Sources, chronology of deposition, and mobility of mercury and methylmercury in the sediments of a contaminated Mediterranean bay

Sci Total Environ. 2024 Nov 1:949:175021. doi: 10.1016/j.scitotenv.2024.175021. Epub 2024 Jul 31.

Abstract

Coastal sediments constitute a major reservoir for natural and anthropogenic mercury (Hg) and can be used as geochronological records of past Hg deposition. They may also act as secondary Hg sources for pelagic ecosystems via the efflux of toxic methylmercury (MeHg) diffusing from sediment porewaters and/or mobilized by sediment resuspension. In Toulon Bay sediments, which are known as one of the Hg hot spots of the northwestern Mediterranean Sea, we explored Hg species accumulation and mobility. The total Hg concentrations averaged 0.014 μg g-1 ca. 2000 years ago, then exhibited three major peaks during the Medieval Period, the Early Modern Period of Europe, and the Industrial Era, reaching 0.06, 0.07, and 13 μg g-1, respectively. The Medieval peak is attributed to the massive development of metallurgy in Europe accompanied by the burning of soil and vegetation, the second peak to the optimum of Hg extraction in Europe (Almadén mine), and the resumption of deforestation after the great plague. The third most recent Hg enrichment is associated with Hg-fulminate production, the scuttling of the French navy fleet during World War II, and ship salvaging and removal in the post-war years. Sampling of the dissolved phase at high vertical resolution above and below the sediment-water interface (SWI) enables us to conclude that MeHg was produced in situ by microbiological pathways and its diffusion across the SWI was negligible. On the other hand, ex-situ resuspension experiments showed that sorption and/or photodemethylation restrict MeHg from the dissolved phase.

Keywords: Mediterranean Sea; Mercury; Methylmercury; Sediment; Toulon Bay.