Abstract: | Eighty-three samples of atmospheric particles were collected at a representative traffic site in the Mediterranean city of Seville during a period of one year. Urban particles were collected on quartz filters with a high-volume sampler coupled with a cascade impactor which separates particles into six size ranges: >10, 10–4.9, 4.9–2.7, 2.7–1.3, 1.3–0.6, and <0.6 m. The total metal content, its distribution by size (physical speciation), and the concentrations of different chemical forms (chemical speciation) in particles less than 0.6 m were determined. The chemical speciation scheme furnished four fractions: soluble and exchangeable metals; carbonates, oxides, and reducible metals; oxidisable and sulfidic metals bound to organic matter; and residual metals. The samples were analysed by ICP–OES for Pb, Ni, Cd, S, Fe, Zn, Cu, Ba, Mn, and V. Gaseous pollutants, traffic intensities, and primary meteorological data provided by the atmospheric and traffic networks were statistically related to the analytical data. Analytical and statistical results from physical and chemical speciation singled out Ba as a valid tracer of vehicular traffic, instead of Pb, in cities with high traffic density. Another important relationship was found between Pb and Cu. Physical speciation of lead showed that the major risk for health was from fine particles less than 2.7 m, because particles between 2.7 and 0.6 m were the size fractions of the total suspended particles with the major mass abundance of lead (mainly particles between 2.7 and 1.3 m) and because particles less than 0.6 m were the fraction of airborne particles most abundant in the urban air. Chemical speciation results showed that special attention must be taken with Ni and Cd concentrations, because of their high potential bioavailability, mainly a result of the high solubility of the chemical forms of Ni in the finest particles. |