ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-275-2011 Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere Henderson B. H. 1 2 Pinder R. W. 2 Crooks J. 2 Cohen R. C. 3 Hutzell W. T. 2 Sarwar G. 2 Goliff W. S. 4 Stockwell W. R. 5 Fahr A. 5 Mathur R. 2 Carlton A. G. 6 Vizuete W. 1 Department of Environmental Science and Engineering, University of North Carolina, Chapel Hill, NC, USA National Exposure Research Laboratory, US Environmental Protection Agency (USEPA), RTP, NC, USA Departments of Chemistry and Earth and Planetary Sciences, University of California, Berkeley, CA, USA College of Engineering-CERT, University of California at Riverside, Riverside, CA, USA Department of Chemistry, Howard University, Washington, DC, USA Department of Environmental Sciences, Rutgers University, New Brunswick, NJ, USA 14 01 2011 11 1 275 291 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/11/275/2011/acp-11-275-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/275/2011/acp-11-275-2011.pdf

Regional and global chemical transport models underpredict NO<sub>x</sub> (NO + NO<sub>2</sub>) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NO<sub>x</sub> bias has been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO<sub>2</sub> (molecules cm<sup>−2</sup>) from satellite observations (Napelenok et al., 2008). The causes of NO<sub>x</sub> underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NO<sub>x</sub>:HNO<sub>3</sub>, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NO<sub>x</sub> removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NO<sub>x</sub> by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties.

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