Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals
Abstract
The heterogeneous oxidation of organic aerosol by hydroxyl radicals (OH) can proceed through two general pathways: functionalization, in which oxygen functional groups are added to the carbon skeleton, and fragmentation, in which carbon–carbon bonds are broken, producing higher volatility, lower molecular weight products. An ongoing challenge is to develop a quantitative molecular description of these pathways that connects the oxidative evolution of the average aerosol properties (e.g. size and hygroscopicity) to the transformation of free radical intermediates. In order to investigate the underlying molecular mechanism of aerosol oxidation, a relatively compact kinetics model is developed for the heterogeneous oxidation of squalane particles by OH using free radical intermediates that convert reactive hydrogen sites into oxygen functional groups. Stochastic simulation techniques are used to compare calculated system properties over ten oxidation lifetimes with the same properties measured in experiment. The time-dependent average squalane aerosol mass, volume, density, carbon number distribution of scission products, and the average elemental composition are predicted using known rate coefficients. For functionalization, the calculations reveal that the distribution of alcohol and carbonyl groups is controlled primarily by the initial OH abstraction rate and to lesser extent by the branching ratio between secondary peroxy radical product channels. Formore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Columbia Hill Technical Consulting, Fremont, CA (United States)
- 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 & Biosciences Division
- OSTI Identifier:
- 1616964
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 6; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Wiegel, A. A., Wilson, K. R., Hinsberg, W. D., and Houle, F. A. Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals. United States: N. p., 2015.
Web. doi:10.1039/c4cp04927f.
Wiegel, A. A., Wilson, K. R., Hinsberg, W. D., & Houle, F. A. Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals. United States. https://doi.org/10.1039/c4cp04927f
Wiegel, A. A., Wilson, K. R., Hinsberg, W. D., and Houle, F. A. Tue .
"Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals". United States. https://doi.org/10.1039/c4cp04927f. https://www.osti.gov/servlets/purl/1616964.
@article{osti_1616964,
title = {Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals},
author = {Wiegel, A. A. and Wilson, K. R. and Hinsberg, W. D. and Houle, F. A.},
abstractNote = {The heterogeneous oxidation of organic aerosol by hydroxyl radicals (OH) can proceed through two general pathways: functionalization, in which oxygen functional groups are added to the carbon skeleton, and fragmentation, in which carbon–carbon bonds are broken, producing higher volatility, lower molecular weight products. An ongoing challenge is to develop a quantitative molecular description of these pathways that connects the oxidative evolution of the average aerosol properties (e.g. size and hygroscopicity) to the transformation of free radical intermediates. In order to investigate the underlying molecular mechanism of aerosol oxidation, a relatively compact kinetics model is developed for the heterogeneous oxidation of squalane particles by OH using free radical intermediates that convert reactive hydrogen sites into oxygen functional groups. Stochastic simulation techniques are used to compare calculated system properties over ten oxidation lifetimes with the same properties measured in experiment. The time-dependent average squalane aerosol mass, volume, density, carbon number distribution of scission products, and the average elemental composition are predicted using known rate coefficients. For functionalization, the calculations reveal that the distribution of alcohol and carbonyl groups is controlled primarily by the initial OH abstraction rate and to lesser extent by the branching ratio between secondary peroxy radical product channels. For fragmentation, the calculations reveal that the formation of activated alkoxy radicals with neighboring functional groups controls the molecular decomposition, particularly at high O/C ratios. Finally, this kinetic scheme provides a framework for understanding the oxidation chemistry of a model organic aerosol and informs parameterizations of more complex systems.},
doi = {10.1039/c4cp04927f},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 6,
volume = 17,
place = {United States},
year = {Tue Jan 06 00:00:00 EST 2015},
month = {Tue Jan 06 00:00:00 EST 2015}
}
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Figures / Tables:
Figure 1: Generalized reaction scheme for the oxidation of hydrocarbons by OH in the absence of NOx. An expanded representation of (R1), (R2), and (R3) is shown in Figure 2..
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Works referenced in this record:
Elemental ratio measurements of organic compounds using aerosol mass spectrometry: characterization, improved calibration, and implications
journal, January 2014
- Canagaratna, M. R.; Jimenez, J. L.; Kroll, J. H.
- Atmospheric Chemistry and Physics Discussions, Vol. 14, Issue 13
The statistical evolution of multiple generations of oxidation products in the photochemical aging of chemically reduced organic aerosol
journal, January 2012
- Wilson, Kevin R.; Smith, Jared D.; Kessler, Sean H.
