Looking for robust indicators of motor vehicle emissions it has been found that brake wear and linings are significant contributors of Cu, Mo and Sb to air particulate matter. These trace elements, whose mutual ratios in airborne particulate matter resulted quite different from those in crustal material, appear to be available fingerprinting tools to identify the contribution of on-road vehicles to traffic-derived particulate matter. In this study, the results of analytical determinations of Cu, Mo and Sb on PM(10), PM(2.5), vegetation and brake dust samples, together with gas (CO, NOx) concentrations, are discussed. Highly significant correlations among Cu, Sb and Mo were observed in particulate matter from Palermo and between Cu-Sb and Cu-Mo at Catania. Further significant positive correlations have been found in pine needles from Palermo, Gela and in platanus leaves from Catania.