Coupling mineral analysis with conceptual groundwater flow modelling: The source and fate of iron, aluminium and manganese in a back-barrier island

Mineral and aqueous geochemical data are combined with a conceptual groundwater flow model, to establish the origin and fate of iron, aluminium and manganese in the groundwater system of a small back-barrier island. The flow model domain consists of an unconfined island fresh groundwater lens overlying a semi-confined hypersaline aquifer. The two aquifers are separated by a discontinuous, clay-rich aquitard and both contain diffusion governed variable density flow fields. High concentrations of dissolved iron and manganese are associated with brackish to hypersaline groundwater, although there is no systematic relationship with salinity. Calculation of S2−/SO42− and Fe2+/Fe3+ redox couples and the results of thermodynamic modelling show that redox disequilibrium in the groundwater is widespread. Groundwater samples containing aqueous sulphide and ferric iron complexes are supersaturated with respect to pyrite, goethite and haematite but the prevailing state of redox disequilibrium controls mineral dissolution and precipitation. Aqueous iron in the deeper regions of both aquifers is derived from the dissolution of iron oxide–hydroxides in lateritic palaeosols controlled by seasonal fluctuations in groundwater redox state. Aqueous manganese is potentially derived from the dissolution of ilmenite and amorphous oxide–hydroxides. The oxidation of iron sulphides contributes to the aqueous iron concentration and sulphuric acid production in the shallow groundwater. The solubility of aluminium is also limited by this process, governed by acidity regulation. A significant proportion of aqueous iron is transmitted from the semi-confined to the overlying unconfined aquifer through discontinuities in the aquitard layer. Movement of metals in solution outside the island groundwater system is restricted by the presence of diffusion boundaries within variable density transition zones.