic lacustrine shales containing kerogen types Ⅱ and Ⅲ are widely distributed in sedimentary basins around the world. Previous studies on gas generation potential and pore characteristics of Jurassic lacustrine shales mainly focused on type Ⅲ kerogen, but ignored the systematic study of the shales containing type Ⅱ kerogen. This led to a poor understanding of the gas generation potential and pore characteristics of Jurassic lacustrine shales, which limits the effective exploration and development of shale gas. Taking the Lower Xinhe (J2x1) shale of the Yabulai Basin in northwestern China as the research object, this paper examines the gas generation potential and pore characteristics of a Jurassic lacustrine shale containing type Ⅱ kerogen. The J2x1 shale is largely classified as a very good source rock, kerogen is predominantly type Ⅱ, with thermal maturity ranging from mature to highly over-mature. The J2x1 shale is characterized by low porosity and permeability, and high content of brittle minerals. Different from the Jurassic lacustrine shales containing type Ⅲ kerogen, the J2x1 shales have a large amount of interparticle and intraparticle dissolution pores in the clay minerals as well as organic pores. The porosity and pore structure of the J2x1 shale are strongly controlled by total organic carbon (TOC) content. The methane adsorption capacity of the J2x1 shale is in the range of 2.10–2.99 m3/t, which is controlled by TOC content, clay mineral content, temperature and pressure. The geochemical characteristics, mineral composition and adsorption capacity suggest that the J2x1 shale has good shale exploration and development potential. A mathematical model is established to describe the various characteristics of methane adsorption capacity with depth and TOC content. The methane adsorption capacity of the J2x1 shale first increases and then decreases with increasing depth, with the depth corresponding to the maximum methane adsorption increases with increasing TOC content. When the TOC values of the J2x1 shale are mainly between 1% and 10%, the corresponding depth of the maximum methane adsorption capacity is 400–800 m, and the adsorption amount of the shale tends to minimize at a depth range of 2600–5100 m. The favorable shale gas exploration depth of the J2x1 shale in the study area increases with increasing TOC content. This research provides a geological reference for the exploration of this Jurassic shale gas in the Yabulai Basin, and the relevant experimental data provide important parameters for the numerical simulation of shale gas reservoirs in the study area. Moreover, the results of this study also provide an important reference for other basins in northwestern China, as well as continental basins with similar geological conditions in other regions.

Molecular dynamics simulations of methane adsorption and displacement from graphenylene shale reservoir nanochannels

Methane is the main component of shale gas and is adsorbed in shale pores. Methane adsorption not only affects the estimation of shale gas reserves but also reduces extraction efficiency. Therefore, investigating the behavior of methane adsorption in shale reservoirs is important for evaluating shale gas resources, as well as understanding its desorption and displacement from the nanochannels of shale gas reservoirs. In this research, molecular dynamics simulations were used to investigate the adsorption behavior of methane gas in organic shale pores made of graphenylene, followed by its displacement by CO2 and N2 injection gases. The effects of pore size, pressure, and temperature on adsorption were examined. It was observed that increasing the pore size at a constant pressure led to a decrease in the density of adsorbed methane molecules near the pore surface, while a stable free phase with constant density formed in the central region of the nanopore. Moreover, adsorption increased with increasing pressure, and at pressures ranging from 0 to 3 MPa, 15 and 20 Å pores exhibited lower methane adsorption compared to other pores. The amount of adsorption decreased with increasing temperature, and the observed adsorption isotherm followed the Langmuir adsorption isotherm. The mechanism of methane displacement by the two injected gases differed. Carbon dioxide filled both vacant adsorption sites and directly replaced the adsorbed methane. On the other hand, nitrogen only adsorbed onto the vacant sites and, by reducing the partial pressure of methane, facilitated the displacement of methane.

