Atmos. Chem. Phys. Discuss., 12, 319-349, 2012
© Author(s) 2012. 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.
Importance of biogenic precursors to the budget of organic nitrates during BEARPEX 2009: observations of multifunctional organic nitrates by CIMS and TD-LIF
M. R. Beaver1,*, J. M. St. Clair1, F. Paulot1, K. M. Spencer1, J. D. Crounse1, B. W. LaFranchi2,**, K. E. Min2, S. E. Pusede2, P. J. Woolridge2, G. W. Schade3, C. Park3,***, R. C. Cohen2, and P. O. Wennberg1
1California Institute of Technology, Pasadena, CA, USA
2University of California, Berkeley, CA, USA
3Texas A&M University, College Station, TX, USA
*now at: National Exposure Research Laboratory, Environmental Protection Agency, Research Triangle Park, NC, USA
**now at: Center for Accelerator Mass Spectrometry, Lawrence Livermore National Laboratory, Livermore, CA, USA
***now at: University of California, Los Angeles, CA, USA

Abstract. Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO2, are products of chain terminating reactions in the tropospheric HOx and NOx catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they serve as reservoir species that can be transported over large distances. If the RONO2 then react to deliver NOx to remote regions they affect ozone production rates in locations distant from the original NOx source. While measurements of total RONO2 (ΣANs) and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO2 molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ΣANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ΣANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO) derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ΣANs, confirming predictions of the importance of biogenic nitrates to the NOy budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ΣANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates from nocturnal chemistry of isoprene and α-pinene is presented.

Citation: Beaver, M. R., Clair, J. M. St., Paulot, F., Spencer, K. M., Crounse, J. D., LaFranchi, B. W., Min, K. E., Pusede, S. E., Woolridge, P. J., Schade, G. W., Park, C., Cohen, R. C., and Wennberg, P. O.: Importance of biogenic precursors to the budget of organic nitrates during BEARPEX 2009: observations of multifunctional organic nitrates by CIMS and TD-LIF, Atmos. Chem. Phys. Discuss., 12, 319-349, doi:10.5194/acpd-12-319-2012, 2012.
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