Redox Interaction between Selenite and Mackinawite in Cement Pore Water

In cement-rich radioactive waste repositories, mackinawite (FeS) forms at the steel corrosion interface within reinforced concrete and potentially retards the transport of redoxsensitive radionuclides (e.g., 79Se) in porous cement media. Redox interactions between selenite and mackinawite under hyperalkaline conditions remain unclear and require further investigations. Here, using comprehensive characterization on both aqueous and solid speciation, we successfully monitored the whole interaction process between selenite and mackinawite under hyperalkaline conditions. The results show similar chemical environments for SeO3 2- and S2-/Sn 2- at the mackinawite-water interface, verifying an immediate reduction. After 192 h of reaction, SeO3 2- was reduced to solid Se0 and SeS2 species, accompanied by the oxidation of S2-/Sn 2- to S2O3 2- and Fe(II) to Fe(III) in mackinawite. Aqueous speciation results showed that similar to 99% of aqueous selenium was present as Se4S nanoparticles due to the dissolution of Se from the solid. In parallel, similar to 62% of S2-/Sn 2- was released into the solution, with mackinawite transforming into magnetite, Fe(OH)3 and FeS2O3 + complexed to Cl- or OH- species, and magnetite subsequently dispersed in the solution. This study provides valuable data about the retardation mechanisms of redox-sensitive radionuclides by soluble iron sulfides, which is critical to advance our understanding of reactive concrete barriers used in nuclear waste disposal systems

Automated summary

In this study, the interaction process between selenite and mackinawite under hyperalkaline conditions was successfully monitored. The results showed that selenite was reduced to solid species, while mackinawite went through oxidation and released some sulfide into the solution. This study provides valuable data about the retardation mechanisms of redox-sensitive radionuclides by soluble iron sulfides, which is critical for advancing our understanding of reactive concrete barriers used in nuclear waste disposal systems.