Context. Comets are considered to be remnants from the formation of the Solar System. ESA s Rosetta mission targeted comet 67P/Churyumov-Gerasimenko and was able to record high-quality data on its chemical composition and outgassing behaviour, including low abundances of N2 that are observed to be correlated with H2O and CO2 in approximately a 63:37 ratio. Aims. In this work, the thermal desorption behaviour of N2 in H2O:CO2 ices was studied in the laboratory to investigate the co-desorption behaviour of N2 within the two most abundant cometary ices in 67P and to derive desorbing fractions in different temperature regimes. Methods. H2O:CO2:N2 ices of various ratios were prepared in a gas mixing system and co-deposited at 15 K onto a copper sample holder. Sublimation of the ice was measured using temperature programmed desorption mass spectrometry. Quantitative values were derived for the fraction of N2 co-desorbing with CO2 and H2O respectively. To validate the results, H2O:CO2:13CO ices were prepared as well. Results. The experiments show that the co-desorption of N2 with CO2 in H2O:CO2:N2 ices depends on the bulk amount of CO2 present in the ice. The fraction of N2 trapped in H2O reduces as more N2 and CO2 are added to the mixture. CO behaves qualitatively similar to N2, but more CO is found to co-desorb with CO2. To reproduce the ratio of N2 desorbing with H2O over that of CO2 (N2(H2O)/N2(CO2)), our ice analogues need to contain =15% CO2, while 67P contains =7.5% CO2. Large fractions of N2 can be removed from the ice due to heating up to 70 K, but for ice that most closely resembles that of 67P, the loss fraction of pure phase N2 is expected to be =20%. Therefore, N2 is suggested to be a minor carrier of nitrogen in the comet.

Context. The ROSINA instrument on board the Rosetta spacecraft measured, among others, the outgassing of noble gases from comet 67P/Churyumov- Gerasimenko. The interpretation of this dataset and unravelling underlying desorption mechanisms requires detailed laboratory studies. Aims. We aim to improve our understanding of the desorption patterns, trapping, and fractionation of noble gases released from the H₂O:CO₂-dominated ice of comet 67P. Methods. In the laboratory, ice films of neon, argon, krypton, or xenon (Ne, Ar, Kr, and Xe) mixed in CO₂:H₂O were prepared at 15 K. Temperature-programmed desorption mass spectrometry is employed to analyse the desorption behaviour of the noble gases. Mass spectrometric ROSINA data of 67P were analysed to determine the fraction of argon associated with CO₂ and H₂O, respectively. Results. CO₂ has a significant effect on noble gas desorption behaviour, resulting in the co-release of noble gases with CO₂, decreasing the amount of noble gas trapped within water, shifting the pure phase noble gas peak desorption temperature to lower temperatures, and prolonging the trapping of neon. These effects are linked to competition for binding sites in the water ice and the formation of crystalline CO₂. Desorption energies of the pure phase noble gas release were determined and found to be higher than those previously reported in the literature. Enhancement of the Ar/Kr and Ar/Xe ratios are at best 40% and not significantly influenced by the addition of CO₂. Analysis of ROSINA mass spectrometric data shows that the fraction of argon associated with H₂O is 0.53 ± 0.30, which cannot be explained by our laboratory results. Conclusions. Multicomponent ice mixtures affect the desorption behaviour of volatiles compared to simple binary mixtures and experiments on realistic cometary ice analogues are vital to understanding comet outgassing.

