Display omitted •Geochemical anomalies of toxic elements in PM10 related to metallurgy have been identified in an urban ambient.•Fugitive emissions from brass industries are an important source of metals and metalloids.•Speciation of Sb(III) and Sb(V) in PM10 can be used as a geochemical tracer to identify the influence of industry and traffic on the air quality. The chemical composition of atmospheric particulate matter (PM) has been studied at the cities of Cordoba and Granada (South of Spain) between 2007 and 2013, considering urban background, traffic and industrial monitoring stations. The results of Principal Component Analysis (PCA) indicated that geochemical anomalies observed in the ambient air of Cordoba (mainly Cu, Zn, Pb and Cd) are closely related to the geochemical profile obtained from fugitive metallurgy emissions of brass industries. These findings have been confirmed performing an Sb speciation analysis of PM10 samples, which allowed to distinguish between Sb(III) and Sb(V). The percentage of Sb(V) in PM10 found in the traffic station of Granada was 64–69%. At Cordoba, the percentage of Sb(V) was found to be higher (73–77%) at both urban background and traffic stations, indicating a possible second source of Sb in the PM of this city. The PM10 samples from the industrial station of Cordoba showed a 85–86% of Sb(V). A similar percentage (84–88%) of Sb(V) was found for the fugitive emissions of the brass industries, confirming this industrial source of Sb. These results show that Sb speciation can be a useful geochemical tracer to identify anthropogenic sources (traffic and industrial) emissions of PM.