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.