Redox dependent arsenic occurrence and partitioning in an industrial coastal aquifer: Evidence from high spatial resolution characterization of groundwater and sediments

Superlative levels of arsenic (As) in groundwater and sediment often result from industrial pollution, as is the case for a coastal aquifer in Southern Italy, with a fertilizer plant atop. Understanding conditions under which As is mobilized from the sediments, the source of that As, is necessary for developing effective remediation plans. Here, we examine hydrogeological and geochemical factors that affect groundwater As concentrations in a contaminated coastal aquifer. Groundwater has been subject to pump-and-treat at a massive scale for more than 15 years and is still ongoing. Nevertheless, As concentrations (0.01 to 100 mg/L) that are four orders of magnitude more than Italian drinking water standard of 10 µg/L are still present in groundwater collected from about 50 monitoring wells over three years (2011, 2016, and 2018). As was quantified in three different locations by sequential extractions of 29 sediment cores in 2018 (depth 2.5 m to −16.5 m b.g.l.), combined with groundwater As composition, the aqueous and solid partitioning of As were evaluated by partition coefficient (Kd ) in order to infer the evolution of the contaminant plumes. Most sediment As is found in easily extractable and/or adsorbed on amorphous iron oxides/hydroxides fractions based on sequential extractions. The study shows that As contamination persists, even after many years of active remediation due to the partitioning to sediment solids. This implies that the choice of remediation techniques requires an improved understanding of the biogeochemical As-cycling and high spatial resolution characterization of both aqueous and solid phases for sites of interest.