Nafion-Protected Sputtered-Bismuth Screen-Printed Electrode for On-site Voltammetric Measurements of Cd(II) and Pb(II) in Natural Water Samples

In this work, we explore the protection with Nafion of commercial sputtered-bismuth screen-printed electrodes (Bi(SP)SPEs), to improve its ability for on-site determination of Cd(II) and Pb(II) ions in ambient water samples. The modified screen-printed platform was coupled with a miniaturized cell, in combination with a battery-operated stirring system and a portable potentiostat operated by a laptop for decentralized electrochemical measurements using Square-Wave Anodic Stripping Voltammetry (SWASV). We also describe a detailed electrode surface characterization by microscopy and surface analysis techniques, before and after the modification with Nafion, to get insight about modification effect on signal size and stability. Optimization of the chemical composition of the medium including the optimization of pH, and instrumental parameters, resulted in a method with detection limits in the low ng/mL range (3.62 and 3.83 ng·mL(−1) for Cd and Pb respectively). Our results show an improvement of the sensitivity and stability for Nafion-protected Bi(SP)SPEs in pH = 4.4 medium, and similar or lower detection limits than comparable methods on commercial Bi(SP)SPEs. The values obtained for Pb(II) and Cd(II) in natural water samples agreed well with those obtained by the much more costly Inductively Coupled Plasma Mass Spectrometry, ICP-MS, technique as a reference method (recoveries from 75% to 111%).