Significance of organo-mineralogical constituents on pore distribution, fractals and gas sorption mechanism of Permian shale beds in Korba sub-basin of the Son-Mahanadi Valley, India

In this study, shale samples obtained from the Korbasub-basin of Central India have been evaluated for the significance of organo-inorganic constituents in terms of their source potential of gas genesis, pore-matrix setup, and gas adsorption and desorption. The samples were analysed for various properties, such as megascopic features, lithological variations, depositional facies, and sources of organic and inorganic sediments. Also, maceral content, mineralogical constituents, kerogen type, pore distribution, pore structure, fractal characteristics and gas storage capacity were examined. The analysis revealed a trend of alternating bands of carbonaceous matter, silts, intercalations, and fluvial bedding lithofacies patterns indicating that the sediments were deposited under fluvio-terrestrial-lacustrine depositional conditions. Ternary facies analysis of maceral composition and van Krevelen diagram suggested the evolutionary path of type IV kerogen and are thermally matured source material located within the dry hydrocarbon generation window. Evaluation of pore types and pore structures using BET sorption plots (hysteresis H3 and isotherm type IV) revealed the presence of cylindrical, slit and combined cylindrical-slit pores with two distinct fractal characteristics. The discrete macerals underwent partial decomposition during transportation and mixing with inorganic components (clay and minerals), which influenced organic matter preservation, gas genesis, pore fractals and storage mechanism. The chemical index of alteration (CIA – 88.36 to 91.97), weathering (CIW – 96.60 to 98.80) and compositional variation (ICV – 0.31 to 0.70) demonstrated the influence of partial decomposition and strong weathering patterns on the organo-inorganic matter. A significant correlation was observed between pore fractals and elemental composition, particularly related to the resistance of weathering elements such as MgO, Al2O3, Fe2O3, SiO2, P2O5, TiO2, etc., which partially contributed to the formation of pore rugged surfaces. Microscopic and XRD analyses were employed to determine the mineral type, grain shape and size, and their amount leading to the development of the shales brittleness index (MBI). The importance of brittle characteristics, governed by minerals and clays within the shale, is discussed in relation to the hydro-fracturing technique for permeability enhancement. The results of high-pressure methane sorption indicated a moderate gas storage potential. The variation in sorption capacity (VL – 6.65 to 8.25 cc/g) is described through relationships with the ICV, pore diameter, pore volume, liptinite and total maceral content. Fractal dimensions D1 (2.4571–2.5611) and D2 (2.5804–2.7529) exhibited a direct relationship with adsorption properties, indicating the presence of rugged surfaces associated with meso- and macro-scale pores, which primarily control gas storage in shale. This research offers detailed insights into shale gas, providing valuable information for CBM and petroleum operators engaged in methane gas exploration and production. While commercial CBM production has been ongoing in India for over a decade, the exploration and understanding of shale gas reservoir characteristics are still in progress. This investigation adds significant value and highlights the extensive opportunities for research and potentially commercially recovering shale gas in the Korba sub-basin.

Pore Characteristics, Oil Contents and Factors Influencing Laminated Shale in the First Member of the Qingshankou Formation in the Gulong Sag, Northern Songliao Basin

