Natural humification-inspired bioenzymatic catalysis drives hydroponic root-zone decontamination and carbon sequestration.

Endocrine disruptors bioaccumulate along food chains, impairing reproductive function in wildlife and elevating chronic disease risk in humans. Natural humification-inspired bioenzymatic catalysis (NH-IBC) can interrupt pollutant transfer from crops to higher trophic levels, but its efficacy in hydroponic root-zone decontamination and carbon sequestration remains poorly characterized. Here, we demonstrated that NH-IBC enhanced the polymerization and humification of dissolved organic carbon in the hydroponic root-zones of ryegrass (Lolium perenne L.), resulting in a 17.3-fold increase in the dissipation kinetic constant of bisphenol A (BPA, a model endocrine disruptor) relative to the bioenzyme-deficient control. Mechanistically, NH-IBC generated reactive radical intermediates that boosted the copolymerization of root exudates (phenolic acids, amino acids) with BPA, forming water-insoluble, high-molar-mass polymers through stable covalent cross-coupling. This efficient polymerization, coupled with carbon sequestration, reduced BPA phytotoxicity and promoted ryegrass root cell proliferation and elongation. Mass balance and 14C-ring-labeled BPA analyses confirmed that NH-IBC diminished BPA uptake and subcellular distribution in ryegrass. Hydrophobic BPA oligomers and polymers accumulated primarily in root epidermal and cortical tissues, limiting translocation to the endodermis and edible aerial parts. Our findings present a natural humification-inspired biocatalytic framework to remediate contaminant pollution and sequester carbon, advancing agroecosystem sustainability and improving crop- and animal-derived food safety.