Enantioselective toxic effects and environmental behavior of ethiprole and its metabolites against Chlorella pyrenoidosa

Insecticide ethiprole, the alternative of fipronil which has been restricted in many countries, may contaminant water bodies through surface runoff after agricultural application, however, the aquatic toxicity and environmental behavior of ethiprole is still unknown. In this study, five metabolites of ethiprole (ethiprole sulfone, ethiprole sulfide, ethiprole amide, desethylsulfinyl ethiprole and ethiprole sulfone amide) were synthesized and their toxic effects on photosynthetic pigment and antioxidase in aquatic plant Chlorella pyrenoidosa (C. pyrenoidosa) were evaluated on an enantiomeric level. Besides, the accumulation and metabolism of rac-ethiprole and its enantiomers in algae suspension and algae were studied. Ethiprole sulfide was found to be more toxic than ethiprole, with the 96h EC₅₀ value seven times lower than ethiprole. Enantioselective toxicity was observed with R-ethiprole more toxic than S-ethiprole. The contents of chlorophyll were significantly reduced by all the chemicals at higher concentrations, and the levels of protein, malondialdehyde (MDA) and the activity of antioxidant defense enzymes were dose-dependent. The half-life of rac-ethiprole in algae suspension was 13.6 days and ethiprole amide was the major metabolite. However, ethiprole sulfide was the main metabolite in algae, suggesting different metabolic pathways in algae suspension and algae. Enantioselective metabolism in algae suspension was found with S-ethiprole metabolized faster than R-ethiprole. The preferentially accumulated and metabolized of R-ethiprole in algae was observed and C. pyrenoidosa had limited capacity to convert one enantiomer into the other. These findings indicated the toxicity of ethiprole to C. pyrenoidosa is lower than fipronil. The individual enantiomers of chiral pollutants and their metabolites should be considered in risk assessments.