- Phys. Chem. Chem. Phys., Vol. 14, Issue 4
A comprehensive and compact n-heptane oxidation model derived using chemical lumping
journal, January 2007
- Ahmed, Syed Sayeed; Mauß, Fabian; Moréac, Gladys
- Phys. Chem. Chem. Phys., Vol. 9, Issue 9
Rate constants for the atmospheric reactions of alkoxy radicals: An updated estimation method
journal, December 2007
- Atkinson, Roger
- Atmospheric Environment, Vol. 41, Issue 38
Laboratory studies of organic peroxy radical chemistry: an overview with emphasis on recent issues of atmospheric significance
journal, January 2012
- Orlando, John J.; Tyndall, Geoffrey S.
- Chemical Society Reviews, Vol. 41, Issue 19
Determination of coupled acid catalysis-diffusion processes in a positive-tone chemically amplified photoresist
journal, January 2000
- Houle, F. A.; Hinsberg, W. D.; Morrison, M.
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 18, Issue 4
SIMPOL.1: a simple group contribution method for predicting vapor pressures and enthalpies of vaporization of multifunctional organic compounds
journal, January 2008
- Pankow, J. F.; Asher, W. E.
- Atmospheric Chemistry and Physics, Vol. 8, Issue 10
Towards cleaner combustion engines through groundbreaking detailed chemical kinetic models
journal, January 2011
- Battin-Leclerc, Frédérique; Blurock, Edward; Bounaceur, Roda
- Chemical Society Reviews, Vol. 40, Issue 9
Lumping procedures in detailed kinetic modeling of gasification, pyrolysis, partial oxidation and combustion of hydrocarbon mixtures
journal, January 2001
- Ranzi, E.; Dente, M.; Goldaniga, A.
- Progress in Energy and Combustion Science, Vol. 27, Issue 1
Kinetics and atmospheric implications of peroxy radical cross reactions involving the CH 3 C(O)O 2 radical
journal, October 1998
- Villenave, Eric; Lesclaux, Robert; Seefeld, Stephan
- Journal of Geophysical Research: Atmospheres, Vol. 103, Issue D19
Known and Unexplored Organic Constituents in the Earth's Atmosphere
journal, March 2007
- Goldstein, Allen H.; Galbally, Ian E.
- Environmental Science & Technology, Vol. 41, Issue 5
Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry
journal, January 2010
- Ng, N. L.; Canagaratna, M. R.; Zhang, Q.
- Atmospheric Chemistry and Physics, Vol. 10, Issue 10
A two-dimensional volatility basis set: 1. organic-aerosol mixing thermodynamics
journal, January 2011
- Donahue, N. M.; Epstein, S. A.; Pandis, S. N.
- Atmospheric Chemistry and Physics, Vol. 11, Issue 7
Elemental Analysis of Organic Species with Electron Ionization High-Resolution Mass Spectrometry
journal, November 2007
- Aiken, Allison C.; DeCarlo, Peter F.; Jimenez, Jose L.
- Analytical Chemistry, Vol. 79, Issue 21
Approximate accelerated stochastic simulation of chemically reacting systems
journal, July 2001
- Gillespie, Daniel T.
- The Journal of Chemical Physics, Vol. 115, Issue 4
Kinetic Model for Positive Tone Resist Dissolution and Roughening
journal, October 2002
- Houle, F. A.; Hinsberg, W. D.; Sanchez, M. I.
- Macromolecules, Vol. 35, Issue 22
Study of the adsorption of sodium dodecyl sulfate (SDS) at the air/water interface: targeting the sulfate headgroup using vibrational sum frequency spectroscopy
journal, January 2005
- Johnson, C. Magnus; Tyrode, Eric
- Physical Chemistry Chemical Physics, Vol. 7, Issue 13
Product Studies of the Mutual Termination Reactions of sec -Alkylperoxy Radicals: Evidence for Non-Cyclic Termination
journal, April 1974
- Bennett, John E.; Summers, Raymond
- Canadian Journal of Chemistry, Vol. 52, Issue 8
Exact stochastic simulation of coupled chemical reactions
journal, December 1977
- Gillespie, Daniel T.
- The Journal of Physical Chemistry, Vol. 81, Issue 25
Chemical Sinks of Organic Aerosol: Kinetics and Products of the Heterogeneous Oxidation of Erythritol and Levoglucosan
journal, September 2010
- Kessler, Sean H.; Smith, Jared D.; Che, Dung L.
