Secondary inorganic aerosols in Europe: sources and the significant influence of biogenic VOC emissions especially on ammonium nitrate

Abstract

Abstract. Contributions of various anthropogenic sources to the secondary inorganic aerosol (SIA) in Europe as well as the role of biogenic emissions on SIA formation were investigated using the three-dimensional regional model CAMx (Comprehensive air quality model with extensions). Simulations were carried out for two periods of EMEP field campaigns (February–March 2009 and June 2006), which are representative of cold and warm seasons, respectively. Biogenic volatile organic compounds (BVOCs) are known mainly as precursors of ozone and secondary organic aerosol (SOA), but their role on inorganic aerosol formation has not attracted much attention so far. In this study, we showed the importance of the chemical reactions of BVOCs and how they affect the oxidant concentrations leading to significant changes in inorganic nitrate and sulfate. A sensitivity test with doubled BVOC emissions in Europe during the warm season showed a large increase in secondary organic aerosol (SOA) concentrations (by about a factor of two) while particulate inorganic nitrate concentrations decreased by up to 35 %. Sulfate concentrations decreased as well, the change, however, was smaller. The changes in inorganic nitrate and sulfate concentrations occurred at different locations in Europe indicating the importance of precursor gases and biogenic emission types for the negative correlation between BVOCs and SIA. Further analysis of the data suggested that reactions of the additional terpenes with nitrate radicals at night were responsible for the decline in inorganic nitrate formation, whereas oxidation of BVOCs with OH radicals led to a decrease in sulfate. Source apportionment results suggest that the main anthropogenic source of precursors leading to formation of particulate inorganic nitrate is road transport (SNAP7), whereas combustion in energy and transformation industries (SNAP1) was the most important contributor to sulfate particulate mass. Emissions from international shipping were also found to be very important for both nitrate and sulfate formation in Europe. In addition, we examined also contributions from the geographical source regions to SIA concentrations in the most densely populated region of Switzerland, the Swiss Plateau. The results suggest that sources of particulate sulfate were mostly of foreign origin (the domestic contributions were 11 % and 3 % in winter and summer, respectively). On the other hand, about 20 % of the particulate nitrate was from domestic sources while contributions from the neighboring countries Germany and France were significant as well. Particulate ammonium was estimated to originate mainly from local agricultural activities.