Coupling of Lipid Peroxidation and Criegee Intermediate Mediated Autoxidation in the Heterogeneous Oxidation of Linoleic Acid Aerosols

Zeng, Meirong; Wilson, Kevin R.

doi:10.1021/acs.est.4c13472

Coupling of Lipid Peroxidation and Criegee Intermediate Mediated Autoxidation in the Heterogeneous Oxidation of Linoleic Acid Aerosols

Journal Article · Thu May 01 00:00:00 EDT 2025 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.4c13472· OSTI ID:2584846

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Shanghai Jiao Tong University (China)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Autoxidation is an established mechanism for the degradation of organic molecules, which is relevant in the atmosphere, combustion processes, the environment, and the rancidification of lipids (commonly known as lipid peroxidation). Autoxidation proceeds via radical chain reactions involving hydroxyl (^•OH), peroxy (RO₂^•), and alkoxy radicals, which are also prominent oxidants in the atmosphere. Recent reports have provided evidence for an alternative autoxidation mechanism driven instead by Criegee intermediates (CIs), which are produced from the reaction of β-hydroxy peroxy radicals (β–OH-RO₂^•). This work evaluates the contributions of these two mechanisms in the ^•OH initiated heterogeneous oxidation of linoleic acid (LA) aerosols. Reaction kinetics and product distributions are monitored using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer. To explain the observed kinetics, a kinetic model is developed that incorporates both the conventional peroxidation and alternative CI-mediated autoxidation mechanisms. Here, we observe that the CI-mediated autoxidation pathways enhance the heterogeneous autoxidation rate, while the peroxidation reactions, although present, contributes less to the overall oxidation rate. α-Acyloxyalkyl hydroperoxides (AAHPs) are identified as key indicators for bimolecular reactions of CI with LA, highlighting the role of LA as a CI scavenger. Moreover, the measured functionalized LA products with hydroxyl or carbonyl group(s), serve as markers for the peroxidation reactions. In summary, this work presents a quantitative framework to understand the coupled reaction network of ^•OH, RO₂^•, β–OH-RO₂^• radicals, and CI in driving heterogeneous autoxidation, which is crucial for understanding degradation mechanisms of organic molecules in the environment and atmosphere.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: National Natural Science Foundation of China; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2584846

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 18 Vol. 59; ISSN 1520-5851; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Coupling of Lipid Peroxidation and Criegee Intermediate Mediated Autoxidation in the Heterogeneous Oxidation of Linoleic Acid Aerosols

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