In situ detection of intermediates from the interaction of dissolved sulfide and manganese oxides with a platinum electrode in aqueous systems

Abstract

Environmental contextDissolved sulfide results in soil acidification and subsequent contaminant leaching via oxidation processes, usually involving manganese oxides. In this work, redox processes were monitored in situ by cyclic voltammetry and HS– concentrations were semi-quantitatively determined. The method provides qualitative and semi-quantitative assessment for dissolved sulfide and its oxidation intermediates in aqueous systems. AbstractDissolved sulfide can be oxidised by manganese oxides in supergene environments, while the intermediates including S0, S2O32– and SO32– are easily oxidised by oxygen in air, resulting in some experimental errors in conventional analyses. In this work, the electrochemical behaviours of HS–, S2O32– and SO32– on a platinum electrode were studied by cyclic voltammetry and constant potential electrolysis, and in situ detection of the intermediates was conducted in aqueous systems of HS– and manganese oxides. The results showed that HS– was first oxidised to S0, and then transformed to SO42–. The peak current for the oxidation of HS– to S0 had a positive linear correlation with the used starting HS– concentration. S2O32– and SO32– were directly electrochemically oxidised to SO42–. The oxidation current peak potentials at 0, 0.45 and 0.7V were respectively observed for HS–, S2O32– and SO32– at pH 12.0. Cyclic voltammetry was conducted to monitor the redox processes of HS– and manganese oxides. The oxidation peak current of HS– to S0 decreased, and that of S2O32– to SO42– was observed to increase as the reaction proceeded. The rate of the decrease of the oxidation peak current of HS– indicated that the oxidation activity followed the order of birnessite>todorokite>manganite.