Possible alkylation of inorganic Hg(II) by photochemical processes in the environment

The methylation of inorganic Hg by anaerobic bacteria in aquatic environments is considered to be the major pathway for methylmercury (MeHg) production. However, recent research has suggested that abiotic or chemical methylation by humic substances and other low-molecular-weight organic compounds in natural environments is also possible. Here, the aqueous photo-transformation of Hg2+ to organomercurials was investigated in the presence of ketones, aldehydes and low molecular weight organic acids under UV irradiation. MeHg and/or ethylmercury (EtHg) were identified as the main organomercurial products by multiple analytical techniques, including chromatography-atomic spectrometry and molecular mass spectrometry and further confirmed by stable isotope tracer experiments. The yield of organomercurials was markedly influenced by pH, NaCl concentration, alkylation donor concentration and the presence of chelating ligands in the aqueous solution. Electron paramagnetic resonance spectrometry demonstrated that the radical reaction was not the predominating alkylation pathway, although methyl radicals were detected in the photo-alkylation procedure. A mechanism based on intra-molecular alkyl transfer in the Hg2+-low-molecular-weight organic compound complex is proposed. The present work helps us better understand of MeHg and EtHg photo-generation in natural environments.

► Aqueous photo-alkylation of Hg2+ by low-molecular-weight organic compounds under UV irradiation.
► Methylmercury and/or ethylmercury were identified as the main organomercurial products.
► Mechanism based on the intra-molecular alkyl transfer in the Hg complex was proposed.
► Photo-methylation of Hg2+ is a possible source of methylmercury in natural environment.