Reactions of bisphenol F and bisphenol S with ozone and hydroxyl radical: Kinetics and mechanisms

Abstract

Bisphenol F (BPF) and bisphenol S (BPS) are the most employed substitutes of bisphenol A (BPA), after being restricted by legislation in different countries because of its endocrine disrupting behaviour. In the present work, a deep study was performed about the reactivity of BPF and BPS with ozone and hydroxyl radical. Firstly, the second order rate constants of ozone with the di-protonated, mono-protonated and deprotonated species of both bisphenols were determined to be 2.38 × 10⁴, 1.31 × 10⁹ and 1.43 × 10⁹ M^-1 s^-1 for BPF and 5.01, 2.82 × 10⁷ and 1.09 × 10⁹ M^-1 s^-1 for BPS. Then, the second order rate constants for the reaction of hydroxyl radical with BPF and BPS were established through UV/H₂O₂ and UV experiments at pH 7, resulting in the values of 8.60 × 10⁹ and 6.60 × 10⁹ M^-1 s^-1, respectively. Finally, a study regarding the transformation products (TPs) from the reaction of both bisphenols with molecular ozone and hydroxyl radical was also performed. Hydroxylation in the ortho position of the phenol rings was observed as main degradation pathway. Additionally, most of the TPs were accumulated over the reactions at relatively high oxidant doses.

Keywords: Competition kinetics; High resolution mass spectrometry; Intermediates; Ozonation; Second order rate constant; UV/H(2)O(2).