Source apportionment of elevated wintertime PAHs by compound-specific radiocarbon analysis

Abstract. Natural abundance radiocarbon analysis facilitates distinct source apportionment between contemporary biomass/biofuel (¹⁴C "alive") versus fossil fuel (¹⁴C "dead") combustion. Here, the first compound-specific radiocarbon analysis (CSRA) of atmospheric polycyclic aromatic hydrocarbons (PAHs) was demonstrated for a set of samples collected in Lycksele, Sweden a small town with frequent episodes of severe atmospheric pollution in the winter. Renewed interest in using residential wood combustion (RWC) means that this type of seasonal pollution is of increasing concern in many areas. Five individual/paired PAH isolates from three pooled fortnight-long filter collections were analyzed by CSRA: phenanthrene, fluoranthene, pyrene, benzo[b+k]fluoranthene and indeno[cd]pyrene plus benzo[ghi]perylene; phenanthrene was the only compound also analyzed in the gas phase. The measured Δ¹⁴C for PAHs spanned from −138.3‰ to 58.0‰. A simple isotopic mass balance model was applied to estimate the fraction biomass (f_biomass) contribution, which was constrained to 71–87% for the individual PAHs. Indeno[cd]pyrene plus benzo[ghi]perylene had an f_biomass of 71%, while fluoranthene and phenanthrene (gas phase) had the highest biomass contribution at 87%. The total organic carbon (TOC, defined as carbon remaining after removal of inorganic carbon) f_biomass was estimated to be 77%, which falls within the range for PAHs. This CSRA data of atmospheric PAHs established that RWC is the dominating source of atmospheric PAHs to this region of the boreal zone with some variations among RWC contributions to specific PAHs.