Context. Sulfur is a biogenic element used as a tracer of the evolution of interstellar clouds to stellar systems. However, most of the expected sulfur in molecular clouds remains undetected. Sulfur disappears from the gas phase in two steps. The first depletion occurs during the translucent phase, reducing the gas-phase sulfur by 7–40 times, while the following freeze-out step occurs in molecular clouds, reducing it by another order of magnitude. This long-standing question awaits an explanation. Aims. The aim of this study is to understand under what form the missing sulfur is hiding in molecular clouds. The possibility that sulfur is depleted onto dust grains is considered. Methods. Experimental simulations mimicking H2S ice UV photoprocessing in molecular clouds were conducted at 8 K under ultra-high vacuum. The ice was subsequently warmed up to room temperature. The ice was monitored using infrared spectroscopy, and the desorbing molecules were measured by quadrupole mass spectrometry in the gas phase. Theoretical Monte Carlo simulations were performed for interpretation of the experimental results and extrapolation to the astrophysical and planetary conditions. Results. H2S2 formation was observed during irradiation at 8 K. Molecules H2Sx with x > 2 were also identified and found to desorb during warm-up, along with S2 to S4 species. Larger Sx molecules up to S8 are refractory at room temperature and remained on the substrate forming a residue. Monte Carlo simulations were able to reproduce the molecules desorbing during warming up, and found that residues are chains of sulfur consisting of 6–7 atoms. Conclusions. Based on the interpretation of the experimental results using our theoretical model, it is proposed that S+ in translucent clouds contributes notoriously to S depletion in denser regions by forming long S chains on dust grains in a few times 104 yr. We suggest that the S2 to S4 molecules observed in comets are not produced by fragmentation of these large chains. Instead, they probably come either from UV photoprocessing of H2S-bearing ice produced in molecular clouds or from short S chains formed during the translucent cloud phase.
2-aminooxazole (2AO), a N-heterocyclic molecule, has been proposed as an intermediate in prebiotic syntheses. It has been demonstrated that it can be synthesized from small molecules such as cyanamide and glycoaldehyde, which are present in interstellar space. The aim of this work is to provide infrared (IR) spectra, in the solid phase for conditions typical of astrophysical environments and to estimate its stability toward UV photons and cosmic rays. IR (4000–600 cm−1) absorption spectra at 20 K, 180 K, and 300 K, IR band strengths, and room-temperature UV (120–250 nm) absorption spectra are given for the first time for this species. Destruction cross sections of ≈9.5 10−18 cm2 and ≈2 10−16 cm2 were found in the irradiation at 20 K of pure 2AO and 2AO:H2O ices with UV (6.3–10.9 eV) photons or 5 keV electrons, respectively. These data were used to estimate half-life times for the molecule in different environments. It is estimated that 2AO could survive UV radiation and cosmic rays in the ice mantles of dense clouds beyond cloud collapse. In contrast, it would be very unstable on the surface of cold solar system bodies like Kuiper Belt objects, but the molecule could still survive within dust grain agglomerates or cometesimals.
At the low temperatures found in the interior of dense clouds and circumstellar regions, along with H 2 O and smaller amounts of species such as CO, CO 2 , or CH 3 OH, the infrared features of CH 4 have been observed on icy dust grains. Ultraviolet (UV) photons induce different processes in ice mantles, affecting the molecular abundances detected in the gas-phase. This work aims to understand the processes that occur in a pure CH 4 ice mantle submitted to UV irradiation. We studied photon-induced processes for the different photoproducts arising in the ice upon UV irradiation. Experiments were carried out in ISAC, an ultra-high vacuum chamber equipped with a cryostat and an F-type UV-lamp reproducing the secondary UV-field induced by cosmic rays in dense clouds. Infrared spectroscopy and quadrupole mass spectrometry were used to monitor the solid and gas-phase, respectively, during the formation, irradiation, and warm-up of the ice. Direct photodesorption of pure CH 4 was not observed. UV photons form CH x · and H· radicals, leading to photoproducts such as H 2 , C 2 H 2 , C 2 H 6 , and C 3 H 8 . Evidence for the photodesorption of C 2 H 2 and photochemidesorption of C 2 H 6 and C 3 H 8 was found, the latter species is so far the largest molecule found to photochemidesorb. 13 CH 4 experiments were also carried out to confirm the reliability of these results. Boogert et al. 1996;Öberg et al. 2008). Methane ice can be formed from successive hydrogenation of carbon atoms over a dust grain surface, from photoprocessing of CH 3 OH ice, or even from gas-phase reactions and subsequent freeze out over dust grains (Öberg et al. 2008, and references therein). CH 4 constitutes a source of carbon atoms in ice mantles, with abundances around 5% and 2% of the water ice in low-mass and high-mass protostars, respectively (Dartois 2005;Öberg et al. 2011;Boogert et al. 2015). Complex organic molecules (COMs), containing six or more atoms and at least one carbon, can be formed from methane processing in the interstellar and circumstellar medium, or comets. These systems contain variable quantities, up to 4% relative to water, of solid methane, which is exposed to vacuum ultraviolet (UV) photons with a spectral energy distribution as simulated in our experiments (Gerakines
Non-thermal desorption of inter-and circum-stellar ice mantles on dust grains, in particular ultraviolet photon-induced desorption, has gained importance in recent years. These processes may account for the observed gas phase abundances of molecules like CO toward cold interstellar clouds. Ice mantle growth results from gas molecules impinging on the dust from all directions and incidence angles. Nevertheless, the effect of the incident angle for deposition on ice photo-desorption rate has not been studied. This work explores the impact on the accretion and photodesorption rates of the incidence angle of CO gas molecules with the cold surface during deposition of a CO ice layer. Infrared spectroscopy monitored CO ice upon deposition at different angles, ultraviolet-irradiation, and subsequent warm-up. Vacuum-ultraviolet spectroscopy and a Ni-mesh measured the emission of the ultraviolet lamp. Molecules ejected from the ice to the gas during irradiation or warm-up were characterized by a quadrupole mass spectrometer. The photodesorption rate of CO ice deposited at 11 K and different incident angles was rather stable between 0 and 45 • . A maximum in the CO photodesorption rate appeared around 70 • -incidence deposition angle. The same deposition angle leads to the maximum surface area of water ice. Although this study of the surface area could not be performed for CO ice, the similar angle dependence in the photodesorption and the ice surface area suggests that they are closely related. Further evidence for a dependence of CO ice morphology on deposition angle is provided by thermal desorption of CO ice experiments.
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