To clarify the reservoir characteristics of laminated shale, the occurrence mechanism of shale oil and its influencing factors in the Gulong Sag, northern Songliao Basin, are studied to better guide the exploration and development of shale oil there. First, X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM) are used to characterize the pore types, pore geneses and factors influencing the pore volume in the study area. Second, the organic matter of the samples is extracted with a mixture of dichloromethane and methanol. Total organic carbon (TOC), nitrogen adsorption and Rock-Eval tests are performed on the samples before and after extraction to reveal the pore size distribution after extraction. The factors influencing free and adsorbed shale oil and the lower limit of pore size are discussed in detail. The results show that interparticle pores (interP pores), intraparticle pores (intraP pores), organic matter pores (OM pores) and microfractures can be found in the laminated shale (Q1) in the Gulong Sag, Songliao Basin, and that the interP pores and intercrystalline pores in clay minerals are the main pores. The FE-SEM results show that the diameters of interP pores vary from several hundred nanometers to several microns, and their morphologies are mainly triangular, strip-shaped or irregular. The morphology of the intercrystalline pores in the clay minerals is generally irregular, depending on the crystal type and arrangement of clay minerals. According to the characteristics of the nitrogen adsorption and desorption curves, the pore morphologies are mainly slit-shaped pores, parallel-plate-shaped pores and ink-bottle-shaped pores. The pore size distribution is mostly bimodal, and the pore volume contribution is the greatest in the pore size range of 10~20 nm. Before and after extraction, the overall characteristics of the pore size distribution change only slightly, but the number of micropores increases significantly. Different minerals have different degrees of influence on the proportions of micropores, mesopores and macropores. Quartz mainly inhibits the formation of micropores, while the overall effect on mesopores and macropores is positive depending on the diagenetic period. Feldspar has a strong positive correlation with the micropore and mesopore proportions but is not highly correlated with the macropore proportions. The influence of the carbonate mineral content on the pore volume is not obvious because of its complex composition. The TOC content and vitrinite reflectance (Ro) are the two most important factors controlling free oil and adsorbed oil, and the contents of mineral components, such as felsic minerals, carbonate minerals and clay minerals, have no obvious correlation with shale oil content. With increasing pore volume, the contents of free oil and adsorbed oil increase, but the proportion of adsorbed oil decreases gradually. The correlation between the specific surface area and adsorbed oil content is poor. At normal temperatures and pressures, the lower limit of the pore diameters that can contain free oil is 4 nm, and the lower limit of the pore diameters that can contain movable oil is 10 nm.

The occurrence characteristics of oil in shales matrix from organic geochemical screening data and pore structure properties: An experimental study

The occurrence characteristics of shale oil are of great significance to the movability of shale oil. In this study, the occurrence characteristics of oil in the shale matrix at Funing Formation shale in Subei Basin were quantitatively evaluated by organic geochemistry and microscopic pore structure characterization experiments. The Multiple Isothermal Stages Pyrolysis (MIS) experiment results show that the content of total oil, adsorbed oil, and free oil in the shales are 3.15–11.25 mg/g, 1.41–4.95 mg/g, and 1.74–6.51 mg/g, respectively. among which the silicon-rich shale has the best oil-bearing. The relative content of free oil shows an increasing trend in pores with pore diameters greater than 3 nm. When the relative content of free oil reaches 100%, the pore size of silicon-rich shale is about 200 nm, while that of calcium-rich shale, clay-rich shale, and siliceous mixed shale is about 10 nm. The occurrence law of adsorbed oil is opposite to that of free oil, which indicates that shale oil will occur in the pores and fractures in a free state in a more extensive pore size range (>200 nm). This study also enables us to further understand the occurrence characteristics of shale oil under the interaction of occurrence state and occurrence space.

The importance of pore-fracture connectivity in overmature marine shale for methane occurrence and transportation

Pore-fracture connectivity is a critical factor in gas occurrence and transportation in shale plays. To investigate the limiting factors of multiscale pore-fracture connectivity, which might control methane occurrence and transportation in shale reservoirs, small-angle neutron scattering (SANS) under vacuum and high-pressure conditions incorporated with repeated mercury intrusion capillary pressure (MICP), and field emission-scanning electron microscopy (FE-SEM) imaging after Wood's metal (WM) impregnation were performed on overmature marine shale samples of the Wufeng-Longmaxi and Niutitang Formations from south China. Based on the electron micrographs of the WM-injected samples, it was found that the sealing of the pore system by brittle minerals is the root cause for a reduction in overall pore connectivity within the shale matrix. Aside from being favorable to the preservation of organic and clay mineral pores, brittle minerals however, resulted in the closure of pore network, thus, forming an isolated pore system. The novel approach of integrating repeated MICP measurement and FE-SEM imaging after WM impregnation provides a new evaluation method for pore-fracture connectivity of shale. The minimum fraction of pores within the overmature shales accessible to methane was at 38% and 78% within 100 nm. Moreover, because of confinement effects, the density of methane in a pore space less than 20 nm under high pressure was greater than that of an ideal gas under the same pressure conditions which even increased with decreasing of pore size to several times of its inert state and formed nanoscale methane clusters. The combination of contrast-matching SANS (CM-SANS) and repeated MICP measurements can effectively reveal the connectivity of pores within the matrix and the connectivity between such pores and microfractures, which helps to evaluate the distribution of closed pores and dominant transport spaces of gas in shale reservoirs. Overall, the pore-fracture connectivity in overmature marine shale controls the amount of gas that is supplied from matrix pores into fracture systems and also affects the density of the gas in pore spaces within the matrix.

