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SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data

McVay, Renee C. and Zhang, Xuan and Aumont, Bernard and Valorso, Richard and Camredon, Marie and La, Yuyi S. and Wennberg, Paul O. and Seinfeld, John H. (2016) SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data. Atmospheric Chemistry and Physics, 16 (5). pp. 2785-2802. ISSN 1680-7324. https://resolver.caltech.edu/CaltechAUTHORS:20160610-123722476

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Abstract

Chemical mechanisms play an important role in simulating the atmospheric chemistry of volatile organic compound oxidation. Comparison of mechanism simulations with laboratory chamber data tests our level of understanding of the prevailing chemistry as well as the dynamic processes occurring in the chamber itself. α-Pinene photooxidation is a well-studied system experimentally, for which detailed chemical mechanisms have been formulated. Here, we present the results of simulating low-NO α-pinene photooxidation experiments conducted in the Caltech chamber with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) under varying concentrations of seed particles and OH levels. Unexpectedly, experiments conducted at low and high OH levels yield the same secondary organic aerosol (SOA) growth, whereas GECKO-A predicts greater SOA growth under high OH levels. SOA formation in the chamber is a result of a competition among the rates of gas-phase oxidation to low-volatility products, wall deposition of these products, and condensation into the aerosol phase. Various processes – such as photolysis of condensed-phase products, particle-phase dimerization, and peroxy radical autoxidation – are explored to rationalize the observations. In order to explain the observed similar SOA growth at different OH levels, we conclude that vapor wall loss in the Caltech chamber is likely of order 10^(−5) s^(−1), consistent with previous experimental measurements in that chamber. We find that GECKO-A tends to overpredict the contribution to SOA of later-generation oxidation products under high-OH conditions. Moreover, we propose that autoxidation may alternatively resolve some or all of the measurement–model discrepancy, but this hypothesis cannot be confirmed until more explicit mechanisms are established for α-pinene autoxidation. The key role of the interplay among oxidation rate, product volatility, and vapor–wall deposition in chamber experiments is illustrated.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.5194/acp-16-2785-2016DOIArticle
http://www.atmos-chem-phys.net/16/2785/2016/PublisherArticle
http://www.atmos-chem-phys.net/16/2785/2016/acp-16-2785-2016-supplement.pdfPublisherSupplementary Information
ORCID:
AuthorORCID
McVay, Renee C.0000-0001-7766-5009
Wennberg, Paul O.0000-0002-6126-3854
Seinfeld, John H.0000-0003-1344-4068
Additional Information:© Author(s) 2016. This work is distributed under the Creative Commons Attribution 3.0 License. Received: 2 November 2015 – Published in Atmos. Chem. Phys. Discuss.: 25 November 2015. Revised: 17 February 2016 – Accepted: 23 February 2016 – Published: 4 March 2016. This work was supported by National Science Foundation grant AGS-1523500. Renee C. McVay acknowledges support by a National Science Foundation Graduate Research Fellowship under grant no. DGE-1144469. Bernard Aumont acknowledges support from the French National Research Agency (ANR) under the MAGNIFY project (ANR-14-CE01-0010).
Funders:
Funding AgencyGrant Number
NSFAGS-1523500
NSF Graduate Research FellowshipDGE-1144469
Agence Nationale pour la Recherche (ANR)ANR-14-CE01-0010
Issue or Number:5
Record Number:CaltechAUTHORS:20160610-123722476
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160610-123722476
Official Citation:McVay, R. C., Zhang, X., Aumont, B., Valorso, R., Camredon, M., La, Y. S., Wennberg, P. O., and Seinfeld, J. H.: SOA formation from the photooxidation of α-pinene: systematic exploration of the simulation of chamber data, Atmos. Chem. Phys., 16, 2785-2802, doi:10.5194/acp-16-2785-2016, 2016.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67840
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:10 Jun 2016 19:47
Last Modified:03 Oct 2019 10:09

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