Atmos. Chem. Phys. Discuss., 11, 12725-12762, 2011
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Observations of hydroxyl and peroxy radicals and the impact of BrO at Summit, Greenland in 2007 and 2008
J. Liao1, L. G. Huey1, D. J. Tanner1, S. Brooks2, J. E. Dibb3, J. Stutz4, J. L. Thomas4,*, B. Lefer5, C. Haman5, and K. Gorham6
1School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA
2NOAA Atmospheric Turbulence and Diffusion Division, TN, USA
3Climate Change Research Center, Institute for the Study of Earth, Oceans and Space, University of New Hampshire, Durham, NH, USA
4University of California Los Angeles, Department of Atmosphere Ocean Science, Los Angeles, CA, USA
5Department of Geosciences, University of Houston, TX, USA
6Chemistry, University of California, Irvine, California, USA
*now at: UPMC Univ. Paris 06; Université Versailles St-Quentin; CNRS/INSU, UMR 8190; LATMOS-IPSL, Paris, France

Abstract. The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring~2007 and summer~2008 to investigate the impact of halogens on HOx (=OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + ROx), ozone (O3), nitrogen oxide (NO), nitric acid (HNO2), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer~2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly change the predictions. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2+RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.

Citation: Liao, J., Huey, L. G., Tanner, D. J., Brooks, S., Dibb, J. E., Stutz, J., Thomas, J. L., Lefer, B., Haman, C., and Gorham, K.: Observations of hydroxyl and peroxy radicals and the impact of BrO at Summit, Greenland in 2007 and 2008, Atmos. Chem. Phys. Discuss., 11, 12725-12762, doi:10.5194/acpd-11-12725-2011, 2011.
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