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Stable isotope composition of gas is widely used in hydrocarbon exploration to determine the composition and thermal maturity of source rocks. Many isotope classification systems used for gas to source rock correlation and thermal maturity determination are primarily based on empirical observations made in conventional reservoirs and the kinetic isotope effects observed during pyrolysis experiments performed on source rocks. However, such relationships may not be readily applicable to onshore unconventional reservoirs due to the strong molecular and isotope fractionation that occur during extensive gas expulsion associated with basin uplift and depressurization.

Degassing studies of freshly recovered core samples can provide useful insight into the behaviour of gas molecules in unconventional reservoirs during basin uplift. The analyses of Australian coal and marine shale samples demonstrate that during desorption both molecular and isotopic compositions of gas change at variable rates. Gas initially desorbed from the samples is mostly CH4, whereas later desorbed gas becomes increasingly enriched in C2H6 and higher hydrocarbons. Hydrocarbon molecules also fractionate according to their isotopic composition, where the early released gas is enriched in 12C causing the remaining gas in the reservoir to be enriched in the heavier 13C isotope. During the release of gas from the Bowen Basin coals the C isotope ratio of CH4 (δ13C1) changes by up to 21‰ (VPDB), whereas that for C2H6 (δ13C2) and C3H8 (δ13C3) changes by <6‰. Similar changes in the isotope composition can be seen during the release of gas from marine source rocks of the Beetaloo Sub-basin. In a fully gas-mature middle Velkerri shale sample, δ13C1 changes by up to 28‰ and δ13C2 by up to 3‰ with no appreciable change occurring in δ13C3.

The extent of molecular fractionation during gas flow through carbonaceous rocks is primarily related to the adsorption–desorption properties of organic matter and diffusivity through the overall rock matrix. Using the current dataset, the magnitude of the contributions exerted by the desorption and diffusion processes cannot be readily distinguished. However, both Bowen Basin coals and Beetaloo Sub-basin shale show similar fractionation effects during gas flow, where the heavier alkane molecules, including those containing more 13C, desorb and move slowly compared with the lighter components, in particular CH4. Different rates of isotope fractionation between hydrocarbon molecules during gas flow cause the shape of compound-specific-isotope (CSI) curve to change with time. Early released gas is characterized by a normal CSI trend where the short-chain hydrocarbons are isotopically lighter compared with the longer-chain hydrocarbons. Because CH4 and C2H6 molecules enriched in 12C desorb and diffuse more readily than the heavier hydrocarbons (including those enriched 13C), the gas remaining in the coal and shale samples after extensive desorption shows a reversed CSI trend where CH4 and C2H6 are isotopically heavier compared with the longer chain hydrocarbons. Reversed isotope trends may also develop over geological time, particularly where the source rock is fully gas-mature and has expelled hydrocarbons due to prolonged degassing. As seen in the Beetaloo Sub-basin, the CSI trend in the dry-gas-mature Velkerri shale is reversed, possibly due to the loss of a large proportion of originally generated CH4 during post-Cambrian basin uplift.

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