Aqueous phase methylation as a potential source of methylmercury in wet deposition

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2006-10-17Author
Hammerschmidt, Chad R.
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Lamborg, Carl H.
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Fitzgerald, William F.
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https://hdl.handle.net/1912/1554As published
https://doi.org/10.1016/j.atmosenv.2006.10.032Keyword
Mercury; Abiotic; Atmosphere; Precipitation; PhotodecompositionAbstract
The source of monomethylmercury (MMHg) in wet deposition is unknown. Volatilization of gaseous MMHg, evasion and demethylation of dimethylmercury, and methylation of Hg0 have been either proposed or tested unsuccessfully as potential sources. Here, we show that MMHg in precipitation, sampled across a wide geographical range in North America, is related positively to an operationally defined and measured reactive Hg species (HgR), but connected weakly to total Hg. The mean molar ratio of MMHg:HgR measured in continental precipitation (0.025 ± 0.006) is comparable to the MMHg:Hg(II) ratio estimated from first-order rate constants for acetate-mediated Hg methylation and MMHg photolysis (0.025 ± 0.002). This suggests MMHg may be formed in the atmosphere through a reaction between labile Hg(II) complexes and an unknown methylating agent(s), potentially acetate or similar molecules. Availability of Hg(II) appears to limit the reaction, and accordingly, increased atmospheric loadings of Hg could lead to enhanced MMHg in precipitation.
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Author Posting. © The Authors, 2006. This is the author's version of the work. It is posted here by permission of Elsevier B.V for personal use, not for redistribution. The definitive version was published in Atmospheric Environment 41 (2007): 1663-1668, doi:10.1016/j.atmosenv.2006.10.032.