Determination of iodide and total iodine in estuarine waters by cathodic stripping voltammetry using a vibrating silver amalgam microwire electrode

Iodide in natural waters is an important nutrient to aquatic organisms and its determination is of relevance to marine aquaculture. For this reason it is of interest to have a simple analytical method for determination of iodide in water samples. Iodide in seawater can be determined electrochemically by cathodic stripping voltammetry (CSV) with a mercury drop electrode which has environmental drawbacks. In an attempt to minimise the use of mercury in voltammetry, a vibrating silver amalgam microwire electrode is used here for the determination by CSV of iodide speciation in natural waters including seawater. Microwire electrodes were made from silver wires (diameter: 12.5µm) and electrochemically coated with mercury. The electrode surface was stable for extended periods of analyses (at least one week) and was then replaced. The optimised conditions include a pH 8, a frequency of 500Hz and a deposition time of 60s, among others. The microwire was reactivated between scans using a conditioning potential at −3 V for 1s. The detection limit for iodide in seawater was found to be 0.7nM I- at a deposition time of 60s. The response increased linearly with the concentration of iodide in seawater up to 100nM I-. The method was successfully applied to various samples from the estuary of the river Mersey (Liverpool Bay). An existing procedure for iodine speciation was modified to enable determination of iodate and total iodine as well as iodide in estuarine waters. [Display omitted] •An amalgamated silver microwire electrode for iodide determination in natural waters.•Sufficient sensitivity to monitor iodide in coastal waters.•Iodate and total iodine after chemical reduction to iodide.•Successful application to the estuary of river Mersey (Liverpool Bay).•Minimisation of mercury use.