In an attempt to take effective action towards mitigating pollution episodes in Athens, precise knowledge of PM_2.5 composition and its sources is a prerequisite. Thus, a 2-year chemical composition dataset from aerosol samples collected in an urban background site in central Athens from December 2013 to March 2016 has been obtained and a positive matrix factorization (PMF) was applied in order to identify and apportion fine aerosols to their sources. A total of 850 aerosol samples were collected on a 12 to 24 h basis and analyzed for major ions, trace elements, and organic and elemental carbon, allowing us to further assess the impact of residential heating as a source of air pollution over Athens. The ionic and carbonaceous components were found to constitute the major fraction of the PM_2.5 aerosol mass. The annual contribution of the ion mass (IM), particulate organic mass (POM), dust, elemental carbon (EC), and sea salt (SS) was calculated at 31 %, 38 %, 18 %, 8 %, and 3 %, respectively, and exhibited considerable seasonal variation. In winter, the share of IM was estimated down to 23 %, with POM + EC being the dominant component accounting for 52 % of the PM_2.5 mass, while in summer, IM (42 %) and carbonaceous aerosols (41 %) contributed almost equally. Results from samples collected on a 12 h basis (day and night) during the three intensive winter campaigns indicated the impact of heating on the levels of a series of compounds. Indeed, PM_2.5, EC, POM, NO₃⁻, C₂O₄²⁻, non sea salt (nss) K⁺ and selected trace metals including Cd and Pb were increased by up to a factor of 4 in the night compared to the day, highlighting the importance of heating on air quality in Athens. Furthermore, in order to better characterize wintertime aerosol sources and quantify the impact of biomass burning on PM_2.5 levels, source apportionment was performed. The data can be interpreted on the basis of six sources, namely biomass burning (31 %), vehicular emissions (19 %), heavy oil combustion (7 %), regional secondary (21 %), marine aerosols (9 %), and dust particles (8 %). Regarding night-to-day patterns their contributions shifted from 19 %, 19 %, 8 %, 31 %, 12 %, and 10 % of the PM_2.5mass during day to 39 %, 19 %, 6 %, 14 %, 7 %, and 7 % during the night, underlining the significance of biomass burning as the main contributor to fine particle levels during nighttime in winter.

This study examines the carbonaceous-aerosol characteristics at three contrasting urban environments in Greece (Ioannina, Athens, and Heraklion), on the basis of 12 h sampling during winter (January to February 2013), aiming to explore the inter-site differences in atmospheric composition and carbonaceous-aerosol characteristics and sources. The winter-average organic carbon (OC) and elemental carbon (EC) concentrations in Ioannina were found to be 28.50 and 4.33 µg m⁻³, respectively, much higher than those in Heraklion (3.86 µg m⁻³ for OC and 2.29 µg m⁻³ for EC) and Athens (7.63 µg m⁻³ for OC and 2.44 µg m⁻³ for EC). The winter OC/EC ratio in Ioannina (6.53) was found to be almost three times that in Heraklion (2.03), indicating a larger impact of wood combustion, especially during the night, whereas in Heraklion, emissions from biomass burning were found to be less intense. Estimations of primary and secondary organic carbon (POC and SOC) using the EC-tracer method, and specifically its minimum R-squared (MRS) variant, revealed large differences between the sites, with a prevalence of POC (67–80%) in Ioannina and Athens and with a larger SOC fraction (53%) in Heraklion. SOC estimates were also obtained using the 5% and 25% percentiles of the OC/EC data to determine the (OC/EC)_pri, leading to results contrasting to the MRS approach in Ioannina (70–74% for SOC). Although the MRS method provides generally more robust results, it may significantly underestimate SOC levels in environments highly burdened by biomass burning, as the fast-oxidized semi-volatile OC associated with combustion sources is classified in POC. Further analysis in Athens revealed that the difference in SOC estimates between the 5% percentile and MRS methods coincided with the semi-volatile oxygenated organic aerosol as quantified by aerosol mass spectrometry. Finally, the OC/K_bb⁺ ratio was used as tracer for decomposition of the POC into fossil-fuel and biomass-burning components, indicating the prevalence of biomass-burning POC, especially in Ioannina (77%).

In an attempt to take effective action towards mitigating pollution episodes in Athens, precise knowledge of PM_2.5 composition and its sources is a prerequisite. Thus, a 2-year chemical composition dataset from aerosol samples collected in an urban background site in central Athens from December 2013 to March 2016 has been obtained and a positive matrix factorization (PMF) was applied in order to identify and apportion fine aerosols to their sources. A total of 850 aerosol samples were collected on a 12 to 24 h basis and analyzed for major ions, trace elements, and organic and elemental carbon, allowing us to further assess the impact of residential heating as a source of air pollution over Athens. The ionic and carbonaceous components were found to constitute the major fraction of the PM_2.5 aerosol mass. The annual contribution of the ion mass (IM), particulate organic mass (POM), dust, elemental carbon (EC), and sea salt (SS) was calculated at 31 %, 38 %, 18 %, 8 %, and 3 %, respectively, and exhibited considerable seasonal variation. In winter, the share of IM was estimated down to 23 %, with POM + EC being the dominant component accounting for 52 % of the PM_2.5 mass, while in summer, IM (42 %) and carbonaceous aerosols (41 %) contributed almost equally. Results from samples collected on a 12 h basis (day and night) during the three intensive winter campaigns indicated the impact of heating on the levels of a series of compounds. Indeed, PM_2.5, EC, POM, NO₃⁻, C₂O₄²⁻, non sea salt (nss) K⁺ and selected trace metals including Cd and Pb were increased by up to a factor of 4 in the night compared to the day, highlighting the importance of heating on air quality in Athens. Furthermore, in order to better characterize wintertime aerosol sources and quantify the impact of biomass burning on PM_2.5 levels, source apportionment was performed. The data can be interpreted on the basis of six sources, namely biomass burning (31 %), vehicular emissions (19 %), heavy oil combustion (7 %), regional secondary (21 %), marine aerosols (9 %), and dust particles (8 %). Regarding night-to-day patterns their contributions shifted from 19 %, 19 %, 8 %, 31 %, 12 %, and 10 % of the PM_2.5mass during day to 39 %, 19 %, 6 %, 14 %, 7 %, and 7 % during the night, underlining the significance of biomass burning as the main contributor to fine particle levels during nighttime in winter.