Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

Jingyi Li; Jingqiu Mao; Kyung-Eun Min; Rebecca A Washenfelder; Steven S Brown; Jennifer Kaiser; Frank N Keutsch; Rainer Volkamer; Glenn M Wolfe; Thomas F Hanisco; Ilana B Pollack; Thomas B Ryerson; Martin Graus; Jessica B Gilman; Brian M Lerner; Carsten Warneke; Joost A de Gouw; Ann M Middlebrook; Jin Liao; André Welti; Barron H Henderson; V Faye McNeill; Samuel R Hall; Kirk Ullmann; Leo J Donner; Fabien Paulot; Larry W Horowitz

doi:10.1002/2016JD025331

Observational constraints on glyoxal production from isoprene oxidation and its contribution to organic aerosol over the Southeast United States

J Geophys Res Atmos. 2016 Aug 27;121(16):9849-9861. doi: 10.1002/2016JD025331. Epub 2016 Jul 31.

Authors

Jingyi Li¹, Jingqiu Mao^{1

2}, Kyung-Eun Min^{3

4}, Rebecca A Washenfelder^{3

4}, Steven S Brown^{3

5}, Jennifer Kaiser⁶, Frank N Keutsch⁷, Rainer Volkamer^{4

5}, Glenn M Wolfe^{8

9}, Thomas F Hanisco⁹, Ilana B Pollack¹⁰, Thomas B Ryerson³, Martin Graus^{3

4}, Jessica B Gilman^{3

4}, Brian M Lerner^{3

4}, Carsten Warneke^{3

4}, Joost A de Gouw^{3

4}, Ann M Middlebrook³, Jin Liao^{3

4}, André Welti^{3

4}, Barron H Henderson¹¹, V Faye McNeill¹², Samuel R Hall¹³, Kirk Ullmann¹³, Leo J Donner², Fabien Paulot^{1

2}, Larry W Horowitz²

Affiliations

¹ Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, New Jersey, USA.
² Geophysical Fluid Dynamics Laboratory/National Oceanic and Atmospheric Administration, Princeton, New Jersey, USA.
³ Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, Colorado, USA.
⁴ Cooperative Institute for Research in Environmental Sciences, University of Colorado Boulder, Boulder, Colorado, USA.
⁵ Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, USA.
⁶ Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA.
⁷ School of Engineering and Applied Sciences and Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, USA.
⁸ Joint Center for Earth System Technology, University of Maryland Baltimore County, Baltimore, Maryland, USA.
⁹ Atmospheric Chemistry and Dynamics Lab, NASA Goddard Space Flight Center, Greenbelt, Maryland, USA.
¹⁰ Department of Atmospheric Science, Colorado State University, Fort Collins, Colorado, USA.
¹¹ Department of Environmental Engineering Sciences, Engineering School of Sustainable Infrastructure and Environment, University of Florida, Gainesville, Florida, USA.
¹² Department of Chemical Engineering, Columbia University, New York, New York, USA.
¹³ Atmospheric Chemistry Observation and Modeling Laboratory, National Center for Atmospheric Research, Boulder, Colorado, USA.

Abstract

We use a 0-D photochemical box model and a 3-D global chemistry-climate model, combined with observations from the NOAA Southeast Nexus (SENEX) aircraft campaign, to understand the sources and sinks of glyoxal over the Southeast United States. Box model simulations suggest a large difference in glyoxal production among three isoprene oxidation mechanisms (AM3ST, AM3B, and MCM v3.3.1). These mechanisms are then implemented into a 3-D global chemistry-climate model. Comparison with field observations shows that the average vertical profile of glyoxal is best reproduced by AM3ST with an effective reactive uptake coefficient γ_glyx of 2 × 10^-3, and AM3B without heterogeneous loss of glyoxal. The two mechanisms lead to 0-0.8 μg m^-3 secondary organic aerosol (SOA) from glyoxal in the boundary layer of the Southeast U.S. in summer. We consider this to be the lower limit for the contribution of glyoxal to SOA, as other sources of glyoxal other than isoprene are not included in our model. In addition, we find that AM3B shows better agreement on both formaldehyde and the correlation between glyoxal and formaldehyde (R_GF = [GLYX]/[HCHO]), resulting from the suppression of δ-isoprene peroxy radicals (δ-ISOPO₂). We also find that MCM v3.3.1 may underestimate glyoxal production from isoprene oxidation, in part due to an underestimated yield from the reaction of IEPOX peroxy radicals (IEPOXOO) with HO₂. Our work highlights that the gas-phase production of glyoxal represents a large uncertainty in quantifying its contribution to SOA.