Arsenic (As) in groundwater from natural and anthropogenic sources is one of the most common pollutants worldwide affecting people and ecosystems. A large dataset from >3600 wells is employed to spatially simulate the depth-averaged As concentration in phreatic and confined aquifers of the Padana Plain (Northern Italy). Results of in-depth geostatistical analysis via PCA and simulations within a Monte Carlo framework allow the understanding of the variability of As concentrations within the aquifers. The most probable As contaminated zones are located along the piedmont areas in the confined aquifers and in the lowland territories in the phreatic aquifers. The distribution of the As contaminated zones has been coupled with hydrogeological, geological, and geochemical information to unravel the sources and mechanisms of As release in groundwater. The reductive dissolution of Fe oxyhydroxides and organic matter mineralization under anoxic conditions resulted to be the major drivers of As release in groundwater. This phenomenon is less evident in phreatic aquifers, due to mixed oxic and reducing conditions. This large-scale study provides a probabilistic perspective on As contamination, e.g. quantifying the spatial probability of exceeding national regulatory limits, and to outline As major sources and drivers.
Keywords: Aquifer matrix; Groundwater quality; Metalloid pollution; Monte Carlo approach; PCA; Redox processes.
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