Kinetic constants and transformation products of ornidazole during ozonation

Abstract

Ornidazole (ONZ), a nitroimidazole antibiotic detected in water bodies, may negatively impact the aquatic ecosystem. Its reaction kinetics during ozonation which is a feasible and applicable technology to control the contamination of emerging contaminants, however, has not been reported in literature. In this study, we measured the apparent second-order kinetic constant of ONZ with ozone molecules via the excessive ozone method and the competing method which led to an average value of 103.8 ± 2.7 M^-1 s^-1 at pH 7. The apparent second-order kinetic constant of ONZ with HO^• was calculated to be 4.65 × 10⁹ M^-1 s^-1 with the concept of R_ct measured via para-chlorobenzoic acid as a probe. The transformation products (TPs) of ONZ during ozonation at pH 3 and pH 11 were separately analyzed with HPLC-MS/MS and some unique products were found at pH 11, reflecting the influence of HO^•. The toxicity of individual TPs was predicted with the tool of T.E.S.T. It was found that 62% of 21 identified TPs could be more toxic than ONZ in terms of at least one acute toxicity endpoint, including chlorinated amines and N-oxides. The analysis with a respirometer further revealed that the toxicity of mixing TPs generated at HO^• rich conditions was slightly lower than O₃ dominated conditions. In general, this study provides the basic kinetic data for designing ozonation processes to eliminate ONZ and the important reference for understanding the toxicity evolution of ONZ during ozonation.

Keywords: Antibiotics; Catalytic ozonation; Ecotoxicity; Pharmaceutical; QSAR; Toxicity.