1Department of Chemistry, University of California, Berkeley, CA, USA
2IEK 8: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany
3Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA
*current address: Chemistry Department, Reed College, Portland, OR, USA
**current address: IEK 8: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany
***current address: Institute for Atmospheric and Climate Science, ETH Zürich, Zürich, Switzerland
Received: 06 Dec 2010 – Published in Atmos. Chem. Phys. Discuss.: 22 Dec 2010
Abstract. The formation of organic nitrates and secondary organic aerosol (SOA) were monitored during the NO3 + limonene reaction in the atmosphere simulation chamber SAPHIR at Research Center Jülich. The 24-h run began in a purged, dry, particle-free chamber and comprised two injections of limonene and oxidants, such that the first experiment measured SOA yield in the absence of seed aerosol, and the second experiment yields in the presence of 10 μg m−3 seed organic aerosol. After each injection, two separate increases in aerosol mass were observed, corresponding to sequential oxidation of the two limonene double bonds. Analysis of the measured NO3, limonene, product nitrate concentrations, and aerosol properties provides mechanistic insight and constrains rate constants, branching ratios and vapor pressures of the products. The organic nitrate yield from NO3 + limonene is ≈30%. The SOA mass yield was observed to be 25–40%. The first injection is reproduced by a kinetic model. PMF analysis of the aerosol composition suggests that much of the aerosol mass results from combined oxidation by both O3 and NO3, e.g., oxidation of NO3 + limonene products by O3. Further, later aerosol nitrate mass seems to derive from heterogeneous uptake of NO3 onto unreacted aerosol alkene.
Revised: 09 Apr 2011 – Accepted: 12 Apr 2011 – Published: 28 Apr 2011
Citation: Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Rohrer, F., Tillmann, R., Wahner, A., Wooldridge, P. J., and Cohen, R. C.: SOA from limonene: role of NO3 in its generation and degradation, Atmos. Chem. Phys., 11, 3879-3894, doi:10.5194/acp-11-3879-2011, 2011.