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Abstract. A systematic study of black carbon (BC) vertical profiles measured at high-resolution over three Italian basin valleys (Terni Valley, Po Valley and Passiria Valley) is presented. BC vertical profiles are scarcely available in literature. The campaign lasted 45 days and resulted in 120 measured vertical profiles. Besides the BC mass concentration, measurements along the vertical profiles also included aerosol size distributions in the optical particle counter range, chemical analysis of filter samples and a full set of meteorological parameters. Using the collected experimental data, we performed calculations of aerosol optical properties along the vertical profiles. The results, validated with AERONET data, were used as inputs to a radiative transfer model (libRadtran). The latter allowed an estimation of vertical profiles of the aerosol direct radiative effect, the atmospheric absorption and the heating rate in the lower troposphere. The present measurements revealed some common behaviors over the studied basin valleys. Specifically, at the mixing height, marked concentration drops of both BC (range: from −48.4 ± 5.3 to −69.1 ± 5.5%) and aerosols (range: from −23.9 ± 4.3 to −46.5 ± 7.3%) were found. The measured percentage decrease of BC was higher than that of aerosols: therefore, the BC aerosol fraction decreased upwards. Correspondingly, both the absorption and scattering coefficients decreased strongly across the mixing layer (range: from −47.6 ± 2.5 to −71.3 ± 3.0% and from −23.5 ± 0.8 to −61.2 ± 3.1%, respectively) resulting in a single-scattering albedo increase along height (range: from +4.9 ± 2.2 to +7.4 ± 1.0%). This behavior influenced the vertical distribution of the aerosol direct radiative effect and of the heating rate. In this respect, the highest atmospheric absorption of radiation was predicted below the mixing height (~ 2–3 times larger than above it) resulting in a heating rate characterized by a vertical negative gradient (range: from −2.6 ± 0.2 to −8.3 ± 1.2 K day−1 km−1). In conclusion, the present results suggest that the BC below the mixing height has the potential to promote a negative feedback on the atmospheric stability over basin valleys, weakening the ground-based thermal inversions and increasing the dispersal conditions.

The fast gas-phase reaction of NO3 radicals with phenol was found to yield 2-nitrophenol as the only relevant nitration product. The yield of this product was high and independent of the concentration of NO2 at the concentrations applied. In the presence of ozone, also significant amounts of 4-nitrophenol and p-benzoquinone were formed. The rate constant of the reaction between NO3 radicals and phenol was determined to be 5.8 x 10(-12) cm3 molecule-1 s-1. The selective formation of 2-nitrophenol (2) is suggested to derive from either the concerted keto-enol tautomerism in the reaction of a phenoxy radical with NO2 or the concerted elimination of nitric acid from a cyclohexa-3,5-diene intermediate.