References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-8883-2011

Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007

Huisman

A. J.

¹ ⁹ Hottle

J. R.

¹ ¹⁰ Galloway

M. M.

¹ ¹¹ DiGangi

J. P.

¹ Coens

K. L.

¹ ¹² Choi

² ¹³ Faloona

I. C.

² Gilman

J. B.

³ Kuster

W. C.

³ de Gouw

³ Bouvier-Brown

N. C.

⁴ ¹⁴ Goldstein

A. H.

⁴ LaFranchi

B. W.

⁵ ¹⁵ Cohen

R. C.

⁵ Wolfe

G. M.

⁶ ¹⁶ Thornton

J. A.

⁶ Docherty

K. S.

⁷ ¹⁷ Farmer

D. K.

⁷ ¹⁸ Cubison

M. J.

⁷ Jimenez

J. L.

⁷ Mao

⁸ ¹⁹ Brune

W. H.

⁸ Keutsch

F. N.

Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA

Department of Land, Air, and Water Resources, Univ. of California-Davis, Davis, California, USA

NOAA Earth System Research Laboratory and Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado, USA

Department of Environmental Science, Policy, and Management, University of California, Berkeley, California, USA

Department of Chemistry, University of California, Berkeley, California, USA

Department of Chemistry, University of Washington, Seattle, Washington, USA

CIRES and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, USA

Department of Meteorology, Pennsylvania State University, University Park, Pennsylvania, USA

now at: Institute for Atmospheric and Climate Science, ETH Zurich, Zurich, Switzerland

now at: Air Force Office of Scientific Research-Physics and Electronics Directorate, Arlington, Virginia, USA

now at: Chemistry Department, Reed College, Portland, Oregon, USA

now at: Air Force Space and Missile Systems Center Weather Directorate, Los Angeles, California, USA

now at: Department of Atmospheric and Oceanic Sciences, University of California, Los Angeles, Los Angeles, California, USA

now at: Chemistry & Biochemistry Department, Loyola Marymount University, Los Angeles, California, USA

now at: Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, California, USA

now at: Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA

now at: Alion Science and Technology and EPA Office of Research and Development, Research Triangle Park, North Carolina, USA

now at: Department of Chemistry, Colorado State University, Fort Collins, Colorado, USA

now at: Program in Atmospheric and Oceanic Sciences, Princeton University, Princeton, New Jersey, USA

01 09 2011

11 17 8883 8897

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.

This article is available from http://www.atmos-chem-phys.net/11/8883/2011/acp-11-8883-2011.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/8883/2011/acp-11-8883-2011.pdf

We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs); thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods. A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %), followed by isoprene (~26 %) and methylchavicol (~6 %), a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This relationship arises from (i) the predominantly secondary- or higher-generation production of glyoxal from (mainly OH-driven, rather than O3-driven) BVOC oxidation at this site and (ii) the relative importance of photolysis in glyoxal loss as compared to reaction with OH. We propose that glyoxal is a useful tracer for OH-driven BVOC oxidation chemistry.

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