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Abstract The oxidative potential (OP) of fine and coarse fractions of ambient aerosols was studied in the urban environment of Athens, Greece. OP was quantified using a dithiothreitol (DTT) assay, applied to the water soluble fraction of aerosol that was extracted from 361 fine and 84 coarse mode of 24-h and 12-h filter samples over a one-year period. During the cold period, samples were collected on a 12-h basis, to assess the impact of night-time biomass burning emissions from domestic heating on OP. The chemical characteristics of aerosols were measured in parallel using an Aerosol Chemical Speciation Monitoring (ACSM) and a 7-wavelength Aethalometer. A source apportionment analysis on the ACSM data resulted in the identification of organic aerosol (OA) factors on a seasonal basis. A good correlation of OP with NO 3 −, NH 4 +, BC (Black Carbon), Organics and LV-OOA (low volatility oxygenated OA) was found during winter, revealing the importance of combustion and aging processes for OP. During the summertime, a good correlation between OP and SO 4 −2 and NH 4 +indicates its association with regional aerosol – thus the importance of oxidative aging that reduces its association with any characteristic source. Multiple regression analysis during winter revealed that highly oxygenated secondary aerosol (LV-OOA) and, to a lesser extent, fresh biomass burning (BBOA) and fossil fuel (HOA) organic aerosol, are the prime contributors to the OP of fine aerosol, with extrinsic toxicities of 54 ± 22 pmol min−1 μg−1, 28 ± 7 and 17 ± 4 pmol min−1μg−1, respectively. In summer, OP cannot be attributed to any of the identified components and corresponds to a background aerosol value. In winter however, the regression model can reproduce satisfactorily the water soluble DTT activity of fine aerosol, providing a unique equation for the estimation of aerosol OP in an urban Mediterranean environment. Graphical abstract Image 1 Highlights • Yearlong oxidative potential measurements on 367 fine aerosol samples. • Fine urban aerosol oxidative potential is 3 times higher compared to coarse mode. • Winter elevated oxidative potential attributed to fresh aerosol emissions. • Summer background aerosol oxidative potential due to long-range transport. • Satisfactory reconstruction of fine aerosol water-soluble dithiothreitol activity. [ABSTRACT FROM AUTHOR]

To identify the sources of aerosols in Greater Athens Area (GAA), a total of 1510 daily samples of fine (PM 2.5 ) and coarse (PM 10–2,5 ) aerosols were collected at a suburban site (Penteli), during a five year period (May 2008–April 2013) corresponding to the period before and during the financial crisis. In addition, aerosol sampling was also conducted in parallel at an urban site (Thissio), during specific, short-term campaigns during all seasons. In all these samples mass and chemical composition measurements were performed, the latest only at the fine fraction. Particulate organic matter (POM) and ionic masses (IM) are the main contributors of aerosol mass, equally contributing by accounting for about 24% of the fine aerosol mass. In the IM, nss-SO 4 − 2 is the prevailing specie followed by NO 3 − and NH 4 + and shows a decreasing trend during the 2008–2013 period similar to that observed for PM masses. The contribution of water in fine aerosol is equally significant (21 ± 2%), while during dust transport, the contribution of dust increases from 7 ± 2% to 31 ± 9%. Source apportionment (PCA and PMF) and mass closure exercises identified the presence of six sources of fine aerosols: secondary photochemistry, primary combustion, soil, biomass burning, sea salt and traffic. Finally, from winter 2012 to winter 2013 the contribution of POM to the urban aerosol mass is increased by almost 30%, reflecting the impact of wood combustion (dominant fuel for domestic heating) to air quality in Athens, which massively started in winter 2013. [ABSTRACT FROM AUTHOR]

This study examines the concentrations and characteristics of carbonaceous aerosols (including saccharides) and inorganic species measured by PM 2.5 filter sampling and a multi-wavelength Aethalometer during two campaigns in a mountainous, medium-sized, Greek city (Ioannina). The first campaign was conducted in summer and used as a baseline of low concentrations, while the second took place in winter under intensive residential wood burning (RWB) emissions. Very high winter-mean OC concentrations (26.0 μg m−3) were observed, associated with an OC/EC ratio of 9.9, and mean BC wb and PM 2.5 levels of 4.5 μg m−3 and 57.5 μg m−3, respectively. Simultaneously, record-high levoglucosan (Lev) concentrations (mean: 6.0 μg m−3; max: 15.9 μg m−3) were measured, revealing a severely biomass burning (BB)-laden environment. The water-soluble OC component (WSOC) accounted for 56 ± 9% of OC in winter, exhibiting high correlations (R2 = 0.93–0.97) with BB tracers (nss-K+, BC wb , Lev), nitrate and light absorption, potentially indicating the formation of water-soluble brown carbon (BrC) from fast oxidation processes. The examination of diagnostic ratios involving BB tracers indicated the prevalence of hardwood burning, while the mean Lev/OC ratio (22%) was remarkably higher than literature values. Applying a mono-tracer method based on levoglucosan, we estimated very high BB contributions to OC (∼92%), EC (∼64%) and WSOC (∼87%) during winter. On the contrary, low levels were registered during summer for all carbonaceous components, with winter/summer ratios of 4–5 for PM 2.5 and BC, 10 for OC, 30 for BC wb and ∼1100 for levoglucosan. The absence of local BB sources in summer, combined with the photochemical processing and aging of regional organic aerosols, resulted in higher WSOC/OC fractions (64 ± 13%). The results indicate highly soluble fine carbonaceous aerosol fraction year-round, which when considered alongside the extreme concentration levels in winter can have important implications for short- and long-term health effects. [Display omitted] • PM 2.5 chemical characterization in a semi-mountainous city of Southeast Europe. • Severe PM 2.5 , OC and levoglusocan levels are found due to wood burning in winter. • Biomass burning contributes 92%, 87%, 64% to OC, WSOC, EC, respectively in winter. • High levoglucosan-to-OC ratio (22%) is found for local hardwood burning emissions. • Fresh wood burning aerosols were highly water-soluble with implication for toxicity. [ABSTRACT FROM AUTHOR]