The stable isotope geochemistry of Australian coals

D/H, ¹³C/¹²C, ¹⁸O/¹⁶O and ³⁴S/³²S ratios in the organic matrix and organic solvent extracts of Australian coals, and in the fluids and minerals associated with these coals, are reported and reviewed against similar isotopic data for coals from other regions.Where coals are immature, original isotopic differences between macrolithotypes, and between solvent extracts (lipid concentrates) and insoluble residues, are largely preserved. However, with increasing maturity these characteristic differences, particularly those between macrolithotypes, are rapidly erased. Conversely, where, as indicated by low total sulfur contents, coals of Cretaceous to Permian age were deposited under essentially freshwater conditions, δ³⁴S values^* for the organically-bound sulfur remain remarkably constant at +4 ± 3‰ relative to meteoritic sulfur. In similar, younger Tertiary coals, the organic sulfur is markedly enriched in ³⁴S.Five distinctive isotopic patterns, which may be interpreted in terms of the environment of sulfate reduction, can be recognized from ³⁴S/³²S ratio measurements on the various forms of sulfur in Australian coals.Isotopic studies of seam gas hydrocarbons collected in situ show these to be unexpectedly strongly depleted in the heavier isotopes of hydrogen and carbon relative to natural gases from proposed humic sources. Furthermore, no pronounced increase in the ¹³C content in methane with increase in rank of the parent coal was observed. In addition, several sources of associated carbon dioxide have been delineated, including normal maturation processes, invasion of the seams by magnetic carbon dioxide, and interaction of the coal with intrusive magma.Isotopic exchange between free seam gases is not accepted as an explanation for some unusual isotopic fractionations seen, rather the data suggest that these gases may be formed in a state approaching isotopic equilibrium. This argument also satisfactorily explains the isotopic compositions of primary siderite and secondary calcite associated with bituminous coal seams. However, where seams are invaded and permeated with externally derived carbon dioxide, usually of magnetic origin, carbonates are frequently absent, presumably as a result of the action of carbonic acid.