The spatial distribution of urban population exposures to ambient air particles was investigated as part of the Genotox'ER study conducted in four metropolitan areas (Grenoble, Paris, Rouen and Strasbourg) in France. In each city, 60 to 90 non-smoking adult and children volunteers were selected. Subjects lived in three different urban sectors: one highly exposed to traffic emissions, one influenced by local industrial sources, and a background urban environment. The Harvard Chempass multi-pollutant personal sampler was used to sample PM10 and PM2.5 particles during 48 h during two different seasons ('hot' and 'cold'). The elemental composition of the filters was analysed by Particle-Induced X-ray Emission (PIXE). Sixteen elements were found to be over the method detection limits: Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn and Pb. The relative concentrations of elements of crustal origin (Si, Al, Ca) were higher in the coarse fraction of PM10 filters, while elements associated with combustion processes (traffic emissions or industrial combustion) presented higher relative concentrations in the PM2.5 fraction (S, Ni, V, Pb). Spatial heterogeneity of elemental exposures by urban sector is substantial for some metals of health concern, with 20% to 90% greater exposure values, on average, in the traffic proximity or industrial sectors, compared to the background sector, for Fe, Zn, Cu, V and Cr. This spatial heterogeneity should not be overlooked in epidemiological or risk assessment studies.