1Atmospheric Chemistry Division, National Center for Atmospheric Research, Boulder, CO, USA
2Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
3CIRES, University of Colorado, Boulder, CO, USA
4Chemical Sciences Division, NOAA Earth System Research Laboratory, Boulder, CO, USA
5Pacific Northwest National Laboratory, Richland, Washington, CO, USA
6Dept. of Civil & Environmental Engineering, University of California, Berkeley, CA, USA
7Dept. of Environmental Science, Policy, and Management, University of California, Berkeley, CA, USA
8Montana State University, Bozeman, MT, USA
9Department of Environmental Toxicology, University of California, Davis, USA
10Aerodyne Research, Inc., Billerica, MA, USA
Received: 19 Jul 2013 – Published in Atmos. Chem. Phys. Discuss.: 15 Oct 2013
Abstract. New pathways to form secondary organic aerosol (SOA) have been postulated recently. Glyoxal, the smallest dicarbonyl, is one of the proposed precursors. It has both anthropogenic and biogenic sources, and readily partitions into the aqueous phase of cloud droplets and deliquesced particles where it undergoes both reversible and irreversible chemistry. In this work we extend the regional scale chemistry transport model WRF-Chem to include detailed gas-phase chemistry of glyoxal formation as well as a state-of-the-science module describing its partitioning and reactions in the aerosol aqueous-phase. A comparison of several proposed mechanisms is performed to quantify the relative importance of different formation pathways and their regional variability. The CARES/CalNex campaigns over California in summer 2010 are used as case studies to evaluate the model against observations. A month-long simulation over the continental United States (US) enables us to extend our results to the continental scale.
Revised: 01 May 2014 – Accepted: 20 May 2014 – Published: 24 Jun 2014
In all simulations over California, the Los Angeles (LA) basin was found to be the hot spot for SOA formation from glyoxal, which contributes between 1% and 15% of the model SOA depending on the mechanism used. Our results indicate that a mechanism based only on a reactive (surface limited) uptake coefficient leads to higher SOA yields from glyoxal compared to a more detailed description that considers aerosol phase state and chemical composition. In the more detailed simulations, surface uptake is found to give the highest SOA mass yields compared to a volume process and reversible formation. We find that the yields of the latter are limited by the availability of glyoxal in aerosol water, which is in turn controlled by an increase in the Henry's law constant depending on salt concentrations ("salting-in"). A time dependence in this increase prevents substantial partitioning of glyoxal into aerosol water at high salt concentrations. If this limitation is removed, volume pathways contribute > 20% of glyoxal-SOA mass, and the total mass formed (5.8% of total SOA in the LA basin) is about a third of the simple uptake coefficient formulation without consideration of aerosol phase state and composition. Results from the continental US simulation reveal the much larger potential to form glyoxal-SOA over the eastern continental US. Interestingly, the low concentrations of glyoxal-SOA over the western continental US are not due to the lack of a potential to form glyoxal-SOA here. Rather these small glyoxal-SOA concentrations reflect dry conditions and high salt concentrations, and the potential to form SOA mass here will strongly depend on the water associated with particles.
Citation: Knote, C., Hodzic, A., Jimenez, J. L., Volkamer, R., Orlando, J. J., Baidar, S., Brioude, J., Fast, J., Gentner, D. R., Goldstein, A. H., Hayes, P. L., Knighton, W. B., Oetjen, H., Setyan, A., Stark, H., Thalman, R., Tyndall, G., Washenfelder, R., Waxman, E., and Zhang, Q.: Simulation of semi-explicit mechanisms of SOA formation from glyoxal in aerosol in a 3-D model, Atmos. Chem. Phys., 14, 6213-6239, doi:10.5194/acp-14-6213-2014, 2014.