Chiral conazole fungicides - (Enantioselective) terrestrial bioaccumulation and aquatic toxicity.

Five conazole fungicides (CFs) (epoxiconazole, tebuconazole, myclobutanil, uniconazole (P), rac-uniconazole, and diniconazole) were tested in order to provide additional information on i) the effects of CFs on the nematode Caenorhabditis elegans and on the aquatic insect Chironomus riparius under acute exposure scenarios and in multi-generation exposure studies, taking advantage of the short life cycle of nematodes and ii) on the bioaccumulation (earthworm Eisenia andrei) profiles of CFs including also the enantiomer-specific assessment of degradation in soils and uptake/elimination by earthworms. Acute toxicity was considered low following the exposure of up to 2.5 mg of CFs per liter of the test medium. In a multigeneration study on nematodes, all five generations exposed to epoxiconazole were significantly negatively affected in terms of reproductive efficiency, and the severity of effects increased from F0 to F1 generation and was sustained thereafter. Adverse effects were also observed in the case of uniconazole (P) and diniconazole, and similarly to epoxiconazole, the effects occurred within the active life of the pesticides and were assumed to be based on their half-lives in soil (e.g., 53.3 to 691 days for uniconazole and diniconazole in our study) and in sediment/water. Bioaccumulation of diniconazole and uniconazole by earthworms varied between soils (Lufa 2.1 ≥ Lufa 2.4 > sandy soil > Lufa 2.2) and compounds (diniconazole > uniconazole) and was enantioselective. Earthworms preferentially accumulated R-uniconazole as a result of faster elimination of the S-form, which was evidenced from the enantiomer-specific uptake/elimination rate constants derived from the bioaccumulation profiles. Our results suggest that multigeneration exposure studies can advantageously be used for assessing the long-term and trans-general effects of pesticides. Also, the enantioselectivity in bioaccumulation observed for both uniconazole and diniconazole suggests that enantioselectivity in the fate and effects should be considered when exploring ways for safer and sustainable use of chiral pesticides.