Mercury contamination in Marano Lagoon (Northern Adriatic sea, Italy): Source identification by analyses of Hg phases

Abstract

Total Hg concentrations and Hg speciation were determined in bottom sediments of Marano lagoon to investigate the consequences of Hg phases on fish farms and shellfish cultivation areas. Mercury phases were separated into cinnabar (HgS) and non-cinnabar compounds, via a thermo-desorption technique, in surface and core sediments; both of which had been contaminated by industrial wastes and mining activity residues. The former are due to an industrial complex, which has been producing cellulose, chlor-alkali and textile artificial fibres since 1940. Processing and seepage wastewaters, which were historically discharged into the Aussa-Corno river system and therefore into the lagoon, have been significantly reduced since 1984 due to the construction of wastewater treatment facilities. The second source is the Isonzo River, which has been the largest contributor of Hg into the northern Adriatic Sea since the 16th century due to Hg mining at the Idrija mine (western Slovenia). Red cinnabar (HgS) derived from the mining area is mostly stable and insoluble under current environmental conditions. In contrast, organically bound Hg, such as Hg bound to humic acids, has the potential to be transformed into bioavailable Hg compounds (for example, methylmercury). The presence of the two Hg forms permitted each Hg source to be quantified. It also allowed the areas with the highest risk of Hg contamination from Hg-rich sediment to be identified; thus potentially avoiding the transfer of Hg from the sediment into the water column and eventually into living biota. The results show that Hg Enrichment Factors in bottom sediments exceed values of 10 and cinnabar dominates the central sector near the main tidal channel where tidal flux is more effective. Non-cinnabar compounds were found to be enriched in fine grained material and organic matter. In fact, up to 98% of total Hg at the Aussa-Corno river mouth and in the inner margin of the basin occurred in an organic form. This evidence, combined with the high contents of total Hg (4.1–6.6 μg g −1 and EF > 10) measured in surface sediments, suggest that Hg in Marano lagoon is involved in biogeochemical transformations (e.g., methylation).