Transformation and Removal of Bisphenol A from Aqueous Phase via Peroxidase-Mediated Oxidative Coupling Reactions: Efficacy, Products, and Pathways

A systematic investigation of the feasibility of and mechanisms for transformation and removal of bisphenol A (BPA) from aqueous phase via oxidative coupling mediated by horseradish peroxidase is described. It is demonstrated that BPA can be effectively transformed into precipitable solid products in HRP-mediated oxidative coupling reactions. A total of 13 reaction intermediates and products are identified using LC/MS and GC/MS techniques, and with the help of ab initio molecular modeling, detailed reaction pathways are proposed. It is postulated that two BPA radicals are coupled primarily by the interaction of an oxygen atom on one radical and propyl-substituted aromatic carbon atom on another, followed by elimination of an isopropylphenol carboncation. All intermediates or products detected can be interpreted as resulting from either coupling or substitution reactions between BPA and other intermediates or products. The efficacy of the reaction at low substrate concentrations is demonstrated using a sensitive analytical procedure involving solid-phase extractions. The results suggest that catalyzed oxidative coupling reactions may be important natural transformation pathways for estrogenic phenolic compounds and indicate their potential use as an efficient means for removal of estrogenicity from waters and wastewaters.