Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA
Prettiny K. Ma1, Yunliang Zhao2, Allen L. Robinson2, David R. Worton3,a, Allen H. Goldstein3,4, Amber M. Ortega5,b, Jose-L. Jimenez5, Peter Zotter6,c, André S. H. Prévôt6, Sönke Szidat7, and Patrick L. Hayes11Department of Chemistry, Université de Montréal, Montréal, QC, Canada 2Center for Atmospheric Particle Studies, Carnegie Mellon University, Pittsburgh, PA, USA 3Department of Civil and Environmental Engineering, University of California, Berkeley, CA, USA 4Department of Environmental Science, Policy and Management, University of California, Berkeley, CA, USA 5Cooperative Institute for Research in the Environmental Sciences and Dept. of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA 6Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, Villigen, Switzerland 7Department of Chemistry and Biochemistry & Oeschger Centre for Climate Change, University of Bern, Bern, Switzerland anow at: Gas and Particle Metrology, National Physical Laboratory, Hampton Rd, Teddington, Middlesex, UK bnow at: Air Pollution Control Division, Colorado Department of Public Health and Environment, Denver, CO, USA cnow at: Lucerne University of Applied Sciences and Arts, School of Engineering and Architecture, Bioenergy Research, Technikumstrasse 21, CH-6048 Horw, Switzerland
Received: 26 Oct 2016 – Accepted for review: 07 Nov 2016 – Discussion started: 11 Nov 2016
Abstract. Secondary Organic Aerosols (SOA) are important contributors to fine PM mass in polluted regions, and their modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of IVOCs reported in Zhao et al. (2014) and of SVOCs reported in Worton et al. (2014) the model is biased high at longer photochemical ages whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas phase wall-losses in environmental chambers, show model/measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil/non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site.
Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model/measurement agreement. However, there are many uncertainties associated with these "aging" mechanisms. Thus, SOA formation in the model is compared against data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass when the "aging" mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case though has SOA formation rates that are more consistent with observations from the OFR.
All the model cases evaluated in this work have a large majority of the urban SOA (70–86 %) at Pasadena coming from the oxidation of P-SVOCs and P-IVOCs. The importance of these two types of precursors is further supported by analyzing the percentage of SOA formed at long photochemical ages (1.5 days) as a function of the precursor rate constant. The P-SVOCs and P-IVOCs have rate constants that are similar to highly reactive VOCs that have been previously found to strongly correlate with SOA formation potential measured by the OFR.
Finally, the volatility distribution of the total organic mass (gas and particle phase) in the model is compared against measurements. The total SVOC mass simulated is similar to the measurements, but there are important differences in the measured and modeled volatility distributions. A likely reason for the difference is the lack of particle-phase reactions in the model that can oligomerize and/or continue to oxidize organic compounds even after they partition to the particle phase.
Ma, P. K., Zhao, Y., Robinson, A. L., Worton, D. R., Goldstein, A. H., Ortega, A. M., Jimenez, J.-L., Zotter, P., Prévôt, A. S. H., Szidat, S., and Hayes, P. L.: Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA, Atmos. Chem. Phys. Discuss., doi:10.5194/acp-2016-957, in review, 2016.