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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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Although the mining activity of the Idrija mine in Slovenia ceased in 1995, a large amount of mining dregs containing high concentrations of mercury remains in the area. The mining dregs were transported with river flow and deposition along the Idrija River. To estimate the dispersion and change in the chemical form of mercury, a total of 28 soil core samples were taken around the river. The individual core samples were separated into layers for the analysis of their chemical composition, carbon contents, total mercury (T-Hg) and methylmercury (MeHg) concentrations. The chemical composition measured by X-ray fluorescence spectrometry was useful to estimate the dispersion of tailings: the fluvial terrace soil had a chemical composition similar to that of the tailings and could be distinguished clearly from the forest soil. The highest T-Hg concentration, 1,100 mg kg -1 , was observed in the fluvial terrace soil near the mine. Although the concentration decreased gradually along with distance from the mine, concentrations higher than 200 mg kg -1 of T-Hg were still observed in the fluvial terrace soil approximately 20 km downstream from the mine. In the vertical distribution of T-Hg in the hillslope soil, a higher value was observed in the upper layers, which suggests the recent atmospheric deposition of mercury. The concentration of MeHg was the lowest at the riverside and higher in the hillslope soil, which was the opposite of the T-Hg distribution. The total organic carbon content tracked similarly with the distribution of MeHg and a linear relation with a significantly high correlation coefficient was obtained. The distinction may be related to the different dispersion process of mercury, and the organic carbon contents may be an important factor for MeHg formation.

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Therefore, deep-sea mercury monitoring is very important to both the caution of environmental pollution and the exploration of underwater mineral deposits. Due to their high sensitivity, cold vapor atomic absorption spectrometry (CV-AAS) (Chakraborty et al., 2014a, c), cold vapor atomic fluorescence spectrometry (CV-AFS) (Fernandez-Martinez et al., 2015), and inductively coupled plasma mass spectrometry (ICP-MS) (Baya et al., 2015) have been the most commonly used for the measurement of total mercury. All of these techniques require expensive and sophisticated instrumentation combined with complicated sample preparation processes (