There are considerable variabilities in the macroscopic structures, fabric development, and petrophysical properties of shale-involved detachment systems, which also alter the nature of organic materials in the weak or “easy-slip” zones on the nanoscale. Bedding-parallel slip is one of the main drivers of organic matter deformation and graphitization and therefore can constrain the evolution of organic nanostructure and porosity. However, the mechanisms and details of such processes are not yet well understood. Deformation in a suite of organic-rich shales (Lower Silurian–Lower Cambrian) selected from six geological sections around the Sichuan Basin, China, is dominated by bedding-parallel slip and tectonic compression that occur at varying scales across the various sections. The deformation results in changes in the shale fabric and its organic thermal maturity. The Raman-estimated organic maturity increases with the grade of deformation. The highest maturity was estimated on the mirror-like slip surface, which indicates the structurally and thermally altered organic material with a slight graphitization. We used transmission electron microscopy to observe an abundance of better-stacked basic structural units (BSUs) with the minimum lattice spacing of ~0.38 nm within the organic component, which is indicative of high aromaticity and partial graphitization of the organic molecular structures in the slip zones. Scanning electron microscope images reveal that the organic porosity is intimately linked to organic types and associated with detachment deformation. As tectonic compression and thermal metamorphism increase, the relative abundance of isolated coarse macropores (pore size >200 nm) and microcracks increases, whereas the relative abundance of organic spongy pores and mesopores to micropores decreases. Associated with this evolution of organic pore networks with increasing deformation/maturity grade, there is a decrease in the gas adsorption capacity, pore surface area, and pore volume. This decrease is caused by a transition to better-stacked BSUs and smaller lattice spacing that correspond to changes in the type and size of organic pores. The reduction in organic micropore and mesopore volumes is attributed to the adjustment of BSUs due to compressive tectonic stress and graphitization of the organic materials, which could emerge as key primary and secondary controls on organic nanoporosity, particularly in overmature shale. We suggest that predicting shale-related bedding-parallel slip events in areas of shale gas exploration could be significant for estimating of total gas resources.

Burial depth can significantly impact the pore structure characteristics of shale. The Lower Silurian Longmaxi Shale in the Weiyuan block of the Sichuan Basin is a marine formation that we studied for deep shale gas exploration. We used two groups of Longmaxi samples, outcrop shale and middle-deep shale, to investigate the pore structure fractal features at varying burial depths using a combination of mineralogy, organic geochemistry, scanning electron microscopy (SEM), and low-temperature gas (CO₂, N₂) adsorption. The V-S fractal model was used to determine the fractal dimension (Dc) of micropores, and the FHH fractal model was used to determine the fractal dimension (D_N) of mesopores. The findings indicate that the pore morphology of organic matter becomes irregular and more broken as the burial depth increases, as does the content and maturity of organic matter. The pore size of organic matter gradually decreases, the SSA (BET, DR) and PV (BJH, DA) of shale pores increase, the pore structure becomes more complex, and the average shale pore size decreases. According to this study, the organic matter content and its maturity show an increasing trend as burial depth increases. Meanwhile, the organic matter’s pore morphology tends to be irregular, and fracture rates rise, which causes the organic matter’s pore size to gradually decrease. In addition, the SSA (comprising the values assessed by BET and DR techniques) and PV (evaluated by BJH and DA methods) of shale pores grew, suggesting that the pore structure became more complex. Correspondingly, the average pore size of the shale decreased. The fractal dimensions of the micropores (D_C), mesoporous surface (D_N1), and mesoporous structure (D_N2) of outcrop shale are 2.6728~2.7245, 2.5612~2.5838, and 2.7911~2.8042, respectively. The mean values are 2.6987, 2.5725, and 2.7977, respectively. The D_C, D_N1, and D_N2 of middle-deep shale are 2.6221~2.7510, 2.6085~2.6390, and 2.8140~2.8357, respectively, and the mean values are 2.7050, 2.6243, and 2.8277, respectively. As the fractal dimension grows, the shale’s pore structure becomes more intricate, and the heterogeneity increases as the buried depth increases. The fractal dimension has a positive association with the pore structure parameters (SSA, PV), TOC, and R_o and a negative association with the mineral component (quartz, feldspar, clay mineral) contents. Minerals like quartz, feldspar, and clay will slow down the expansion of pores, but when SSA and PV increase, the pore heterogeneity will be greater and the pore structure more complex.

Structural evolution and characterization of organic-rich shale from macroscopic to microscopic resolution: The significance of tectonic activity

Nanoscale mineralogy and organic structure characterization of shales: Insights via AFM-IR spectroscopy

This paper tries to determine the key evaluation parameters of shale reservoirs in the complex tectonic provinces outside the Sichuan Basin in South China, and also to target the sweet spots of shale reservoirs accurately. The pore-structure characteristics of the Lower Silurian Longmaxi shale gas reservoirs in Well LD1 of the Laifeng–Xianfeng Block, Upper Yangtze region, were evaluated. N₂ adsorption and helium ion microscope (HIM) were used to investigate the pore features including pore volume, pore surface area, and pore size distribution. The calculated results show good hydrocarbon storage capacity and development potential of the shale samples. Meanwhile, the reservoir space and migration pathways may be affected by the small pore size. As the main carrier of pores in shale, organic matter contributes significantly to the pore volume and surface area. Samples with higher total organic carbon (TOC) content generally have higher porosity. Based on the Frenkel–Halsey–Hill equation (FHH model), two different fractal dimensions, D₁ and D₂, were observed through the N₂ adsorption experiment. By analyzing the data, we found that large pores usually have large values of fractal dimension, owing to their complex pore structure and rough surface. In addition, there exists a good positive correlation between fractal dimension and pore volume as well as pore surface area. The fractal dimension can be taken as a visual indicator that represents the degree of development of the pore structure in shale.

The characteristics of the nanopore structure in shale play a crucial role in methane adsorption and in determining the occurrence and migration of shale gas. In this study, using an integrated approach of X-ray diffraction (XRD), N₂ adsorption, and field emission scanning electron microscopy (FE-SEM), we systematically focused on eight drilling samples of marine Taiyuan shale from well ZK1 in southern North China to study the characteristics and heterogeneity of their nanopore structure. The results indicated that different sedimentary environments may control the precipitation of clay and quartz between transitional shale and marine shale, leading to different organic matter (OM)–clay relationships and different correlations between total organic carbon (TOC) and mineral content. The shale with high TOC content tended to have more heterogeneous micropores, leading to a higher fractal dimension and a more complex nanopore structure. With the increase of TOC content and thermal evolution of OM, the heterogeneity of the pore structure became more significant. Quartz from marine shale possessed abundant macropores, resulting in a decrease of the Brunauere–Emmette–Teller (BET) surface area (SA) and an increase of the average pore size (APS), while clay minerals developed a large number of micropores which worked together with OM to influence the nanopore structure of shale, leading to the increase of the SA and the decrease of the APS. The spatial order of interlayer pores increased with the increase of mixed-layer illite–smectite (MLIS) content, which naturally reduced the fractal dimensions. In contrast, kaolinite, chlorite, and illite have a small number of nanopores, which might enhance the complexity and reduce the connectivity of the nanopore system by mean of pore-blocking. Taiyuan shale with higher heterogeneity is highly fractal, and its fractal dimensions are principally related to the micropores. The fractal dimensions correlate positively with the SA and total pore volume, suggesting that marine shale with higher heterogeneity may possess a larger SA and a higher total pore volume.