The chemical composition of ambient particulate matter (PM) varies widely as a function of its main emission sources and of the chemical reactions which take place in the atmosphere. The aim of this study is to obtain the chemical profile of PM10 and PM2.5 during peak PM episodes, thus identifying the main emission sources and/or atmospheric processes which originate the PM episodes. To this end, cluster analysis was applied to a set of PM10 and PM2.5 data collected throughout 2001 in two urban and industrialised areas in NE Spain. As a result of this analysis, five clusters were identified for each site, and the interpretation of their chemical profiles lead to the identification of five types of peak PM episodes for each site: industrial, traffic and regional re-circulation episodes at both sites, plus crustal episodes in Barcelona, and peak traffic and industrial episodes (T+I) in Tarragona. Traffic episodes are characterised by daily means of 23 and 10 microg/m3 of OM+EC in Barcelona and Tarragona in PM10. Levels of secondary inorganic aerosols reach average daily means of 19 and 11 microg/m3 in Barcelona and Tarragona in PM10 during industrial episodes. High levels of sulphate (>5 microg/m3) and ozone (up to 77 microg/m3 daily mean) are good tracers of regional re-circulation episodes. During crustal episodes daily means of crustal elements reach up to 34 microg/m3 in Barcelona. Special attention has been drawn to the composition of the mineral matter during the different PM episodes.