Phloem Redistribution of Pesticide Phenamacril in Plants Followed by Extensive Biotransformation

Here, we evaluated the uptake and biotransformation mechanism of the systemic fungicide phenamacril in hydroponic/soil–plant systems. Phenamacril was preferentially accumulated in shoots with the translocation factor up to 3.5 (or 6.9) in wheat (or rice) during 144 h of the uptake kinetic experiment. Apart from upward xylem translocation, phenamacril could also be redistributed from shoots to roots (0.4%) through phloem transport and then released into the rhizosphere surrounding solution (1.7%) through plant excretion via a split-root experiment. Then, 76.4% (or 70.4%) of phenamacril was transformed to 14 (or 12) metabolites in hydroponic-wheat (or hydroponic-rice) systems after 28 days of exposure, with nine of them first identified based on nontarget analysis. The proposed metabolic pathways included hydroxylation, hydrolysis, isomerization, dehydrogenation, deamination, dehydration, decarboxylation, reduction, and conjugation reactions, which were modulated by genes overexpression of metabolic enzymes (e.g., cytochrome P450). Notably, metabolite M-157 was predicted to be more persistent in environments and more toxic to rats and aquatic organisms than phenamacril by theoretical calculation. This study highlights that phloem transport and plant excretion may result in cycling chemical contamination, and the transformation products may possess elevated toxicities, thus should be considered in estimating the contamination of pesticides in crops and environments.