Enantioselective Toxicity of Chiral Herbicide Metolachlor to Microcystis aeruginosa

The enantioselective effects of chiral herbicides on aquatic organisms have received increasing attention. As one kind of freshwater algae responsible for most algal blooms, Microcystis aeruginosa can produce hepatotoxic microcystin and cause serious health concerns for drinking water. Thus, the effects of chiral herbicides on M. aeruginosa are of vital significance but poorly understood, especially as the structures of chiral herbicides become more complex. In this study, the enantioselective effects of four metolachlor enantiomers based on carbon center and axis chirality on M. aeruginosa were investigated for the first time at an enantiomeric level. The results of the investigation into algal growth inhibition, chlorophyll a content, and cell integrity indicated that (S)-metolachlor [(S)-Met] was significantly more toxic than any other isomer. The toxicity ranking of different enantiomers at the highest concentration (15 mg/L) against M. aeruginosa was (S)-Met > (alpha R,1'S)-Met > (alpha S,1'S)-Met > (alpha S,1'R)-Met > (alpha R,1'R)-Met, with (alpha S,1'S)-Met and (alpha R,1'S)-Met displaying a synergistic effect. Additionally, the Fe distribution in M. aeruginosa presented distinct enantioselectivity, which may contribute to the enantioselective toxicity of metolachlor. Furthermore, metolachlor upregulated the expression of genes mcyD and mcyH in an enantioselective manner, indicating that this herbicide can potentially promote the synthesis and efflux of microcystin, thus aggravating agricultural water contamination to different extents. Overall, this study will help to understand the ecotoxicity of metolachlor at a deeper level and provide theoretical insights into the enantioselective behaviors of metolachlor.