Modeling organic aerosols during MILAGRO: importance of biogenic secondary organic aerosols

The meso-scale chemistry-transport model CHIMERE is used to assess our understanding of major sources and formation processes leading to a fairly large amount of organic aerosols - OA, including primary OA (POA) and secondary OA (SOA) - observed in Mexico City during the MILAGRO field project (March 2006). Chemical analyses of submicron aerosols from aerosol mass spectrometers (AMS) indicate that organic particles found in the Mexico City basin contain a large fraction of oxygenated organic species (OOA) which have strong correspondence with SOA, and that their production actively continues downwind of the city. The SOA formation is modeled here by the one-step oxidation of anthropogenic (i.e. aromatics, alkanes), biogenic (i.e. monoterpenes and isoprene), and biomass-burning SOA precursors and their partitioning into both organic and aqueous phases. Conservative assumptions are made for uncertain parameters to maximize the amount of SOA produced by the model. The near-surface model evaluation shows that predicted OA correlates reasonably well with measurements during the campaign, however it remains a factor of 2 lower than the measured total OA. Fairly good agreement is found between predicted and observed POA within the city suggesting that anthropogenic and biomass burning emissions are reasonably captured. Consistent with previous studies in Mexico City, large discrepancies are encountered for SOA, with a factor of 2-10 model underestimate. When only anthropogenic SOA precursors were considered, the model was able to reproduce within a factor of two the sharp increase in OOA concentrations during the late morning at both urban and near-urban locations but the discrepancy increases rapidly later in the day, consistent with previous results, and is especially obvious when the column-integrated SOA mass is considered instead of the surface concentration. The increase in the missing SOA mass in the afternoon coincides with the sharp drop in POA suggesting a tendency of the model to excessively evaporate the freshly formed SOA. Predicted SOA concentrations in our base case were extremely low when photochemistry was not active, especially overnight, as the SOA formed in the previous day was mostly quickly advected away from the basin. These nighttime discrepancies were not significantly reduced when greatly enhanced partitioning to the aerosol phase was assumed. Model sensitivity results suggest that observed nighttime OOA concentrations are strongly influenced by a regional background SOA (~1.5 μg/m³) of biogenic origin which is transported from the coastal mountain ranges into the Mexico City basin. The presence of biogenic SOA in Mexico City was confirmed by SOA tracer-derived estimates that have reported 1.14 (±0.22) μg/m³ of biogenic SOA at T0, and 1.35 (±0.24) μg/m³ at T1, which are of the same order as the model. Consistent with other recent studies, we find that biogenic SOA does not appear to be underestimated significantly by traditional models, in strong contrast to what is observed for anthropogenic pollution. The relative contribution of biogenic SOA to predicted monthly mean SOA levels (traditional approach) is estimated to be more than 30% within the city and up to 65% at the regional scale which may help explain the significant amount of modern carbon in the aerosols inside the city during low biomass burning periods. The anthropogenic emissions of isoprene and its nighttime oxidation by NO₃ were also found to enhance the SOA mean concentrations within the city by an additional 15%. Our results confirm the large underestimation of the SOA production by traditional models in polluted regions (estimated as 10-20 tons within the Mexico City metropolitan area during the daily peak), and emphasize for the first time the role of biogenic precursors in this region, indicating that they cannot be neglected in urban modeling studies.