Sulfide-modified zerovalent iron for enhanced antimonite sequestration: Characterization, performance, and reaction mechanisms

Zerovalent iron (ZVI) is commonly used for water treatment under aerobic conditions such as sequestration of metals. Sulfide-modified ZVI (S-ZVI) is attracting increasing attention for its easy preparation and high reactivity with environmental pollutants. The processes responsible for contaminant removal can be a complex mixture of redox, sorption, and coprecipitation processes. In this paper, ZVI and S-ZVI were used to sequester antimonite (Sb(III)). The rates of Sb(III) sequestration were determined in open, well-mixed, batch reactors. The effects of various experimental variables were investigated, including pH, iron dose, initial concentrations of Sb(III), aging time of the ZVI and S-ZVI, addition of Fe²⁺, mixing rate, etc. The results showed that S-ZVI can significantly enhance the Sb(III) sequestration, and under basic conditions in this study, the k_obs (0.018 min⁻¹) obtained in the S-ZVI system was approximately 15 times higher than the 0.0012 min⁻¹ obtained in the ZVI system. Solid phase characterizations were conducted to assess the influence of sulfidation on the morphology and surface geochemistry of ZVI. Scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS) confirmed the presence of sulfur. X-ray photoelectron spectroscopy (XPS) indicated the oxidation of Sb(III) to Sb(V) and adsorption and coprecipitation onto the iron oxides is the mainly sequestration process. The FeS layer on ZVI is more conductive than oxides and therefore accelerates electron transfer. In addition sulfidation promotes the corrosion of iron and the formation of ferrous iron, which further enhances the ferric iron oxide formation, thereby favoring adsorption and oxidation of Sb(III).