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An innovative method for the ultrasensitive detection of mercury by solution anode glow discharge atomic emission spectroscopy (SAGD-AES) coupled with hydride generation (HG) was first investigated.In this method, the mercury vapor generated by the HG was transmitted to the SAGD through the miniature hollow tungsten tube for excitation and detected by a miniaturized spectrograph. A thorough parametric evaluation of the HG and SAGD systemwas performed, including the type and concentration of carrier acid, He flowrate, concentrations of NaBH4, discharge current and discharge gap. Under optimal operating conditions, the detection limit for Hg2+ achieved 0.03μg/L, with a relative standard deviation of 1.1% at the Hg2+ concentration of 5μg/L. Moreover, the correlation coefficient of the calibration curve was 0.9996 in the range between 0.1 and 10μg/L. The accuracy and practicability of HG-SAGD-AES were verified by measuring GBW09101b (human hair), GBW10029 (fish), soil and rice samples. The results showed good agreement with the certified values and values from direct mercury analyzer (DMA).