References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-10-31083-2010

SOA from limonene: role of NO3 in its generation and degradation

Fry

J. L.

¹ ⁴ Kiendler-Scharr

² Rollins

A. W.

¹ Brauers

² Brown

S. S.

³ Dorn

H.-P.

² Dubé

W. P.

³ Fuchs

³ ⁵ Mensah

² Rohrer

² Tillmann

² Wahner

² Wooldridge

P. J.

¹ Cohen

R. C.

Department of Chemistry, University of California, Berkeley, CA, USA

ICG-2: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany

Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA

now at: Chemistry Department, Reed College, Portland, OR, USA

now at: ICG-2: Troposphäre, Forschungszentrum Jülich, 52425 Jülich, Germany

22 12 2010

10 12 31083 31121

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.

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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.

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