Abstract. We investigate optical–microphysical–chemical properties of brown carbon (BrC) in the urban ambient atmosphere of the Po Valley. In situ ground measurements of aerosol spectral optical properties, PM1 chemical composition (HR-ToF-AMS), and particle size distributions were carried out in Bologna. BrC was identified through its wavelength dependence of light absorption at visible wavelengths, as indicated by the absorption Ångström exponent (AAE). We found that BrC occurs in particles with a narrow monomodal size distribution peaking in the droplet mode, enriched in ammonium nitrate and poor in black carbon (BC), with a strong dependance on OA-to-BC ratios, and SSA530 of 0.98 ± 0.01. We demonstrate that specific complex refractive index values (k530 = 0.017 ± 0.001) are necessary in addition to a proper particle size range to match the large AAEs measured for this BrC (AAE467 − 660 = 3.2 ± 0.9 with values up to 5.3). In terms of consistency of these findings with literature, this study i. provides experimental evidence of the size distribution of BrC associated with the formation of secondary aerosol;ii. shows that in the lower troposphere AAE increases with increasing OA-to-BC ratios rather than with increasing OA – contributing to sky radiometer retrieval techniques (e.g., AERONET);iii. extends the dependence of AAE on BC-to-OA ratios previously observed in chamber experiments to ambient aerosol dominated by wood-burning emissions. These findings are expected to bear important implications for atmospheric modeling studies and remote sensing observations as regards the parametrization and identification of BrC in the atmosphere.