Water-Rock Interaction Processes: A Local Scale Study on Arsenic Sources and Release Mechanisms from a Volcanic Rock Matrix

Arsenic is a potentially toxic element (PTE) that is widely present in groundwater, with concentrations often exceeding the WHO drinking water guideline value (10.0 μg/L), entailing a prominent risk to human health due to long-term exposure. We investigated its origin in groundwater in a study area located north of Rome (Italy) in a volcanic-sedimentary aquifer. Some possible mineralogical sources and main mechanisms governing As mobilization from a representative volcanic tuff have been investigated via laboratory experiments, such as selective sequential extraction and dissolution tests mimicking different release conditions. Arsenic in groundwater ranges from 0.2 to 50.6 μg/L. It does not exhibit a defined spatial distribution, and it shows positive correlations with other PTEs typical of a volcanic environment, such as F, U, and V. Various potential As-bearing phases, such as zeolites, iron oxyhydroxides, calcite, and pyrite are present in the tuff samples. Arsenic in the rocks shows concentrations in the range of 17–41 mg/kg and is mostly associated with a minor fraction of the rock constituted by FeOOH, in particular, low crystalline, containing up to 70% of total As. Secondary fractions include specifically adsorbed As, As-coprecipitated or bound to calcite and linked to sulfides. Results show that As in groundwater mainly originates from water-rock interaction processes. The release of As into groundwater most likely occurs through desorption phenomena in the presence of specific exchangers and, although locally, via the reductive dissolution of Fe oxy-hydroxides.