Agar-stabilized sulfidated microscale zero-valent iron: Its stability and performance in chromate reduction

Sulfidated microscale zero-valent iron (SmZVI) attracts much attention recently in remediation of contaminated groundwater, but whether polymer coating on SmZVI would impact on its reactivity and capacity is yet to be understood. In this work, SmZVI was prepared by milling mZVI with elemental sulfur, and its stability in agar solution was evaluated. The impact of polymer coating on SmZVI grains' capacity and reactivity for chromate reduction was then examined. Experimental results indicated that SmZVI having the best overall performance was attained by grinding mZVI with elemental sulfur at 0.05 S/Fe molar ratio for 10 h. SmZVI's stability can be substantially improved if dispersed in 2.0 g/L agar solution. Existence of agar films on the SmZVI grain (ASmZVI) lowered the material's capacity for chromate reduction by 56%, and the associated reaction kinetics by 70.4%, as estimated by pseudo first-order reaction model using the early-stage experimental data. Analysis of XPS spectra of A-SmZVI post reaction with chromate indicated that multiple reductive species including Fe0, Fe (II), FeS, and S(-II) may have jointly participated in the redox reaction taking place on the A-SmZVI-water interface. Fitting of XPS data supported that S(-II) was oxidized to SO42-, S2O32-, and S0, in order of decreasing surface concentration.