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The Lower Paleozoic marine shale in southern China has undergone several strong tectonic transformations in an extensive region outside the Sichuan Basin. Although some shale strata underwent strong deformation, they still contain a significant amount of shale gas. The gas preservation mechanism in the strongly deformed shale has become the focus of attention. In this paper, the Lower Cambrian gas-bearing shale samples with a strong deformation taken from an exploration well in northern Chongqing, China, were investigated on their pore types and structure, with the aim to reveal the reason for the gas preservation. The pore types of the Lower Cambrian shale are dominated by microfractures and interparticle (interP) pores occurring mainly between clay minerals and between organic matter (OM) and clay minerals, while pores within OM that can be observed by FE-SEM (field emission-scanning electron microscopy) are rare. The shale has a low porosity, with an average of 1.56%, which is mainly controlled by the clay mineral content. The adsorption experiments of low pressure N2 (LPNA) and CO2 (LPCA) indicate that the shale is rich in micropores and small mesopores (<2–3 nm) provided mainly by OM, but mesopores with a size range of 3–50 nm are underdeveloped. The shale, as revealed by LPNA data, has dominant slit-like or plate-like pores and an obvious low-pressure hysteresis (LPH), indicating a low gas diffusion. The deformed shale samples with a removal of OM by oxidation and their isolated kerogen further indicate that the LPH is completely related to OM, without any relationship with minerals, while an undeformed shale sample, taken from another well for a comparison, has no obvious LPH for both of its OM-removed sample and kerogen. Based on a comprehensive analysis of the relative data, it is suggested that the nanopores related to OM and clay minerals in the shale were significantly altered owing to the deformation, with a result of the pores being squeezed into the slit-like shape and converted into micropores. This extraordinary pore structure of the shale formed during the deformation process should be the main preservation mechanism of shale gas.

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Recently, deep and ultra-deep shales (depth >3500 m) of the Lower Paleozoic Wufeng–Longmaxi formations (WF–LMX) have become attractive targets for shale gas exploration and development in China, and their gas contents may be influenced by the occurrence of water to some extent. However, the water content and its distribution in the different nanopores of the deep and ultra-deep shales have rarely been reported. In this study, a suite of the WF–LMX ultra-deep shale samples (5910–5965 m depth) from the Well PS1 was collected for water content measurements, and low-pressure CO2 and N2 adsorption experiments of both as-received and experimentally dried shale samples were carried out to investigate the distribution of water in the different nanopores. Since the studied ultra-deep shales are characterized by higher thermal maturity (equivalent vitrinite reflectance (EqVRo) > 2.5 %) and ultra-low water saturation, the pore water is generally dominated by irreducible water. The content of irreducible water of the studied shales varies from 1.57 to 13.66 mg/g, averaging 6.74 mg/g. Irreducible water may mainly occur in the clay-hosted pores, while it could also be hosted in parts of organic pores of organic-rich shales. Irreducible water is primarily distributed in non-micropores rather than in micropores of the studied shales, which mainly occurs in micopores with a diameter of 0.4–0.6 nm and mesopores with a diameter of 2–10 nm. Very low contents of irreducible water could reduce the specific surface area and volume of non-micropores of the shales to some extent, but the effect of irreducible water on the specific surface area of non-micropores was more significant than the volume of non-micropores, especially for organic-rich shale samples. The ultra-deep shale gas may be predominately composed of free gas, so low contents of irreducible water may play a limited role in its total gas contents. Overall, our findings can be helpful for a better understanding of water distribution in the highly-matured shales, and provide a scientific basis for ultra-deep shale gas exploration.

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