Semi-Automated Computational Investigation of the Oxidative Degradation Mechanisms of Bisphenol A in Fenton-Type Processes

Bisphenol A (BPA) is a widespread industrial contaminant and known endocrine disruptor, whose effective removal from aquatic environments remains a significant environmental challenge. In this study, we present a semi-automated, first-principles computational approach to characterize and streamline the radical-mediated degradation mechanism of BPA under Fenton-type advanced oxidation conditions. Based on extensive DFT-level exploration of the relevant potential energy surfaces, we identified all plausible OH-addition and H-abstraction channels leading to hydroxylation, oxidative cleavage, and ring opening products. Reaction rate constants were computed using Pilgrim, and product distributions were quantified through Kinetic Monte Carlo (KMC) simulations under both fixed [OH]:[BPA] initial ratios and a linearly increasing OH radical concentration. Moreover, fixed-ratio conditions were used to simplify the network by applying a one‐at‐a‐time reaction sensitivity protocol: each elementary reaction was removed in turn, and those whose exclusion altered any species final concentration by ≥ 0.04 μM were retained. Under Fenton-type OH ramp-up conditions, this compact model reproduces full-network kinetics. Our integrated approach delivers mechanistic insight and a predictive, computationally efficient model for BPA degradation.