Environmental context
Aromatic amines are widely used chemicals, which show enhanced toxicity and longer environmental persistence when halogenated. We investigated the chlorination of aniline in seawater and in natural aqueous solutions containing Fe3+ and Cl–, under simulated sunlight irradiation. The results increase our understanding of the transformation pathway of typical nitrogen-containing aromatic contaminants in the environment.
Abstract
Photochlorination of aniline was observed in aqueous solutions containing dissolved FeIII and chloride ions under simulated solar light irradiation. Effects of O2, Cl–, Fe3+ and pH on the formation of chloroanilines (CAs) were investigated. para-chloroaniline (4CA) was identified as the main chlorinated product. The formation of 4CA is enhanced with increased concentrations of Cl– or Fe3+, and decreased pH, whereas oxygen plays a negligible role in the process. The results indicate that, Cl• is formed mainly by the photodissociation of FeCl2+–FeCl2+ complexes, and reacts with Cl– to produce Cl2•–. Aniline is then oxidised by Cl2•– into an anilino radical cation, which further reacts with Cl2•– to generate CAs. The photochlorination of aniline in natural seawater was also observed. Other phototransformation products of aniline were detected and a transformation pathway was proposed. This work provides evidence for the photochemical chlorination path of aniline-based aromatic amines in aqueous solutions.
