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Seasonal and spatial variations of dissolved and particulate methylmercury were evaluated for the first time in sediment cores from the Tagus Estuary. Results showed the highest MeHg concentrations in summer months indicating that the “seasonally” methylation process occurs not only at the topmost layers of the sediments but also in the deeper layers of the sediment column. The proportion of MeHg (up to 92%) in some of our pore water samples was higher than values reported in the literature for other estuaries suggesting that the sedimentary environment in the Tagus tends to favour Hg methylation. This work points to the importance of seasonal variation of the MeHg production in sediment cores. In physically dominated estuaries this enhances seasonal MeHg production in deeper sediments that can have serious ecological impacts due to resuspension or advection processes under extreme events by the increase of MeHg transported to the water column. [ABSTRACT FROM AUTHOR]

Intertidal sediments of Tagus estuary regularly experiences complex redistribution due to tidal forcing, which affects the cycling of mercury (Hg) between sediments and the water column. This study quantifies total mercury (Hg) and methylmercury (MMHg) concentrations and fluxes in a flooded mudflat as well as the effects on water-level fluctuations on the air-surface exchange of mercury. A fast increase in dissolved Hg and MMHg concentrations was observed in overlying water in the first 10 min of inundation and corresponded to a decrease in pore waters, suggesting a rapid export of Hg and MMHg from sediments to the water column. Estimations of daily advective transport exceeded the predicted diffusive fluxes by 5 orders of magnitude. A fast increase in dissolved gaseous mercury (DGM) concentration was also observed in the first 20–30 min of inundation (maximum of 40 pg L − 1 ). Suspended particulate matter (SPM) concentrations were inversely correlated with DGM concentrations. Dissolved Hg variation suggested that biotic DGM production in pore waters is a significant factor in addition to the photochemical reduction of Hg. Mercury volatilization (ranged from 1.1 to 3.3 ng m − 2 h − 1 ; average of 2.1 ng m − 2 h − 1 ) and DGM production exhibited the same pattern with no significant time-lag suggesting a fast release of the produced DGM. These results indicate that Hg sediment/water exchanges in the physical dominated estuaries can be underestimated when the tidal effect is not considered. [ABSTRACT FROM AUTHOR]