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Title: Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields

Abstract

We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.

Authors:
ORCiD logo; ORCiD logo; ; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1356476
Report Number(s):
PNNL-SA-123725
Journal ID: ISSN 0013-936X; KP1701000
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 51; Journal Issue: 9; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

D’Ambro, Emma L., Møller, Kristian H., Lopez-Hilfiker, Felipe D., Schobesberger, Siegfried, Liu, Jiumeng, Shilling, John E., Lee, Ben Hwan, Kjaergaard, Henrik G., and Thornton, Joel A. Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields. United States: N. p., 2017. Web. doi:10.1021/acs.est.7b00460.
D’Ambro, Emma L., Møller, Kristian H., Lopez-Hilfiker, Felipe D., Schobesberger, Siegfried, Liu, Jiumeng, Shilling, John E., Lee, Ben Hwan, Kjaergaard, Henrik G., & Thornton, Joel A. Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields. United States. https://doi.org/10.1021/acs.est.7b00460
D’Ambro, Emma L., Møller, Kristian H., Lopez-Hilfiker, Felipe D., Schobesberger, Siegfried, Liu, Jiumeng, Shilling, John E., Lee, Ben Hwan, Kjaergaard, Henrik G., and Thornton, Joel A. 2017. "Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields". United States. https://doi.org/10.1021/acs.est.7b00460.
@article{osti_1356476,
title = {Isomerization of Second-Generation Isoprene Peroxy Radicals: Epoxide Formation and Implications for Secondary Organic Aerosol Yields},
author = {D’Ambro, Emma L. and Møller, Kristian H. and Lopez-Hilfiker, Felipe D. and Schobesberger, Siegfried and Liu, Jiumeng and Shilling, John E. and Lee, Ben Hwan and Kjaergaard, Henrik G. and Thornton, Joel A.},
abstractNote = {We report chamber measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation, where radical concentrations were systematically varied and the molecular composition of semi to low volatility gases and SOA were measured online. Using a detailed chemical mechanism, we find that to explain the behavior of low volatility products and SOA mass yields relative to input H2O2 concentrations, the second generation dihydroxy hydroperoxy peroxy radical (C5H11O6•) must undergo an intra-molecular H-shift with a net forward rate constant of order 0.1 s-1 or higher, consistent with quantum chemical calculations which suggest a net forward rate constant of 0.3-0.9 s-1. Furthermore, these calculations suggest the dominant product of this isomerization is a dihydroxy hydroperoxy epoxide (C5H10O5) which is expected to have a saturation vapor pressure ~2 orders of magnitude higher than the dihydroxy dihydroperoxide, ISOP(OOH)2 (C5H12O6), a major product of the peroxy radical reacting with HO2. These results provide strong constraints on the likely volatility distribution of isoprene oxidation products under atmospheric conditions and thus on the importance of non-reactive gas-particle partitioning of isoprene oxidation products as an SOA source.},
doi = {10.1021/acs.est.7b00460},
url = {https://www.osti.gov/biblio/1356476}, journal = {Environmental Science and Technology},
issn = {0013-936X},
number = 9,
volume = 51,
place = {United States},
year = {Tue Apr 11 00:00:00 EDT 2017},
month = {Tue Apr 11 00:00:00 EDT 2017}
}

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