Beyond the hydrogen wave: new frontier in the detection of trace elements by stripping voltammetry

Stripping voltammetry is limited in acidic conditions to relatively high deposition potentials because of the interfering effects of the hydrogen produced at the working electrode. We report here a simple procedure to perform reliable and sensitive trace metal analysis in such conditions. Measurements are made at a gold microwire electrode. After applying a simple electrochemical conditioning procedure, hydrogen does not block the electrode, allowing reproducible analysis and smooth stripping signals to be obtained. Advantages of working inside the hydrogen wave are exemplified through the detection of the often considered electroinactive antimony(V). Sb(V) is detected in relatively low acidic conditions (pH ≤ 1) using low deposition potentials (≤-1.8 V). The detection limit is 5 pM (0.63 ppt), the lowest ever reported for an electroanalytical technique and one of the lowest analytical methods. The method is simple, robust, and free from the common arsenic interference due to selective electrochemical hydride generation of arsine over stibine during the deposition step. Analytical methods were optimized and tested on mineral, river, tap, and coastal seawater. Results favorably compare against Certified Reference Materials data (NASS-4 and SLRS-3) and ICPMS analysis. Deposition well below the hydrogen wave pushes the frontier of stripping voltammetry, and new analytical applications in this combined range of acidity and deposition potential are to be expected.