In situ control of local pH using a boron doped diamond ring disk electrode: optimizing heavy metal (mercury) detection.

A novel electrochemical approach to modifying aqueous solution pH in the vicinity of a detector electrode in order to optimize the electrochemical measurement signal is described. A ring disk electrode was employed where electrochemical decomposition of water on the ring was used to generate a flux of protons which adjusts the local pH controllably and quantifiably at the disk. Boron doped diamond (BDD) functioned as the electrode material given the stability of this electrode surface especially when applying high potentials (to electrolyze water) for significant periods of time. A pH sensitive iridium oxide electrode electrodeposited on the disk electrode demonstrated that applied positive currents on the BDD ring, up to +50 μA, resulted in a local pH decrease of over 4 orders of magnitude, which remained stable over the measurement time of 600 s. pH generation experiments were found to be in close agreement with finite element simulations. The dual electrode arrangement was used to significantly improve the stripping peak signature for Hg in close to neutral conditions by the generation of pH = 2.0, locally. With the ability to create a localized pH change electrochemically in the vicinity of the detector electrode, this system could provide a simple method for optimized analysis at the source, e.g., river and sea waters.