The importance of unsaturated zone biogeochemical processes in determining groundwater composition, southeastern Australia

Analysis of soil, soil water and groundwater in the Mount William Creek catchment, southeastern Australia, shows that Mg²⁺ and Ca²⁺ within infiltrating rainfall are rapidly depleted by plant uptake and adsorption on clay minerals. Na⁺ and K⁺ may exhibit minor enrichment at shallow depths but are quickly readsorbed, so that cation/Cl^– ratios typical of groundwater are observed in soil water within the upper 200 cm of the soil profile for all species. The concentrations of K⁺ and Ca²⁺ in soil and groundwater are more depleted than Na⁺ and Mg²⁺ due to preferential uptake by vegetation. Removal of organic matter results in a continuing, long-term export of all major cations from the soil profiles. The processes of biogeochemical fractionation within the unsaturated zone rapidly modify the cation/Cl^– ratios of infiltrating rainfall to values characteristic of seawater. These mechanisms may have reached steady state, because groundwaters with seawater ion/Cl^– ratios are thousands of years old; the exchange sites on the soil clays are probably saturated, so cations supplied in rainfall are exported in organic matter and incorporated into recharge infiltrating into the groundwater. Much of the chemical evolution of groundwater traditionally attributed to processes within the aquifer is complete by the time recharge occurs; this evolutionary model may have broad application.