A Caltech Library Service

Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation

Chan, A. W. H. and Chan, M. N. and Surratt, J. D. and Chhabra, P. S. and Loza, C. L. and Crounse, J. D. and Yee, L. D. and Flagan, R. C. and Wennberg, P. O. and Seinfeld, J. H. (2010) Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation. Atmospheric Chemistry and Physics, 10 (15). pp. 7169-7188. ISSN 1680-7316. doi:10.5194/acp-10-7169-2010.

PDF - Published Version
Creative Commons Attribution.

[img] PDF - Supplemental Material
Creative Commons Attribution.


Use this Persistent URL to link to this item:


Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C_4-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO_2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO_2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO_2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO_2) formation is structurally unfavorable. At atmospherically relevant NO_2/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO_2/NO ratios. At sufficiently high NO_2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO_2 can exceed that from RO_2+HO_2 reactions under the same inorganic seed conditions, making RO_2+NO_2 an important channel for SOA formation.

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Chan, A. W. H.0000-0001-7392-4237
Chan, M. N.0000-0002-2384-2695
Surratt, J. D.0000-0002-6833-1450
Crounse, J. D.0000-0001-5443-729X
Flagan, R. C.0000-0001-5690-770X
Wennberg, P. O.0000-0002-6126-3854
Seinfeld, J. H.0000-0003-1344-4068
Additional Information:© Author(s) 2010. This work is distributed under the Creative Commons Attribution 3.0 License. Received: 7 April 2010 – Published in Atmos. Chem. Phys. Discuss.: 19 April 2010. Revised: 13 July 2010 – Accepted: 16 July 2010 – Published: 4 August 2010. This research was funded by US Department of Energy Biological and Environmental Research Program DE-FG02-05ER63983, US Environmental Protection Agency STAR grant RD-83374901, US National Science Foundation grant ATM-0432377, and the Electric Power Research Institute. This publication has not been formally reviewed by the EPA. The views expressed in this document are solely those of the authors and EPA does not endorse any products mentioned in this publication. The authors would like to thank K. E. Kautzman and A. J. Kwan for experimental assistance, and F. Paulot for helpful discussion. Edited by: M. Gysel.
Funding AgencyGrant Number
Department of Energy (DOE)DE-FG02-05ER63983
Environmental Protection Agency (EPA)RD-83374901
Electric Power Research Institute (EPRI)UNSPECIFIED
Issue or Number:15
Record Number:CaltechAUTHORS:20100915-133230350
Persistent URL:
Official Citation:Chan, A. W. H., Chan, M. N., Surratt, J. D., Chhabra, P. S., Loza, C. L., Crounse, J. D., Yee, L. D., Flagan, R. C., Wennberg, P. O., and Seinfeld, J. H.: Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation, Atmos. Chem. Phys., 10, 7169-7188, doi:10.5194/acp-10-7169-2010, 2010
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:19974
Deposited By: Tony Diaz
Deposited On:15 Sep 2010 20:48
Last Modified:08 Nov 2021 23:56

Repository Staff Only: item control page