Abstract. Submicron ambient aerosol was characterized in summer 2005 at an urban background site in Zurich, Switzerland, during a three-week measurement campaign. Highly time-resolved samples of non-refractory aerosol components were analyzed with an Aerodyne aerosol mass spectrometer (AMS). Positive matrix factorization (PMF) was used for the first time for aerosol mass spectra to identify the main components of the total organic aerosol and their sources. The PMF retrieved factors were compared to measured reference mass spectra and were correlated with tracer species of the aerosol and gas phase measurements from collocated instru-

Real-time measurements of submicrometer aerosol were performed using an Aerodyne aerosol mass spectrometer (AMS) during three weeks at an urban background site in Zurich (Switzerland) in January 2006. A hybrid receptor model which incorporates a priori known source composition was applied to the AMS highly time-resolved organic aerosol mass spectra. Three sources and components of submicrometer organic aerosols were identified: the major component was oxygenated organic aerosol (OOA), mostly representing secondary organic aerosol and accounting on average for 52-57% of the particulate organic mass. Radiocarbon (14C) measurements of organic carbon (OC) indicated that approximately 31 and approximately 69% of OOA originated from fossil and nonfossil sources, respectively. OOA estimates were strongly correlated with measured particulate ammonium. Particles from wood combustion (35-40%) and 3-13% traffic-related hydrocarbon-like organic aerosol (HOA) accounted for the other half of measured organic matter (OM). Emission ratios of modeled HOA to measured nitrogen oxides (NOx) and OM from wood burning to levoglucosan from filter analyses were found to be consistent with literature values.

Nitrogen oxides (NOx = NO + NO2) in the atmosphere are often measured using instruments equipped with molybdenum converters. NO2 is catalytically converted to NO on a heated molybdenum surface and subsequently measured by chemiluminescence after reaction with ozone. The drawback of this technique is that other oxidized nitrogen compounds such as peroxyacetyl nitrate and nitric acid are also partly converted to NO. Thus such NO2 measurements are really surrogate NO2 measurements because the resultant values systematically overestimate the true value because of interferences of these compounds, especially when sampling photochemically aged air masses. However, molybdenum converters are widely used, and a dense network of surrogate NO2 measurements exists. As an alternative with far less interference, photolytic converters using ultraviolet light are nowadays applicable also for long‐term measurements. This work presents long‐term collocated NO2 measurements using molybdenum and photolytic converters at two rural sites in Switzerland. On a relative scale, the molybdenum converter instruments overestimate the NO2 concentrations most during spring/summer because of prevalent photochemistry. On a monthly basis, only 70–83% of the “surrogate” NO2 can be attributed to “real” NO2 at the non‐elevated site and even less (43–76%) at the elevated one. The observed interferences have to be taken into account for monitoring and regulatory issues and to be considered when using these data for ground‐truthing of satellite data or for validation of chemical transport models. Alternatively, an increased availability of artifact‐free data would also be beneficial for these issues.

The atmospheric layer closest to the ground is strongly influenced by variable surface fluxes (emissions, surface deposition) and can therefore be very heterogeneous. In order to perform air quality measurements that are representative of a larger domain or a certain degree of pollution, observatories are placed away from population centres or within areas of specific population density. Sites are often categorised based on subjective criteria that are not uniformly applied by the atmospheric community within different administrative domains yielding an inconsistent global air quality picture. A novel approach for the assessment of parameters reflecting site representativeness is presented here, taking emissions, deposition and transport towards 34 sites covering Western and Central Europe into account. These parameters are directly inter-comparable among the sites and can be used to select sites that are, on average, more or less suitable for data assimilation and comparison with satellite and model data. Advection towards these sites was simulated by backward Lagrangian Particle Dispersion Modelling (LPDM) to determine the sites' average catchment areas for the year 2005 and advection times of 12, 24 and 48 h. Only variations caused by emissions and transport during these periods were considered assuming that these dominate the short-term variability of most but especially short lived trace gases. The derived parameters describing representativeness were compared between sites and a novel, uniform and observation-independent categorisation of the sites based on a clustering approach was established. Six groups of European background sites were identified ranging from <i>generally remote</i> to more polluted <i>agglomeration</i> sites. These six categories explained 50 to 80% of the inter-site variability of median mixing ratios and their standard deviation for NO₂ and O₃, while differences between group means of the longer-lived trace gas CO were insignificant. The derived annual catchment areas strongly depended on the applied LPDM and input wind fields, the catchment settings and the year of analysis. Nevertheless, the parameters describing representativeness showed considerably less variability than the catchment geometry, supporting the applicability of the derived station categorisation

No abstract