Search

This work focuses on the ice features toward the binary protostellar system Ced 110 IRS 4A and 4B, and observed with JWST as part of the Early Release Science Ice Age collaboration. We aim to explore the JWST observations of the binary protostellar system Ced~110~IRS4A and IRS4B to unveil and quantify the ice inventories toward these sources. We compare the ice abundances with those found for the same molecular cloud. The analysis is performed by fitting or comparing laboratory infrared spectra of ices to the observations. Spectral fits are carried out with the ENIIGMA fitting tool that searches for the best fit. For Ced~110~IRS4B, we detected the major ice species H$_2$O, CO, CO$_2$ and NH$_3$. All species are found in a mixture except for CO and CO$_2$, which have both mixed and pure ice components. In the case of Ced~110~IRS4A, we detected the same major species as in Ced~110~IRS4B, as well as the following minor species CH$_4$, SO$_2$, CH$_3$OH, OCN$^-$, NH$_4^+$ and HCOOH. Tentative detection of N$_2$O ice (7.75~$\mu$m), forsterite dust (11.2~$\mu$m) and CH$_3^+$ gas emission (7.18~$\mu$m) in the primary source are also presented. Compared with the two lines of sight toward background stars in the Chameleon I molecular cloud, the protostar has similar ice abundances, except in the case of the ions that are higher in IRS4A. The clearest differences are the absence of the 7.2 and 7.4~$\mu$m absorption features due to HCOO$^-$ and icy complex organic molecules in IRS4A and evidence of thermal processing in both IRS4A and IRS4B as probed by the CO$_2$ ice features. We conclude that the binary protostellar system Ced~110~IRS4A and IRS4B has a large inventory of icy species. The similar ice abundances in comparison to the starless regions in the same molecular cloud suggest that the chemical conditions of the protostar were set at earlier stages in the molecular cloud., Comment: 33 pages, 19 Figures. Accepted for publication in Astronomy & Astrophysics

Complex organic molecules (COMs) have been detected ubiquitously in protostellar systems. However, at shorter wavelengths (~0.8mm) it is more difficult to detect larger molecules than at longer wavelengths (~3mm) because of the increase of millimeter dust opacity, line confusion, and unfavorable partition function. We aim to search for large molecules (>8 atoms) in the ALMA Band 3 spectrum of IRAS 16293-2422 B. We search for more than 70 molecules and identify as many lines as possible in the spectrum. The spectral settings were set to specifically target three-carbon species such as propanol and glycerol. We identify lines of 31 molecules including many oxygen-bearing COMs such as CH3OH and c-C2H4O and a few nitrogen- and sulfur-bearing ones such as HOCH2CN and CH3SH. The largest detected molecules are gGg-(CH2OH)2 and CH3COCH3. We do not detect glycerol or propanol but provide upper limits for them which are in line with previous laboratory and observational studies. The line density in Band 3 is only ~2.5 times lower in frequency space than in Band 7. From the detected lines in Band 3 at a $\gtrsim 6\sigma$ level, ~25-30% of them could not be identified indicating the need for more laboratory data of rotational spectra. We find similar column densities and column density ratios of COMs (within a factor ~2) between Band 3 and Band 7. The effect of dust optical depth for IRAS 16293-2422 B at an off-source location on column densities and column density ratios is minimal. Moreover, for warm protostars, long wavelength spectra are not only crowded, but also take longer integration times to reach the same sensitivity limit. The 3mm search has not yet resulted in detection of larger and more complex molecules in warm sources. A full deep ALMA Band 2-3 (i.e., 3-4 mm) survey is needed to assess whether low frequency data have the potential to reveal more complex molecules in warm sources., Comment: Accepted for publication in A&A

