Occurrence and risk assessment of azole fungicides during the urban water cycle:A year-long study along the Yangtze River,China

Azole fungicides(AFs)play an important role in the prevention and treatment of fungal diseases in agricultural crops.However,limited studies are addressing the fate and ecological risk of AFs in the urban water cycle at a large watershed scale.To address this gap,we investigated the spatiotemporal distribution and ecological risk of twenty AFs in the lower reaches of the Yangtze River across four seasons.Carbendazim(CBA),tebuconazole(TBA),tricyclazole(TCA),and propiconazole(PPA)were found to be the dominant compounds.Their highest concentrations were measured in January(188.3 ng/L),and November(2197.1 ng/L),July(162.0 ng/L),and November(1801.9 ng/L),respectively.The comparison between wastewater treatment plants(WWTPs)effluents and surface water suggested that industrial WWTPs are major sources of AFs in the Yangtze River.In particular,TBA and PPA were found to be the most recalcitrant AFs in industrial WWTPs,while difenoconazole(DFA)was found to be the most potent pollutant in municipal WWTPs,with an average removal rate of less than60%.The average risk quotient(RQ)for the entire AFs was 6.45 in the fall,which was higher than in January(0.98),April(0.61),and July(0.40).This indicates that AFs in surface water posed higher environmental risks during the dry season.Additionally,the exposure risk of AFs via drinking water for sensitive populations deserves more attention.This study provides benchmark data on the occurrence of AFs in the lower reaches of the Yangtze River,and offers suggestions for better reduction of AFs.

Biodegradation of typical azole fungicides in activated sludge under aerobic conditions

Widespread use of azole fungicides and low removal efficiency in wastewater treatment plants(WWTPs) have led to the elevated concentration of azole fungicides in receiving environment. However, there was limited research about the removal mechanism of azole fungicides in the biological treatment of WWTPs. Imidazole fungicide climbazole and triazole fungicide fluconazole were selected to investigate the biodegradation mechanism of azole fungicides in activated sludge under aerobic conditions. Climbazole was found to be adsorbed to solid sludge and resulted in quick biodegradation. The degradation of climbazole in the aerobic activated sludge system was fitted well by the first-order kinetic model with a half-life of 5.3 days, while fluconazole tended to stay in liquid and had only about 30% of loss within 77 days incubation. Ten biotransformation products of climbazole were identified by high resolution mass spectrometry using suspect and non-target screening method. But no biodegradation products of fluconazole were identified due to its limited removal. The possible biodegradation pathways for climbazole were proposed based on the products identification and pathway prediction system, and involves oxidative dehalogenation, side chain oxidation and azole ring loss. The findings from this study suggest that it should be a concern for the persistence of fluconazole in the environment.