Arsenic in the groundwater aquifers of the Venetian Plain: geochemical modelling and occurrence of As-sulfides minerals, a review of data from the medio Brenta domain (Italy)

The Venetian Plain is known for areas with high concentrations of arsenic (As) in groundwater (up to more than 400 AgIL; exceptionally 647 mu gIL, in selected areas). A study area was chosen, north of Padua, which exhibits typical residential, industrial, and agricultural characteristics similar to most Western countries and lacks hydrothermal, volcanic, or anthropogenic sources of arsenic. The pilot area was the focus of several studies which are reviewed in this note. The objectives of the studies were to verify the distribution of As concentrations in groundwater and sediments (mineralogical and geochemical analysis of groundwater sediments and of filtered and unfiltered groundwater) and to model the mobility of arsenic arising from water-rock interaction. The grain size of aquifer reservoirs includes gravel, sand, silt, and clay. The amount of organic matter in the aquifer sediments of the study area seems peculiar (higher) compared to other plains in the world; it influences the redox potential and the relative concentration of As in groundwater. Arsenic contamination in groundwater and redox conditions varied greatly in the area. Groundwater under oxidizing and highly reducing conditions had much lower arsenic concentrations compared to groundwater under intermediate reducing conditions. Arsenic minerals (such as realgar-pararealgar) occur in aquifer sediments and they were documented in the studied materials by different analytical techniques for the first time in the context of the Italian plains. Since these minerals are rare throughout the world in plain sediments not affected by volcanic or hydrothermal activity, their occurrence is a distinctive feature of the Venetian Plain aquifer. These arsenic minerals were found in peat sediments of the study area, consistent with geochemical modeling results, which require highly reducing conditions for their precipitation from groundwater. Modeling suggests that under oxidizing and up to slightly reducing conditions (from 200 mV to -50 mV), arsenic is adsorbed on solid phases, but a further decrease in redox potential leads arsenic desorption from solids and consequent groundwater contamination (from -50 mV to -250 mV). If the redox potential becomes even more negative (below -250 mV), geochemical conditions are favorable to the formation of arsenic sulfides. The precipitation of the realgar-pararealgar phases, predicted by the geochemical model, proceeds by extracting arsenic from the groundwater and quantitatively accounts for the lower arsenic concentration measured in the highly reducing groundwater of the study area.