We report on the CuPbZn content of PM10 and PM2.5 samples collected from three sites (urban T0, suburban T1 and rural T2) during the Mexico City MILAGRO campaign of March 2006. Daytime city centre concentrations of summation operator CuZnPb(PM10) were much higher (T0 > 450 ng m(-3)) than at the suburban site (T1 < 200 ng m(-3)). Rural site (T2) summation operator CuZnPb(PM10) concentrations exceeded 50 ng m(-3) when influenced by the megacity plume but dropped to 10 ng m(-3) during clean northerly winds. Nocturnal metal concentrations more than doubled at T0, as pollutants became trapped in the nightly inversion layer, but decreased at the rural site. Transient spikes in concentrations of different metals, e.g. a "copper event" at T0 (CuPM10 281 ng m(-3)) and "zinc event" at T1 (ZnPM10 1481 ng m(-3)) on the night of March 7-8, demonstrate how industrial pollution sources produce localised chemical inhomogeneities in the city atmosphere. Most metal aerosols are <2.5 microm and SEM study demonstrates the dominance of Fe, Ti, Ba, Cu, Pb and Zn (and lesser Sn, Mo, Sb, W, Ni, V, As, Bi) in metalliferous particles that have shapes including spherical condensates, efflorescent CuZnClS particles, cindery Zn, and Cu wire. Metal aerosol concentrations do not change in concert with PM10 mass, which is more influenced by wind resuspension than industrial emissions. Metalliferous particles can induce cell damage, and PM composition is probably more important than PM mass, with respect to negative health effects, so that better monitoring and control of industrial emissions would likely produce significant improvements in air quality.