Deposition and dissolution of metal sulfide layers at the Hg electrode surface in seawater electrolyte conditions

Environmental context The electrochemical detection of many sulfur compounds in natural waters is based on the deposition of a HgS layer at the Hg electrode. In samples containing metal ions in excess of sulfide species, electrochemical exchange reactions between the HgS and the metal ion produce metal-sulfide voltammetric peaks. These peaks can easily be misinterpreted as dissolved sulfide species, and hence do not reflect the bulk state of the solution. Abstract Cyclic voltammetry on a Hg electrode was used to investigate the influence of metal ion (Zn, Cd, Cu, Fe, Pb, Co) on HgS deposition–dissolution in seawater conditions. Due to the exchange of electrons between Hg2+ from a HgS layer and free metal (M2+) from the solution (HgSlayer + M2+ + 2e– ↔ MSlayer + Hg0), the Hg electrode becomes the site for surface metal sulfide (MS) formation. The exchange reaction is reversible, and the surface-formed MS layer reduces at a more negative potential than HgS (MSlayer + 2e– + H+ → M0 + HS). The potentials of both electrode reactions, and the formation and reduction of the MS layer, are determined by the MS solubility product. In solutions containing excess of the free metal ions in comparison to the free sulfide, the exchange reaction produces MS voltammetric peaks, which can be misrepresented for the dissolved sulfide species. This research indirectly confirmed that the FeS electrochemical signal, usually recorded in an iron- and sulfide-rich environment at ~–1.1V v. Ag/AgCl, is not due to FeS reduction. The connection between the studied MS reduction peak potentials and the solubility products shows that the FeS layer formed by an electrochemical exchange reaction with HgS should be reduced at the Hg surface ~100mV more negative than free Fe2+.