Origin and nature of pores in the Toolebuc Formation, a potential unconventional target in Australia

The Toolebuc Formation of Australia, a potential unconventional hydrocarbon resource, has limited studies on its pore structure and sorption characteristics. In this study, shale samples covering the lower mixed argillaceous mudstone (MAM) lithofacies, the middle interbedded calcareous mudstone and shelly thin beds (CM-STB) lithofacies, and the upper interbedded calcareous mudstone and shelly horizons (CM-SH) lithofacies of the Toolebuc Formation were collected. These samples were analysed for pore structure using a combination of scanning electron microscopy, X-ray diffraction, helium pycnometry, mercury intrusion porosimetry, and N₂ physisorption techniques. Additionally, methane sorption isotherms were measured under in-situ conditions. The results reveal that most pores are mineral-related intraparticle (intraP) and interparticle pores, with slit, equant and elongated shapes. Organic matter (OM) pores are rare. Porosity, total pore volume and BET specific surface area (SSA) are 3.25–8.26%, 1.32–3.55 cm³/100 g, and 1.26–9.65 m²/g, respectively. Pore volume is dominated by mesopores and macropores while specific surface area is dominated by fine mesopores and micropores. The porosity of the organic matter is significantly low due to the rarity of OM pores in the stage of early oil-window thermal maturity; organic matter consequently occludes pore space and also negatively impacts the average porosity. Clay by contrast is positively correlated to the average porosity. Carbonate provides intraP pores in fecal pellets, but also fills in other pore spaces as occlusion. Methane isotherms exhibit linear shapes, suggesting that a portion of the gas is stored in solution. The lower MAM lithofacies, characterised by rich clay, high porosity and BET SSA, was measured to have an in-situ methane sorption capacity of 4.32 cm³/g; the middle CM-STB lithofacies has intermediate porosity, but exhibits excellent gas generation potential and high in-situ methane sorption capacity (4.12–5.5 cm³/g). Within the CM-STB lithofacies, porosity declines with depth. The upper CM-SH lithofacies is carbonate-rich, exhibiting the lowest porosity and in-situ methane sorption capacity (2.56 cm³/g), but may act as an intraformational seal. The combination and vertical stacking pattern of the three lithofacies provided a favourable setting for gas storage.