Are radicals responsible for of the variable deuterium enrichments in chondritic insoluble organic material?

1C.M.O’D.Alexander,2M.J.Nilges,1G.D.Cody,3C.D.K.Herd
Geochimica et Cosmochimica Acta (in Press) Link to Article [https://doi.org/10.1016/j.gca.2021.10.007]
1Earth and Planets Laboratory, Carnegie Institution for Science, 5241 Broad Branch Road NW, Washington, DC 20015, USA
2EPR Laboratory, School of Chemical Sciences, Univ. Illinois at Urbana-Champaign, 505 S. Mathews Avenue, Urbana, IL 61801, USA
3Dept. Earth and Atmospheric Sciences, Univ. Alberta, Edmonton, Alberta T6G 2E3, Canada
Copyright Elsevier

The insoluble organic material (IOM) in primitive chondritic meteorites is very enriched in D (up to δD≈3500 ‰ in bulk). Based largely on a series of electron paramagnetic resonance (EPR) studies of IOM from three meteorites (Orgueil, Murchison and Tagish Lake), it has been suggested that these enrichments are the result of exchange with H2D+ in the solar nebula and that exchange with radicals in the IOM was particularly facile so that they are enormously enriched in D (δD≥95000 ‰). To try to test whether radicals are largely responsible for the D enrichments in IOM, we have used EPR to measure the radical concentrations (spins/g) and g-factors of 18 IOM separates from C1-2 chondrites of varying petrologic type and chemical group that have a much wider range of H isotopic compositions (δD≈600-3500 ‰) than in previous studies. We confirm the previous studies findings that IOM exhibits non-Curie law behavior and that it does not completely saturate even at microwave excitation powers of 200 mW. We also have obtained similar g-factor values. However, our IOM samples typically exhibit a lower and more limited range of spin concentrations, and smaller deviations from Curie law behavior than in previous studies. Nor do we observe correlations between bulk δD and either spins/g or non-Curie law behavior that would be expected if exchange between H2D+ and radicals, as previously proposed, was the cause of the D-enrichments in IOM. Indeed, in general the radical concentrations and the degree of non-Curie law behavior do not seem to correlate with any of the measured IOM properties, with chondrite group or parent body history (e.g., degree of aqueous alteration). The only exceptions are the IOM in four Tagish Lake lithologies whose spin concentrations increase with increasing degree of thermal processing as indicated by decreasing H/C and δD, and increasing aromaticity.

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