Oxidative transformations of environmental pharmaceuticals by Cl2, ClO2, O3, and Fe(VI): Kinetics assessment

Several pharmaceuticals have been detected globally in surface water and drinking water, which indicate their insufficient removal from water and wastewater using conventional treatment methods. This paper reviews the kinetics of oxidative transformations of pharmaceuticals (antibiotics, lipid regulators, antipyretics, anticonvulsants, and beta-blockers) by Cl2, ClO2, O3, and ferrate(VI) (FeVIO42-,Fe(VI)) under treatment conditions. In the chlorination of sulfonamide antibiotics, HOCl is the major reactive Cl2 species whereas in the oxidation by Fe(VI), HFeO4- is the dominant reactive species. Both oxidation processes can oxidize sulfonamides in seconds at a neutral pH (t1/2 ⩽ 220 s; 1 mg L−1 HOCl or K2FeO4). The reactivity of O3 with pharmaceuticals is generally higher than that of HOCl (kapp,pH 7 (O3) = 1–107 M−1 s−1; kapp,pH 7 (HOCl) = 10−2–105 M−1 s−1). Ozone selectively oxidizes pharmaceuticals and reacts mainly with activated aromatic systems and non-protonated amines. Oxidative transformation of most pharmaceuticals by O3 occurs in seconds (t1/2 ⩽ 100 s; 1 mg L−1 O3) while half-lives for oxidations by HOCl differ by at least two orders of magnitude. Ozone appears to be efficient in oxidizing pharmaceuticals in aquatic environments. The limited work on Fe(VI) shows that it can also potentially transform pharmaceuticals in treatment processes.