Atmospheric particles were collected with a high-volume sampling system at an urban site in Helsinki (Finland). The samples were analysed by on-line coupled supercritical fluid extraction-liquid chromatography-gas chromatography-mass spectrometry (SFE-LC-GC-MS). The aerosol sample was first extracted by SFE. The extract was then transferred to a liquid chromatograph where it was fractionated into four fractions according to polarity. Each fraction from the liquid chromatograph was transferred to a gas chromatograph by large-volume injection, where final separation was carried out. The first LC fraction (280 microl) contained nonpolar compounds, such as n-alkanes, hopanes and steranes. The second fraction (840 microl) included polycyclic aromatic hydrocarbons (PAHs) and alkyl-PAHs, while the third and fourth fractions (840 microl each) contained more polar compounds, such as n-alkan-2-ones, n-alkanals, oxy-PAHs and quinones.