DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols

Abstract

We report that a key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas–particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive–diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0–12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core–shell configuration. The results indicate a reactive–diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10-6 cm2/s) of ozone in squalane to be determined. In conclusion, the reactive–diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.

Authors:
 [1];  [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:
1456955
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 34; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lee, Lance, and Wilson, Kevin. The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b05285.
Lee, Lance, & Wilson, Kevin. The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols. United States. https://doi.org/10.1021/acs.jpca.6b05285
Lee, Lance, and Wilson, Kevin. Wed . "The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols". United States. https://doi.org/10.1021/acs.jpca.6b05285. https://www.osti.gov/servlets/purl/1456955.
@article{osti_1456955,
title = {The Reactive–Diffusive Length of OH and Ozone in Model Organic Aerosols},
author = {Lee, Lance and Wilson, Kevin},
abstractNote = {We report that a key step in the heterogeneous oxidation of atmospheric aerosols is the reaction of ozone (O3) and hydroxyl radicals (OH) at the gas–particle interface. The formation of reaction products and free radical intermediates and their spatial distribution inside the particle is a sensitive function of the length over which these oxidants diffuse prior to reaction. The reactive–diffusive length of OH and ozone at organic aerosol interfaces is determined by observing the change in the effective uptake coefficient for size-selected model aerosols comprising a reactive core and a thin nanometer-sized (0–12 nm) organic shell. The core and shell materials are selected so that they are immiscible and adopt an assumed core–shell configuration. The results indicate a reactive–diffusive length of 1.4 nm for hydroxyl (OH) radicals in squalane and 1.0 nm for ozone in squalene. Measurements for a purely diffusive system allow for an estimate for diffusion constant (1.6 × 10-6 cm2/s) of ozone in squalane to be determined. In conclusion, the reactive–diffusive length offers a simple first order estimate of how shielding of aerosols by immiscible layers can alter estimates of oxidative lifetimes of aerosols in the atmosphere.},
doi = {10.1021/acs.jpca.6b05285},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 34,
volume = 120,
place = {United States},
year = {Wed Aug 10 00:00:00 EDT 2016},
month = {Wed Aug 10 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 28 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass: GASOLINE DOMINATES SOA FORMATION
journal, March 2012

  • Bahreini, R.; Middlebrook, A. M.; de Gouw, J. A.
  • Geophysical Research Letters, Vol. 39, Issue 6
  • DOI: 10.1029/2011GL050718

Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions
journal, October 2012

  • Gentner, D. R.; Isaacman, G.; Worton, D. R.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 45
  • DOI: 10.1073/pnas.1212272109

Enhanced SOA formation from mixed anthropogenic and biogenic emissions during the CARES campaign
journal, January 2013

  • Shilling, J. E.; Zaveri, R. A.; Fast, J. D.
  • Atmospheric Chemistry and Physics, Vol. 13, Issue 4
  • DOI: 10.5194/acp-13-2091-2013

Lubricating Oil Dominates Primary Organic Aerosol Emissions from Motor Vehicles
journal, March 2014

  • Worton, David R.; Isaacman, Gabriel; Gentner, Drew R.
  • Environmental Science & Technology, Vol. 48, Issue 7
  • DOI: 10.1021/es405375j

A chemical kinetic model for reactive transformations of aerosol particles: REACTIVE TRANSFORMATION OF AEROSOL PARTICLES
journal, October 2002

  • Worsnop, D. R.; Morris, J. W.; Shi, Q.
  • Geophysical Research Letters, Vol. 29, Issue 20
  • DOI: 10.1029/2002GL015542

Reactive Uptake of Ozone by Aerosol-Associated Unsaturated Fatty Acids:  Kinetics, Mechanism, and Products
journal, July 2002

  • Moise, Tamar; Rudich, Yinon
  • The Journal of Physical Chemistry A, Vol. 106, Issue 27
  • DOI: 10.1021/jp025597e

Reactive Uptake of O 3 by Multicomponent and Multiphase Mixtures Containing Oleic Acid
journal, June 2005

  • Knopf, Daniel A.; Anthony, Lori M.; Bertram, Allan K.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 25
  • DOI: 10.1021/jp0512513

Toxicity of aged gasoline exhaust particles to normal and diseased airway epithelia
journal, June 2015

  • Künzi, Lisa; Krapf, Manuel; Daher, Nancy
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep11801

Quantifying the reactive uptake of OH by organic aerosols in a continuous flow stirred tank reactor
journal, January 2009

  • Che, Dung L.; Smith, Jared D.; Leone, Stephen R.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 36
  • DOI: 10.1039/b904418c

Collision dynamics and reactive uptake of OH radicals at liquid surfaces of atmospheric interest
journal, January 2011

  • Waring, Carla; King, Kerry L.; Bagot, Paul A. J.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 18
  • DOI: 10.1039/c0cp02734k

Reactive uptake kinetics of NO3 on multicomponent and multiphase organic mixtures containing unsaturated and saturated organics
journal, January 2011

