Functionalization and fragmentation during ambient organic aerosol aging

Application of the 2-D volatility basis set to field studies

B. N. Murphy, N. M. Donahue, Christos Fountoukis, M. Dall'Osto, C. O'Dowd, A. Kiendler-Scharr, S. N. Pandis

Research output: Contribution to journalArticle

47 Citations (Scopus)

Abstract

Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

Original languageEnglish
Pages (from-to)10797-10816
Number of pages20
JournalAtmospheric Chemistry and Physics
Volume12
Issue number22
DOIs
Publication statusPublished - 2012
Externally publishedYes

Fingerprint

fragmentation
aerosol
oxidation
organic compound
oxygen
volcanic cloud
hydroxyl radical
volatility
field study
parameterization
air quality
chemical composition
saturation
winter
carbon
climate
summer
gas
effect

ASJC Scopus subject areas

  • Atmospheric Science

Cite this

Functionalization and fragmentation during ambient organic aerosol aging : Application of the 2-D volatility basis set to field studies. / Murphy, B. N.; Donahue, N. M.; Fountoukis, Christos; Dall'Osto, M.; O'Dowd, C.; Kiendler-Scharr, A.; Pandis, S. N.

In: Atmospheric Chemistry and Physics, Vol. 12, No. 22, 2012, p. 10797-10816.

Research output: Contribution to journalArticle

Murphy, B. N. ; Donahue, N. M. ; Fountoukis, Christos ; Dall'Osto, M. ; O'Dowd, C. ; Kiendler-Scharr, A. ; Pandis, S. N. / Functionalization and fragmentation during ambient organic aerosol aging : Application of the 2-D volatility basis set to field studies. In: Atmospheric Chemistry and Physics. 2012 ; Vol. 12, No. 22. pp. 10797-10816.
@article{0d6e5f564fad4eeabc0945df17549021,
title = "Functionalization and fragmentation during ambient organic aerosol aging: Application of the 2-D volatility basis set to field studies",
abstract = "Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55{\%} and 25{\%}, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.",
author = "Murphy, {B. N.} and Donahue, {N. M.} and Christos Fountoukis and M. Dall'Osto and C. O'Dowd and A. Kiendler-Scharr and Pandis, {S. N.}",
year = "2012",
doi = "10.5194/acp-12-10797-2012",
language = "English",
volume = "12",
pages = "10797--10816",
journal = "Atmospheric Chemistry and Physics",
issn = "1680-7316",
publisher = "European Geosciences Union",
number = "22",

}

TY - JOUR

T1 - Functionalization and fragmentation during ambient organic aerosol aging

T2 - Application of the 2-D volatility basis set to field studies

AU - Murphy, B. N.

AU - Donahue, N. M.

AU - Fountoukis, Christos

AU - Dall'Osto, M.

AU - O'Dowd, C.

AU - Kiendler-Scharr, A.

AU - Pandis, S. N.

PY - 2012

Y1 - 2012

N2 - Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

AB - Multigenerational oxidation chemistry of atmospheric organic compounds and its effects on aerosol loadings and chemical composition is investigated by implementing the Two-Dimensional Volatility Basis Set (2-D-VBS) in a Lagrangian host chemical transport model. Three model formulations were chosen to explore the complex interactions between functionalization and fragmentation processes during gas-phase oxidation of organic compounds by the hydroxyl radical. The base case model employs a conservative transformation by assuming a reduction of one order of magnitude in effective saturation concentration and an increase of oxygen content by one or two oxygen atoms per oxidation generation. A second scheme simulates functionalization in more detail using group contribution theory to estimate the effects of oxygen addition to the carbon backbone on the compound volatility. Finally, a fragmentation scheme is added to the detailed functionalization scheme to create a functionalization-fragmentation parameterization. Two condensed-phase chemistry pathways are also implemented as additional sensitivity tests to simulate (1) heterogeneous oxidation via OH uptake to the particle-phase and (2) aqueous-phase chemistry of glyoxal and methylglyoxal. The model is applied to summer and winter periods at three sites where observations of organic aerosol (OA) mass and O:C were obtained during the European Integrated Project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaigns. The base case model reproduces observed mass concentrations and O:C well, with fractional errors (FE) lower than 55% and 25%, respectively. The detailed functionalization scheme tends to overpredict OA concentrations, especially in the summertime, and also underpredicts O:C by approximately a factor of 2. The detailed functionalization model with fragmentation agrees well with the observations for OA concentration, but still underpredicts O:C. Both heterogeneous oxidation and aqueous-phase processing have small effects on OA levels but heterogeneous oxidation, as implemented here, does enhance O:C by about 0.1. The different schemes result in very different fractional attribution for OA between anthropogenic and biogenic sources.

UR - http://www.scopus.com/inward/record.url?scp=84869194060&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84869194060&partnerID=8YFLogxK

U2 - 10.5194/acp-12-10797-2012

DO - 10.5194/acp-12-10797-2012

M3 - Article

VL - 12

SP - 10797

EP - 10816

JO - Atmospheric Chemistry and Physics

JF - Atmospheric Chemistry and Physics

SN - 1680-7316

IS - 22

ER -