The early history of oxygen and ozone in the atmosphere

There may have been three stages in the growth of oxygen in the terrestrial atmosphere. Prior to the origin of photosynthesis the only source of oxygen was photolysis of water vapor followed by escape of hydrogen to space. The rate of this process was probably less than the rate of release of reduced gases (principally hydrogen) from volcanoes, so the oxygen partial pressure was held to negligibly low values by photochemical reactions with an excess of hydrogen. The photosynthetic source of oxygen was probably in operation as long ago as 3.8 billion years. It released oxygen to the ocean. Presumably most of this oxygen was destroyed in the ocean as long as its rate of supply was less than the rate of supply of readily oxidizable material (principally Fe²⁺) provided by the weathering of rocks. This phase appears to have lasted until about 2 billion years ago, during which period most banded iron formations were deposited. During this period the production of oxygen by algae was limited by competition with photosynthetic bacteria, which preempted the supply of nutrient phosphorus as long as reduced chemicals were available in the environment. Once the photosynthetic oxygen source exceeded the rate of supply of reduced minerals exposed by erosion and weathering, the accumulation of oxygen in the ocean and atmosphere could be controlled only by reaction of oxygen with reduced organic material. This is the stabilization mechanism that operates today. It seems unlikely that oxygen could be consumed at a significant rate by this process until oxygen levels sufficiently high to support respiration had been achieved. I therefore suggest that atmospheric oxygen rose rapidly from essentially zero to approximately its present value (within a factor of 10) when the photosynthetic source of oxygen rose above the weathering source of reduced minerals, probably about 2 billion years ago. The ozone layer and the ultraviolet screen were absent prior to this time and essentially fully developed after this time.Presented at IAGA/IAMAP Symposium on Minor Neutral Constituents in Middle Atmosphere-Chemistry and Transport, Seattle, August, 1977.