Size-resolved aerosol composition at an urban and a rural site in the Po Valley in summertime: implications for secondary aerosol formation

The aerosol size-segregated chemical composition was analyzed at an urban (Bologna) and a rural site (San Pietro Capofiume) in the Po Valley, Italy, during June and July 2012, to investigate sources and mechanisms of secondary aerosol formation during the summer. A significant enhancement of secondary organic and inorganic aerosol mass was observed under anticyclonic conditions with recirculation of planetary boundary layer air, but with substantial differences between the urban and the rural site. The data analysis, including a Principal Component Analysis (PCA) on the size-resolved dataset of chemical concentrations, indicated that the photochemical oxidation of inorganic and organic gaseous precursors was an important mechanism of secondary aerosol formation at both sites. In addition at the rural site a second formation process, explaining the largest fraction (22 %) of the total variance, was active at night-time, especially under stagnant conditions. Nocturnal chemistry in the rural Po Valley was associated with the formation of ammonium nitrate in large accumulation mode (0.42–1.2 µm) aerosols favored by local thermodynamic conditions (higher relative humidity and lower temperature compared to the urban site). Nocturnal concentrations of fine nitrate were, in fact, on average five times higher at the rural site than in Bologna. The water uptake by this highly hygroscopic compound under high RH conditions provided the medium for increased nocturnal aerosol uptake of water soluble organic gases and possibly also for aqueous chemistry, as revealed by the shifting of peak concentrations of secondary compounds (WSOC and sulfate) toward the large accumulation mode (0.42–1.2 µm). Contrarily, the diurnal production of WSOC (proxy for secondary organic aerosol) by photochemistry was similar at the two sites but mostly affected the small accumulation mode of particles (0.14–0.42 µm) in Bologna, while a shift to larger accumulation mode was observed at the rural site. A significant increment in carbonaceous aerosol concentration (for both WSOC and WINC) at the urban site was recorded mainly in the size range 0.05–0.14 µm indicating a direct influence of traffic emissions on the mass concentrations of quasi-ultrafine particles.