Ices are the main carriers of volatiles in protoplanetary disks and are crucial to our understanding of the chemistry that ultimately sets the organic composition of planets. The ERS program Ice Age on the JWST follows the ice evolution through all stages of star and planet formation. JWST/NIRSpec observations of the edge-on Class II protoplanetary disk HH~48~NE reveal spatially resolved absorption features of the major ice components H$_2$O, CO$_2$, CO, and multiple weaker signatures from less abundant ices NH$_3$, OCN$^-$, and OCS. Isotopologue $^{13}$CO$_2$ ice has been detected for the first time in a protoplanetary disk. Since multiple complex light paths contribute to the observed flux, the ice absorption features are filled in by ice-free scattered light. The $^{12}$CO$_2$/$^{13}$CO$_2$ ratio of 14 implies that the $^{12}$CO$_2$ feature is saturated, without the flux approaching 0, indicative of a very high CO$_2$ column density on the line of sight, and a corresponding abundance with respect to hydrogen that is higher than ISM values by a factor of at least a few. Observations of rare isotopologues are crucial, as we show that the $^{13}$CO$_2$ observation allows us to determine the column density of CO$_2$ to be at an order of magnitude higher than the lower limit directly inferred from the observed optical depth. Radial variations in ice abundance, e.g., snowlines, are significantly modified since all observed photons have passed through the full radial extent of the disk. CO ice is observed at perplexing heights in the disk, extending to the top of the CO-emitting gas layer. We argue that the most likely interpretation is that we observe some CO ice at high temperatures, trapped in less volatile ices like H$_2$O and CO$_2$. Future radiative transfer models will be required to constrain the implications on our current understanding of disk physics and chemistry., Comment: 16 pages, 8 figures, accepted for publication in A&A

Icy grain mantles are the main reservoir of the volatile elements that link chemical processes in dark, interstellar clouds with the formation of planets and composition of their atmospheres. The initial ice composition is set in the cold, dense parts of molecular clouds, prior to the onset of star formation. With the exquisite sensitivity of JWST, this critical stage of ice evolution is now accessible for detailed study. Here we show the first results of the Early Release Science program "Ice Age" that reveal the rich composition of these dense cloud ices. Weak ices, including, $^{13}$CO$_2$, OCN$^-$, $^{13}$CO, OCS, and COMs functional groups are now detected along two pre-stellar lines of sight. The $^{12}$CO$_2$ ice profile indicates modest growth of the icy grains. Column densities of the major and minor ice species indicate that ices contribute between 2 and 19% of the bulk budgets of the key C, O, N, and S elements. Our results suggest that the formation of simple and complex molecules could begin early in a water-ice rich environment., Comment: To appear in Nature Astronomy on January 23rd, 2023. 33 pages, 16 figures, 3 tables; includes extended and supplemental data sections. Part of the JWST Ice Age Early Release Science program's science enabling products. Enhanced spectra downloadable on Zenodo at the following DOI: 10.5281/zenodo.7501239

The detection of the amino acid glycine and its amine precursor methylamine on the comet 67P/Churyumov-Gerasimenko by the Rosetta mission provides strong evidence for a cosmic origin of prebiotics on Earth. How and when such complex organic molecules form along the process of star- and planet-formation remains debated. We report the first laboratory detection of glycine formed in the solid phase through atom and radical-radical addition surface reactions under cold dense interstellar cloud conditions. Our experiments, supported by astrochemical models, suggest that glycine forms without the need for energetic irradiation, such as UV photons and cosmic rays, in interstellar water-rich ices, where it remains preserved, in a much earlier star-formation stage than previously assumed. We also confirm that solid methylamine is an important side-reaction product. A prestellar formation of glycine on ice grains provides the basis for a complex and ubiquitous prebiotic chemistry in space enriching the chemical content of planet-forming material., Comment: Preprint of the original submitted version

The design, implementation, and performance of a customized carbon atom beam source for the purpose of investigating solid-state reaction routes in interstellar ices in molecular clouds are discussed. The source is integrated into an existing ultrahigh vacuum setup, SURFace REaction SImulation DEvice (SURFRESIDE$^{2}$), which extends this double atom (H/D, O, and N) beamline apparatus with a third atom (C) beamline to a unique system that is fully suited to explore complex organic molecule solid-state formation under representative interstellar cloud conditions. The parameter space for this system is discussed, which includes the flux of the carbon atoms hitting the ice sample, their temperature, and the potential impact of temperature on ice reactions. Much effort has been put into constraining the beam size to within the limits of the sample size with the aim to reduce carbon pollution inside the setup. How the C-atom beam performs is quantitatively studied through the example experiment, C + $^{18}$O$_2$, and supported by computationally-derived activation barriers. The potential for this source to study the solid-state formation of interstellar complex organic molecules through C-atom reactions is discussed., Comment: Accepted for publication in Review of Scientific Instruments

