Ultrasound-Enhanced Anodic Stripping Voltammetry Using Perfluorosulfonated Ionomer-Coated Mercury Thin-Film Electrodes

The high mass transport caused by ultrasonic radiation in the preconcentration of trace metal species in anodic stripping voltammetry (ASV), leads to an order of magnitude enhancement in sensitivity. A Nafion-coated mercury thin-film working electrode is placed in a specially designed small-volume sonovoltammetric cell. The preparation and curing procedure for the Nafion film on a glassy carbon electrode substrate as well as ultrasound-enhanced mercury deposition through the Nafion film are optimized. The resulting electrode assembly is stable under ultrasonic irradiation. Optical microscopy observations show the formation of closely spaced mercury droplets of micrometer dimensions under the Nafion film. The performance characteristics of ultrasound-enhanced ASV at the Nafion-coated mercury thin-film electrode are studied in detail. The detection limit obtained for lead and cadmium test species is 3 × 10-11 M (30 s preconcentration in the presence of ultrasound). A relative standard deviation of 1.2% is obtained for repetitive determinations of 10 nM Cd2+ (n ) 9).