Determination of mercury species in fish reference materials by isothermal multicapillary gas chromatography with atomic emission detection after microwave-assisted solubilization and solvent extraction

Abstract

A simple and rapid procedure for the simultaneous determination of methylmercury and Hg²⁺ in fish reference materials was developed. The procedure was based on a rapid (2.5 min) microwave-assisted solubilization of biomaterial with tetramethylammonium hydroxide, simultaneous quantitative ethylation–extraction of the mercury species into hexane (15 min) and flash isothermal separation (15–30 s) using a multicapillary regular column (100 cm) or a minicolumn (22 cm). The chromatographic hardware necessary for sample introduction into a microwave induced plasma was downscaled to a split injection port and a 20×20×10 cm compartment (housing the 1 m column) or a 22 cm×1 cm od thermally insulated tube (housing the minicolumn) maintained at a constant temperature and connected directly to the detector. No dilution of the GC eluent (60–120 ml min^–1) with make-up gas was necessary to achieve optimum sensitivity. Detection limits (as Hg) were 0.5 pg µl^–1 (20 ng g^–1 dry mass) and 2 pg µl^–1 (80 ng g^–1 dry mass)for MeHg⁺ and Hg²⁺, respectively. The method was validated for speciation analysis for mercury in BCR 463, BCR 464 (Tuna Fish) and NRCC DORM-1 (Dogfish Mussel) certified reference materials.