Arsenic movement and fractionation in agricultural soils which received wastewater from an adjacent industrial site for 50 years

Arsenic (As) is an element with important environmental and human health implications due to its toxic properties. It is naturally occurring since it is contained in minerals, but it can also be enriched and distributed in the environment by anthropogenic activities. This paper reports on the historic As contamination of agricultural soils in one of the most important national relevance site for contamination in Italy, the so-called SIN Brescia-Caffaro, in the city of Brescia, northern Italy. These agricultural areas received As through the use of irrigation waters from wastewater coming from a factory of As-based pesticides (lead and calcium arsenates, sodium arsenite). Pesticide production started in 1920 and ended in the '70. Concentrations in the areas are generally beyond the legal threshold values for different soil uses and are up to >200 mg/kg. Arsenic contamination was studied to assess the long-time trend and the dynamics related to the vertical movement of As down to 1 m depth and its horizontal diffusion with surface irrigation in the entire field. Arsenic fractionation analysis (solid phase speciation by sequential extraction procedure) was also performed on samples collected from these areas and employed in greenhouse experiments with several plant species to evaluate the long-term contamination and the role of plant species in modifying As availability in soil. The results of this work can help in the evaluation of the conditions controlling the vertical transfer of As towards surface aquifers, the bioaccumulation likelihood in the agricultural food chain and the selection of sustainable remediation techniques such as phytoextraction.