In 1983, Thiemens and Heidenreich reported the first chemically produced mass-independent isotope effect. This work has been shown to have a wide range of applications, including atmospheric chemistry, solar system evolution, and chemical physics. This work has recently been reviewed (Weston, R. E. Chem. Rev. 1999, 99, 2115-2136; Thiemens, M. H. Science 1999, 283, 341-345). In this Account, observations of mass-independent isotopic compositions in terrestrial and Martian solids are reviewed. A wide range of applications, including formation and transport of aerosols in the present atmosphere, chemistry of ancient atmospheres and oceans, history and coupling of the atmosphere-surface in the Antarctic dry valleys, origin and evolution of oxygen in the Earth's earliest environment, and the chemistry of the atmosphere and surface of Mars, are discussed.