PbO₂ reductive dissolution by dissolved Mn(III) in the presence of low molecular weight organic acids and humic acid

Although Mn(III) complexes with organic ligands have been previously identified, the information about their stability and reactivity is scarce. In the present study, we analyzed the formation and stability of three different complexes: Mn(III)-citrate, Mn(III)-tartrate, and Mn(III)-humic acid (HA), as well as their reactivity toward an element of high environmental concern, lead (Pb).Our results indicate that the stability of studied complexes is highly dependent on pH. The Mn(III) complexes with citrate and tartrate degrade below pH 8, due to the electron transfer reaction between Mn(III) and the ligand, while the Mn(III)-HA complex's degradation is slower and less sensitive to pH. At pH 4, less than 40% of the initial Mn(III)-HA was found to be stable.The reactivity of the complexes was different depending on the ligand and its concentration. The Mn(III)-citrate and Mn(III)-tartrate complexes effectively reduced PbO₂ and releases aqueous Pb²⁺, although significant differences were found with increasing ligand concentration. There was no evidence of the reduction of PbO₂ by Mn(III) when it forms a complex with HA. This is likely due to the large size of HA moieties that prevent the Mn(III) component of the complex from getting close enough to the PbO₂ surface to initiate electron transfer and lead to the reduction of Pb(IV) by HA itself.