Quantum Chemical Investigation and Experimental Verification on the Aquatic Photochemistry of the Sunscreen 2-Phenylbenzimidazole-5-Sulfonic Acid

摘要

For ecological risk assessment of the large and ever-increasing number of chemical pollutants, it is of importance to develop computational methods to screen or predict their environmental photodegradation behavior. This study developed a computational method based on the density functional theory (DFT) to predict and evaluate the photodegradation behavior and effects of water constituents, taking a sunscreen and personal care product 2-phenylbenzimidazole-5-sulfonic acid (PBSA) as a model compound. Energy and electron transfer reactions of excited state PBSA (PBSA*) with ~3O_2 and water constituents were evaluated. The computational results indicated that PBSA* could photogenerate ~1O_2 and O_2~-·, triplet excited state humic/fulvic acid analogs could not photosensitize the degradation, and the anions (Cl~-, Br~-, and HCO_3~-) could not quench PBSA* or its radical cation chemically. Experiments employing simulated sunlight confirmed that PBSA photodegraded via the direct and self-sensitization mechanism involving O_2~-·. The photodegradation was pH-dependent The direct and self-sensitized photodegradation was inhibited by fulvic acid. The main photodegradation products were identified, and the pathways were clarified. These results indicate that the DFT-based computational method can be employed to assess the environmental photochemical fate of organic pollutants.