  • Xiao, S.; Bertram, A. K.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 14
  • DOI: 10.1039/c0cp02682d

Observation of rates and products in the reaction of NO 3 with submicron squalane and squalene aerosol
journal, January 2013

  • Lee, Lance; Wooldridge, Paul; Nah, Theodora
  • Phys. Chem. Chem. Phys., Vol. 15, Issue 3
  • DOI: 10.1039/C2CP42500A

Ozonolysis of oleic acid particles: evidence for a surface reaction and secondary reactions involving Criegee intermediates
journal, January 2005

  • Hearn, John D.; Lovett, Amanda J.; Smith, Geoffrey D.
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 3
  • DOI: 10.1039/b414472d

Infrared spectroscopic studies of the heterogeneous reaction of ozone with dry maleic and fumaric acid aerosol particles
journal, January 2009

  • Nájera, Juan J.; Percival, Carl J.; Horn, Andrew B.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 40
  • DOI: 10.1039/b909623j

Kinetic studies of the heterogeneous oxidation of maleic and fumaric acid aerosols by ozone under conditions of high relative humidity
journal, January 2010

  • Nájera, Juan J.; Percival, Carl J.; Horn, Andrew B.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 37
  • DOI: 10.1039/b924775k

Reactive uptake of NO 3 by liquid and frozen organics
journal, January 2002


Burial Effects of Organic Coatings on the Heterogeneous Reactivity of Particle-Borne Benzo[ a ]pyrene (BaP) toward Ozone
journal, June 2012

  • Zhou, S.; Lee, A. K. Y.; McWhinney, R. D.
  • The Journal of Physical Chemistry A, Vol. 116, Issue 26
  • DOI: 10.1021/jp3030705

Kinetic limitations in gas-particle reactions arising from slow diffusion in secondary organic aerosol
journal, January 2013

  • Zhou, Shouming; Shiraiwa, Manabu; McWhinney, Robert D.
  • Faraday Discuss., Vol. 165
  • DOI: 10.1039/C3FD00030C

OH-Initiated Heterogeneous Oxidation of Internally-Mixed Squalane and Secondary Organic Aerosol
journal, March 2014

  • Kolesar, Katheryn R.; Buffaloe, Gina; Wilson, Kevin R.
  • Environmental Science & Technology, Vol. 48, Issue 6
  • DOI: 10.1021/es405177d

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
  • DOI: 10.5194/acp-9-3209-2009

Role of Water and Phase in the Heterogeneous Oxidation of Solid and Aqueous Succinic Acid Aerosol by Hydroxyl Radicals
journal, March 2014

  • Chan, Man Nin; Zhang, Haofei; Goldstein, Allen H.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 50
  • DOI: 10.1021/jp5012022

Deliquescence behaviour and crystallisation of ternary ammonium sulfate/dicarboxylic acid/water aerosols
journal, January 2009

  • Treuel, L.; Pederzani, S.; Zellner, R.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 36
  • DOI: 10.1039/b905007h

Temperature-dependent ozonolysis kinetics of selected alkenes in the gas phase: an experimental and structure–activity relationship (SAR) study
journal, January 2010

  • Leather, Kimberley E.; McGillen, Max R.; Percival, Carl J.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 12
  • DOI: 10.1039/b919731a

Reaction between ozone and allene in the gas phase
journal, May 1974

  • Toby, Frina S.; Toby, Sidney
  • International Journal of Chemical Kinetics, Vol. 6, Issue 3
  • DOI: 10.1002/kin.550060311

Tracer diffusion in polyatomic liquids
journal, January 1981

  • Evans, D. F.; Tominaga, T.; Davis, H. T.
  • The Journal of Chemical Physics, Vol. 74, Issue 2
  • DOI: 10.1063/1.441190

Reference Correlation of the Viscosity of Squalane from 273 to 373 K at 0.1 MPa
journal, September 2013

  • Comuñas, M. J. P.; Paredes, X.; Gaciño, F. M.
  • Journal of Physical and Chemical Reference Data, Vol. 42, Issue 3
  • DOI: 10.1063/1.4812573

Density of Liquid Ozone
journal, October 1957

  • Brabets, Robert I.; McDonough, John M.
  • The Journal of Chemical Physics, Vol. 27, Issue 4
  • DOI: 10.1063/1.1743870

Diffusion of Squalene in n -Alkanes and Squalane
journal, February 2014

  • Kowert, Bruce A.; Watson, Michael B.; Dang, Nhan C.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 8
  • DOI: 10.1021/jp411471r

Reactions of ozone with double bonds in polymer and biosystem chemistry
journal, December 2008


The Kinetics of Tetramethylethene Ozonolysis: Decomposition of the Primary Ozonide and Subsequent Product Formation in the Condensed Phase
journal, December 2008

  • Epstein, Scott A.; Donahue, Neil M.
  • The Journal of Physical Chemistry A, Vol. 112, Issue 51
  • DOI: 10.1021/jp807682y

Theoretical study of the reactions of Criegee intermediates with ozone, alkylhydroperoxides, and carbon monoxide
journal, January 2015

