The effect of Bi(III) concentration (over the wide concentration range of 10(-7) to 10(-4) M) on the determination of Pb and Cd metal ions (in the 10(-8) to 10(-5) M range), by means of anodic stripping voltammetry (ASV) at in situ bismuth-coated carbon paste (CPE) and gold electrodes, has been studied. It is shown that in square wave anodic stripping voltammetry (SWASV) experiments the sensitivity of the technique generally depends on the Bi(III)-to-metal ion concentration ratio. It was found that, unlike the usually recommended at least 10-fold Hg(II) excess in anodic stripping experiments at in situ prepared mercury film electrodes, Bi(III)-to-metal ion ratios less than 10 are either optimal or equally effective at CPE and An electrode substrates. Detection limits down to 0.1 mu g L-1 for Pb(II) and 0.15 mu g L-1 for Cd(II) were estimated at CPEs under conditions of small or moderate Bi(III) excess. Depending on Bi(III) concentration and deposition time, multiple stripping peaks attributed to Bi were recorded (especially in the case of Au substrates), indicating various forms of Bi deposits. (c) 2006 Elsevier Ltd. All rights reserved.