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Geobiology. 2011 Jul;9(4):313-20. doi: 10.1111/j.1472-4669.2011.00286.x.

Greenhouse warming by nitrous oxide and methane in the Proterozoic Eon.

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Department of Geosciences, Pennsylvania State University, University Park, PA, USA.


An anoxic, sulfidic ocean that may have existed during the Proterozoic Eon (0.54-2.4 Ga) would have had limited trace metal abundances because of the low solubility of metal sulfides. The lack of copper, in particular, could have had a significant impact on marine denitrification. Copper is needed for the enzyme that controls the final step of denitrification, from N(2) O to N(2) . Today, only about 5-6% of denitrification results in release of N(2) O. If all denitrification stopped at N(2) O during the Proterozoic, the N(2) O flux could have been 15-20 times higher than today, producing N(2) O concentrations of several ppmv, but only if O(2) levels were relatively high (>0.1 PAL). At lower O(2) levels, N(2) O is rapidly photodissociated. Methane concentrations may also have been elevated during this time, as has been previously suggested. A lack of dissolved O(2) and sulfate in the deep ocean could have produced a high methane flux from marine sediments, as much as 10-20 times today's methane flux from land. The photochemical lifetime of CH(4) increases as more CH(4) is added to the atmosphere, so CH(4) concentrations of up to 100 ppmv are possible during this time. The combined greenhouse effect of CH(4) and N(2) O could have provided up to 10° of warming, thereby keeping the surface warm during the Proterozoic without necessitating high CO(2) levels. A second oxygenation event near the end of the Proterozoic would have resulted in a reduction in both atmospheric N(2) O and CH(4) , perhaps triggering the Neoproterozoic "Snowball Earth" glaciations.

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