Oxidative treatment of diclofenac via ferrate(VI) in aqueous media: effect of surfactant additives

The potential reaction of diclofenac (DCF) with ferrate(VI) and influences of coexisting surfactants have not been investigated in depth, and are the focus of this study. The results demonstrated that DCF reacted effectively and rapidly with Fe(VI) and approximately 75% of DCF (0.03 mM) was removed by excess Fe(VI) (0.45 mM) within 10 min. All of the reactions followed pseudo first-order kinetics with respect to DCF and Fe(VI), where the apparent second-order rate constant (k_app) was 5.07 M⁻¹ s⁻¹ at pH 9.0. Furthermore, the degradation efficiencies of DCF were clearly dependent on the concentrations of dissolved organic matter additives in the substrate solution. Primarily, inhibitory effects were observed with the samples that contained anionic (sodium dodecyl-benzene sulfonate, SDBS) or non-ionic (Tween-80) surfactants, which have been attributed to the side reactions between Fe(VI) and surfactants, which led to a reduction in the available oxidant for DCF destruction. Furthermore, the addition of a cationic surfactant (cetyltrimethyl ammonium bromide, CTAB) and humic acid (HA) conveyed significantly promotional effects on the DCF-Fe(VI) reaction. The rate enhancement effect for CTAB might be due to micellar surface catalysis, through the Coulomb attraction between the reactants and positively charged surfactants, while the catalytic action for HA resulted from the additional oxidation of Fe(V)/Fe(IV) in the presence of HA. The results provided the basic knowledge required to understand the environmental relevance of DCF oxidation via Fe(VI) in the presence of surfactant additives.