Characteristics and controlling factors of pore structure of shale in the 7th member of Yanchang Formation in Huachi area, Ordos Basin, China

To clarify the influence of organic matter and mineral composition on the pore structure of shale reservoirs in the 7th member of the Yanchang Formation (Chang 7 Member) in the Ordos Basin, we characterized the pore structure of Chang 7 shale reservoirs using argon ion polishing-field emission scanning electron microscopy (FE-SEM) and low-pressure nitrogen adsorption (LP-N2A). This characterization was combined with whole-rock mineral composition and organic geochemical experiments to analyze the main controlling factors of the pore structure of Chang 7 Member shale. The results reveal the presence of various pore types in shale, including organic matter pores, intergranular pores, intercrystalline pores, dissolved pores, and micro-cracks. The LP-N2A isotherms of shale consistently exhibit type Ⅱ isotherms with H3 and H4 hysteresis loop characteristics, indicating the relatively developed nature of mesopores and a pore morphology characterized by parallel lamellar and “ink bottle” shapes. The primary determinants of shale pore structure are identified as organic matter, clay minerals, quartz, feldspar, and pyrite. Among these factors, clay mineral phase transformation generates a substantial number of micropores and mesopores within the mineral crystal layers, serving as the main source of shale pores in the study area. Additionally, liquid hydrocarbons generated, solid bitumen, and euhedral pyrite fill inorganic mineral pores, thereby reducing the pore space of Chang 7 shale to a certain extent. These results provide a new cognition into understanding the pore structure characteristics and controlling factors of Chang 7 shale.

The impact of organic pores on estimation of overpressure generated by gas generation in organic-rich shale: Example from Devonian Duvernay Shale, Western Canada Sedimentary Basin

The impact of organic pores on estimation of overpressure generated by gas generation in organic-rich shale: Example from Devonian Duvernay Shale, Western Canada Sedimentary Basin

Characteristics and Key Controlling Factors of the Interbedded-Type Shale-Oil Sweet Spots of Qingshankou Formation in Changling Depression

Different types of shale-oil sweet spots have developed and are vertically stacked in multiple layers of the Qingshankou Formation in the Changling Depression, southern Songliao Basin. Furthermore, this area lacks a classification standard in the optimization of its shale-oil sweet-spot area/layers. Through relevant tests of the region in question’s organic geochemistry, physical properties, oiliness, and pore structure, this paper investigates the formation elements of shale-oil sweet spots. In addition, summaries of its enrichment-controlling factors are given, and the classification standard and evaluation method for understanding the comprehensive sweet spots of the interbedded-type shale oil are then established. The interbedded-type shale oil is enriched in the Qingshankou I Member in the Changling Depression, and it has the features of medium-to-high maturity, the development of inorganic pores and micro-cracks, as well as higher oil saturation and better oil mobility. The sweet-spot enrichment is affected by lamina type, sedimentary facies, maturity, and sand–shale combinations. Both silty-laminated felsic shale and argillaceous-laminated felsic shale, which are developed in semi-deep lakes, are favorable shale lithofacies as they have excellent brittleness and oil mobility. The high maturity and the interbedded combination of sand and shale ensure the efficient production of shale oil, among which the pure-shale section issues a continuous contribution to the production process. Combined with oil testing, sweet-spot classification standards and a comprehensive evaluation of interbedded-type shale oil were established. An area of 639.2 km2 for the interbedded-type shale-oil sweet spots was preferred, among which type I (193 km2) belonged to the combination of “good shale and good siltstone interlayers adjacent”, and type II belonged to “good shale and medium siltstone interlayers adjacent” combination (which have long-term low and stable production prospects). The research provides theoretical guidance on the effective exploration and development of the shale oil of the Qingshankou Formation in the Changling Depression.

