Abstract 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 CH 4 , whereas later desorbed gas becomes increasingly enriched in C 2 H 6 and higher hydrocarbons. Hydrocarbon molecules also fractionate according to their isotopic composition, where the early released gas is enriched in 12 C causing the remaining gas in the reservoir to be enriched in the heavier 13 C isotope. During the release of gas from the Bowen Basin coals the C isotope ratio of CH 4 (δ 13 C 1) changes by up to 21‰ (VPDB), whereas that for C 2 H 6 (δ 13 C 2) and C 3 H 8 (δ 13 C 3) 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, δ 13 C 1 changes by up to 28‰ and δ 13 C 2 by up to 3‰ with no appreciable change occurring in δ 13 C 3 . 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 13 C, desorb and move slowly compared with the lighter components, in particular CH 4 . 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 CH 4 and C 2 H 6 molecules enriched in 12 C desorb and diffuse more readily than the heavier hydrocarbons (including those enriched 13 C), the gas remaining in the coal and shale samples after extensive desorption shows a reversed CSI trend where CH 4 and C 2 H 6 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 CH 4 during post-Cambrian basin uplift.

Abstract In traditional organic geochemical investigations analyses are usually segmented in rather time-consuming single working steps that also require off-line preparation for each analytical instrument which can add to analytical bias. Since industry laboratories need to be precise, as well as cost- and time-efficient, we present a flexible and modular analytical concept which enables the user to perform advanced organic geochemical methods on a single gas chromatograph coupled to multiple detectors. The coupled analytical system can perform analyses of natural gas composition up to n -butane, stable carbon isotopes of natural gas compounds up to n -butane, identification and quantification of major compounds in oils and extracts, and compound-specific isotopes of oil and extracts. The analytical methodologies are appropriate for enhancement to broaden the application spectrum of coupled detectors.

Abstract: Organic compounds are ubiquitous in the Earth’s surface, sediments and many rocks, and preserve records of geological, geochemical and biological history; they are also critical natural resources and major environmental pollutants. The naturally occurring stable isotopes of volatile elements (D, 13 C, 15 N, 17,18 O, 33,34,36 S) provide one way of studying the origin, evolution and migration of geological organic compounds. The study of bulk stable isotope compositions (i.e. averaged across all possible molecular isotopic forms) is well established and widely practised, but frequently results in non-unique interpretations. Increasingly, researchers are reading the organic isotopic record with greater depth and specificity by characterizing stable isotope ‘structures’ – the proportions of site-specific and multiply substituted isotopologues that contribute to the total rare-isotope inventory of each compound. Most of the technologies for measuring stable isotope structures of organic molecules have been only recently developed and to date have been applied only in an exploratory way. Nevertheless, recent advances have demonstrated that molecular isotopic structures provide distinctive records of biosynthetic origins, conditions and mechanisms of chemical transformation during burial, and forensic fingerprints of exceptional specificity. This paper provides a review of this young field, which is organized to follow the evolution of molecular isotopic structure from biosynthesis, through diagenesis, catagenesis and metamorphism.