Yearlong variability of oxidative potential of particulate matter in an urban Mediterranean environment

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 nighttime 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 NO3−, NH4+, 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 SO4−2 and NH4+ 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.