Perfluoropolyethers (PFPEs) are a family of perfluorinated fluids used mainly in industrial applications. Lower molecular weight commercial PFPE fractions have boiling points ranging between 55 and 270 degrees C, and have the potential to escape into the atmosphere. To improve our understanding of the atmospheric chemistry of PFPEs, a distilled fraction of a commercial mixture containing perfluoropolymethylisopropyl ethers (PFPMIEs) was introduced into an atmospheric chamber system. Relative rate techniques were used to determine upper limits for the rate constants for reactions of OH and Cl with PFPMIE in 700 Torr of air at 296 K. The reactivity of PFPMIE with Cl was less than 2 x 10(-17) cm3 molecule(-1) s(-1), while the reactivity with OH was less than 6.8 x 10(-16) cm3 molecule(-1) s(-1), indicating low reactivity in the troposphere. Consequently, the lifetime of PFPMIE should be limited bytransport to the mesosphere, where photolysis by Lyman-alpha radiation at 121.6 nm will be efficient. By analogy to perfluorinated alkanes, the lower limit for the total atmospheric lifetime is 800 years. PFPMIE was shown to have instantaneous radiative forcing of 0.65 W m(-2) ppb(-1), which corresponds to a global warming potential on a 100 year time scale of 9000 relative to CO2 and 1.95 relative to CFC-11.