Long-term brown carbon spectral characteristics in a Mediterranean city (Athens)

[Display omitted] •Pronounced seasonal variation in aerosol absorption in Athens over a 4-year period.•Significant BrC contribution (23.7%) to the total aerosol absorption at 370 nm.•Strong winter-time correlations between BrC and BB-related organic aerosols.•The BrCsec absorption is related to residential wood burning during winter nights. This study analyses 4-years of continuous 7-λ Aethalometer (AE-33) measurements in an urban-background environment of Athens, to resolve the spectral absorption coefficients (babs) for black carbon (BC) and brown carbon (BrC). An important BrC contribution (23.7 ± 11.6%) to the total babs at 370 nm is estimated for the period May 2015–April 2019, characterized by a remarkable seasonality with winter maximum (33.5 ± 13.6%) and summer minimum (18.5 ± 8.1%), while at longer wavelengths the BrC contribution is significantly reduced (6.8 ± 3.6% at 660 nm). The wavelength dependence of the total babs gives an annual-mean AAE370-880 of 1.31, with higher values in winter night-time. The BrC absorption and its contribution to babs presents a large increase reaching up to 39.1 ± 13.6% during winter nights (370 nm), suggesting residential wood burning (RWB) emissions as a dominant source for BrC. This is supported by strong correlations of the BrC absorption with OC, EC, the fragment ion m/z 60 derived from ACSM and PMF-analyzed organic fractions related to biomass burning (e.g. BBOA). In contrast, BrC absorption decreases significantly during daytime as well as in the warm period, reaching to a minimum during the early-afternoon hours in all seasons due to photo-chemical degradation. Estimated secondary BrC absorption is practically evident only during winter night-time, implying the fast oxidation of BrC species from RWB emissions. Changes in mixing-layer height do not significantly affect the BrC absorption in winter, while they play a major role in summer.