Influence of shale bedding on development of microscale pores and fractures

The characteristics of bedding development have an important impact on the spatial distribution of shale pores and fractures. However, there is a lack of systematic study on the pore and fracture structure of bedding development characteristics. In this paper, the geological control mode of shale type on the development characteristics of pores and fractures is revealed; pore-throat models under different shale lithology conditions are constructed; the control mechanism of bedding development characteristics on the spatial distribution pattern of pores and fractures is clarified. Results show that: (a) The pore space size varies widely from nanoscale to micron-scale or even millimeter scale, and is mainly concentrated in the nanoscale range. (b) For shale samples No. 1-7-1 No. 21-7-1, although the proportion of organic matter and mineral area in different samples varies greatly, the difference between the proportion of organic pore area and the proportion of mineral pore area is not significant, and the proportion of organic pore area is much higher than that of mineral pore area. (c) The pore diameter of shale has strong heterogeneity; minerals have an important impact on throat diameter; maturity has an important impact on throat length; geological compaction and tectonism will have an impact on the tortuosity of shale reservoir pores; the controlling effect of pore connectivity on shale wettability is mainly reflected in the connectivity of hydrophilic and lipophilic pores.

Maceral evolution of lacustrine shale and its effects on the development of organic pores during low mature to high mature stage: A case study from the Qingshankou Formation in northern Songliao Basin, northeast China

Organic matter (OM) hosted pores are crucial for the storage and migration of petroleum in shale reservoirs. Thermal maturity and macerals type are important factors controlling the development of pores therein. In this study, six lacustrine shale samples with different thermal maturities from the first member of the Qingshankou Formation in the Songliao Basin, of which vitrinite reflectance (Ro) ranging from 0.58% to 1.43%, were selected for a comparative analysis. Scanning electron microscopy (SEM) and reflected light microscopy were combined to investigate the development of organic pores in different macerals during thermal maturation. The results show that alginite and liptodetrinite are the dominant primary macerals, followed by bituminite. Only a few primary organic pores developed in the alginite at the lowest maturity (Ro = 0.58%). As a result of petroleum generation, oil-prone macerals began to transform to initial-oil solid bitumen at the early oil window (Ro = 0.73%) and shrinkage cracks were observed. Initial-oil solid bitumen cracked to oil, gas and post-oil bitumen by primary cracking (Ro = 0.98%). Moreover, solid bitumen (SB) was found to be the dominant OM when Ro > 0.98%, which indicates that SB is the product of oil-prone macerals transformation. Many secondary bubble pores were observed on SB, which formed by gas release, while devolatilization cracks developed on migrated SB. Additionally, at the late oil window (Ro = 1.16%), migrated SB filled the interparticle pore spaces. With further increase in temperature, the liquid oil underwent secondary cracking into pyrobitumen and gas, and spongy pores developed on the pyrobitumen at higher levels of maturity (Ro = 1.43%), which formed when pyrobitumen cracked into gas. Vitrinite and inertinite are stable without any visible pores over the range of maturities, verifying their low petroleum generation potential. In addition, it was concluded that clay minerals could have a catalytic effect on the petroleum generation, which may explain why organic-clay mixtures had more abundant pores than single OM particles. However, after Ro > 0.98%, authigenic minerals occupied the organic pore spaces on the organic-clay mixtures, resulting in fewer pores compared to those observed in samples at the early to peak oil window.

