The chemical composition of fine (PM2.5) and coarse (PM2.5-10) particulate matter was investigated in 7-week field campaigns of contrasting air pollution at six urban background sites in Europe. The campaigns were scheduled to include seasons of local public health concern due to high particulate concentrations or findings in previously conducted epidemiological studies. The sampling campaigns were carried out as follows: Duisburg/Germany October-November 2002 (autumn), Prague/Czech Republic November 2002-January 2003 (winter), Amsterdam/Netherlands January-March 2003 (winter), Helsinki/Finland March-May 2003 (spring), Barcelona/Spain March-May 2003 (spring) and Athens/Greece June-July 2003 (summer). Aerosol samples were collected in 3+4-day periods per week (N=14) using two identical virtual impactors (VI). All the filter samples were analysed with the same instruments to obtain particulate mass, inorganic ions, total and watersoluble elements, and elemental and organic carbon content. The campaign means of PM2.5 and PM2.5-10 ranged from 8.3 to 30 and 5.4 to 29 μg m-3, respectively. The "wet and cool" seasons favoured a low coarse-to-fine particulate mass ratio (<1), whereas the ratio was high (>1) during the warmer and drier spring and summer campaigns. According to chemical mass closure, the major components in PM2.5 were carbonaceous compounds (organic matter+elemental carbon), secondary inorganic ions and sea salt, whereas those in PM2.5-10 were soil-derived compounds, carbonaceous compounds, sea salt and nitrate. The major and minor components together accounted for 79-106% and 77-96% of the gravimetrically measured PM2.5 and PM2.5-10 mass, respectively. In conclusion, the measured PM2.5 and PM2.5-10 in the campaigns could be reconstructed to a large extent with the help of harmonized particulate sampling and analysis of the selected chemical constituents. The health significance of the observed differences in chemical composition and emission sources between the size-segregated particulate samples will be investigated in toxicological cell and animal studies. © 2006 Elsevier Ltd. All rights reserved.