A comparative study on degradation kinetics and toxicity changes of BPA and BPS in UV-based advanced oxidation processes.

Bisphenol A (BPA) and Bisphenol S (BPS) are endocrine-disrupting chemicals that pose significant ecological and health risks due to their persistence and toxicity. This study presents a comprehensive comparison of three UV-based advanced oxidation processes (UV-AOPs: UV/Cl, UV/PDS, and UV/H2O2) for degrading BPA and BPS, with an emphasis on correlating degradation efficiency to the toxicity of transformation products (TPs). Using a 500 W mercury vapor lamp, we demonstrate how differences in electronic properties (e.g., BPA's electron-rich rings vs. BPS's electron-withdrawing sulfonyl group) influence radical selectivity (SO4•-, •OH, RCS) and by-product risks. The effects of oxidant dosage, pH, and dissolved organic matter were examined. The toxicity of degradation by-products was evaluated using an integrated approach combining ECOSAR predictions and Vibrio fischeri bioassays to reveal critical trade-offs between degradation rates and TP safety. The UV/PDS system demonstrated the highest BPA removal efficiency (96.5 % in 10 min, k = 0.3185 ± 0.034 min-1) under alkaline conditions, primarily via sulfate radicals (SO4•-). In contrast, BPS degradation was less efficient (k = 0.0910 min-1) due to the lower reactivity of its sulfonyl group. The UV/Cl process generated chlorinated by-products, such as TP07, with toxicity levels 1.5 to 2.0 times higher than the parent compounds, while UV/H2O2 produced hydroxylated by-products that were 25 % more toxic than BPA. Notably, chlorinated derivatives increased toxicity in BPA but reduced it in BPS due to steric hindrance from the sulfonyl group, a structural nuance not previously reported in AOP studies. Oxidized by-products were generally less toxic, whereas fragmented products exhibited higher toxicity than their precursors. These findings support pollutant-specific optimization of UV-AOPs, identifying UV/PDS as the most effective for BPA degradation while emphasizing the need for sulfonyl-targeted refinement in BPS treatment.