- Environmental Science & Technology, Vol. 44, Issue 18
A statistical description of the evolution of cloud condensation nuclei activity during the heterogeneous oxidation of squalane and bis(2-ethylhexyl) sebacate aerosol by hydroxyl radicals
journal, January 2013
- Harmon, Christopher W.; Ruehl, Christopher R.; Cappa, Christopher D.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 24
Gas uptake and chemical aging of semisolid organic aerosol particles
journal, June 2011
- Shiraiwa, M.; Ammann, M.; Koop, T.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 27
Structure-activity relationship for the estimation of OH-oxidation rate constants of aliphatic organic compounds in the aqueous phase: alkanes, alcohols, organic acids and bases
journal, October 2008
- Monod, A.; Doussin, J. F.
- Atmospheric Environment, Vol. 42, Issue 33
Peroxy radicals
journal, January 1969
- Ingold, Keith U.
- Accounts of Chemical Research, Vol. 2, Issue 1
Measurement of fragmentation and functionalization pathways in the heterogeneous oxidation of oxidized organic aerosol
journal, January 2009
- Kroll, Jesse H.; Smith, Jared D.; Che, Dung L.
- Physical Chemistry Chemical Physics, Vol. 11, Issue 36
The carbon number-polarity grid: A means to manage the complexity of the mix of organic compounds when modeling atmospheric organic particulate matter
journal, June 2009
- Pankow, James F.; Barsanti, Kelley C.
- Atmospheric Environment, Vol. 43, Issue 17
Decomposition of substituted alkoxy radicals—part I: a generalized structure–activity relationship for reaction barrier heights
journal, January 2009
- Vereecken, L.; Peeters, J.
- Physical Chemistry Chemical Physics, Vol. 11, Issue 40
Thermal and acid-catalyzed deprotection kinetics in candidate deep ultraviolet resist materials
journal, November 1994
- Wallraff, G.
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 12, Issue 6
Evolution of Organic Aerosols in the Atmosphere
journal, December 2009
- Jimenez, J. L.; Canagaratna, M. R.; Donahue, N. M.
- Science, Vol. 326, Issue 5959
Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol
journal, January 2011
- Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.
- Nature Chemistry, Vol. 3, Issue 2
Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase
journal, January 2013
- Doussin, J. -F.; Monod, A.
- Atmospheric Chemistry and Physics, Vol. 13, Issue 23
The Influence of Molecular Structure and Aerosol Phase on the Heterogeneous Oxidation of Normal and Branched Alkanes by OH
journal, May 2013
- Ruehl, Christopher R.; Nah, Theodora; Isaacman, Gabriel
- The Journal of Physical Chemistry A, Vol. 117, Issue 19
Kinetics and products from reaction of Cl radicals with dioctyl sebacate (DOS) particles in O2: a model for radical-initiated oxidation of organic aerosols
journal, January 2007
- Hearn, John D.; Renbaum, Lindsay H.; Wang, Xi
- Physical Chemistry Chemical Physics, Vol. 9, Issue 34
Oxidation of a model alkane aerosol by OH radical: the emergent nature of reactive uptake
journal, January 2015
- Houle, F. A.; Hinsberg, W. D.; Wilson, K. R.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 6
Transitions from Functionalization to Fragmentation Reactions of Laboratory Secondary Organic Aerosol (SOA) Generated from the OH Oxidation of Alkane Precursors
journal, May 2012
- Lambe, Andrew T.; Onasch, Timothy B.; Croasdale, David R.
- Environmental Science & Technology, Vol. 46, Issue 10
The Bimolecular Self-reactions of Secondary Peroxy Radicals. Product Studies
journal, March 1973
- Lindsay, D.; Howard, J. A.; Horswill, E. C.
- Canadian Journal of Chemistry, Vol. 51, Issue 6
The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols
journal, January 2009
- Smith, J. D.; Kroll, J. H.; Cappa, C. D.
- Atmospheric Chemistry and Physics, Vol. 9, Issue 9
Discrete simulation methods in combustion kinetics
journal, December 1974
- Bunker, Don L.; Garrett, Bruce; Kleindienst, Tadeusz
- Combustion and Flame, Vol. 23, Issue 3
HO 2 ELIMINATION FROM α-HYDROXYALKYLPEROXYL RADICALS IN AQUEOUS SOLUTION
journal, October 1978
- Bothe, Eberhard; Schuchmann, Man Nien; Schulte-Frohlinde, Dietrich
- Photochemistry and Photobiology, Vol. 28, Issue 4-5
Kinetic electron paramagnetic resonance study of the reactions of t-butylperoxyl radicals in aqueous solution
journal, January 1990
- Bennett, John E.
