Electrochemical speciation analysis of metals at membrane‐coated electrodes

Speciation of model Cu complexes on the basis of size and charge was achieved by anodic stripping voltammetry (ASV) at mercury film electrodes (MFE) coated with Nafion or cellulose acetate Nafion (CANMFE). The Nafion‐coated MFE effectively excludes negatively charged Cu complexes, and evidence for the containment of the diffusion layer beneath the Nafion coating is provided. The CANMFE excludes complexes with molecular weights greater than 200, including the Cu‐fulvic acid complex, which is of particular interest for speciation in natural waters. Complexation titrations of fulvic acid with Cu show the unsuitability of differential pulse ASV for providing a realistic estimate of the end point (complexation capacity). Differential pulse polarography, which provides results more comparable with bioassays, can be used for the determination of complexation capacity. Results for the speciation analysis of coastal seawater and polluted fresh water are presented. The CANMFE is insufficiently sensitive for seawater analysis, but in polluted fresh water its use indicates that organic and inorganic complexes with molecular weights greater than 200 dominate the speciation for Cd (72%), Pb (96%), and Cu (> 99.8%).