Infrared reflection absorption spectroscopy and quartz crystal microbalance, integrated into a one-surface analytical system, and complemented with tapping mode atomic force microscopy, has been used to explore the metal/atmosphere interfacial region under atmospheric pressure conditions. This unique combination of ill situ techniques, all possessing submonolayer sensitivity, has revealed information on the different accelerating roles of ozone (O-3) and nitrogen dioxide (NO2) on the SO2-induced atmospheric corrosion of copper. The formation of reaction products could be followed quantitatively with respect to chemical identity and kinetics. Exposure in SO2-containing humidified air resulted in CuSO3. xH(2)O-like species, formed atop a cuprous oxide, designated Cu2O, all over the copper surface. O-3 introduction resulted in an accelerated mass gain with an increased formation rate of both Cu2O and of CuSO4. xH(2)O all over the surface. NO2 introduction resulted in less mass gain than observed under SO2 and O-3, with no formation of new Cu2O, an initial oxidation of CuSO3. xH(2)O to CuSO4. xH(2)O, and with sulfite oxidation gradually replaced by copper nitrate formation, possibly as CuNO3(OH)(3) The formation rates of the dominating end products, CuSO4. xH(2)O in SO2/O-3 and Cu2NO3(OH)(3) in SO2/NO2 seemed to be limited by the supply of the gaseous constituents.