Abstract. This paper describes a series of experiments designed to investigate the influence of litho!ogy on the compactional loss of porosity and permeability in mudstones. Two intact samples of London Clay with clay fractions of 40% and 67% were compacted to 33 MPa effective stress. Clay fraction, permeability, porosity, pore size distribution, and specific surface area were measured and their evolution was monitored throughout the compaction process. Electron microscopy was combined with mercury porosimetry to trace the collapse of the pore structure with increasing effective stress. In both cases, porosity loss occurred primarily by the collapse of large pores. This process is more obvious in the coarser-grained sample because throughout the compaction process it has a much broader range of pore radii and a much greater mean pore radius. Consistent with the pore size distributions, the permeability of the coarser sample ranges from ,• 1040 rn s 4 to 1042 rn s 4 while that of the finer-grained sample ranges from ~ 4 x 1042 rn s 4 tO 5 x 104'* rn s 4 during progressive compaction from 2 to 33 MPa. The compressibility of the finer-grained sample is greater than that of the coarser-grained sample (0.15 as opposed to 0.07). However, in both cases the compressibility is much lower than that inferred for lithologically similar samples compacted over geological timescales. The demonstration that both porosity and litho!ogy (clay fraction) influence the permeability of mudstones should allow the development of more realistic porositypermeability relationships which take into account lithological variations exhibited by mudstones.

Abstract. We report the results of a series of hydraulic conductivity tests carried out on seven natural, well-characterised specimens of London Clay mudstone. The clay fractions of the samples range from 27% to 66% and enabled a test of the influence of clay fraction on the hydraulic conductivity, pore size distribution, compressibility and specific surface area of natural mudstones. s over a porosity range of 48% to 25%. At a given porosity the hydraulic conductivities of two silt-rich samples (27 and 33% clay fraction) were 40-250 times greater than those of the five clayrich samples. Variations in hydraulic conductivity are directly related to pore size distributions and are accurately predicted by a model which uses pore size distribution as its primary input. Clay-rich samples have unimodal pore size distributions with modal throat radii around 60-120 nm. Silt-rich samples have bimodal pore throat size distributions. One modal size is similar to that observed in clay-rich samples with a second modal value at 3-6 gm. Compaction under effective stresses up to 10 MPa results in the preferential collapse of larger pores, so that the rate of loss of hydraulic conductivity is greater in the silt-rich samples. Differences in hydraulic conductivity between silt-rich and clay-rich mudstones therefore decline with decreasing porosity. The range of porosity-hydraulic conductivity relationships means that hydraulic conductivity is not easily predicted from porosity alone; additional constraining parameters such as grain and pore size distributions are required.

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Shale gas is an important hydrocarbon resource in a global context. It has had a significant impact on energy resources in the US, but the worldwide development of this methane resource requires further research to increase the understanding of the relationship of shale structural characteristics to methane storage capacity. In this study a range of gas adsorption, microscopic, mercury injection capillary pressure porosimetry and pycnometry techniques were used to characterize the full range of porosity in a series of shales of different thermal maturity. Supercritical methane adsorption methods for shale under conditions which simulate geological conditions (up to 473 K and 15 MPa) were developed. These methods were used to measure the methane adsorption isotherms of Posidonia shales where the kerogen maturity ranged from immature, through oil window, to gas window. Subcritical methane and carbon dioxide adsorption studies were used for determining pore structure characteristics of the shales. Mercury injection capillary pressure porosimetry was used to characterize the meso and macro porosity of shales. The sum of the CO 2 sorption pore volume at 195 K and mercury injection capillary pressure pore volumes (1093-5.6 nm) were equal to the corresponding total pore volume (< 1093 nm) thereby giving an equation accounting for virtually all the available shale porosity. These measurements allowed quantification of all the available porosity in shales and were used for estimating the contributions of methane stored as 'free' compressed gas and as adsorbed gas to overall methane storage capacity of shales. Both the mineral and kerogen components of shale were studied by comparing shale and the corresponding isolated kerogens so that the relative contributions of these components could be assessed. The results show that the methane adsorption characteristics were much higher for the kerogens and represented 35-60% of the total adsorption capacity for the shales used in this study, which had total organic contents in range 5.8-10.9 wt%. Microscopy studies revealed that the pore systems in clay-rich, organic-rich and microfossil-rich parts of shale are very different, and also the importance of the inter-granular organic-mineral interface.

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