A diffusive gradient in thin films technique (DGT) was combined with liquid chromatography (LC) and cold vapor atomic fluorescence spectrometry (CV-AFS) for the simultaneous quantification of four mercury species (Hg(2+), CH3Hg(+), C2H5Hg(+), and C6H5Hg(+)). After diffusion through an agarose diffusive layer, the mercury species were accumulated in resin gels containing thiol-functionalized ion-exchange resins (Duolite GT73, and Ambersep GT74). A microwave-assisted extraction (MAE) in the presence of 6M HCl and 5 M HCl (55 °C, 15 min) was used for isolation of mercury species from Ambersep and Duolite resin gels, respectively. The extraction efficiency was higher than 95.0% (RSD 3.5%). The mercury species were separated with a mobile phase containing 6.2% methanol+0.05% 2-mercaptoethanol+0.02 M ammonium acetate with a stepwise increase of methanol content up to 80% in the 16th min on a Zorbax C18 reverse phase column. The LODs of DGT-MAE-LC-CV-AFS method were 38 ng L(-1) for CH3Hg(+), 13 ng L(-1) for Hg(2+), 34 ng L(-1) for C2H5Hg(+) and 30 ng L(-1) for C6H5Hg(+) for 24 h DGT accumulation at 25 °C.

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