Methane pore accessibility, densification, and accommodation by organic matter in the Niobrara Formation at wet-gas thermal maturity conditions

Petroleum within unconventional source-rock reservoirs is hosted in organic matter and mineral pore space as well as in voids and microfractures. Recent work has shown that for source-rock reservoirs in the dry gas window, significant portions of methane (CH4), the main component of petroleum at elevated maturities, can be stored within fine (<5 nm) organic matter porosity. However, within reservoirs at lower thermal maturities (e.g., peak oil or wet-gas conditions), the distribution and behavior of CH4 and the higher alkanes that comprise gas condensates across pore sizes is unclear, especially for pores with diameters <50 nm. Understanding CH4 distribution within these settings provides insight for petroleum generation, movement, and recoverability, enabling increased accuracy of estimated ultimate recovery. Here wide Q-range total neutron scattering was used to evaluate perdeuterated methane (CD4) behavior at reservoir pressures (200–750 bar) and temperature (60 °C) in a sample at the late oil/wet gas thermal maturity stage from the Late Cretaceous Niobrara Formation, an active petroleum producing formation within the Denver-Julesburg Basin, U.S.Neutron scattering data show that mesopores within the Niobrara Formation sample exhibit mass fractal scattering, similar to previously measured U.S. marine shale samples. In the presence of CD4, scattering intensities between Q = 0.02–0.1 Å−1 (corresponding to nominal pore diameters from 25 to 5 nm, respectively) decrease with increased pressure up to 750 bar where at least 80% of all pores with ∼25 nm diameters are CD4 accessible. In contrast, between Q = 0.1–1 Å−1 (corresponding to nominal pore diameters from 5 to 0.5 nm, respectively), scattering intensity initially increased at the lowest CD4 pressure tested (200 bar) before decreasing with increasing pressure. These signal fluctuations with CD4 pressure are interpreted to arise from the creation of pores with diameters <5 nm, likely through deformation of solid bitumen by supercritical CD4, and/or the incorporation of CD4 within sample organic matter. This new porosity represents an increase of at least 8% in available pore volume within the sample, although the majority of these pores do not persist following removal of CD4. Additionally, there is strong evidence for densification of CD4 within the sample indicated by a shift in the CD4 intermolecular scattering peak to higher Q-values compared to bulk CD4. These results provide insight into fluid properties within source-rock reservoirs at late oil/wet gas thermal maturities, especially as they relate to organic porosity interconnectivity, and are discussed with perspective toward pressure management of gas condensate wells.

Pore Types and Characteristics of Ultra-Deep Shale of the Lower Paleozoic Wufeng-Longmaxi Formations in the Eastern Sichuan Basin

Recently, shale gas exploration of the Wufeng-Longmaxi formations (WF-LMX) in the Sichuan Basin has gradually stepped into deep to ultra-deep layers, but the pore types and characteristics of ultra-deep shale still remain unclear. In this study, the WF-LMX ultra-deep organic-rich shale samples in the Eastern Sichuan Basin were collected, and the types and development characteristics of shale pores were investigated by using high-resolution scanning electron microscopy (SEM). Our results showed that the pores of the WF-LMX ultra-deep shale reservoirs mainly included organic pores, mineral matrix pores (interparticle pores and intraparticle pores), and micro-fractures, which were dominated by organic pores, displaying oval, slit, and irregular shapes and a diameter of mainly 5–45 nm. Organic pores were poorly developed in primary organic matter (e.g., graptolite and radiolarian), while they were well developed in solid bitumen, being the most important nanopore type in shale. The pore development of ultra-deep shale was mainly controlled by the contents of organic matter and brittle minerals. Higher contents of organic matter and quartz are conducive to the development and preservation of organic pores, which are also favorable for ultra-deep shale gas exploration.

