Removal of Antibiotic Florfenicol by Sulfide-Modified Nanoscale Zero-Valent Iron

Florfenicol (FF, C₁₂H₁₄Cl₂FNO₄S), an emerging halogenated organic contaminant of concern was effectively degraded in water by sulfidized nanoscale zerovalent iron (S-nZVI). Sulfidized nZVI (62.5 m² g^-1) that was prepared using a one-step method resulted in small Fe⁰/Fe-sulfide particles that were more stable against aggregation than unsulfidized nZVI (10.2 m² g^-1). No obvious removal of FF was observed by unsulfidized nZVI. S-nZVI degraded FF, having a surface area normalized reaction rate constant of 3.1 × 10^-4 L m^-2 min^-1. The effects of the S/Fe molar ratio, initial FF concentration, initial pH, temperature, and water composition on the removal of FF by S-nZVI, and on the formation of reaction products, were systematically investigated. Both dechlorination and defluorination were observed, resulting in four degradation products (C₁₂H₁₅ClFNO₄S, C₁₂H₁₆FNO₄S, C₁₂H₁₇NO₄S, and C₁₂H₁₇NO₅S). High removal efficiencies of FF by S-nZVI were achieved in groundwater, river water, seawater, and wastewater. The reactivity of S-nZVI was relatively unaffected by the presence of both dissolved ions and organic matter in the waters tested.