Total individual concentrations (in both gaseous and particulate phases) of 80 polycyclic aromatic compounds (PACs) including 32 nitro-PAHs, 27 oxy-PAHs (polycyclic aromatic hydrocarbons) and 21 parent PAHs have been investigated over a year in the ambient air of Grenoble (France) together with an extended aerosol chemical characterization. The results indicated that their concentrations were strongly affected by primary emissions in cold period, especially from residential heating (i.e. biomass burning). Besides, secondary processes occurred in summer but also in cold period under specific conditions such as during long thermal inversion layer periods and severe PM pollution events. Different secondary processes were involved during both PM pollution events observed in March–April and in December 2013. During the first one, long range transport of air masses, nitrate chemistry and secondary nitro-PAH formation seemed linked. During the second one, the accumulation of primary pollutants over several consecutive days enhanced secondary chemical processes notably highlighted by the dramatic increase of oxy-PAH concentrations. The study of the time trends of ratios of individual nitro- or oxy-PAHs to parent PAHs, in combination with key primary or secondary aerosol species and literature data, allowed the identification of potential molecular markers of PAH oxidation. Finally, 6H-dibenzo[b,d]pyran-6-one, biphenyl-2,2’-dicarboxaldehyde and 3-nitrophenanthrene have been selected to be the best candidates as markers of PAH oxidation processes in ambient air.< Réduire