Photo-transformation of atrazine in aqueous solution in the presence of Fe3+-montmorillonite clay and humic substances.

As one of the most troublesome herbicides, the natural behavior of atrazine has drawn great attentions. Currently, most studies investigated the adsorption of atrazine on clay minerals and humic substances (HSs), whereas, the transformation of atrazine catalyzed by clay and HSs was still unknown. In the present study, photo-degradation of atrazine in the presence of Fe3+-montmorillonite and Suwannee river fulvic acid (SRFA) in aqueous solution was systematically studied. In the Fe3+-montmorillonite system, the hydroxyl radical (OH) induced removal of atrazine was strongly pH-dependent and the reaction rate increased with the decrease of pH. The presence of SRFA suppressed the atrazine degradation by Fe3+-montmorillonite at pH 3 but promoted its removal rate in the pH range of 4-6. Our results demonstrated that both OH and singlet oxygen are responsible for the degradation process in the Fe3+-montmorillonite/SRFA hybrid system. The degradation of atrazine followed the cleavage of the CN bonds in aliphatic chains of atrazine, and three major products, desethylatrazine, desisopropylatrazine and desethyldesisopropylatrazine were detected. The toxicity assessment showed that the toxicity of the reaction solution significantly decreased after the radical reactions, indicating that the transformation of atrazine on natural clay minerals with/without HSs could be considered as a detoxification pathway, which might be important to evaluate the environmental risk of atrazine in a natural system.