Trace vanadium analysis by catalytic adsorptive stripping voltammetry using mercury-coated micro-wire and polystyrene-coated bismuth film electrodes.

An electrochemical technique has been developed for ultra-trace (ng L(-1)) vanadium (V) measurement. Catalytic adsorptive stripping voltammetry for V analysis was developed at mercury-coated gold micro-wire electrodes (MWEs, 100 microm) in the presence of gallic acid (GA) and bromate ion. A potential of -0.275 V (vs Ag/AgCl) was used to accumulate the complex in acetate buffer (pH 5.0) at the electrode surface followed by a differential pulse voltammetric scan. Parameters affecting the electrochemical response, including pH, concentration of GA and bromate, deposition potential and time have been optimized. Linear response was obtained in the 0-1000 ng L(-1) range (2 min deposition), with a detection limit of 0.88 ng L(-1). The method was validated by comparison of results for an unknown solution of V by atomic absorption measurement. The protocol was evaluated in a real sample by measuring the amount of V in river water samples. Thick bismuth film electrodes with protective polystyrene films have also been made and evaluated as a mercury free alternative. However, ng L(-1) level detection was only attainable with extended (10 min) deposition times. The proposed use of MWEs for the detection of V is sensitive enough for future use to test V concentration in biological fluids treated by the advanced oxidation process (AOP).