Simulating fluoride evolution in groundwater using a reactive multicomponent transient transport model: Application to a crystalline aquifer of Southern India

Overexploitation of crystalline aquifers in a semi-arid climate leads to a degradation of water quality, with the main processes responsible for the observed salt loads probably being irrigation return flow (IRF) and a high evaporation rate. The present study has focused on modelling the F− accumulation caused by IRF below rice paddy fields in the small endorheic Maheshwaram watershed (Andhra Pradesh, Southern India). The transient simulation was performed with a 1D reactive transport PHREEQC column and took into account IRF evaporation, kinetically controlled mineral dissolution/precipitation, ion adsorption on Fe hydroxides, and mixing with fresh groundwater. The results revealed the role of cationic exchange capacity (CEC) in Ca/Na exchange and calcite precipitation, both favouring a decrease of the Ca2+ activity that prevents fluorite precipitation. Iron hydroxide precipitation offers a not inconsiderable adsorption capacity for F− immobilization. The principal sources of F− are fluorapatite dissolution and, to a lesser extent, allanite and biotite dissolution. Anthropogenic sources of F−, such as fertilizers, are probably very limited. After simulating an entire dry-season irrigation cycle (120 days), the results are in good agreement with the observed overall increase of Cl− in the Maheshwaram groundwater. The model enables one to decipher the processes responsible for water-resource degradation through progressive salinization. It shows that F− enrichment of the groundwater is likely to continue in the future if groundwater overexploitation is not controlled.

► Simulation of F accumulation in Southern India groundwater under paddy field irrigation.
► A solute recycling model was constructed on measured field data.
► The model describes the F progressive enrichment in the irrigation return flow.
► F build-up is caused by evaporation and mineral dissolution processes.