Urban air quality impairment by ultrafine particles has become a matter of concern due to the adverse effects on human health. Most of the studies of ultrafine particles in urban air quality have focused on vehicle exhaust emissions. We studied how industrial emissions contribute to ultrafine particle concentrations in downwind urban ambient air. This research is based on experimental data collected in the ambient air of the industrial city of Huelva (SW Spain) over April 2008–December 2009 period (particle number, gaseous pollutants and black carbon concentrations and levels and chemical composition of PM10 and PM2.5 with daily and hourly resolution). This city is affected by emissions from the second largest Cu-smelter in Europe, phosphoric acid and fertilizer production plants and an oil refinery and petrochemical plant. Industrial emissions are the main cause of ultrafine particle episodes. When vehicle exhaust emissions are the main source, ultrafine particles typically show (24-h mean) concentrations within the range 14,700–5000 cm−3 (50th–1st), with 60% of these linked to this source and 30% to industrial emissions. In contrast, when daily mean levels of N are within the range 50,000–25,500 cm−3 (100th–70th), industrial and vehicle exhaust emissions accounted for 49 and 30%, respectively. High concentrations of toxic trace metals (As, Cu, Cd, Zn and Pb) were recorded when the study city suffered fumigations of the Cu-smelter plumes (e.g. 10–25 ng m−3 As, 1–2 ng m−3 Cd and >105 cm−3 of ultrafine particles). Because of these industrial emissions, ultrafine particle concentrations during daylight are about two times higher than those observed in other European cities. Recently, ultrafine particle emissions in vehicle exhausts have been subject to limit values in a recent stage of the EURO standards. Industrial emissions should also be considered. and 30% to industrial emissions. In contrast, when daily mean levels of N are within the range 50,000 e25,500 cm 3 (100the70th), industrial and vehicle exhaust emissions accounted for 49 and 30%, respectively. High concentrations of toxic trace metals (As, Cu, Cd, Zn and Pb) were recorded when the study city suffered fumigations of the Cu-smelter plumes (e.g. 10e25 ng m 3 As, 1e2 ng m 3 Cd and >105 cm 3 of ultrafine particles). Because of these industrial emissions, ultrafine particle concentrations during daylight are about two times higher than those observed in other European cities. Recently, ultrafine particle emissions in vehicle exhausts have been subject to limit values in a recent stage of the EURO standards. Industrial emissions should also be considered