On the electron-induced isotope fractionation in low temperature 32O2/36O2 ices - Ozone as a case study

The formation of six ozone isotopomers and isotopologues, 16O16O16O, 18O18O 18O, 16O16O18O, 18O 18O16O, 16O18O16O, and 18O16O18O, has been studied in electron-irradiated solid oxygen 16O2 and 18O2 (11) ices at 11 K. Significant isotope effects were found to exist which involved enrichment of 18O-bearing ozone molecules. The heavy 18O18O18O species is formed with a factor of about six higher than the corresponding 16O16O16O isotopologue. Likewise, the heavy 18O18O16O species is formed with abundances of a factor of three higher than the lighter 16O16O 18O counterpart. No isotope effect was observed in the production of 16O18O16O versus18O 16O18O. Such studies on the formation of distinct ozone isotopomers and isotopologues involving non-thermal, non-equilibrium chemistry by irradiation of oxygen ices with high energy electrons, as present in the magnetosphere of the giant planets Jupiter and Saturn, may suggest that similar mechanisms may contribute to the 18O enrichment on the icy satellites of Jupiter and Saturn such as Ganymede, Rhea, and Dione. In such a Solar System environment, energetic particles from the magnetospheres of the giant planets may induce non-equilibrium reactions of suprathermal and/or electronically excited atoms under conditions, which are quite distinct from isotopic enrichments found in classical, thermal gas phase reactions.