CH3OH Ice Research Articles

Infrared Spectra of Solid HCN Embedded in Various Molecular Environments for Comparison with the Data Obtained with JWST

Hydrogen cyanide (HCN) molecules serve as an important tracer for the chemical evolution of elemental nitrogen in the regions of star and planet formation. This is largely explained by the fact that N atoms and N2 molecules are poorly accessible for observation in the radio and infrared (IR) ranges. In turn, gas-phase HCN can be observed at various stages of star formation, including disks around young stars, cometary comas, and atmospheres of the planetary satellites. Despite the large geography of gas-phase observations, an identification of interstellar HCN ice is still lacking. In this work we present a series of IR spectroscopic measurements performed at the new ultrahigh vacuum cryogenic apparatus aiming to facilitate the search for interstellar HCN ice. A series of high-resolution laboratory IR spectra of HCN molecules embedded in the H2O, H2O:NH3, CO, CO2, and CH3OH ices at 10 K temperature is obtained. These interstellar ice analogues aim to simulate the surroundings of HCN molecules by the main constituents of the icy mantles on the surface of the interstellar grains. In addition, the spectra of HCN molecules embedded in the solid C6H6, C5H5N, and C6H5NH2 are obtained to somehow simulate the interaction of HCN molecules with carbonaceous material of the grains rich in polycyclic aromatic hydrocarbons. The acquired laboratory spectroscopic data are compared with the publicly available results of NIRSpec James Webb Space Telescope observations toward quiescent molecular clouds performed by the IceAge team.

Infrared Spectroscopic and Physical Properties of Methanol Ices—Reconciling the Conflicting Published Band Strengths of an Important Interstellar Solid

Infrared spectroscopic observations have established the presence of solid methanol (CH3OH) in the interstellar medium and in solar system ices, but the abundance of frozen CH3OH cannot be deduced without accurate band strengths, optical constants, and reference spectra. In this paper we identify disagreements, omissions, and gaps in the literature on infrared (IR) intensities of methanol ices, including unaddressed concerns that reach back several decades. New spectra are presented with intensity measurements aided by new data on the index of refraction and density of solid CH3OH. The result is that the large discordant results from different laboratory groups can now be reconciled. Multiple ices have been used to determine, apparently for the first time, IR intensities of H2O + CH3OH mixtures of accurately known composition for use with observations of interstellar ices. Also for the first time, measurements on CH3OH ices with different thicknesses have allowed us to report both near-IR band strengths and optical constants for two near-IR features used by planetary scientists. We have used our new IR results to determine vapor pressures of solid CH3OH and have compared them to measurements made with a quartz-crystal microbalance. Thermal annealings of methanol ices have been carried out and phase changes in the solid state examined. Comparisons of our results to earlier work are presented where possible, and electronic versions of our new results are made available.

Carbon Isotope Fractionation of Complex Organic Molecules in Star-forming Cores

Recent high-resolution and sensitivity Atacama Large Millimeter/submillimeter Array observations have unveiled the carbon isotope ratios (12C/13C) of complex organic molecules (COMs) in a low-mass protostellar source. To understand the 12C/13C ratios of COMs, we investigated the carbon isotope fractionation of COMs from prestellar cores to protostellar cores with a gas-grain chemical network model. We confirmed that the 12C/13C ratios of small molecules are bimodal in the prestellar phase: CO and species formed from CO (e.g., CH3OH) are slightly enriched in 13C compared to the local interstellar medium (by ∼10%), while those from C and C+ are depleted in 13C owing to isotope exchange reactions. COMs are mainly formed on the grain surface and in the hot gas (> 100 K) in the protostellar phase. The 12C/13C ratios of COMs depend on which molecules the COMs are formed from. In our base model, some COMs in the hot gas are depleted in 13C compared to the observations. Thus, we additionally incorporate reactions between gaseous atomic C and H2O ice or CO ice on the grain surface to form H2CO ice or C2O ice, as suggested by recent laboratory studies. The direct C-atom addition reactions open pathways to form 13C-enriched COMs from atomic C and CO ice. We find that these direct C-atom addition reactions mitigate 13C-depletion of COMs, and the model with the direct C-atom addition reactions better reproduces the observations than our base model. We also discuss the impact of the cosmic-ray ionization rate on the 12C/13C ratio of COMs.

JWST Mid-infrared Spectroscopy Resolves Gas, Dust, and Ice in Young Stellar Objects in the Large Magellanic Cloud

