A long-term series (2001-2008) of chemical analysis of atmospheric particulate matter (PM(10) and PM(2.5)) collected in the city of Huelva (SW Spain) is considered in this study. The impact of emission plumes from one of the largest Cu-smelters in the world on air quality in the city of Huelva is evidenced by the high daily and hourly levels of As, other potentially toxic elements (e.g. Cu, Zn, Cd, Se, Bi, and Pb) in particulate matter, as well as the high levels of some gaseous pollutants (NO(2) and SO(2)). Mean arsenic levels in the PM10 fraction were higher than the target value set by European Directive 2004/107/EC (6 ngAs m(-3)) for 1(st) January 2013. Hourly peak concentrations of As and other metals and elements (Zn, Cu, P and Se) analyzed by PIXE can reach maximum hourly levels as high as 326 ngAs m(-3), 506 ngZn m(-3), 345 ngCu m(-3), 778 ngP m(-3) and 12 ngSe m(-3). The contribution of Cu-smelter emissions to ambient PM is quantified on an annual basis in 2.0-6.7 µg m(-3) and 1.8-4.2 µg m(-3) for PM(10) and PM(2.5), respectively. High resolution outputs of the HYSPLIT dispersion model show the geographical distribution of the As ambient levels into the emission plume, suggesting that the working regime of the Cu-smelter factory and the sea breeze circulation are the main factors controlling the impact of the Cu-smelter on the air quality of the city. The results of this work improve our understanding of the behaviour of industrial emission plumes and their impact on air quality of a city, where the population might be exposed to very high ambient concentrations of toxic metals during a few hours.