The abundance and the behavior of metals (Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Se, Ag, Cd, Sn, Ba, Pt, Hg, and Pb) and (Na+ K+ Mg2+ Ca2+, NH4+, Cl-, NO3-, SO42-, PO43- and oxalate) in size-fractionated atmospheric particulate matter (PM) were studied in the U. K. and Ireland at four observation sites simulating extreme degrees of vehicular traffic influence in the environment. Trace metals in urban PM showed distinct types of size-fractionated behavior depending on the particle sources from which they originate. In coarse PM (1.5 <D-p <3.0 mu m) the concentrations of copper, barium, and iron correlated closely across over 2 orders of magnitude in urban air, which is seen as evidence that major portions of transition metals (Cu, Ba, Fe, and Mn) are released through abrasive vehicular emissions, particularly the wear of brake linings. Further results are strongly indicative of a decoupling of coarse iron and calcium, the former arising predominantly from vehicles, the latter from soil resuspension. In fine PM (D-p <0.5 mu m), several combustion and secondary sources of particulates were identified, but these were much less unique in terms of elemental fingerprints. An analysis of the water solubility of trace metals yielded that solubility varies considerably with element and, to a lesser extent, with particle size. Notable differences were found to the elemental water solubilities determined in previous work, partially explained by differences in extraction procedures.