  • Vereecken, L.; Rickard, A. R.; Newland, M. J.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/C5CP03862F

Ozone Interaction with Polycyclic Aromatic Hydrocarbons and Soot in Atmospheric Processes:  Theoretical Density Functional Study by Molecular and Periodic Methodologies
journal, December 2005

  • Maranzana, Andrea; Serra, Giovanni; Giordana, Anna
  • The Journal of Physical Chemistry A, Vol. 109, Issue 48
  • DOI: 10.1021/jp053672q

Relative Rate and Product Studies of the OH−Acetone Reaction
journal, June 2005

  • Raff, Jonathan D.; Stevens, Philip S.; Hites, Ronald A.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 21
  • DOI: 10.1021/jp0501547

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
  • DOI: 10.1021/es101465m

Role of Water in the Physical Stability of Solid Dosage Formulations
journal, October 2005

  • Airaksinen, Sari; Karjalainen, Milja; Shevchenko, Anna
  • Journal of Pharmaceutical Sciences, Vol. 94, Issue 10
  • DOI: 10.1002/jps.20411

Characteristics of erythritol and formulation of a novel coating with erythritol termed thin-layer sugarless coating
journal, July 2004


Tracer Diffusion of Water in Organic Liquids
journal, January 1996

  • Easteal, Allan J.
  • Journal of Chemical & Engineering Data, Vol. 41, Issue 4
  • DOI: 10.1021/je9600109

Низкая селективность реакций Oh-радикалов с алканами в водных растворах
journal, June 1981

  • Рудаков, Э. С.; Волкова, Л. К.; Третьяков, В. П.
  • Reaction Kinetics and Catalysis Letters, Vol. 16, Issue 4
  • DOI: 10.1007/BF02066586

Compilation of Henry's law constants (version 4.0) for water as solvent
journal, January 2015


Ozone Solubility in Liquids
journal, May 2006


Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species
journal, January 2006

  • Atkinson, R.; Baulch, D. L.; Cox, R. A.
  • Atmospheric Chemistry and Physics, Vol. 6, Issue 11
  • DOI: 10.5194/acp-6-3625-2006

Measurement and Prediction of Oxygen Solubility in Toluene at Temperatures from 298.45 K to 393.15 K and Pressures up to 1.0 MPa
journal, September 2007

  • Li, Airong; Tang, Shengwei; Tan, Pinghua
  • Journal of Chemical & Engineering Data, Vol. 52, Issue 6
  • DOI: 10.1021/je700330c

The mechanism and rate parameters for the pyrolysis ofn-hexane in the range 723-823 K
journal, February 1987

  • Imbert, Freddy E.; Marshall, Roger M.
  • International Journal of Chemical Kinetics, Vol. 19, Issue 2
  • DOI: 10.1002/kin.550190202

Autoxidation of Organic Compounds in the Atmosphere
journal, September 2013

  • Crounse, John D.; Nielsen, Lasse B.; Jørgensen, Solvejg
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 20
  • DOI: 10.1021/jz4019207

Generation and chemistry of cyclohexyloxy radicals
journal, December 1985

  • Druliner, J. D.; Krusic, P. J.; Lehr, G. F.
  • The Journal of Organic Chemistry, Vol. 50, Issue 26
  • DOI: 10.1021/jo00350a078

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
  • DOI: 10.1039/c2cs35166h

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
  • DOI: 10.1139/v73-131

Intramolecular H-transfer reactions during the Decomposition of Alkylhydroperoxides in hydrocarbons as the solvents
journal, January 1994

  • Jinsheng, Li; Pritzkow, Wilhelm; Voerckel, Volkmar
  • Journal f�r Praktische Chemie/Chemiker-Zeitung, Vol. 336, Issue 1
  • DOI: 10.1002/prac.19943360109

Stochastic methods for aerosol chemistry: a compact molecular description of functionalization and fragmentation in the heterogeneous oxidation of squalane aerosol by OH radicals
journal, January 2015

  • Wiegel, A. A.; Wilson, K. R.; Hinsberg, W. D.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 6
  • DOI: 10.1039/C4CP04927F

Nanoscale interfacial gradients formed by the reactive uptake of OH radicals onto viscous aerosol surfaces
journal, January 2015

  • Davies, James F.; Wilson, Kevin R.
  • Chemical Science, Vol. 6, Issue 12
  • DOI: 10.1039/C5SC02326B

Natural radionuclides in fine aerosols in the Pittsburgh area
journal, June 2004


Works referencing / citing this record:

Heterogeneous OH oxidation of secondary brown carbon aerosol
journal, January 2018

  • Schnitzler, Elijah G.; Abbatt, Jonathan P. D.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 19
  • DOI: 10.5194/acp-18-14539-2018

Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone
journal, January 2019

  • Alpert, Peter A.; Corral Arroyo, Pablo; Dou, Jing
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 37
  • DOI: 10.1039/c9cp03731d

Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry
journal, January 2019


Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone
text, January 2019