Seasonal changes of sources and volatility of carbonaceous aerosol at urban, coastal and forest sites in Eastern Europe (Lithuania)

Abstract

We measured stable carbon isotope ratios of total carbon (TC) and organic carbon (OC) in fine carbonaceous aerosol fraction sampled in August and September 2013 at urban, coastal and forest sites in Lithuania. δ13C values of TC for all three sites over the whole measurement period varied from −29.3 to −26.6‰, which is in the range of particles emitted by fossil fuel combustion in Eastern Europe. The isotopic composition at the forest and coastal site showed a similar variation during two contrasting pollution periods. δ13C values in the clean period were more variable, whereas the polluted period was characterized by a gradual enrichment in δ13C compared to the clean period. In the polluted period air masses originated from southern, southeastern or southwestern direction, indicating long-range transport of pollutants from Eastern Europe and Southern Europe to Lithuania. Oxidative processing during long-range transport or the different source signatures (e.g., enriched 13C signature of gasoline used in Western Europe vs. Eastern Europe) could cause the less negative δ13COC values during the polluted episode. δ13C for OC desorbed from the filter samples was separately measured during three different temperature steps (200 °C, 350 °C and 650 °C). OC desorbed at 200 °C had the most depleted 13C signature of around −29‰ at all three sites.A comparison with previously published data measured during the winter at the same sites showed that both TC and OC had less negative δ13C values in winter than in summer, which can be explained by the contribution of biomass/coal burning sources in winter. At the urban site δ13C of OC did not change much with increasing desorption temperature in winter, which is typical for primary sources, but in the summer δ13C of OC was depleted for lower desorption temperatures, possibly due to the influence of SOA formation. A higher fraction of more refractory OC in summer compared to winter-time suggests active photochemical processing of the primary organic aerosol as an important process at all three sites.