References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-7169-2010

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

Chan

A. W. H.

¹ Chan

M. N.

² Surratt

J. D.

¹ ⁴ Chhabra

P. S.

¹ Loza

C. L.

¹ Crounse

J. D.

¹ Yee

L. D.

² Flagan

R. C.

¹ ² Wennberg

P. O.

² ³ Seinfeld

J. H.

¹ ²

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA

Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA

now at: Department of Environmental Sciences and Engineering, The University of North Carolina at Chapel Hill, Chapel Hill, NC, USA

04 08 2010

10 15 7169 7188

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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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 C4-unsaturated aldehyde) under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/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-NO2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO2) formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3–8), the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

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