Fungal laccase-triggered 17β-estradiol humification kinetics and mechanisms in the presence of humic precursors.

Naturally-occurring phenolic acids (PAs) act as humic precursors that participate in the conversion behaviors and coupling pathways of steroidal estrogens (SEs) during laccase-triggered humification processes (L-THPs). Herein, the influences and mechanisms of PAs on Trametes versicolor laccase-evoked 17β-estradiol (E2) conversion kinetics and humification routes were explored. Fungal laccase was fleet in converting > 99% of E2, and the calculated pseudo-first-order velocity constant and half-time values were respectively 0.039 min and 17.906 min. PAs containing an O-dihydroxy moiety such as gallic acid and caffeic acid evidently hampered E2 humification owning to the yielded highly reactive O-quinones reversed E2 radicals by hydrogen transfer mechanism, implying that the inhibition effect was enormously dependent upon the number and position of the phenolic -OH present in humic precursors. Oligomers and polymers with carbon-carbon/oxygen links were tentatively found as E2 main humified species resulting from laccase-evoked successive oxidative-coupling. Note that PAs participating in the humification also encountered oxydehydrogenation, self-polymerization, and cross-binding to E2. Interestingly, the -COOH and -OCH groups of PAs could be deprived in radical-caused self/co-polymerization. The generation of humified products not only circumvented the environmental risks of parent compounds but accelerated global carbon sequestration. To our knowledge, this is the first in-depth revelation of the humification pathways and related mechanisms of SEs with humic precursors in aquatic ecosystems by L-THPs.