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Alexandra McKinnon

Publications and source records attributed to Alexandra McKinnon.

2 recordsLinked to original sources

CO and N2 Produced from H2O, CO2, and NH3 Cometary Ice Analogs

Hypervolatile species such as carbon monoxide (CO) and molecular nitrogen (N2) have been detected in comets, and could be used to constrain comet formation temperature conditions if their presence is due to freeze-out and/or entrapment. Here we instead explore another plausible origin of cometary hypervolatiles: photodissociation of less volatile species. We characterize CO and N2 formation following ultraviolet (UV) irradiation and electron bombardment of carbon dioxide (CO2), ammonia (NH3), H2O:CO2, H2O:NH3, and H2O:CO2:NH3 cometary ice analogs. We find that CO and N2 form in all photoprocessed ices at temperatures between 10 K and 100 K, resulting in 0.4-0.9 % CO and 0.03-0.7 % N2 relative to water, and CO/CO2 and N2/NH3 mixing ratios of 2.5-62 % and 0.7-9 %, respectively, across the experiments. Because our initial ices are reasonably well-matched to interstellar ices and we use UV exposure similar to a dark cloud, we can compare the resulting ratios directly to cometary abundances. Such a comparison shows that while only a few of CO observations in comets are readily explained by photodissociation, almost all observed cometary N2 can be accounted for by photodissociation of NH3 embedded in water ice. The latter result is also consistent with observed similarly elevated isotopic ratios of N2 and NH3 in 67P. Taken together, our results suggest that N2/H2O ratios less than 1 % should be used cautiously when inferring a comet's formation location, while the more substantial CO abundances seen in many comets do likely imply entrapment at low ice temperatures.

astro-ph.EP

Functionalization of Benzene Ices by Atomic Oxygen

Small aromatic molecules, including functionalized derivatives of benzene, are known to be present throughout the different stages of star and planet formation. In particular, oxygen-bearing monosubstituted aromatics, likely including phenol, have been identified in the coma of comet 67P. This suggests that, earlier in the star and planet formation evolution, icy grains may act as both reservoirs and sites of functionalization for these small aromatics. We investigate the ice-phase reactivity of singlet oxygen atoms (O($^1$D)) with benzene, using ozone as a precursor that is readily photodissociated by relatively low-energy. Our experiments show that O($^1$D) efficiently reacts with benzene, forming phenol, benzene oxide, and oxepine as the main products. Phenol formation is temperature-independent, consistent with a barrierless insertion mechanism. In contrast, the formation of benzene oxide/oxepine shows a slight temperature dependence, suggesting that additional reaction pathways involving either ground-state or excited-state oxygen atoms may contribute. In H$_2$O and \COO ice matrices we find that dilution does not suppress formation of phenol. We extrapolate an experimental upper limit for the benzene-to-phenol conversion fraction of 27-44$\%$ during the lifetime of an interstellar cloud, assuming O($^1$D) production rates based on CO$_2$ ice abundances and a cosmic-ray induced UV field. We compare these estimates with a new analysis of data from the comet 67P, where the C$_6$H$_6$O/C$_6$H$_6$ ratio is 20$\pm$6$\%$. This value lies within our estimated range, suggesting that O($^1$D)-mediated chemistry is a viable pathway for producing oxygenated aromatics in cold astrophysical ices, potentially enriching icy planetesimals with phenol and other biorelevant compounds.

astro-ph.EP