| Title: | Multiphase Ozonolysis of Oleic Acid-Based Lipids: Quantitation of Major Products and Kinetic Multilayer Modeling |
| Author(s): | Zhou Z; Lakey PSJ; von Domaros M; Wise N; Tobias DJ; Shiraiwa M; Abbatt JPD; |
| Address: | "Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada. Department of Chemistry, University of California, Irvine, California 92697-2025, United States" |
| ISSN/ISBN: | 1520-5851 (Electronic) 0013-936X (Linking) |
| Abstract: | "Commonly found in atmospheric aerosols, cooking oils, and human sebum, unsaturated lipids rapidly decay upon exposure to ozone, following the Criegee mechanism. Here, the gas-surface ozonolysis of three oleic acid-based compounds was studied in a reactor and indoors. Under dry conditions, quantitative product analyses by (1)H NMR indicate up to 79% molar yield of stable secondary ozonides (SOZs) in oxidized triolein and methyl oleate coatings. Elevated relative humidity (RH) significantly suppresses the SOZ yields, enhancing the formation of condensed-phase aldehydes and volatile C9 products. Along with kinetic parameters informed by molecular dynamics simulations, these results were used as constraints in a kinetic multilayer model (KM-GAP) simulating triolein ozonolysis. Covering a wide range of coating thicknesses and ozone levels, the model predicts a much faster decay near the gas-lipid interface compared to the bulk. Although the dependence of RH on SOZ yields is well predicted, the model overestimates the production of H(2)O(2) and aldehydes. With negligible dependence on RH, the product composition for oxidized oleic acid is substantially affected by a competitive reaction between Criegee intermediates (CIs) and carboxylic acids. The resulting alpha-acyloxyalkyl hydroperoxides (alpha-AAHPs) have much higher molar yields (29-38%) than SOZs (12-16%). Overall, the ozone-lipid chemistry could affect the indoor environment through 'crust' accumulation on surfaces and volatile organic compound (VOC) emission. In the atmosphere, the peroxide formation and changes in particle hygroscopicity may have effects on climate. The related health impacts are also discussed" |
| Keywords: | Aldehydes Humans Hydrogen Peroxide *Oleic Acid/chemistry *Ozone/chemistry Triolein Criegee intermediate kinetic modeling molecular dynamics simulations oleic acid ozone secondary ozonide; |
| Notes: | "MedlineZhou, Zilin Lakey, Pascale S J von Domaros, Michael Wise, Natsuko Tobias, Douglas J Shiraiwa, Manabu Abbatt, Jonathan P D eng Research Support, Non-U.S. Gov't 2022/06/08 Environ Sci Technol. 2022 Jun 21; 56(12):7716-7728. doi: 10.1021/acs.est.2c01163. Epub 2022 Jun 7" |
