Mercury methylation,demethylation and reduction rates in coastal and marine surface waters of the Mediterranean Sea

In situ experiments using isotopically labeled mercury species (¹⁹⁹Hg(II) and Me²⁰¹Hg) are used to investigate mercury transformation mechanisms, such as methylation, demethylation and reduction, in coastal and marine surface waters of the Mediterranean Sea. The aim of this work is to assess the relative contribution of photochemical versus biological processes to Hg transformation mechanisms. For this purpose, potential transformation rates measured under diurnal and dark incubation conditions are compared with major biogeochemical parameters (i.e. hydrological and biological data) in order to obtain the relative contribution of various biotic and abiotic mechanisms in both surface (high light) and bottom (low light) waters of the euphotic zone. The results demonstrate that coastal and marine euphotic zones are significant reactors for all Hg transformations investigated (i.e. methylation, demethylation, reduction). A major outcome demonstrates that Hg methylation is taking place in oxic surface seawater (0.3–6.3% day^− 1) and is mainly influenced by pelagic microorganism abundance and activities (phyto- and bacterioplankton). This evidences a new potential MeHg source in the marine water column, especially in oligotrophic deep-sea basins in which biogeochemistry is mostly governed by heterotrophic activity. For coastal and marine surface waters, although MeHg is mainly photochemically degraded (6.4–24.5% day^− 1), demethylation yields observed under dark condition may be attributed to microbial or chemical pathways (2.8–10.9% day^− 1). Photoreduction and photochemical reactions are the major mechanisms involved in DGM production for surface waters (3.2–16.9% day^− 1) but bacterial or phytoplanktonic reduction of Hg(II) cannot be excluded deeper in the euphotic zone (2.2–12.3% day^− 1). At the bottom of the euphotic zone, photochemical processes are thus avoided due to the attenuation of UV-visible sunlight radiation allowing biotic processes to be the most significant. These results suggest a new potential route for Hg species cycling in surface seawater and especially at the maximum biomass depth located at the bottom of the euphotic zone (i.e. maximum chlorophyll fluorescence). In this environment, DGM production and demethylation mechanisms are thus probably reduced whereas Hg methylation is enhanced by autotrophic and heterotrophic processes. Experimental results on mercury species uptake during these investigations further evidenced the strong affinity of MeHg for biogenic particles (i.e. microorganisms) that correspond to the first trophic level of the pelagic food web.