Insights into the Photodegradation of the Contact Allergen Fragrance Cinnamyl Alcohol: Kinetics, Mechanism, and Toxicity.

Abstract

Fragrances can cause general health issues, and special concerns exist surrounding the issue of skin safety. Cinnamyl alcohol (CAL) is a frequent fragrance contact allergen that has various toxic effects on indiscriminate animals. In the present study, the photodegradation transformation mechanism of CAL and toxicity evolution during this process were examined. The results showed that CAL (50 μM) can be completely degraded after 90-min ultraviolet (UV) irradiation with a degradation rate of 0.086 min-1 . Increased toxicity on bioluminescent bacteria was observed during this process, with lethality increasing from 10.6% (0 min) to 50.2% (90 min) under UV light irradiation. Further, the photodegradation mechanisms of CAL were explored to find the reason behind the increased toxicity observed. Laser flash photolysis and quenching experiments showed that O2•- , 1 O2 , and • OH were mainly responsible for CAL photodegradation, together with 3 CAL* and eaq- . The 5 main photodegradation products were cinnamyl aldehyde, benzaldehyde, benzenepropanal, cinnamic acid, and toluene, as identified using gas chromatography-mass spectrometry and liquid chromatography-quadrupole-time-of-flight-mass spectrometry. Once exposed to air, CAL was found to be easily oxidized to cinnamyl aldehyde and subsequently to cinnamic acid by O2•- - or 1 O2 -mediated pathways, leading to increased toxicity. Benzaldehyde exhibited bioreactive toxicity, increasing the toxicity through • OH-mediated pathways. Theoretical prediction of skin irritation indicated that cinnamyl aldehyde (0.83), benzenepropanal (0.69), cinnamyl aldehyde (0.69), and benzaldehyde (0.70) were higher than CAL (0.63), which may cause a profound impact on an individual's health and well-being. Overall, the present study advances the understanding of the photodegradation processes and health impacts of fragrance ingredients. Environ Toxicol Chem 2021;40:2705-2714. © 2021 SETAC.