Methane is one of the simplest stable molecules that is both abundant and widely distributed across space. It is thought to have partial origin from interstellar molecular clouds, which are near the beginning of the star formation cycle. Observational surveys of CH$_4$ ice towards low- and high-mass young stellar objects showed that much of the CH$_4$ is expected to be formed by the hydrogenation of C on dust grains, and that CH$_4$ ice is strongly correlated with solid H$_2$O. Yet, this has not been investigated under controlled laboratory conditions, as carbon-atom chemistry of interstellar ice analogues has not been experimentally realized. In this study, we successfully demonstrate with a C-atom beam implemented in an ultrahigh vacuum apparatus the formation of CH$_4$ ice in two separate co-deposition experiments: C + H on a 10 K surface to mimic CH$_4$ formation right before H$_2$O ice is formed on the dust grain, and C + H + H$_2$O on a 10 K surface to mimic CH$_4$ formed simultaneously with H$_2$O ice. We confirm that CH$_4$ can be formed by the reaction of atomic C and H, and that the CH$_4$ formation rate is 2 times greater when CH$_4$ is formed within a H$_2$O-rich ice. This is in agreement with the observational finding that interstellar CH$_4$ and H$_2$O form together in the polar ice phase, i.e., when C- and H-atoms simultaneously accrete with O-atoms on dust grains. For the first time, the conditions that lead to interstellar CH$_4$ (and CD$_4$) ice formation are reported, and can be incorporated into astrochemical models to further constrain CH$_4$ chemistry in the interstellar medium and in other regions where CH$_4$ is inherited.

Complex organic molecules (COMs) have been identified toward high- and low-mass protostars as well as molecular clouds, suggesting that these interstellar species originate from the early stage(s) of starformation. The reaction pathways resulting in COMs described by the formula C$_2$H$_\text{n}$O are still under debate. In this work, we investigate the laboratory possible solid-state reactions that involve simple hydrocarbons and OH-radicals along with H$_2$O ice under translucent cloud conditions (1$\leq$A$_V$$\leq$5 and \textit{n}$_\text{H}$$\sim$10$^3$ cm$^{-3}$). We focus on the interactions of C$_2$H$_2$ with H-atoms and OH-radicals, which are produced along the H$_2$O formation sequence on grain surfaces at 10 K. Ultra-high vacuum (UHV) experiments were performed to study the surface chemistry observed during C$_2$H$_2$ + O$_2$ + H codeposition, where O$_2$ was used for the in-situ generation of OH-radicals. Reflection absorption infrared spectroscopy (RAIRS) was applied to in situ monitor the initial and newly formed species. After that, a temperature-programmed desorption experiment combined with a Quadrupole mass spectrometer (TPD-QMS) was used as a complementary analytical tool. The investigated 10 K surface chemistry of C$_2$H$_2$ with H-atoms and OH-radicals not only results in semi and fully saturated hydrocarbons, such as ethylene (C$_2$H$_4$) and ethane (C$_2$H$_6$), but it also leads to the formation of COMs, such as vinyl alcohol, acetaldehyde, ketene, ethanol, and possibly acetic acid. It is concluded that OH-radical addition reactions to C$_2$H$_2$, acting as a molecular backbone, followed by isomerization (i.e., keto-enol tautomerization) via an intermolecular pathway and successive hydrogenation provides a so far experimentally unreported solid-state route for the formation of these species without the need of energetic input., Comment: 17 pages, 12 figures, 2 tables

Complex organic molecules (COMs) have been detected in the gas-phase in cold and lightless molecular cores. Recent solid-state laboratory experiments have provided strong evidence that COMs can be formed on icy grains through 'non-energetic' processes. In this contribution, we show that propanal and 1-propanol can be formed in this way at the low temperature of 10 K. Propanal has already been detected in space. 1-propanol is an astrobiologically relevant molecule, as it is a primary alcohol, and has not been astronomically detected. Propanal is the major product formed in the C2H2 + CO + H experiment, and 1-propanol is detected in the subsequent propanal + H experiment. The results are published in Qasim et al. (2019c). ALMA observations towards IRAS 16293-2422B are discussed and provide a 1-propanol:propanal upper limit of < 0.35 - 0.55, which are complemented by computationally-derived activation barriers in addition to the performed laboratory experiments., Comment: Proceedings IAU Symposium No. 350, 2019, Laboratory Astrophysics: from Observations to Interpretation

