Application of bismuth bulk annular band electrode for determination of ultratrace concentrations of thallium(I) using stripping voltammetry.

A study of a new type of mercury-free working electrode - the bismuth bulk annular band working electrode (BiABE) - applied for thallium(I) detection via differential pulse anodic stripping voltammetry (DP ASV), preceded by the complexation of interfering ions (Cd(2+), Pb(2+)) with EDTA in an acetate buffer (pH 4.5), is reported. The optimisation of experimental conditions included selection of the appropriate supporting electrolyte solution, potential and time of preconcentration, and DP mode parameters. The peak current was proportional to the concentration of Tl(I) in the range from 0.5 to 49nmolL(-1) (R=0.9992) and from 0.05 to 1.4nmolL(-1) (R=0.9987) for accumulation times of 60s and 300s, respectively. For 60s of accumulation time, the LOD was 0.005nmolL(-1) (1ngL(-1)) (at S/N=3), and the sensitivity of 18.5nA/nM was achieved. The relative standard deviation for 4.9nmolL(-1) of Tl(I) was 4.3% (n=5). Finally, the proposed method was successfully applied to determine Tl(I) in the certified reference materials-waters (SPS-SW1 and SPS-SW2) as well as the spiked tap and river water samples.