Abstract. Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants in fine particulate matter (PM) long known to have mutagenic and carcinogenic effects, but much is unknown about the importance of local and remote sources for PAH levels observed in population-dense urban environments. A year-long sampling campaign in Athens, Greece, where more than 150 samples were analyzed for 31 PAHs and a wide range of chemical markers, was combined with positive matrix factorization (PMF) to constrain the temporal variability, sources, and carcinogenic risk associated with PAHs. It was found that biomass burning (BB), a source mostly present during wintertime intense pollution events (observed for 18 % of measurement days in 2017), led to wintertime PAH levels that were 7 times higher than in other seasons and was as important for annual mean PAH concentrations (31 %) as diesel and oil (33 %) and gasoline (29 %) sources. The contribution of non-local sources, although limited on an annual basis (7 %), increased during summer, becoming comparable to that of local sources combined. The fraction of PAHs (12 members that were included in the PMF analysis) that was associated with BB was also linked to increased health risk compared to the other sources, accounting for almost half the annual PAH carcinogenic potential (43 %). This can result in a large number of excess cancer cases due to BB-related high PM levels and urges immediate action to reduce residential BB emissions in urban areas facing similar issues.

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Ion Name Abbreviation Detection Limit (ng m -3 ) Rings TEF Carcinogenic Group (IARC 2018) 128 Napthalene Nap 0.042 2 0.001 2B

Abstract. Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants in fine particulate matter (PM) long known to have mutagenic and carcinogenic effects, but much is unknown about the importance of local and remote sources to PAH levels observed in population-dense urban environments. A year-long sampling campaign in Athens, Greece, where more than 150 samples were analyzed for 31 PAHs and a wide range of chemical markers were used in combination with Positive Matrix Factorization (PMF) to constrain the temporal variability, sources and carcinogenic risk associated with PAHs. We find that biomass burning (BB), a source mostly effective during wintertime intense pollution events (observed for 18 % of measurement days in 2017), lead to wintertime PAH levels 7 times higher than in other seasons and was responsible for annual mean PAH concentrations (31 %) comparable to those from diesel/oil (33 %) and gasoline (29 %) sources. The contribution of non-local sources, although limited on an annual basis (7 %), was increased during summer, becoming comparable to that of local sources combined. The fraction of PAHs associated with BB is linked to increased health risk compared to the other sources, accounting for almost half the annual carcinogenic potential of PAHs (43 %). This can result in a larger number of excess cancer cases due to BB-related high PM levels and urges immediate action to reduce residential BB emissions in urban areas facing similar issues.