Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis
Abstract
Criegee intermediates (CI), formed in alkene ozonolysis, are central for controlling the multiphase chemistry of organic molecules in both indoor and outdoor environments. Here in this study, we examine the heterogeneous ozonolysis of squalene, a key species in indoor air chemistry. Aerosol mass spectrometry is used to investigate how the ozone (O3) concentration, relative humidity (RH), and particle size control reaction rates and mechanisms. Although the reaction rate is found to be independent of RH, the reaction products and particle size depend upon H2O. Under dry conditions (RH = 3%) the reaction produces high-molecular-weight secondary ozonides (SOZ), which are known skin irritants, and a modest change in particle size. Increasing the RH reduces the aerosol size by 30%, while producing mainly volatile aldehyde products, increases potential respiratory exposure. Chemical kinetics simulations link the elementary reactions steps of CI to the observed kinetics, product distributions, and changes in particle size. The simulations reveal that ozonolysis occurs near the surface and is O3-transport limited. Finally, the observed secondary ozonides are consistent with the formation of mainly secondary CI, in contrast to gas-phase ozonolysis mechanisms.
- Authors:
-
[1];
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1456986
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Environmental Science and Technology
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 23; Related Information: © 2017 American Chemical Society.; Journal ID: ISSN 0013-936X
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES
Citation Formats
Heine, Nadja, Houle, Frances A., and Wilson, Kevin R. Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis. United States: N. p., 2017.
Web. doi:10.1021/acs.est.7b04197.
Heine, Nadja, Houle, Frances A., & Wilson, Kevin R. Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis. United States. https://doi.org/10.1021/acs.est.7b04197
Heine, Nadja, Houle, Frances A., and Wilson, Kevin R. Thu .
"Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis". United States. https://doi.org/10.1021/acs.est.7b04197. https://www.osti.gov/servlets/purl/1456986.
@article{osti_1456986,
title = {Connecting the Elementary Reaction Pathways of Criegee Intermediates to the Chemical Erosion of Squalene Interfaces during Ozonolysis},
author = {Heine, Nadja and Houle, Frances A. and Wilson, Kevin R.},
abstractNote = {Criegee intermediates (CI), formed in alkene ozonolysis, are central for controlling the multiphase chemistry of organic molecules in both indoor and outdoor environments. Here in this study, we examine the heterogeneous ozonolysis of squalene, a key species in indoor air chemistry. Aerosol mass spectrometry is used to investigate how the ozone (O3) concentration, relative humidity (RH), and particle size control reaction rates and mechanisms. Although the reaction rate is found to be independent of RH, the reaction products and particle size depend upon H2O. Under dry conditions (RH = 3%) the reaction produces high-molecular-weight secondary ozonides (SOZ), which are known skin irritants, and a modest change in particle size. Increasing the RH reduces the aerosol size by 30%, while producing mainly volatile aldehyde products, increases potential respiratory exposure. Chemical kinetics simulations link the elementary reactions steps of CI to the observed kinetics, product distributions, and changes in particle size. The simulations reveal that ozonolysis occurs near the surface and is O3-transport limited. Finally, the observed secondary ozonides are consistent with the formation of mainly secondary CI, in contrast to gas-phase ozonolysis mechanisms.},
doi = {10.1021/acs.est.7b04197},
journal = {Environmental Science and Technology},
number = 23,
volume = 51,
place = {United States},
year = {Thu Nov 09 00:00:00 EST 2017},
month = {Thu Nov 09 00:00:00 EST 2017}
}
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