Imidazolium ionic liquids as potential persistent pollutants in aqueous environments: Indirect photochemical degradation kinetics and mechanism

Ionic liquids (ILs) with promising application are likely to become ubiquitous contaminants in water environment for their high hydrophilicity, low biodegradability, and especially its potential toxicity. In this work, we have investigated photochemical transformation of six imidazolium ILs for fate prediction and ecological risk assessment. We found that the reaction rates of the ILs with •OH, CO3•─ and 1O2 enhanced with their increasing alkyl chain and varied slightly with the paired anions. Meanwhile, modelled results under different scenarios indicate that the primary contributors to transformation of the ILs are triplet-stated dissolved matter (3CDOM*), •OH and CO3•–. Besides, the overall half-lives of the ILs can reach 670 days, which indicates persistence of these ILs in the environment. Products for ILs in reaction with •OH and triplet-stated sodium anthraquinone-2-sulfonate (3AQ2S*) were probed by UHPLC-Q-TOF-MS/MS and there is a difference between their products: Products by •OH are likely formed by hydrogen abstraction from the side alkyl chain, followed by dehydrogenation, hydroxylation and carbonylation, while one of the products by 3AQ2S* is formed by dihydroxyl-addition of the imidazolium ring. Furthermore, the ILs and its products were estimated to have toxicity and non-readily biodegradability, suggesting potential eco-risk for the environmental water.