New insights into humic acid-boosted conversion of bisphenol A by laccase-activated co-polyreaction: Kinetics, products, and phytotoxicity

How humic acid (HA) modifies bisphenol A (BPA) conversion in exoenzyme-activated polyreaction is poorly understood. Herein, the influencing mechanism of HA on laccase-induced BPA self-polymerization was investigated, and the phytotoxicity of the produced BPA self/co-polymers was assessed for the first time. HA prominently boosted BPA elimination, and the rate constants of BPA conversion augmented from 0.61 to 1.43 h-1 as HA level raised from 0 to 50 mg·L-1. It is because the generated BPA-HA co-polymers promptly lowered the yields of long-chain BPA self-oligomers, consequently maintaining laccase activity through opening enzymatic substrate-binding pockets. Notably, a few BPA monomers were re-released from the loosely bound self-polymers and co-polymers, and the releasing amounts respectively were 13.9 - 22.4% and 0.3 - 0.5% at pH 2 - 11. Formation of self/co-polymers was greatly conducive to avoiding BPA biotoxicity. Compared with BPA self-polymers, the phytotoxicity of BPA co-polymers to germinated radish (Raphanus sativus L.) seeds was lower due to these covalently bound products were more complex and stable. It follows that laccase-mediated co-polymerization played a significant role in BPA conversion, contaminant detoxification, and carbon sequestration. These findings are not only beneficial to clarifying exoenzyme-activated the generation mechanism of BPA co-polymers in water, but to reusing these supramolecular aggregates in crop growth.