•Geochemical anomalies of toxic elements in PM10 related to mining have been studied.•High concentrations of Cu and As have been detected in rural and background stations.•As speciation explains the low impact of the mining area on the rural surrounding.•Pyrometallurgic activity produces fine particles which are transported long-distance. A characterization of chemical composition and source contribution of PM10 in three representative environments of southwest Spain related to mining activities (mineral extraction, mining waste and Cu-smelting) has been performed. A study of geochemical anomalies was conducted in the samples collected at the three stations between July 2012 and October 2013. The influence of Cu-smelting processes was compared to other mining activities, where common tracers were identified. The Cu and As concentrations in the study area are higher than in other rural and urban stations of Spain, in which geochemical anomalies of As, Se, Bi, Cd, and Pb have been reported. The results of source contribution showed similar geochemical signatures in the industrial and mining factors. However, the contribution to PM10 is different according to the type of industrial activity. These results have been confirmed performing an arsenic speciation analysis of the PM10 samples, in which the mean extraction efficiency of arsenic depended on the origin of the samples. These finding indicate that the atmospheric particulate matter emitted from Cu-smelting has a high residence time in the atmosphere. This indicates that the Cu-smelter can impact areas of high ecological interest and considered as clean air.