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.