Atmos. Chem. Phys. Discuss., 9, 23755-23790, 2009
© Author(s) 2009. This work is distributed
under the Creative Commons Attribution 3.0 License.
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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.
Alkyl nitrate production and persistence in the Mexico City Plume
A. E. Perring1,*,**, T. H. Bertram1,***, D. K. Farmer1,**, P. J. Wooldridge1, J. Dibb2, N. J. Blake3, D. R. Blake3, H. B. Singh4, H. Fuelberg5, G. Diskin6, G. Sachse6, and R. C. Cohen1,7
1Department of Chemistry, University of California Berkeley, Berkeley, CA, USA
2Climate Change Research Institute, University of New Hampshire, Durham, NH, USA
3Department of Chemistry, University of California Irvine, Irvine, CA, USA
4NASA Ames Research Center, Moffett Field, CA, USA
5Department of Meteorology, Florida State University, Tallahassee, FL, USA
6NASA Langley Research Center, Hampton, VA, USA
7Department of Earth and Planetary Sciences, University of California Berkeley, Berkeley, CA, USA
*now at: National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Chemical Sciences Division, Boulder, CO, USA
**now at: University of Colorado, Cooperative Institute for Research in Environmental Sciences, Boulder, CO, USA
***now at: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA, USA

Abstract. Alkyl and multifunctional nitrates (ΣANs) have been observed to be a significant fraction of NOy in a number of different chemical regimes. Their formation is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. ΣANs also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Numerous studies have investigated the role of nitrate formation from biogenic compounds. Less attention has been paid to the role ΣANs may play in the complex mixtures of hydrocarbons typical of urban settings. Measurements of ΣANs, NO2, total peroxy nitrates (ΣPNs), HNO3 and a wide suite of hydrocarbons were obtained from the NASA DC-8 aircraft during spring of 2006 in and around Mexico City and the Gulf of Mexico. ΣANs were observed to be 10–20% of NOy in the Mexico City plume and to increase in importance with increased photochemical age. We describe three conclusions: 1) Correlations of ΣANs with odd-oxygen (Ox) indicate a stronger role for ΣANs in the photochemistry of Mexico City than is expected based on currently accepted photochemical mechanisms, 2) ΣAN formation suppresses peak ozone production rates by as much as 30% in the near-field of Mexico City and 3) ΣANs play a comparable role to ΣPNs in the export of NOy to the Gulf Region.

Citation: Perring, A. E., Bertram, T. H., Farmer, D. K., Wooldridge, P. J., Dibb, J., Blake, N. J., Blake, D. R., Singh, H. B., Fuelberg, H., Diskin, G., Sachse, G., and Cohen, R. C.: Alkyl nitrate production and persistence in the Mexico City Plume, Atmos. Chem. Phys. Discuss., 9, 23755-23790, doi:10.5194/acpd-9-23755-2009, 2009.
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