Redox-Driven Recrystallization of PbO₂

Lead(IV) oxide (PbO₂) is one of the lead corrosion products that forms on the inner surface of lead pipes used for drinking water supply. It can maintain low dissolved Pb(II) concentrations when free chlorine is present. When free chlorine is depleted, PbO₂and soluble Pb(II) will co-occur in these systems. This study used a stable lead isotope (²⁰⁷Pb) as a tracer to examine the interaction between aqueous Pb(II) and solid PbO₂at conditions with no net change in dissolved Pb concentration. While the dissolved Pb(II) concentration remained unchanged, significant isotope exchange occurred that indicated that substantial amounts (24.3-35.0% based on the homogeneous recrystallization model) of the Pb atoms in the PbO₂solids had been exchanged with those in solution over 264 h. Neither α-PbO₂nor β-PbO₂displayed a change in mineralogy, particle size, or oxidation state after reaction with aqueous Pb(II). The combined isotope exchange and solid characterization results indicate that redox-driven recrystallization of PbO₂had occurred. Such redox-driven recrystallization is likely to occur in water that stagnates in lead pipes that contain PbO₂, and this recrystallization may alter the reactivity of PbO₂with respect to its stability and susceptibility to reductive dissolution.