1Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA, USA
2Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA
3Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, USA
*now at: Department of Environmental Science, Policy and Management, University of California, Berkeley, USA
**now at: Department of Chemistry, Towson University, Towson, MD, USA
***now at: Aerodyne Research Inc., Billerica MA, USA
****now at: Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
*****now at: Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Canada
Received: 20 Jan 2013 – Published in Atmos. Chem. Phys. Discuss.: 06 Feb 2013
Abstract. The formation of secondary organic aerosol from oxidation of phenol, guaiacol (2-methoxyphenol), and syringol (2,6-dimethoxyphenol), major components of biomass burning, is described. Photooxidation experiments were conducted in the Caltech laboratory chambers under low-NOx (< 10 ppb) conditions using H2O2 as the OH source. Secondary organic aerosol (SOA) yields (ratio of mass of SOA formed to mass of primary organic reacted) greater than 25% are observed. Aerosol growth is rapid and linear with the primary organic conversion, consistent with the formation of essentially non-volatile products. Gas- and aerosol-phase oxidation products from the guaiacol system provide insight into the chemical mechanisms responsible for SOA formation. Syringol SOA yields are lower than those of phenol and guaiacol, likely due to novel methoxy group chemistry that leads to early fragmentation in the gas-phase photooxidation. Atomic oxygen to carbon (O : C) ratios calculated from high-resolution-time-of-flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) measurements of the SOA in all three systems are ~ 0.9, which represent among the highest such ratios achieved in laboratory chamber experiments and are similar to that of aged atmospheric organic aerosol. The global contribution of SOA from intermediate volatility and semivolatile organic compounds has been shown to be substantial (Pye and Seinfeld, 2010). An approach to representing SOA formation from biomass burning emissions in atmospheric models could involve one or more surrogate species for which aerosol formation under well-controlled conditions has been quantified. The present work provides data for such an approach.
Revised: 13 Jun 2013 – Accepted: 20 Jun 2013 – Published: 21 Aug 2013
Yee, L. D., Kautzman, K. E., Loza, C. L., Schilling, K. A., Coggon, M. M., Chhabra, P. S., Chan, M. N., Chan, A. W. H., Hersey, S. P., Crounse, J. D., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from biomass burning intermediates: phenol and methoxyphenols, Atmos. Chem. Phys., 13, 8019-8043, doi:10.5194/acp-13-8019-2013, 2013.