Technological progress related to astronomical observatories such as the recently launched James Webb Space Telescope (JWST) allows searching for signs of life beyond our solar system, namely, in the form of unambiguous biosignature gases in exoplanetary atmospheres. The tentative assignment of a 1σ-2.4σ spectral feature observed with JWST in the atmosphere of exoplanet K2-18b to the biosignature gas dimethyl sulfide (DMS; sum formula C₂H₆S) raised hopes that, although controversial, a second genesis had been found. Terrestrial atmospheric DMS is exclusively stemming from marine biological activity, and no natural abiotic source has been identified—neither on Earth nor in space. Therefore, DMS is considered a robust biosignature. Since comets possess a pristine inventory of complex organic molecules of abiotic origin, we have searched high-resolution mass spectra collected at comet 67P/Churyumov-Gerasimenko, target of the European Space Agency’s Rosetta mission, for the signatures of DMS. Previous work reported the presence of a C₂H₆S signal when the comet was near its equinox, but distinction of DMS from its structural isomer ethanethiol remained elusive. Here we reassess these and evaluate additional data. Based on differences in the electron ionization-induced fragmentation pattern of the two isomers, we show that DMS is significantly better compatible with the observations. Deviations between expected and observed signal intensities for DMS are <1σ, while for ethanethiol they are 2σ-4σ. The local abundance of DMS relative to methanol deduced from these data is (0.13 ± 0.04)%. Our results provide the first evidence for the existence of an abiotic synthetic pathway to DMS in pristine cometary matter and hence motivate more detailed studies of the sulfur chemistry in such matter and its analogs. Future studies need to investigate whether or not the present inference of cometary DMS could provide an abiotic source of DMS in a planetary atmosphere.

Context. Complex organic molecules are detected in many sources in the warm inner regions of envelopes surrounding deeply embedded protostars. Exactly how these species form remains an open question. Aims. This study aims to constrain the formation of complex organic molecules through comparisons of their abundances towards the Class 0 protostellar binary IRAS 16293-2422. Methods. We utilised observations from the ALMA Protostellar Interferometric Line Survey of IRAS 16293-2422. The species identification and the rotational temperature and column density estimation were derived by fitting the extracted spectra towards IRAS 16293-2422 A and IRAS 16293-2422 B with synthetic spectra. The majority of the work in this paper pertains to the analysis of IRAS 16293-2422 A for a comparison with the results from the other binary component, which have already been published. Results. We detect 15 different complex species, as well as 16 isotopologues towards the most luminous companion protostar IRAS 16293-2422 A. Tentative detections of an additional 11 isotopologues are reported. We also searched for and report on the first detections of methoxymethanol (CH3OCH2OH) and trans-ethyl methyl ether (t-C2H5OCH3) towards IRAS 16293-2422 B and the follow-up detection of deuterated isotopologues of acetaldehyde (CH2DCHO and CH3CDO). Twenty-four lines of doubly-deuterated methanol (CHD2OH) are also identified. Conclusions. The comparison between the two protostars of the binary system shows significant differences in abundance for some of the species, which are partially correlated to their spatial distribution. The spatial distribution is consistent with the sublimation temperature of the species; those with higher expected sublimation temperatures are located in the most compact region of the hot corino towards IRAS 16293-2422 A. This spatial differentiation is not resolved in IRAS 16293-2422 B and will require observations at a higher angular resolution. In parallel, the list of identified CHD2OH lines shows the need of accurate spectroscopic data including their line strength.

Nitrogen oxides are thought to play a significant role as a nitrogen reservoir and to potentially participate in the formation of more complex species. Until now, only NO, NO, and HNO have been detected in the interstellar medium. We report the first interstellar detection of nitrous acid (HONO). Twelve lines were identified towards component B of the low-mass protostellar binary IRAS 16293-2422 with the Atacama Large Millimeter/submillimeter Array, at the position where NO and NO have previously been seen. A local thermodynamic equilibrium model was used to derive the column density (∼9 × 1014 cm in a 0 .″5 beam) and excitation temperature (∼100 K) of this molecule. HNO, NO, NO+, and HNO3 were also searched for in the data, but not detected. We simulated the HONO formation using an updated version of the chemical code Nautilus and compared the results with the observations. The chemical model is able to reproduce satisfactorily the HONO, NO, and NO abundances, but not the NO, HNO, and NHOH abundances. This could be due to some thermal desorption mechanisms being destructive and therefore limiting the amount of HNO and NHOH present in the gas phase. Other options are UV photodestruction of these species in ices or missing reactions potentially relevant at protostellar temperatures.