Volatile element behaviour in cometary ice analogues under irradiation

Comets represent some of the most pristine and unprocessed bodies in our solar system. As such, their analysis can provide a unique insight into the chemical makeup of the early Solar System. Furthermore, due to their volatile-rich nature, comets may have played an important role in delivering volatile elements (e.g., H, C, N, O) and organic materials to the early Earth. Understanding how comets form can therefore provide a wealth of information on how the composition of volatile elements evolved in the solar system, from the pre-solar molecular cloud up until the formation of the terrestrial planets. Decades of cometary studies, and the recent ESA Rosetta mission to comet 67P/Churyumov-Gerasimenko (67P/C-G), have demonstrated that volatile species trapped in comets have a composition that is distinct from any other known reservoir in the Solar System. Cometary nitrogen, in particular, shows strong enrichments in the rare ¹⁵N isotope. The origin of these enrichments remains unclear, potentially reflecting the isotopic fractionation of an initial ¹⁵N-poor nebular gas, or inheritance from an unknown isotopic reservoir. During this PhD, I have developed an experimental setup to form cometary ices (i.e., water-rich ices formed at very low temperatures and pressures), with the overarching objective of exploring how volatile elements (including N and noble gases) were incorporated into cometary ice during water condensation from the protosolar nebula. Different temperatures of formation (from 28 K to 80 K) and irradiation conditions have been tested in order to investigate the conditions that best reproduce the actual volatile composition of comet 67P/C-G. It was found that condensing cometary ice analogues at temperatures ∼70 K is best able to reproduce the nitrogen and noble gas abundances measured in 67P/C-G. Moreover, we discovered that the incorporation of nitrogen and noble gases into, and subsequent release from, cometary ices does not produce significant isotope variations, indicating that isotope signatures in comets were most likely inherited from their environment of formation rather than the result of fractionation during ice formation. Finally, I also investigated the effect that UV irradiation can have on the composition of volatiles trapped within cometary ice. Irradiation during and after ice deposition was found to not have a significant effect on the isotopic composition of the trapped volatile species. However, it was discovered that irradiating the surface of the ice had a major effect on the release pattern of trapped volatiles, with the ice being retentive of trapped volatiles even after the amorphous-to-crystalline ice transition (120-140 K), temperatures at which point all trapped volatiles are released from non-irradiated ice. The enhanced retention of volatiles in irradiated cometary ice may have major implications on the potential for comets to deliver volatile elements to the inner solar system. (author)