A detailed physical and chemical characterization of coarse particulate matter (PM10) and fine particulate matter (PM2.5) in the city of Huelva (in Southwestern Spain) was carried out during 2001 and 2002. To identify the major emission sources with a significant influence on PM10 and PM2.5, a methodology was developed based on the combination of: (1) real-time measurements of levels of PM10, PM2.5, and very fine particulate matter (PM1); (2) chemical characterization and source apportionment analysis of PM10 and PM2.5; and (3) intensive measurements in field campaigns to characterize the emission plumes of several point sources. Annual means of 37, 19, and 16 microg/m3 were obtained for the study period for PM10, PM2.5, and PM1, respectively. High PM episodes, characterized by a very fine grain size distribution, are frequently detected in Huelva mainly in the winter as the result of the impact of the industrial emission plumes on the city. Chemical analysis showed that PM at Huelva is characterized by high PO4(3-) and As levels, as expected from the industrial activities. Source apportionment analyses identified a crustal source (36% of PM10 and 31% of PM2.5); a traffic-related source (33% of PM10 and 29% of PM2.5), and a marine aerosol contribution (only in PM10, 4%). In addition, two industrial emission sources were identified in PM10 and PM2.5: (1) a petrochemical source, 13% in PM10 and 8% in PM2.5; and (2) a mixed metallurgical-phosphate source, which accounts for 11-12% of PM10 and PM2.5. In PM2.5 a secondary source has been also identified, which contributed to 17% of the mass. A complete characterization of industrial emission plumes during their impact on the ground allowed for the identification of tracer species for specific point sources, such as petrochemical, metallurgic, and fertilizer and phosphate production industries.