dc.contributor.author | Murphy, B. N. | |
dc.contributor.author | Donahue, N. M. | |
dc.contributor.author | Fountoukis, C. | |
dc.contributor.author | Dall'Osto, M. | |
dc.contributor.author | O'Dowd, C. | |
dc.contributor.author | Kiendler-Scharr, A. | |
dc.contributor.author | Pandis, S. N. | |
dc.date.accessioned | 2018-09-20T16:18:41Z | |
dc.date.available | 2018-09-20T16:18:41Z | |
dc.date.issued | 2012-11-16 | |
dc.identifier.citation | Murphy, B. N. Donahue, N. M.; Fountoukis, C.; Dall'Osto, M.; O'Dowd, C.; Kiendler-Scharr, A.; Pandis, S. N. (2012). Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-d volatility basis set to field studies. Atmospheric Chemistry and Physics 12 (22), 10797-10816 | |
dc.identifier.issn | 1680-7324 | |
dc.identifier.uri | http://hdl.handle.net/10379/13031 | |
dc.description.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. | |
dc.publisher | Copernicus GmbH | |
dc.relation.ispartof | Atmospheric Chemistry and Physics | |
dc.rights | Attribution-NonCommercial-NoDerivs 3.0 Ireland | |
dc.rights.uri | https://creativecommons.org/licenses/by-nc-nd/3.0/ie/ | |
dc.subject | chemical-transport model | |
dc.subject | quality interactions eucaari | |
dc.subject | european integrated project | |
dc.subject | wild-land fires | |
dc.subject | air-quality | |
dc.subject | measurement experiment-2008 | |
dc.subject | biogenic hydrocarbons | |
dc.subject | airborne measurements | |
dc.subject | mass-spectrometry | |
dc.subject | global scales | |
dc.title | Functionalization and fragmentation during ambient organic aerosol aging: application of the 2-d volatility basis set to field studies | |
dc.type | Article | |
dc.identifier.doi | 10.5194/acp-12-10797-2012 | |
dc.local.publishedsource | https://www.atmos-chem-phys.net/12/10797/2012/acp-12-10797-2012.pdf | |
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