Mercury speciation by high-performance liquid chromatography atomic fluorescence spectrometry using an integrated microwave/UV interface. Optimization of a single step procedure for the simultaneous photo-oxidation of mercury species and photo-generation of Hg 0 ☆

Abstract We described the hyphenation of photo-induced chemical vapor generation with high performance liquid chromatography–atomic fluorescence spectrometry (HPLC–AFS) for the quantification of inorganic mercury, methylmercury (MeHg) and ethylmercury (EtHg). In the developed procedure, formic acid in mobile phase was used for the photodecomposition of organomercury compounds and reduction of Hg 2 + to mercury vapor under microwave/ultraviolet (MW/UV) irradiation. We optimized the proposed method studying the influence of several operating parameters, including the type of organic acid and its concentration, MW power, composition of HPLC mobile phase and catalytic action of TiO 2 nanoparticles. Under the optimized conditions, the limits of detection were 0.15, 0.15 and 0.35 μg L − 1 for inorganic mercury, MeHg and EtHg, respectively. The developed method was validated by determination of the main analytical figures of merit and applied to the analysis of three certified reference materials. The online interfacing of liquid chromatography with photochemical-vapor generation–atomic fluorescence for mercury determination is simple, environmentally friendly, and represents an attractive alternative to the conventional tetrahydroborate (THB) system.