An improved method for rapid and safe preparation and measurement of dimethylmercury using gas chromatography-atomic fluorescence spectrometry.

Transformations between dimethylmercury (DMHg) and other mercury (Hg) species have been one of the critical knowledge gaps in the Hg global biogeochemical cycle due to the lack of detailed studies. The preparation and measurement of DMHg are challenging due to the high toxicity and volatility of DMHg. In this work, we invented a new DMHg generator for successfully preparing high-purity DMHg in a highly controllable and safe way. The DMHg could be spontaneously volatilized and diffused from the original preparation solution to the solution to be studied. The parameters for generating DMHg were optimized to be the pH value of 4.0 with a MeCo/Hg molar ratio of 10 at 20 °C. The following measurement method of DMHg in the presence of various species of Hg was also investigated and optimized. Hg and DMHg could be separated effectively with the carrier gas flow rate of 15 mL min and the gas chromatography column temperature of 30 °C. The interferences of Hg, monomethylmercury and other species were excluded by systematic control experiments. A sensitive and reliable approach for quantifying trace DMHg in water was developed. Under the optimal conditions, the limits of detection for Hg, MMHg and DMHg were 0.03, 0.002 and 0.024 ng L, respectively, with the relative standard deviation below 8.2%. The developed method was validated by the determination Hg species of different natural water samples. This work is expected to provide a new and safe strategy for DMHg preparation and a verified method for DMHg measurement.