Sensitive determination of trace Cd(ii) and Pb(ii) in soil by an improved stripping voltammetry method using two different in situ plated bismuth-film electrodes based on a novel electrochemical measurement system

In this study, a simple but effective electrochemical method was developed to minimize the interference from real soil samples and increase the sensitivity of Pb(ii) and Cd(ii) detection by square-wave anodic stripping voltammetry (SWASV) using a novel electrochemical measurement system, which can be used for the on-site determination of trace Cd(ii) and Pb(ii) in real soil samples. The method involved performing SWASV following double deposition and stripping steps at two in situ plated bismuth-film electrodes with drastically different surface properties. Pb(ii) and Cd(ii) were first deposited on an in situ plated bismuth-film graphite carbon paste electrode (Bi/GCPE). When the first deposition was finished, the GCPE was moved to a micro-electrolytic cell to perform the first stripping step. The following measurements were performed with the other deposition and stripping steps using a highly sensitive in situ plated bismuth-film multiwalled carbon nanotube–Nafion composite modified glassy carbon electrode (Bi/MWCNT–Nafion/GCE) as the working electrode. Pb(ii), Cd(ii) and Bi(iii) stripped from the GCPE in the micro-electrolytic cell were partially deposited on the MWCNT–Nafion/GCE, and the stripping current signals were obtained from their oxidation during the second stripping step. Considering the small volume of the micro-electrolytic cell, the concentrations of Cd(ii) and Pb(ii) were drastically higher than those in the bulk solution, and therefore, the detection limits were reduced. Under the optimized conditions, the concentrations in the linear range spanned from 1.0 to 45.0 μg L(−1) for both Pb(ii) and Cd(ii), with a detection limit of 0.03 μg L(−1) for Pb(ii) and 0.02 μg L(−1) for Cd(ii) (S/N = 3). Finally, analyses of real samples were performed to detect trace levels of Pb(ii) and Cd(ii) in soil with satisfactory results.