Determination of Picogram Levels of Methylmercury by Aqueous Phase Ethylation, Followed by Cryogenic Gas Chromatography with Cold Vapour Atomic Fluorescence Detection

Abstract

A technique is presented, which allows the rapid and precise determination of methylmercury in aqueous samples. The sample is first reacted with sodium tetraethylborate, to convert the nonvolatile monomethyl mercury to gaseous methylethylmercury. The volatile adduct is then purged from solution, and recollected on a graphitic carbon column at room temperature. The methylethylmercury is then thermally desorbed from the column, and analyzed by cryogenic gas chromatography with cold vapour atomic fluorescence detection. The method allows the simultaneous determination of labile Hg(II) species, through the formation of diethylmercury, and of dimethylmercury, which is not ethylated. The methylmercury detection limit is about 0.6 pg Hg, or 0.003 ng∙L−1 for a 200-mL sample. The technique has been successfully applied directly to a wide variety of freshwater samples and alkaline tissue digestates. Seawater is analyzed following a simple extraction step to separate the methylmercury from the interfering chloride matrix. Analyses of natural surface waters have shown methylmercury levels typically in the range of 0.02–0.10 ng∙L−1, with values as high as 0.64 ng∙L−1 in a polluted urban lake. Waters collected from the anoxic bottom waters of a stratified remote lake have shown methylmercury levels as high as 4 ng∙L−1 as Hg.