Abstract: Knowledge of the natural baseline quality of groundwaters is an essential prerequisite for understanding pollution and for imposing regulatory limits. The natural baseline of groundwaters may show a range of concentrations depending on aquifer mineralogy, facies changes, flow paths and residence time. The geochemical controls on natural concentrations are discussed and an approach to defining baseline concentrations using geochemical and statistical tools is proposed. The approach is illustrated using a flowline from the Chalk aquifer in Berkshire, UK where aerobic and anaerobic sections of the aquifer are separately considered. The baseline concentrations for some elements are close to atmospheric values whereas others evolve through time-dependent water–rock interaction. Certain solutes (K, NH4+), often considered contaminants, reach naturally high concentrations due to geochemical controls; transition metal concentrations are generally low, although their concentrations may be modified by redox controls. It is recommended that the baseline approach be incorporated into future management strategies, notably monitoring.

Abstract: The distribution of uranium isotopes (238U and 234U) in groundwaters of the south-western margin of the Great Artesian Basin (GAB), Australia, and underlying Arckaringa Basin were examined using groundwater samples and a sequential extraction of aquifer sediments. Rock weathering, the geochemical environment and α-recoil of daughter products control the 238U and 234U isotope distributions giving rise to large spatial variations. Generally, the shallowest aquifer (J aquifer) contains groundwater with higher 238U activity concentrations and 234U/238U activity ratios close to secular equilibrium. However, the source input of uranium is spatially variable as intermittent recharge from ephemeral rivers passes through rocks that have already undergone extensive weathering and contain low 238U activity concentrations. Other locations in the J aquifer that receive little or no recharge contain higher 238U activity concentrations because uranium from localised uranium-rich rocks have been leached into solution and the geochemical environment allows the uranium to be kept in solution. The geochemical conditions of the deeper aquifers generally result in lower 238U activity concentrations in the groundwater accompanied by higher 234U/238U activity ratios. The sequential extraction of aquifer sediments showed that α-recoil of 234U from the solid mineral phases into the groundwater, rather than dissolution of, or exchange with the groundwater accessible minerals in the aquifer, caused enrichment of groundwater 234U/238U activity ratios in the Boorthanna Formation. Decay of 238U in uranium-rich coatings on J aquifer sediments caused resistant phase 234U/238U activity ratio enrichment. The groundwater 234U/238U activity ratio is dependent on groundwater residence time or flow rate, depending on the flow path trajectory. Thus, uranium isotope variations confirmed earlier groundwater flow interpretations based on other tracers; however, spatial heterogeneity, and the lack of clear regional correlations, made it difficult to identify recharge and inter-aquifer leakage.