Biogeochemical Cycle of Mercury and Methylmercury in Two Highly Contaminated Areas of Tagus Estuary (Portugal)

Cesário, Rute; Hintelmann, Holger; O’Driscoll, Nelson J.; Monteiro, Carlos E.; Caetano, Miguel; Nogueira, Marta; Mota, Ana M.; Canário, João

Biogeochemical Cycle of Mercury and Methylmercury in Two Highly Contaminated Areas of Tagus Estuary (Portugal)

2017

Mercury (Hg) dynamics was evaluated in contaminated sediments and overlying waters from Tagus estuary, in two sites with different Hg anthropogenic sources: Cala Norte (CNOR) and Barreiro (BRR). Environmental factors affecting methylmercury (MMHg) production and Hg and MMHg fluxes across sediment/water interface were reported. [THg] and [MMHg] in solids (0.31–125 μg g⁻¹ and 0.76–201 ng g⁻¹, respectively) showed high variability with higher values in BRR. Porewater [MMHg] (0.1–63 ng L⁻¹, 0.5–86% of THg) varied local and seasonally; higher contents were observed in the summer campaign, thus increasing sediment toxicity affecting the sediment/water Hg (and MMHg) fluxes. In CNOR and BRR sediments, Hg availability and organic carbon were the main factors controlling MMHg production. Noteworthy, an upward MMHg diffusive flux was observed in winter that was inverted in summer. Although MMHg production increases in warmer month, the MMHg concentrations in overlying water increase in a higher proportion compared to the levels in porewaters. This opposite trend could be explained by different extension of MMHg demethylation in the water column. The high concentrations of Hg and MMHg and their dynamics in sediments are of major concern since they can cause an exportation of Hg from the contaminated areas up to ca. 14,600 mg year⁻¹ and an MMHg deposition of up to ca. 6000 mg year⁻¹. The results suggest that sediments from contaminated areas of Tagus estuary should be considered as a primary source of Hg for the water column and a sink of MMHg to the sedimentary column.

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