Using a comprehensive data set (dissolved CH4, δ13C-CH4, δ2H-CH4, δ13C-DIC, δ37Cl, δ2H-H2O, δ18O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. δ13C-CH4 data in the gas reservoir (−58‰ to −49‰) and shallow coal measures underlying the alluvium (−80‰ to −65‰) are distinct. CO2 reduction is the dominant methanogenic pathway in all aquifers, and it is controlled by SO4 concentrations and competition for reactants such as H2. At isolated, brackish sites in the shallow coal measures and alluvium, highly depleted δ2H-CH4 (<310‰) indicate acetoclastic methanogenesis where SO4 concentrations inhibit CO2 reduction. Evidence of CH4 migration from the deep gas reservoir (200–500 m) to the shallow coal measures (<200 m) or the alluvium was not observed. The study demonstrates the importance of understanding CH4 at different depth profiles within and between aquifers. Further research, including culturing studies of microbial consortia, will improve our understanding of the occurrence of CH4 within and between aquifers in these basins.
The groundwater tracers, deuterium ( 2 H or D) and oxygen-18 ( 18 O) are widely used to determine groundwater recharge origin, rate and temperature. Quantitative methods able to interpret δD and δ 18 O mobility in the subsurface, especially under high pressure and temperature conditions, remain the focus of ongoing research.Here we developed an isotope transport module as an add-on to the TOUGH2 simulator, which is able to describe the evolution of δD and δ 18 O in groundwater induced by advection, dispersion, water-rock interaction, and fractionation due to changes of water phase and density. The new model was tested by modelling the groundwater flow, temperature, fluid density and isotopic composition in a faulted, geothermal system in the Guide Basin, China. We found that the density-driven flow induced by temperature variations can lead to isotope fractionation between low-3 ] Highlights
Isometric log ratios of proportions of major ions, derived from intuitive sequential binary partitions, are used to characterize hydrochemical variability within and between coal seam gas (CSG) and surrounding aquifers in a number of sedimentary basins in the USA and Australia. These isometric log ratios are the coordinates corresponding to an orthonormal basis in the sample space (the simplex). The characteristic proportions of ions, as described by linear models of isometric log ratios, can be used for a mathematical-descriptive classification of water types. This is a more informative and robust method of describing water types than simply classifying a water type based on the dominant ions. The approach allows (a) compositional distinctions between very similar water types to be made and (b) large data sets with a high degree of variability to be rapidly assessed with respect to particular relationships/compositions that are of interest. A major advantage of these techniques is that major and minor ion components can be comprehensively assessed and subtle processes-which may be masked by conventional techniques such as Stiff diagrams, Piper plots, and classic ion ratios-can be highlighted. Results show that while all CSG groundwaters are dominated by Na, HCO 3 , and Cl ions, the proportions of other ions indicate they can evolve via different means and the particular proportions of ions within total or subcompositions can be unique to particular basins. Using isometric log ratios, subtle differences in the behavior of Na, K, and Cl between CSG water types and very similar Na-HCO 3 water types in adjacent aquifers are also described. A complementary pair of isometric log ratios, derived from a geochemically-intuitive sequential binary partition that is designed to reflect compositional variability within and between CSG groundwater, is proposed. These isometric log ratios can be used to model a hydrochemical pathway associated with methanogenesis and/or to delineate groundwater associated with high gas concentrations.
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