Modelling winter organic aerosol at the European scale with CAMx: evaluation and source apportionment with a VBS parameterization based on novel wood burning smog chamber experiments

摘要

We evaluated a modified VBS (volatility basis set) scheme to treat biomass-burning-like organic aerosol (BBOA) implemented in CAMx (Comprehensive Air Quality Model with extensions). The updated scheme was parameterized with novel wood combustion smog chamber experiments using a hybrid VBS framework which accounts for a mixture of wood burning organic aerosol precursors and their further functionalization and fragmentation in the atmosphere. The new scheme was evaluated for one of the winter EMEP intensive campaigns (February–March 2009) against aerosol mass spectrometer (AMS) measurements performed at 11?sites in Europe. We found a considerable improvement for the modelled organic aerosol (OA) mass compared to our previous model application with the mean fractional bias (MFB) reduced from ?61 to ?29?%. We performed model-based source apportionment studies and compared results against positive matrix factorization (PMF) analysis performed on OA AMS data. Both model and observations suggest that OA was mainly of secondary origin at almost all sites. Modelled secondary organic aerosol (SOA) contributions to total OA varied from 32 to 88?% (with an average contribution of 62?%) and absolute concentrations were generally under-predicted. Modelled primary hydrocarbon-like organic aerosol (HOA) and primary biomass-burning-like aerosol (BBPOA) fractions contributed to a lesser extent (HOA from 3 to 30?%, and BBPOA from 1 to 39?%) with average contributions of 13 and 25?%, respectively. Modelled BBPOA fractions were found to represent 12 to 64?% of the total residential-heating-related OA, with increasing contributions at stations located in the northern part of the domain. Source apportionment studies were performed to assess the contribution of residential and non-residential combustion precursors to the total SOA. Non-residential combustion and road transportation sector contributed about 30–40?% to SOA formation (with increasing contributions at urban and near industrialized sites), whereas residential combustion (mainly related to wood burning) contributed to a larger extent, around 60–70?%. Contributions to OA from residential combustion precursors in different volatility ranges were also assessed: our results indicate that residential combustion gas-phase precursors in the semivolatile range (SVOC) contributed from 6 to 30?%, with higher contributions predicted at stations located in the southern part of the domain. On the other hand, the oxidation products of higher-volatility precursors (the sum of intermediate-volatility compounds (IVOCs) and volatile organic compounds (VOCs)) contribute from 15 to 38?% with no specific gradient among the stations. Although the new parameterization leads to a better agreement between model results and observations, it still under-predicts the SOA fraction, suggesting that uncertainties in the new scheme and other sources and/or formation mechanisms remain to be elucidated. Moreover, a more detailed characterization of the semivolatile components of the emissions is needed.