Fe-based nanomaterial transformation to amorphous Fe: Enhanced alfalfa rhizoremediation of PCBs-contaminated soil

Nano-enabled phytoremediation is an emerging remediation strategy for soils that are moderately contaminated with persistent organic contaminants, and there is a significant need for increased mechanistic understanding and for case studies. Herein, we evaluated the remediation of PCB28-contaminated soil using combined alfalfa and Fe-based materials, including zero-valent iron at 20 nm, 100 nm, and 5 µm, and also iron oxide nanomaterials including α-Fe₂O₃, γ-Fe₂O₃, and Fe₃O₄ around 20-30 nm. Compared with alfalfa remediation alone (63.2%), Fe-based nanomaterials increased PCB28 removal values to 72.4-93.5% in planted soil, with α-Fe₂O₃ treatment promoting the most effective pollutant removal. Mechanistically, the crystalline Fe-based nanoparticles were transformed into amorphous forms in the plant rhizosphere, resulting in greater availability and enhanced iron nutrition. This nutritional shift induced root metabolic reprogramming of amino acid and carbohydrate cycling, and related functional bacterial enrichment of Ramlibacter, Dyella, Bacillus, and Paraburkholderia in rhizosphere. A significant positive correlation between amorphous iron and root metabolites-associated microbes with PCB28 removal was evident, implying that iron supplementation selected for rhizospheric microorganisms favored PCBs degradation. Overall, this rhizoremediation promotion strategy of Fe species-metabolites-microbes highlights the potential for the hybrid application of nano-enabled phytotechnology in the remediation of soils contaminated with persistent organic xenobiotics.