1Department of Environmental Science and Engineering, University of North Carolina, Chapel Hill, NC, USA
2National Exposure Research Laboratory, US Environmental Protection Agency (USEPA), RTP, NC, USA
3National Health and Environmental Effects Research Laboratory, US Environmental Protection Agency (USEPA), RTP, NC, USA
4Departments of Chemistry and Earth and Planetary Sciences, University of California, Berkeley, CA, USA
5Department of Environmental Sciences, Rutgers, New Brunswick, NJ, USA
Received: 18 Jul 2011 – Discussion started: 29 Aug 2011
Abstract. Tropospheric ozone is the third strongest greenhouse gas, and has the highest uncertainty in radiative forcing of the top five greenhouse gases. Throughout the troposphere, ozone is produced by radical oxidation of nitrogen oxides (NOx = NO + NO2). In the upper troposphere (8–10 km), current chemical transport models under-estimate nitrogen dioxide (NO2) observations. Improvements to simulated NOx production from lightning have increased NO2 predictions, but the predictions in the upper troposphere remain biased low. The upper troposphere has low temperatures (T < 250 K) that increase the uncertainty of many important chemical reaction rates. This study constrains uncertain reaction rates by combining model predictions with measurements from the Intercontinental Chemical Transport Experiment-North America observational campaign. The results show that the nitric acid formation rate, which is the dominant sink of NO2 and radicals, is currently over-estimated by 22% in the upper troposphere. The results from this study suggest that the temperature sensitivity of nitric acid formation is lower than currently recommended. Since the formation of nitric acid removes nitrogen dioxide and radicals that drive the production of ozone, the revised reaction rate will affect ozone concentrations in upper troposphere impacting climate and air quality in the lower troposphere.
Revised: 06 Dec 2011 – Accepted: 05 Jan 2012 – Published: 16 Jan 2012
Henderson, B. H., Pinder, R. W., Crooks, J., Cohen, R. C., Carlton, A. G., Pye, H. O. T., and Vizuete, W.: Combining Bayesian methods and aircraft observations to constrain the HO. + NO2 reaction rate, Atmos. Chem. Phys., 12, 653-667, doi:10.5194/acp-12-653-2012, 2012.