Aerosol particle samples (PM10) were collected at urban, industrial and rural sites located in Rio de Janeiro, Brazil, between October 2008 and September 2009. Aerosol samples for each site were analyzed for total and soluble metals, water-soluble ions, carboxylic acids, and water-soluble organic carbon (WSOC). The results showed that the mean PM10 concentrations were 34 μg m(-3); 47 μg m(-3) and 71 μg m(-3) at the rural, urban and industrial sites, respectively. An increase in the average concentration of these particles due to air stagnation was observed during the period from May to September for all sites, and an increase in hospitalization for respiratory problems was also reported. On average, the anions species represented 4 to 14% of total content, while cations species corresponded to 1 to 11% and 7.5% for WSOC. The overall metal content at the industrial site was nearly the double that at the rural site. The concentrations of the studied species are influenced mainly by site location and the specific characteristics present at each site. However, higher concentrations of some species were observed on particular dates and were probably due to biomass burning and African dust events. The acid/aqueous percentiles showed that the most efficiently extracted metals from the aqueous phase were V and Ni (40%), while Al and Fe represented a lower percentage (<3%). Analysis of the aqueous fraction provides important information about the bioavailability of metals that is associated with the inflammatory process in the lungs.