Extracellular laccase-activated humification of phenolic pollutants and its application in plant growth

Humification processes of phenolic pollutants may play a profound role in environment purification and plant growth. However, little literature is performed to explore exoenzyme-driven humification to polymerize 17β-estradiol (E2) and humic constituents (HCs), and the effects of their polymeric precipitates on plant growth are usually overlooked. Herein, E2 conversion and radish (Raphanus sativus L.) growth were systematically investigated under humification mediated by extracellular laccase (EL) of Trametes versicolor. Results disclosed that EL-assisted humification achieved a wonderful E2 conversion efficiency (>99%) within 2-h, but the presence of HCs such as humic acid (HA), vanillic acid (VA), and ferulic acid (FA) impeded E2 elimination significantly. Compared with HC-free, the kinetics constants declined by 2.84-, 5.72-, and 5.22-fold with HA, VA, and FA present, respectively. Intriguingly, three close-knit self/cross-linked precipitates (i.e., E2-HA, E2-VA, and E2-FA hybrid precipitates) in dark gray, dark brown, and deep yellow were created after a continuous humification by phenolic radical-initiated polymerization mechanisms. The formation of these humified precipitates was extremely effective on circumventing phytotoxicity caused by monomeric E2, VA, or FA. Furthermore, they acted as humic-like organic fertilizers, accelerating seed germination, root elongation, and enhancing NaCl-tolerance of radish through the combination of oxygen-contained functional components and auxin structural analogues with unstable and stubborn carbon skeletons. This is the first study reporting the pollution purification and plant growth promotion in EL-activated humification. Our findings frame valuable perspectives regarding the natural detoxification and carbon sequestration of phenolic pollutants and the application of their polymeric precipitates in global crop production.