1-propanol (CH3CH2CH2OH) is a three carbon-bearing representative of primary linear alcohols that may have its origin in the cold dark cores in interstellar space. To test this, we investigated in the laboratory whether 1-propanol ice can be formed along pathways possibly relevant to the prestellar core phase. We aim to show in a two-step approach that 1-propanol can be formed through reaction steps that are expected to take place during the heavy CO freeze-out stage by adding C2H2 into the CO + H hydrogenation network via the formation of propanal (CH3CH2CHO) as an intermediate and its subsequent hydrogenation. Temperature programmed desorption-quadrupole mass spectrometry (TPD-QMS) is used to identify the newly formed propanal and 1-propanol. Reflection absorption infrared spectroscopy (RAIRS) is used as a complementary diagnostic tool. The mechanisms that can contribute to the formation of solid-state propanal and 1-propanol, as well as other organic compounds, during the heavy CO freeze-out stage are constrained by both laboratory experiments and theoretical calculations. Here it is shown that recombination of HCO radicals, formed upon CO hydrogenation, with radicals formed upon C2H2 processing - H2CCH and H3CCH2 - offers possible reaction pathways to solid-state propanal and 1-propanol formation. This extends the already important role of the CO hydrogenation chain in the formation of larger COMs (complex organic molecules). The results are used to compare with ALMA observations. The resulting 1-propanol:propanal ratio concludes an upper limit of < 0:35-0:55, which is complemented by computationally-derived activation barriers in addition to the experimental results., Comment: Accepted for publication in Astronomy and Astrophysics

Formic acid (HCOOH) and carbon dioxide (CO2) are simple species that have been detected in the interstellar medium. The solid-state formation pathways of these species under experimental conditions relevant to prestellar cores are primarily based off of weak infrared transitions of the HOCO complex and usually pertain to the H2O-rich ice phase, and therefore more experimental data are desired. In this article, we present a new and additional solid-state reaction pathway that can form HCOOH and CO2 ice at 10 K 'non-energetically' in the laboratory under conditions related to the "heavy" CO freeze-out stage in dense interstellar clouds, i.e., by the hydrogenation of an H2CO:O2 ice mixture. This pathway is used to piece together the HCOOH and CO2 formation routes when H2CO or CO reacts with H and OH radicals. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to confirm the formation and pathways of newly synthesized ice species as well as to provide information on relative molecular abundances. Reflection absorption infrared spectroscopy (RAIRS) is additionally employed to characterize reaction products and determine relative molecular abundances. We find that for the conditions investigated in conjunction with theoretical results from the literature, H+HOCO and HCO+OH lead to the formation of HCOOH ice in our experiments. Which reaction is more dominant can be determined if the H+HOCO branching ratio is more constrained by computational simulations, as the HCOOH:CO2 abundance ratio is experimentally measured to be around 1.8:1. H+HOCO is more likely than OH+CO (without HOCO formation) to form CO2. Isotope experiments presented here further validate that H+HOCO is the dominant route for HCOOH ice formation in a CO-rich CO:O2 ice mixture that is hydrogenated. These data will help in the search and positive identification of HCOOH ice in prestellar cores., Comment: Accepted for publication in Astronomy and Astrophysics

A number of recent experimental studies have shown that solid-state complex organic molecules (COMs) can form under conditions that are relevant to the CO freeze-out stage in dense clouds. In this work, we show that alcohols can be formed well before the CO freeze-out stage (i.e., in the H2O-rich ice phase). This joint experimental and computational investigation shows that the isomers, n- and i-propanol (H3CCH2CH2OH and H3CCHOHCH3) and n- and i-propenol (H3CCHCHOH and H3CCOHCH2), can be formed in radical-addition reactions starting from propyne (H3CCCH) + OH at the low temperature of 10 K, where H3CCCH is one of the simplest representatives of stable carbon chains already identified in the interstellar medium (ISM). The resulting average abundance ratio of 1:1 for n-propanol:i-propanol is aligned with the conclusions from the computational work that the geometric orientation of strongly interacting species is influential to the extent of which 'mechanism' is participating, and that an assortment of geometries leads to an averaged-out effect. Three isomers of propanediol are also tentatively identified in the experiments. It is also shown that propene and propane (H3CCHCH2 and H3CCH2CH3) are formed from the hydrogenation of H3CCCH. Computationally-derived activation barriers give additional insight into what types of reactions and mechanisms are more likely to occur in the laboratory and in the ISM. Our findings not only suggest that the alcohols studied here share common chemical pathways and therefore can show up simultaneously in astronomical surveys, but also that their extended counterparts that derive from polyynes containing H3C(CC)nH structures may exist in the ISM. Such larger species, like fatty alcohols, are the possible constituents of simple lipids that primitive cell membranes on the early Earth are thought to be partially composed of., Comment: Published in ACS Earth and Space Chemistry, Complex Organic Molecules (COMs) in Star-Forming Regions special issue

