A photochemical answer to the 'xenon paradox'

Xenon is depleted by one order of magnitude relative to other volatile elements when normalized to the chondritic composition. Furthermore, atmospheric xenon is far more enriched in the heavy isotopes relatively to chondritic and solar compositions (3-4%.amu^-1) than atmospheric krypton (< 1%.amu^-1). This discrepancy, known as the 'xenon paradox', has led to sophisticated models of atmospheric evolution coupled with mantle geodynamics (Pepin, 1991; Tolstikhin and Marty, 1998) and cometary contributions (Dauphas, 2003; Owen et al., 1992) that could explain terrestrial noble gas patterns under ad hoc conditions during the building stages of the Earth, no more than ~200 Ma following the beginning of solar system formation. Yet, xenon having an isotopic composition intermediate between the atmospheric and the chondritic ones has been recently documented in Archean (≤3 Ga-old) sedimentary rocks (Pujol et al., 2011), suggesting that isotopic fractionation of Xe occurred over a much longer period of time than previously thought, during the Hadean and the Archean eons. In that case, assuming a Rayleigh type isotope evolution for atmospheric Xe requires an enrichment fractionation factor of 1.3% in heavy isotopes for Xe remaining in the atmosphere. This is clearly within the range of values observed in laboratory experiments aimed at trapping and fractionating Xe isotopes in solids, which is only effective upon ionization (Marrocchi et al., 2011; Kuga et al., 2012). We report here a possibility for explaining the 'xenon paradox' through interaction of the Hadean/Archean atmosphere with EUV light from the young Sun. By using a new photochemical model, we have found out that atmospheric Xe depletion and enrichment in heavy Xe isotopes could be achieved by EUV photoionization deep enough in the atmosphere to allow the preferential implantation of the heavier Xe isotopes in organic aerosols, the formation of which is itself triggered by UV photochemistry. Most of the ionized Xe would have escaped from the atmosphere into space by hydrodynamic escape (Zahnle, 2011). We have established that this mechanism specifically affected Xe and was particularly effective during the Hadean/Archean times, since the irradiation flux was expected to be orders of magnitude higher than today (Ribas et al., 2010). Dauphas (2003), Icarus 165, 326-339. Kuga et al. (2012), #2347 Goldschmidt 2012 Marrocchi et al. (2011), GCA 75, 6255-6266. Owen et al. (1992), Nature 358, 43-46. Pepin (1991), Icarus 92, 1-79. Pujol et al. (2011), Earth Planet. Sci. Lett. 308, 298-306. Ribas et al. (2010), Astrophys. J. 714, 384-395. Srinivasan, (1976), Earth Planet. Sci. Lett. 31, 129-141. Tolstikhin and Marty (1998), Chem. Geol. 147, 27-52. Zahnle (2011), #2241 Goldschmidt 2011