Fe and As geochemical self-removal dynamics in mineral waters: evidence from the Ferrarelle groundwater system...

A theoretical pattern for Fe and As co-precipitation was tested directly in a groundwater natural system. Several monitoring wells were sampled to identify the different endmembers that govern the hydrodynamics of the Ferrarelle Groundwater System in the Riardo Plain (Southern Italy). In agreement with recent investigations, we found a mix of a deep and a shallow component in different proportions, resulting in a specific chemical composition of groundwater in each well depending on the percentages of each component. The shallow component was characterized by EC ~ 430 µS/cm, Eh ~ 300 mV, Fe ~ 0.06 µmol/L and As ~ 0.01-0.12 µmol/L, while the deep component was characterized by EC ~ 3400 µS/cm, Eh ~ 170 mV, Fe ~ 140 µmol/L and As ~ 0.59 µmol/L. A general attenuation of As and Fe concentration that was not due to a simple dilution effect was observed in the mixing process. The oxidation of Fe(II) to Fe(III) produces solid precipitates which adsorb As from solution and then co-precipitate. The reactions pattern of Fe(II) oxidation and As adsorption gave a linear function between [As] and [Fe], where the angular coefficient depends on the [O₂]/[H⁺] ratio. Chemical data obtained from our samples showed a very good agreement with this theoretical relationship. The investigated geochemical dynamics represented a natural process of attenuation of Fe and As, two undesirable elements that usually affect groundwater quality in volcanic aquifers in central-southern Italy, which are exploited to supply drinking water.