Structural Transformation of MnO₂ during the Oxidation of Bisphenol A

Bisphenol A (BPA) is an endocrine-disrupting compound widely used in the plastic industry and found in natural waters at concentrations considered harmful for aquatic life. BPA is susceptible to oxidation by Mn(III/IV) oxides, which are commonly found in near-surface environments. Here, we quantify BPA oxidation rates and the formation of its predominant product, 4-hydroxycumyl alcohol (HCA), in tandem with transformation of a synthetic, Mn(III)-rich δ-MnO₂. To investigate the effect of Mn oxide structural changes on BPA oxidation rate, 12 sequential additions of 80 μM BPA are performed at pH 7. During the additions, BPA oxidation rate decreases by 3 orders of magnitude, and HCA yield decreases from 40% to 3%. This is attributed to the accumulation of interlayer Mn(II/III) produced during the reaction, as observed using X-ray absorption spectroscopy, as well as additional spectroscopic and wet chemical techniques. HCA is oxidized at a rate that is 12.6 times slower than BPA and accumulates in solution. These results demonstrate that BPA degradation by environmentally relevant Mn(III/IV) oxides is inhibited by the buildup of solid-phase Mn(II/III), specifically in interlayer sites. Nevertheless, Mn oxides may limit BPA migration in near-surface environments and have potential for use in drinking and wastewater treatment.