Puertollano is the largest industrial centre in central Spain, and includes fossil fuel burning power plants as well as petrochemical and fertilizer complexes. The coal-fired power plants use locally mined coal from extensive coal deposits which continue to be exploited and used locally. The coal deposits have a distinctive geochemistry, being particularly enriched in Sb and Pb, as well as several other metals/metalloids that include Zn and As. ICP-AES and ICP-MS chemical analysis of particulate matter samples (both PM 10 and PM 2.5) collected at Puertollano over a 57-week period in 2004–2005 reveals enhanced levels of several metallic trace elements, especially in the finer (PM 2.5) aerosol fraction. Factor analysis applied to the data indicates that at least some of these metallic elements are likely to originate from hydrocarbon combustion: Sb and Pb are markers linked to the local coals, whereas V and Ni are, at least in the finer (PM 2.5) fraction, likely associated with other anthropogenic sources. Other factors measured are related to natural sources such as crustal/mineral and sea spray particles. Our study provides an example of how chemical analysis of large numbers of ambient PM samples, combined with statistical factor analysis and coal geochemistry, can reveal airborne emissions from the combustion of specifically identifiable fuels.