Sulfidation of Zero-valent Iron Nanoparticles for Environmental Remediation

The ability of nano-sized zero-valent iron (nZVI) to remove environmental contaminants, from heavy metals to polyhalogenated hydrocarbons, has been well established. However, the reactivity of nZVI towards contaminants is hampered due to competing for side reactions with oxygen and water. Sulfidemodified nZVI (S-nZVI) has become a viable option as S-nZVI has been shown to reduce organic compounds such as trichloroethylene faster than nZVI while also maintaining an increased resistance to oxidation by water. The Fulton group has established that nZVI supported on a naturally occurring microsilicate (Microsilica600, or “misi”), from a Rotorua geothermal deposit, is capable of removing nitrates from water. This material, or nZVI@misi, minimises the potential bioaccumulation path that nZVI has, and is easier to handle than unsupported nZVI. This research investigated the effect of sulfidation of nZVI@misi (or S-nZVI@misi) on the reactivity towards the degradation of a variety of different potential contaminants.  S-nZVI@misi was synthesised using sodium thiosulfate for sulfidation. Increasing the concentration of the reagent and sulfidation time from 3 hours to 24 hours resulted in high percentages of sulfur-to-iron (S/Fe) for each material. This increase in S/Fe had a significant impact on the removal of cadmium and chromium as with higher the percentage of S/Fe, the faster the removal of these species occurred. Compared to pristine nZVI@misi, S-nZVI@misi was significantly faster at removing both cadmium and chromium. However, sulfidation of nZVI@misi proved to reduce the rate of 4-nitrophenol reduction and prevent nitrate reduction from occurring. Experimental analysis also showed that cadmium removal was faster with S-nZVI supported by FeOOH-coated microsilica, compared to material supported by un-coated microsilica. Therefore, we have synthesised supported S-nZVI that quickly removes cadmium and chromium from solution compared to standard supported nZVI.