Context. In dense clouds, hydrogenation reactions on icy dust grains are key in the formation of molecules, like formaldehyde, methanol, and complex organic molecules (COMs). These species form through the sequential hydrogenation of CO ice. Although molecular hydrogen (H2) abundances can be four orders of magnitude higher than those of free H-atoms in dense clouds, H2 surface chemistry has been largely ignored; several laboratory studies show that H2 does not actively participate in non-energetic ice chemistry because of the high activation energies required. Aims. For the example of CO ice hydrogenation, we experimentally investigated the potential role of H2 molecules on the surface chemistry when energetic processing (i.e., UV photolysis) is involved. We test whether additional hydrogenation pathways become available upon UV irradiation of a CO:H2 ice mixture and whether this reaction mechanism also applies to other chemical systems. Methods. Ultra-high vacuum (UHV) experiments were performed at 8~20 K. A pre-deposited solid mixture of CO:H2 was irradiated with UV-photons. Reflection absorption infrared spectroscopy (RAIRS) was used as an in situ diagnostic tool. Single reaction steps and possible isotopic effects were studied by comparing results from CO:H2 and CO:D2 ice mixtures. Results. After UV-irradiation of a CO:H2 ice mixture, two photon-induced products, HCO and H2CO, are unambiguously detected. The proposed reaction mechanism involves electronically excited CO in the following reaction steps: CO + h{\nu}->CO*, CO* + H2->HCO + H where newly formed H-atoms are then available for further hydrogenation reactions. The HCO formation yields have a strong temperature dependence for the investigated regime, which is most likely linked to the H2 sticking coefficient. Finally, the astronomical relevance of this photo-induced reaction channel is discussed., Comment: 8 pages, 6 figures

The astronomical gas-phase detection of simple species and small organic molecules in cold pre-stellar cores, with abundances as high as $\sim$$10^{-8}-10^{-9}$ n$_\text{H}$, contradicts the generally accepted idea that at $10$ K, such species should be fully frozen out on grain surfaces. A physical or chemical mechanism that results in a net transfer from solid-state species into the gas phase offers a possible explanation. Reactive desorption, i.e., desorption following the exothermic formation of a species, is one of the options that has been proposed. In astronomical models, the fraction of molecules desorbed through this process is handled as a free parameter, as experimental studies quantifying the impact of exothermicity on desorption efficiencies are largely lacking. In this work, we present a detailed laboratory study with the goal of deriving an upper limit for the reactive desorption efficiency of species involved in the CO-H$_2$CO-CH$_3$OH solid-state hydrogenation reaction chain. The limit for the overall reactive desorption fraction is derived by precisely investigating the solid-state elemental carbon budget, using reflection absorption infrared spectroscopy and the calibrated solid-state band-strength values for CO, H$_2$CO and CH$_3$OH. We find that for temperatures in the range of $10$ to $14$ K, an upper limit of $0.24\pm 0.02$ for the overall elemental carbon loss upon CO conversion into CH$_3$OH. This corresponds with an effective reaction desorption fraction of $\leq$$0.07$ per hydrogenation step, or $\leq$$0.02$ per H-atom induced reaction, assuming that H-atom addition and abstraction reactions equally contribute to the overall reactive desorption fraction along the hydrogenation sequence. The astronomical relevance of this finding is discussed., Comment: 9 pages, 7 figures

The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH -> CH3 + H2O and CH3 + OH -> CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation (Lamberts et al. 2017). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed., Comment: Accepted for publication in Astronomy and Astrophysics

Complex organic molecules (COMs) have been identified in different environments in star- forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a non-energetic (atom-addition) or energetic (UV-photon absorption) trigger. So far, such studies have been largely performed for single processes. Here, we present the first work that quantitatively investigates both the relative importance and the cumulative effect of (non-)energetic processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF HC(O)OCH3), glycolaldehyde (GA HC(O)CH2OH) and ethylene glycol (EG H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO-CH3OH molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid-state conditions investigated here., Comment: 14 pages, 8 figures, 1 table