Dimethylmercury in natural waters—analytical and experimental considerations

Mono- and dimethylmercury (MMHg and DMHg, respectively) are the two primary organic forms of mercury (Hg) found in natural waters. While experimental approaches to characterize the environmental behavior of MMHg and inorganic forms of Hg are widely used today, few laboratories conduct experimental studies entailing the use of DMHg. In this paper, we have evaluated and developed different analytical and experimental approaches to quantify and use DMHg in laboratory studies. We demonstrate that DMHg can be analyzed from samples where MMHg is derivatized using sodium tetraethyl borate and where the matrix effects of dissolved sulfide are masked using copper sulfate. Tests, where the calibration curves of MMHg and DMHg were used, showed that MMHg may be used to calibrate for DMHg. For the pre-concentration of DMHg, both traps filled with Tenax® TA and Bond Elut ENV were found suitable. We observed good recoveries of DMHg added to different types of natural waters or purified water containing aquarium salt, sodium chloride and dissolved sulfide, iron sulfide, and cadmium sulfide at DMHg : sulfide molar ratios > 10⁻⁶. In addition to evaluating these analytical aspects, we present suitable subsampling techniques for DMHg-containing solutions, the recovery of DMHg when filtering DMHg through different types of filters, and experimental data on the long-term stability of DMHg added to different types of waters and stored at different temperatures. Finally, we present and discuss a new synthetization protocol for preparing aqueous solutions containing DMHg free of organic solvents and where handling DMHg in a pure form is prevented.