Assessment of sulfamethoxazole removal by nanoscale zerovalent iron

Abstract

Removal of pharmaceutical compounds, such as sulfamethoxazole (SMX) from the aquatic environments, is critical in order to mitigate their adverse environmental and human health effects. In this study, the effectiveness of nanoscale zerovalent iron (nZVI) particles for the removal of SMX was investigated under varying conditions of initial solution pH (3, 5, 7 and 11) and nZVI to SMX mass ratios (1:1, 5:1, 10:1, 13:1, 25:1). Batch kinetic studies, which were well represented using both pseudo-first-order and pseudo-second-order kinetic models (R2 > 0.98), showed that both solution pH and mass ratios strongly influenced SMX removal. At a fixed mass ratio of 10:1, removal efficiencies were higher in acidic conditions (83% to 91%) compared to neutral (29%) and alkaline (6%) conditions. A similar trend was observed for removal rates and removal amounts. For mass ratios between 1:1 and 10:1, an optimum pH existed (pH 5) wherein highest removal efficiencies were attained. Increasing the mass ratio above 10:1 resulted in virtually complete removal efficiencies at pH 3 and 5, and 70% at pH 7. Analysis of SMX speciation and zeta potential of nZVI particles provided insights into the role of pH on the efficiencies, rates and extents of SMX removal. Total organic carbon analysis and mass spectrometry measurements of SMX solution before and after exposure to nZVI particles suggested the transformation of SMX via redox reactions, which are likely the dominant process compared to adsorption. Five transformation products were observed at m/z 156 (TP1), 192 (TP2), 256 (TP3), 294 (TP4) and 296 (TP5). TP1, TP2 and TP3 were further identified using ion fragment analysis. Overall, results from this study indicate a strong potential for SMX removal by nZVI particles, and could be useful towards identifying reaction conditions for optimum SMX transformation.