In Winter 2009 an intensive experimental campaign (DAURE) was conducted in an urban site (Barcelona) and in an elevated rural background station (Montseny) in the western Mediterranean basin. During this period three main scenarios were identified based on distinct meteorological conditions: A) temperature inversion, B) cloudy days in normal conditions, and C) intense sea breeze. Filter samples of the submicron fraction (PM1) collected during these scenarios were analysed for organic tracer compounds to gain insight into the composition, sources, formation and processing of aerosol organic matter in the region under contrasting conditions. The results were compared to on-line Aerosol Mass Spectrometry (AMS) measurements. Scenario A conditions had the highest pollution concentrations in Barcelona (traffic and secondary aerosol formation) and lowest in Montseny whose sampling station remained above the mixing layer. Under scenario B the biomass burning contribution was highest in Montseny, reflecting nearby biomass burning sources. Under scenario C, the traffic-related contributions were highest in Montseny and lowest in Barcelona in comparison to the other samples, reflecting the enhanced pollution transport to Montseny and greater dilution in Barcelona. In this scenario, secondary organic aerosol was highest in Montseny. Molecular marker data and AMS source apportionment showed strong to moderate correlation for a) dicarboxylic acids and oxygenated organic aerosol, b) levoglucosan and biomass burning organic aerosol and c) Σn-alkanes and hydrocarbon-like organic aerosol.