Predicted and observed changes in summertime biogenic and total organic aerosol in the southeast United States from 2001 to 2010

Abstract

Biogenic secondary organic aerosol (bSOA) is a major component of atmospheric particulate matter (PM2.5) in the southeast United States especially during the summer, when emissions of biogenic volatile organic compound (VOCs) are high and emissions from anthropogenic sources enhance the formation of secondary particulate matter. In this work we test the hypothesis whether a chemical transport model (PMCAMx) that includes a detailed description of gas-phase chemistry, secondary organic aerosol (SOA) formation based on the volatility basis set (VBS), and interactions among compounds based on partitioning theory can predict organic aerosol (OA) concentrations that are consistent with the observed changes in OA in response to significant changes in anthropogenic emissions during the summers of 2001 and 2010. The model had good performance for OA for both periods and its predictions were consistent with the observed changes in both the urban and rural areas. The fractional error of OA predictions remained practically the same (0.41 and 0.44 at Chemical Speciation Network (CSN) sites and 0.40 to 0.41 at Interagency Monitoring of Protected Visual Environments (IMPROVE) sites in the summers of 2001 and 2010 respectively) in the two examined periods. The fractional bias of OA predictions increased from 0.10 to 0.22 at CSN sites and decreased from 0 to −0.09 at IMPROVE sites between the two periods. Average predicted bSOA concentrations in the southeast US did not change appreciably from the summer of 2001 to the summer of 2010, while the anthropogenic SOA decreased by 45%. As a result, the biogenic fraction of predicted total OA increased from 0.46 in 2001 to 0.63 in 2010. Partitioning effects due to reduced anthropogenic OA from 2001 resulted in 0.4 μg m−3 less biogenic OA on average in the southeast US in the summer of 2010. This was offset by biogenic SOA increases due to higher biogenic vapor emissions in the warmer 2010 summer. Removing the NOx-dependence of SOA formation yields resulted in higher fractional error and fractional bias at both CSN and IMPROVE sites in both summer periods, demonstrating the efficacy of the current formulation of SOA yields. The results of the analysis support the conclusion that a CTM that simulates NOx-dependent SOA chemistry and semivolatile partitioning of SOA material can consistently predict the observed changes in a region rich in biogenic VOCs and SOA.