Quartz types and origins of the Upper Permian Dalong Formation shale of the Sichuan Basin: Implications for pore preservation in deep shale reservoirs

Quartz is critical to reservoir properties (e.g., rock mechanical behavior and porosity) of organic mudstones, exerting an important effect on shale gas production. However, the types and origins of quartz in deeply-buried Upper Permian mudstones, a potential target of shale gas exploration in South China, remain poorly understood. A suite of deeply buried (5636–5645 m) mudstone samples of the Upper Permian Dalong Formation (DL) in the Sichuan Basin (South China) was selected to characterize quartz minerals using petrological and geochemical approaches, including SEM-CL observation. The studied mudstone samples are relatively enriched in organic matter (OM) (total organic carbon (TOC) = 1.88–18.46 wt%) and have been thermally over-matured. The DL organic mudstones accumulated in a failed rift basin, far removed from provenance areas, are chiefly composed of intrabasinal quartz and carbonate (mostly calcite). Quartz is represented by six major forms, including detrital quartz grains, siliceous skeletal fragments, silica nanospheres, microquartz aggregates, grain-replacive quartz, and matrix-dispersed microquartz, of which the latter five are of authigenic origin. Detrital quartz grains are not common in the DL mudstones. Silica reprecipitated as authigenic quartz was largely sourced from dissolved siliceous skeletal fragments (mostly radiolarians), and some silica appeared to have been released from the alteration of volcanic debris (mainly plagioclase) to form matrix-dispersed microquartz grains. Authigenic quartz influenced pore development and preservation of shale reservoirs in two ways. A rigid framework formed from numerous authigenic quartz grains (e.g., microquartz aggregates, silica nanospheres, and siliceous skeletal fragments) shields organic pores during mechanical compaction, whereas authigenic quartz precipitation (e.g., cavity-filling quartz, grain-replacive quartz) reduces porosity by filling voids. A moderate abundance of authigenic quartz (Sixs = ∼20%) is most favorable for development and preservation of pores (especially organic pores) in deep mudstone. Organic pores, widely developed in the studied DL deep mudstones, seem to be largely preserved in the samples with TOC values as much as 18.46 wt%. In summary, the DL mudstone deposits enriched in OM and contained moderate contents of authigenic quartz are especially favorable targets of deep shale gas exploration.

Simultaneous enhancement of soil properties along with water-holding and restriction of Pb–Cd mobility in a soil-plant system by the addition of a phosphorus-modified biochar to the soil

Soil quality deterioration and heavy metal contamination have greatly limited soil productivity in mining areas. As soil is a complex system with various properties and interactions, it is imperative to conduct a comprehensive investigation to understand the amendment's mechanisms at work in the soil in mining areas as well as effective ways to address its deteriorating quality. In this study, a potassium dihydrogen phosphate-modified maize straw-cow dung biochar (PBC) was applied as a soil amendment. Various physicochemical properties of the soil including organic matter, total nitrogen, available phosphorus, and pore characteristics were analyzed. This study also assessed soil-saturated water content and soil moisture characteristic curve. Lettuce biomass was measured and changes in various speciation of Pb and Cd in the soil, and the accumulation of Pb and Cd in lettuce were examined. Results showed that the addition of PBC increased soil organic matter, total nitrogen, and available phosphorus while reducing soil bulk density, it also increased soil porosity, saturated water content, and capillary water capacity. Soil structure analysis using CT scanning revealed that 3% PBC increased the macrospores volume fraction while 5% PBC made the pores more uniform. Lettuce biomass increased by 53.3%. 5% PBC resulted in a 56.79% and 38.30% reduction in Pb and a 44.56% and 16.60% reduction in Cd in roots and shoots of lettuce respectively. PBC facilitated the transformation of Pb and Cd from unstable fractions to stable fractions through complexation and precipitation. Overall, the addition of PBC effectively improved soil nutrients, porosity, and water-holding capacity, promoted plant growth, immobilized Pb and Cd, as well as reduced the bioavailability in contaminated-soil from mining areas. This study provides an effective strategy and a new perspective for the remediation of Pb–Cd-contaminated soils.