Sulfur, ultraviolet radiation, and the early evolution of life

The present biosphere is shielded from harmful solar near ultraviolet (UV) radiation by atmospheric ozone. We suggest here that elemental sulfur vapor could have played a similar role in an anoxic, ozone-free, primitive atmosphere. Sulfur vapor would have been produced photochemically from volcanogenic SO2 and H2S. It is composed of ring molecules, primarily S8, that absorb strongly throughout the near UV, yet are expected to be relatively stable against photolysis and chemical attack. It is also insoluble in water and would thus have been immune to rainout or surface deposition over the oceans. The concentration of S8 in the primitive atmosphere would have been limited by its saturation vapor pressure, which is a strong function of temperature. Hence, it would have depended on the magnitude of the atmospheric greenhouse effect. Surface temperatures of 45 degrees C or higher, corresponding to carbon dioxide partial pressures exceeding 2 bars, are required to sustain an effective UV screen. Two additional requirements are that the ocean was saturated with sulfite and bisulfite, and that linear S8 chains must tend to reform rings faster than they are destroyed by photolysis. A warm, sulfur-rich, primitive atmosphere is consistent with inferences drawn from molecular phylogeny, which suggest that some of the earliest organisms were thermophilic bacteria that metabolized elemental sulfur.