Assessment of sulfidated nanoscale zerovalent iron for in-situ remediation of cadmium-contaminated acidic groundwater at a zinc smelter

Unprecedented high concentrations of heavy metals have been detected in the groundwater at a zinc smelter in Seokpo, South Korea. The outflow of the contaminated groundwater into the nearby Nakdong River must be prevented by some means such as permeable reactive barrier (PRB). As a reactive material for injection-type PRB, we have tested sulfidated nanoscale zerovalent iron (S-nZVI) to assess its efficacy in remediating the groundwater from the smelter. The S-nZVI efficiently removed Zn, Ni, and Al in the groundwater, and neutralized the groundwater to pH > 6. Sulfidation of nZVI greatly increased the removal of Cd (99.8%) compared to that by nZVI (7.2%). MINEQL+ modeling and particle characterization were performed to elucidate the forms of heavy metals in the solution and on the surface of S-nZVI. Raman and XPS results suggested that FeS on the surface of S-nZVI reacted with Cd(II) and Zn(II), forming more-stable CdS and ZnS. Sequential application of NaHCO₃ after S-nZVI treatment in a column setup was suited for the removal of remaining Zn and Fe as well as the reduction of microbial toxicity. This study guides to use of S-nZVI for in-situ remediation of cadmium-contaminated groundwater with other coexisting heavy metals from a zinc smelter.