The photochemistry of the paleoatmosphere

The ideas of Harold Urey on the origin and evolution of the atmosphere have dominated thinking in this area for 3 decades. Recent progress in this area is reviewed, with particular emphasis on photochemical modeling studies of atmospheric evolution. Research into the paleoatmosphere can be divided into 3 distinct areas: (1) The photochemistry/chemistry of the prebiological paleoatmosphere, (2) the evolution of oxygen and the transition to an oxidizing atmosphere, and (3) the origin and evolution of ozone. Photochemical calculations indicate that the stability of a heavily reducing paleoatmosphere of CH4--NH3 was extremely shortlived, if such a prebiological atmosphere ever existed at all. A more mildly reducing early atmosphere of CO2--N2 is favored by photochemical considerations. Recent calculations of O2 in the prebiological paleoatmosphere vary from less than 10(-14) of present atmospheric level (PAL) to 10(-1) PAL. Clearly, additional work is indicated. The evolution of O3 as a function of O2 level has been investigated with increasingly detailed photochemical models that have included the photochemistry/chemistry of the oxygen, hydrogen, nitrogen, carbon, and chlorine species, as well as the effects of eddy transport, the rainout of water-soluble species, dry deposition and lightning as a source of trace atmospheric gases.