Simulating fluoride evolution in groundwater using a reactive multicomponent transient transport model: Application to a crystalline aquifer of Southern India by Marie Pettenati, Jerome Perrin, Helene Pauwels Shakeel Ahmed

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.