Occurrence of minor toxic elements in volcanic-sedimentary aquifers: a case study in central Italy

The occurrence of minor toxic elements (arsenic, vanadium and fluoride among others) in the volcanic aquifers of central Italy, with concentrations often above the national standards for drinking waters, has been recognized since the 1970s. However, these groundwaters are still often used for human consumption. With the aim of providing insight into the water–rock interaction processes, as well as into the evolution of arsenic and other elements, water-sampling campaigns where undertaken within a 100 km² area at the eastern margin of the Viterbo region, where volcanites overlie an alluvial aquifer complex. The samples were analysed and geochemical modelling was applied to characterize the thermodynamic state of the waters. The results indicate the existence of direct relations among arsenic, vanadium and fluoride concentrations and of their inverse relationship with calcium concentration. An evolution scheme of groundwater composition from the upstream volcanic aquifer to the downstream sedimentary aquifer is also discussed. Two hypotheses are proposed which justify the observed decrease of the cited minor element concentrations, i.e. dilution processes and/or precipitation of fluorapatite, which can include in its structure small amounts of these elements. The precipitation hypothesis is supported by modelling results.