Oxygen and magnesium mass-independent isotopic fractionation induced by chemical reactions in plasma

Enrichment or depletion ranging from −40 to +100% in the major isotopes 16O and 24Mg were observed experimentally in solids condensed from carbonaceous plasma composed of CO2/MgCl2/Pentanol or N2O/Pentanol for O and MgCl2/Pentanol for Mg. In NanoSims imaging, isotope effects appear as micrometer-size hotspots embedded in a carbonaceous matrix showing no isotope fractionation. For Mg, these hotspots are localized in carbonaceous grains, which show positive and negative isotopic effects so that the whole grain has a standard isotope composition. For O, no specific structure was observed at hotspot locations. These results suggest that MIF (mass-independent fractionation) effects can be induced by chemical reactions taking place in plasma. The close agreement between the slopes of the linear correlations observed between δ25Mg versus δ26Mg and between δ17O versus δ18O and the slopes calculated using the empirical MIF factor η discovered in ozone [M. H. Thiemens, J. E. Heidenreich, III. Science 219, 1073–1075; C. Janssen, J. Guenther, K. Mauersberger, D. Krankowsky. Phys. Chem. Chem. Phys. 3, 4718–4721] attests to the ubiquity of this process. Although the chemical reactants used in the present experiments cannot be directly transposed to the protosolar nebula, a similar MIF mechanism is proposed for oxygen isotopes: at high temperature, at the surface of grains, a mass-independent isotope exchange could have taken place between condensing oxides and oxygen atoms originated form the dissociation of CO or H2O gas.

A prolonged, two-step oxygenation of Earth’s early atmosphere: Support from confidence intervals

The Great Oxidation Event (GOE), among Earth’s most transformative events, marked the sustained presence of oxygen above 10–5 times the present atmospheric level. Estimates of the onset of the GOE span 2501–2225 Ma and are based primarily on the loss of mass-independent fractionation of sulfur isotopes (MIF-S) in pyrite. To better constrain the timing of the GOE, we apply probabilistic techniques to estimate the confidence intervals of four proxies: MIF-S, redox-sensitive detrital minerals, "red beds," and I/(Ca + Mg). These GOE proxies are drawn from a highly fragmentary geologic record, and consequently, estimates of the 95% confidence intervals span tens to hundreds of millions of years—orders of magnitude larger than suggested by radiometric constraints on individual successions. Confidence interval results suggest that red beds and nonzero I/(Ca + Mg) values may have appeared earlier than 2480 Ma and 2460 Ma, respectively, whereas redox-sensitive detrital minerals and MIF-S may have disappeared after 2210 Ma and 2190 Ma, respectively. These data suggest a delay of potentially >300 m.y. between initial and permanent oxygenation of the atmosphere and a delay of tens of millions of years between onset of the Lomagundi-Jatuli carbon isotope excursion and permanent oxygenation of the atmosphere.