In urban areas of Brazil, vehicle emissions are the principal source of fine particulate matter (PM(2.5)). The World Health Organization air quality guidelines state that the annual mean concentration of PM(2.5) should be below 10 μg m(-3). In a collaboration of Brazilian institutions, coordinated by the University of São Paulo School of Medicine and conducted from June 2007 to August 2008, PM(2.5) mass was monitored at sites with high traffic volumes in six Brazilian state capitals. We employed gravimetry to determine PM(2.5) mass concentrations, reflectance to quantify black carbon concentrations, X-ray fluorescence to characterize elemental composition, and ion chromatography to determine the composition and concentrations of anions and cations. Mean PM(2.5) concentrations and proportions of black carbon (BC) in the cities of São Paulo, Rio de Janeiro, Belo Horizonte, Curitiba, Recife, and Porto Alegre were 28.1 ± 13.6 μg m(-3) (38% BC), 17.2 ± 11.2 μg m(-3) (20% BC), 14.7 ± 7.7 μg m(-3) (31% BC), 14.4 ± 9.5 μg m(-3) (30% BC), 7.3 ± 3.1 μg m(-3) (26% BC), and 13.4 ± 9.9 μg m(-3) (26% BC), respectively. Sulfur and minerals (Al, Si, Ca, and Fe), derived from fuel combustion and soil resuspension, respectively, were the principal elements of the PM(2.5) mass. We discuss the long-term health effects for each metropolitan region in terms of excess mortality risk, which translates to greater health care expenditures. This information could prove useful to decision makers at local environmental agencies.