Atmos. Chem. Phys. Discuss., 9, 8857-8902, 2009
www.atmos-chem-phys-discuss.net/9/8857/2009/
doi:10.5194/acpd-9-8857-2009
© Author(s) 2009. This work is distributed
under the Creative Commons Attribution 3.0 License.
Review Status
This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields
A. W. Rollins1, A. Kiendler-Scharr3, J. Fry1, T. Brauers3, S. S. Brown4, H.-P. Dorn3, W. P. Dubé4, H. Fuchs4, A. Mensah3, T. F. Mentel3, F. Rohrer3, R. Tillmann3, R. Wegener3, P. J. Wooldridge1, and R. C. Cohen1,2
1Department of Chemistry, University of California Berkeley, Berkeley, CA 94720, USA
2Department of Earth and Planetary Science, University of California Berkeley, Berkeley, CA 94720, USA
3Institute of Chemistry and Dynamic of the Geosphere, Forschungszentrum Jülich, Germany
4Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA

Abstract. Alkyl nitrates and secondary organic aerosol (SOA) produced during the oxidation of isoprene by nitrate radicals has been observed in the SAPHIR chamber. We find the yield of nitrates is 70±8% from the isoprene+NO3 reaction, and the yield for secondary dinitrates produced in the reaction of primary isoprene nitrates with NO3 is 40±20%. We find an effective rate constant for reaction of NO3 with the group of first generation oxidation products to be 7×10−14 cm3 s−1. At the low total organic aerosol concentration in the chamber (max ≈0.6 μg m−3) we observed a mass yield (ΔSOA mass/Δisoprene mass) of 2% for the entire 16 h experiment. However a comparison of the timing of the observed SOA production to a box model simulation of first and second generation oxidation products shows that the yield from the first generation products was <0.2% while the further oxidation of the initial products leads to a yield of 10% (defined as ΔSOA/Δisoprene2x where Δisoprene2x is the mass of isoprene which reacted twice with NO3). The SOA yield of 10% is consistent with equilibrium partitioning of highly functionalized C5 products of isoprene oxidation.

Citation: Rollins, A. W., Kiendler-Scharr, A., Fry, J., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Mentel, T. F., Rohrer, F., Tillmann, R., Wegener, R., Wooldridge, P. J., and Cohen, R. C.: Isoprene oxidation by nitrate radical: alkyl nitrate and secondary organic aerosol yields, Atmos. Chem. Phys. Discuss., 9, 8857-8902, doi:10.5194/acpd-9-8857-2009, 2009.
 
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