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Catling, David

Publications and source records attributed to Catling, David.

Sulfur during the Transition from Anoxic to Oxic Atmospheres

The invention of oxygenic photosynthesis was likely accompanied by the introduction of large amounts of O2 and complementary reduced gases (chiefly CH4) into the atmosphere. To first approximation the venting of O2 and CH4 are stochiometrically linked. We therefore present a suite of numerical photochemical models that address the anoxic-oxic transition in an atmosphere driven by large linked inputs of biogenic 02 and CH4. We find in general that, in steady state, there are two solutions, one oxic and the other anoxic. The anoxic solution appears to be linearly stable. If volcanic SO2 fluxes are large, S disproportionates into oxidized (H2S04) and reduced (S8) exit channels. As elemental sulfur is insoluble it provides a means of preserving photochemical mass-independent fractionation (MIF). On the other hand, if the source of volcanic SO2 is smaller than today, all S can leave the atmosphere as S8. Under these conditions there would be no MIF signal. The oxic solution appears to be linearly unstable. In the oxic solutions S is invariably oxidized to sulfate, and the MIF signal would be absent. The transitional atmosphere is relatively unstable and is also the most photochemically active. Consequently it is the transitional atmosphere, not the oxic or anoxic atmospheres, that has the lowest CH4 levels and weakest greenhouse warming. As a practical matter we expect the transitional atmospheres to vary strongly in response to diurnal and seasonal biological forcing.

Zahnle, Kevin↗

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