New geochemical data for defining origin and distribution of mercury in groundwater of a coastal area in southern Tuscany (Italy)

A geochemical study was conducted in a coastal plain in the Orbetello Lagoon area in southern Tuscany (Italy), acquiring new data on groundwater, lagoon water, and stream sediment for insights into the origin, distribution, and behaviour of mercury in a Hg-enriched carbonate aquifer. The main hydrochemical features of the groundwater are ruled by the mixing of Ca-SO4 and Ca-Cl continental fresh waters of the carbonate aquifer and Na-Cl saline waters of the Tyrrhenian Sea and Lagoon of Orbetello. Groundwater had highly variable Hg concentrations (< 0.1-11 μg/L) that were not correlated with the percentage of saline water, depth in the aquifer, or distance from the lagoon. This excluded the possibility that saline water could be the direct source of Hg in groundwater and responsible for release of the element through interaction with the carbonate lithologies of the aquifer. The origin of Hg in groundwater could be ascribed to the Quaternary continental sediments overlying the carbonate aquifer because i) high Hg concentrations were found in the continental sediments of the coastal plain and in the contiguous lagoon sediments; ii) waters from the upper part of aquifer had the highest Hg concentrations; iii) Hg levels in groundwater increased with increasing thickness of the continental deposits. The high Hg content in the continental and lagoon sediments is geogenic due to regional and local Hg anomalies and to sedimentary and pedogenetic processes. It can be assumed that i) water circulating in these sediments dissolves the solid Hg-bearing constituents and mobilises this element mainly as chloride complexes; ii) Hg-enriched water moves from the upper part of the carbonate aquifer due to the cone of depression generated by intense pumping of groundwater by fish farms in the study area.