Aqueous chlorination of fenamic acids: Kinetic study, transformation products identification and toxicity prediction. (May 2017)

• Record Type: Journal Article
• Authors: Ma, Liyun; Li, Jian; Xu, Li
• Is Part Of: Chemosphere. Volume 175(2017)
• Page Start: 114
• Page End: 122
• Publication Date: 2017-05
• Subjects: Fenamic acids -- Chlorination -- Kinetics -- Transformation products -- Toxicity; Pollution -- Periodicals; Pollution -- Physiological effect -- Periodicals; Environmental sciences -- Periodicals; Atmospheric chemistry -- Periodicals; 551.511
• DOI: 10.1016/j.chemosphere.2017.02.045
• Languages: English
• ISSNs: 0045-6535

Abstract

Abstract: Fenamic acids, one important type of non-steroidal anti-inflammatory drugs, are ubiquitous in environmental matrices. Thus it is of high significance to know the fate of them during chlorination disinfection considering their potential toxicity to the environment and humans. In the present study, the chlorination kinetics of three fenamic acids, i.e. mefenamic acid (MEF), tolfenamic acid (TOL) and clofenamic acid (CLO), were examined at different pHs, which followed second-order reaction under studied conditions. The studied fenamic acids degraded fast, with the largest apparent second-order rate coefficient ( k app ) values of 446.7 M −1 s −1 (pH 7), 393.3 M −1 s −1 (pH 8) and 360.0 M −1 s −1 (pH 6) for MEF, TOL and CLO, respectively. The transformation products (TPs) were identified by solid-phase extraction-liquid chromatography-mass spectrometer and ion-pair liquid-liquid extraction and injection port derivatization-gas chromatography-mass spectrometer. Despite different numbers of TPs were detected for each studied fenamic acid through these two analytical methods, the types of TPs were almost the same; chlorine substitution, oxidation and the joint oxidation with chlorine substitution are transformation reactions involved in chlorination. Moreover, the total toxicity of the TPs was assayed based on luminescent bacteria. Under different pHs, the different types of TPs might form, resulting in the varied total toxicity. The toxicity of all three fenamic acids chlorinated at pH of 8 was greater than those at pHs of 6 and 7. This study provided the information about the kinetics, transformation and toxicity of three fenamic acids during water chlorination, which is important to the drinking water safety. Graphical abstract: Highlights: Kinetics of three fenamic acids during chlorination obeyed second-order reaction. Transformation products were identified by LC-MS and GC-MS. Electrophilic and nucleophilic substitutions were the main transformation pathways. Transformation products with more toxicity than the parent compounds were found.