Results obtained during a winter field campaign for the fine fractions of particulate matter are presented. A high pollution episode together with an analysis of the main factors, which influence accumulation of pollutants is described. The measurement campaigns were carried out simultaneously at two sites in Northern Italy, Milan and Erba, during the winter of 2000. The daily variability in the mass concentration values and PM2.5/PM10 ratios appeared to be strongly dependent upon meteorological and atmospheric stability conditions and, in particular, wind regimes. During the intensive field campaign a high-pollution episode occurred that led to TSP and fine fraction concentrations well above the attention and alarm thresholds, reaching values of up to 200–250 μg m −3. The elemental concentrations were determined by ED-XRF analysis. The elemental composition of the particulate matter indicated that crustal matter oxides (soil dust) were the main component in particles with aerodynamic diameter d ae>10 μm. They were an important part also in particles with 2.5<d ae<10 μm, but strongly decreased in particles with d ae<2.5 μm. In the finer fraction sulphates nitrogen and carbon compounds played a major role. The temporal patterns of mass and elemental concentrations, as well as the main components of PM were very similar at the two sites. The high-pollution episode was recorded at many locations in the Po plain, highlighting the role of meteorology and thermodynamic atmospheric conditions on pollution build-up on a large area.