1Institute of Chemical Engineering and High Temperature Chemical Processes, Foundation for Research and Technology Hellas, Patras, Greece
2Dept. of Chemical Engineering, University of Patras, Patras, Greece
3Dept. of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology (MIT), USA
4Molina Center for Energy and the Environment (MCE2), USA
5Dept. of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213, USA
Abstract. Urban areas are large sources of organic aerosols and their precursors. Nevertheless, the contributions of primary (POA) and secondary organic aerosol (SOA) to the observed particulate matter levels have been difficult to quantify. In this study the three-dimensional chemical transport model PMCAMx-2008 is used to investigate the temporal and geographic variability of organic aerosol in the Mexico City Metropolitan Area (MCMA) during the MILAGRO campaign that took place in the spring of 2006. The organic module of PMCAMx-2008 is based on the volatility basis-set approach: both primary and secondary organic components are assumed to be semi-volatile and photochemically reactive and are distributed in logarithmically spaced volatility bins. The MCMA emission inventory is modified and the POA emissions are distributed by volatility based on dilution experiments. The model predictions are compared with observations from four different types of sites, an urban (T0), a suburban (T1), a rural (T2), and an elevated site in Pico Tres Padres (PTP). The performance of the model in reproducing organic mass concentrations in these sites was encouraging. The average predicted PM1 OA concentration in T0, T1, and T2 was 18 μg m−3, 11.7 μg m−3, and 10.5 μg m−3 respectively, while the corresponding measured values were 17.2 μg m−3, 11 μg m−3, and 9 μg m−3. The average predicted fresh primary OA concentrations were 4.4 μg m−3 at T0, 1.2 μg m−3 at T1 and 1.7 μg m−3 at PTP in reasonably good agreement with the corresponding PMF analysis estimates based on the AMS observations of 4.5, 1.3, and 2.9 μg m−3 respectively. The model reproduced reasonably well the average oxygenated OA (OOA) levels in T0 (7.5 μg m−3 predicted versus 7.5 μg m−3 measured), in T1 (6.3 μg m−3 predicted versus 4.6 μg m−3 measured) and in PTP (6.6 μg m−3 predicted versus 5.9 μg m−3 measured). Inside Mexico City, the locally produced OA is predicted to be on average 53% fresh primary (POA), 11% semi-volatile (S-SOA) and intermediate volatile (I-SOA) organic aerosol, and 36% traditional SOA from the oxidation of VOCs (V-SOA). The long range transport from biomass burning activities and other sources in Mexico is predicted to contribute on average almost as much as the local sources during the MILAGRO period.