Analytical Sciences

Sensitive Determination Method for Mercury Ion, Methyl-, Ethyl-, and Phenyl-mercury in Water and Biological Samples Using High-Performance Liquid Chromatography with Chemiluminescence Detection

Hitoshi KODAMATANI,*1 Akito MATSUYAMA,*2 Keiitsu SAITO,*3 Yuriko KONO,*4 Ryo KANZAKI,*1 and Takashi TOMIYASU*1

*1 Division of Earth and Environmental Sciences, Graduate School of Science and Engineering, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
*2 National Institute for Minamata Disease, Minamata, Kumamoto 867-0008, Japan
*3 Division of Human Environment, Graduate School of Human Development and Environment, Kobe University, 3-11 Tsurukabuto, Nada, Kobe 657-8501, Japan
*4 Environment and Safety Section, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan

A sensitive determination method for mercury speciation analysis was developed. Four mercury species, mercury ion, methylmercury, ethylmercury, and phenylmercury, were complexed with emetine-dithiocarbamate (emetine-CS₂), and then injected onto a HPLC instrument coupled with a tris(2,2′-bipyridine)ruthenium(III) chemiluminescence detection system. The emetine-CS₂ complexing agent was effectively used to measure the concentration in addition to serving as a separation and detection reagent. The calibration curves for these mercury complexes were linear in the range of 0.050 – 10 μg L⁻¹ (as Hg). The limit of detection for (emetine-CS₂)₂Hg, emetine-CS₂-methylmercury, emetine-CS₂-ethylmercury, and emetine-CS₂-phenylmercury were 30, 17, 21, and 22 ng L⁻¹, respectively. The sensitivity of this method enables the determination of mercury species in water samples at sub-ppb levels. Furthermore, the method was applied to biological samples in combination with acid leaching and liquid–liquid extraction using emetine-CS₂ as an extraction reagent. The determination results were in good agreement with the values of the certified reference materials.

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