- Journal of the Chemical Society, Faraday Transactions, Vol. 86, Issue 19
Atmospheric Chemistry of Propionaldehyde: Kinetics and Mechanisms of Reactions with OH Radicals and Cl Atoms, UV Spectrum, and Self-Reaction Kinetics of CH 3 CH 2 C(O)O 2 Radicals at 298 K
journal, December 2005
- Le Crâne, Jean-Paul; Villenave, Eric; Hurley, Michael D.
- The Journal of Physical Chemistry A, Vol. 109, Issue 51
Deuterium-isotope Effects in the Autoxidation of Aralkyl Hydrocarbons. Mechanism of the Interaction of PEroxy Radicals 1
journal, July 1957
- Russell, Glen A.
- Journal of the American Chemical Society, Vol. 79, Issue 14
Heterogeneous oxidation of saturated organic aerosols by hydroxyl radicals: uptake kinetics, condensed-phase products, and particle size change
journal, January 2007
- George, I. J.; Vlasenko, A.; Slowik, J. G.
- Atmospheric Chemistry and Physics, Vol. 7, Issue 16
Wide-Range Kinetic Modeling Study of the Pyrolysis, Partial Oxidation, and Combustion of Heavy n -Alkanes
journal, July 2005
- Ranzi, Eliseo; Frassoldati, Alessio; Granata, Silvia
- Industrial & Engineering Chemistry Research, Vol. 44, Issue 14
Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds
journal, January 2003
- Saunders, S. M.; Jenkin, M. E.; Derwent, R. G.
- Atmospheric Chemistry and Physics, Vol. 3, Issue 1
Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP): linking condensation, evaporation and chemical reactions of organics, oxidants and water
journal, January 2012
- Shiraiwa, M.; Pfrang, C.; Koop, T.
- Atmospheric Chemistry and Physics, Vol. 12, Issue 5
Electron spin resonance studies. Part 61. The generation and reactions of the t-butoxyl radical in aqueous solution
journal, January 1981
- Gilbert, Bruce C.; Marshall, P. David R.; Norman, Richard O. C.
- Journal of the Chemical Society, Perkin Transactions 2, Issue 10
Mechanism of the First Order Decay of 2-Hydroxy-propyl-2-peroxyl Radicals and of O2~ Formation in Aqueous Solution
journal, August 1977
- Bothe, Eberhard; Behrens, Günther; Schulte-Frohlinde, Dietrich
- Zeitschrift für Naturforschung B, Vol. 32, Issue 8
Atmospheric Degradation of Volatile Organic Compounds
journal, December 2003
- Atkinson, Roger; Arey, Janet
- Chemical Reviews, Vol. 103, Issue 12
Atmospheric Chemistry of Pivalaldehyde and Isobutyraldehyde: Kinetics and Mechanisms of Reactions with Cl Atoms, Fate of (CH 3 ) 3 CC(O) and (CH 3 ) 2 CHC(O) Radicals, and Self-Reaction Kinetics of (CH 3 ) 3 CC(O)O 2 and (CH 3 ) 2 CHC(O)O 2 Radicals
journal, February 2004
- Le Crâne, Jean-Paul; Villenave, Eric; Hurley, Michael D.
- The Journal of Physical Chemistry A, Vol. 108, Issue 5
OH-Initiated Heterogeneous Aging of Highly Oxidized Organic Aerosol
journal, February 2012
- Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.
- The Journal of Physical Chemistry A, Vol. 116, Issue 24
Coupled Partitioning, Dilution, and Chemical Aging of Semivolatile Organics
journal, April 2006
- Donahue, N. M.; Robinson, A. L.; Stanier, C. O.
- Environmental Science & Technology, Vol. 40, Issue 8
Works referencing / citing this record:
Effect of Bulk Composition on the Heterogeneous Oxidation of Semi-Solid Atmospheric Aerosols
journal, December 2019
- Fan, Hanyu; Goulay, Fabien
- Atmosphere, Vol. 10, Issue 12
Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols
journal, January 2017
- Chim, Man Mei; Cheng, Chiu Tung; Davies, James F.
- Atmospheric Chemistry and Physics, Vol. 17, Issue 23
Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol
journal, January 2018
- Li, Ziyue; Smith, Katherine A.; Cappa, Christopher D.
- Atmospheric Chemistry and Physics, Vol. 18, Issue 19
Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate
journal, January 2019
- Lam, Hoi Ki; Kwong, Kai Chung; Poon, Hon Yin
- Atmospheric Chemistry and Physics, Vol. 19, Issue 4
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