In this work, we present spectra of 11 young stellar objects (YSOs) taken with the Mid-Infrared Instrument / Medium Resolution Spectroscopy (MRS) instrument on board the James Webb Space Telescope (JWST). The YSOs are located in the N79 region of the Large Magellanic Cloud (LMC), an active star-forming region with hundreds of Spitzer- and Herschel-identified YSOs and host to super star cluster (SSC) candidate H72.97-69.39. The three giant molecular clouds in N79 (East, West, and South) have varying star formation rates and stellar populations. MRS follow-up observations of four Spitzer-identified YSOs in N79 East, West, and South have revealed that what seemed to be a single, massive YSO is actually a cluster of YSOs. We discuss the emission and absorption lines of six YSOs that have complete or almost-complete spectral coverage from 4.9–27.9 μm. YSO Y3, located in N79 East, is the youngest source in this study and likely to be less than 10,000 yr old, as inferred from the prominent CH4, NH3, CH3OH, CH3OCHO, and CO2 ice absorption features. The most luminous source is the central ionizing YSO of SSC H72.97-69.39, Y4, which has dozens of fine-structure and H2 emission lines. Unlike the other YSOs in this work, Y4 has no polyaromatic hydrocarbon emission lines, due to the intense ionizing radiation destroying these large carbon-chain molecules. The mass accretion rates based on the H i (7-6) line luminosities of YSOs Y1, Y2, Y4, and Y9 range between 1.22 × 10−4–1.89 × 10−2 M ⊙ yr−1. For the first time in the mid-infrared, we are able to resolve individual high-mass protostars forming in small clusters in an extragalactic environment like the LMC.

Carbonates and ices in the z = 0.89 galaxy-absorber towards PKS 1830–211 and within star-forming regions of the Milky Way

ABSTRACT A pair of 6.0 and 6.9 μm absorption features are frequently observed in Milky Way (MW) molecular-clouds and YSOs; they also occur in the z = 0.886 rest-frame of a molecule-rich spiral galaxy obscuring blazar PKS 1830–211. I calibrate χ2-fitting methods, which match observations with two or three laboratory spectra. The 6.0-μm component is dominated by H2O ice, as expected. Included MW sources were selected using opacity criteria which limit the range of explored H2O-ice column densities to 1.6–2.4 × 1018 molecules cm−2, while the H2O-ice density in the galaxy absorber is (2.7 ± 0.5) × 1018 molecules cm−2. CH3OH ice and / or small (< 0.1-μm-sized) Ca- and Mg-bearing carbonates contribute at 6.9 μm. The 41 per cent CH3OH:H2O molecular ratio in the PKS 1830–211 absorber is significantly higher than in the molecular cloud towards Taurus-Elias 16 (<7.5 per cent) and similar to the highest value in MW YSOs (35 per cent in AFGL 989). Fitted carbonate (-CO3):H2O ratios in the galaxy absorber of 0.091 per cent are low in comparison to most of the ratios detected in the MW sample (0.2 per cent–0.4 per cent; ∼0 per cent in AFGL 989). Inorganic carbonates could explain the increased oxygen depletion at the diffuse-medium-to-molecular-cloud transition, which Jones and Ysard associated with unobserved organic carbonates or materials with a C:O ratio of 1:3.

Simulation of CH3OH ice UV photolysis under laboratory conditions

Context. Methanol is the most complex molecule that is securely identified in interstellar ices. It is a key chemical species for understanding chemical complexity in astrophysical environments. Important aspects of the methanol ice photochemistry are still unclear, such as the branching ratios and photodissociation cross sections at different temperatures and irradiation fluxes. Aims. This work aims at a quantitative agreement between laboratory experiments and astrochemical modelling of the CH3OH ice UV photolysis. Ultimately, this work allows us to better understand which processes govern the methanol ice photochemistry present in laboratory experiments. Methods. We used the code ProDiMo to simulate the radiation fields, pressures, and pumping efficiencies characteristic of laboratory measurements. The simulations started with simple chemistry consisting only of methanol ice and helium to mimic the residual gas in the experimental chamber. A surface chemical network enlarged by photodissociation reactions was used to study the chemical reactions within the ice. Additionally, different surface chemistry parameters such as surface competition, tunnelling, thermal diffusion, and reactive desorption were adopted to check those that reproduce the experimental results. Results. The chemical models with the code ProDiMo that include surface chemistry parameters can reproduce the methanol ice destruction via UV photodissociation at temperatures of 20, 30, 50, and 70 K as observed in the experiments. We also note that the results are sensitive to different branching ratios after photolysis and to the mechanisms of reactive desorption. In the simulations of a molecular cloud at 20 K, we observed an increase in the methanol gas abundance of one order of magnitude, with a similar decrease in the solid-phase abundance. Conclusions. Comprehensive astrochemical models provide new insights into laboratory experiments as the quantitative understanding of the processes that govern the reactions within the ice. Ultimately, these insights can help us to better interpret astronomical observations.

Resonant infrared irradiation of CO and CH3OH interstellar ices

Context. Solid-phase photo-processes involving icy dust grains greatly affect the chemical evolution of the interstellar medium by leading to the formation of complex organic molecules and by inducing photodesorption. So far, the focus of laboratory studies has mainly been on the impact of energetic ultraviolet (UV) photons on ices, but direct vibrational excitation by infrared (IR) photons is expected to influence the morphology and content of interstellar ices as well. However, little is still known about the mechanisms through which this excess vibrational energy is dissipated, as well as its implications for the structure and ice photochemistry. Aims. In this work, we present a systematic investigation of the behavior of interstellar relevant CO and CH3OH ice analogs following the resonant excitation of vibrational modes using tunable IR radiation. We seek to quantify the IR-induced photodesorption and gain insights into the impact of vibrational energy dissipation on ice morphology. Methods. We utilized an ultrahigh vacuum setup at cryogenic temperatures to grow pure CO and CH3OH ices, as well as mixtures of the two. We exposed the ices to intense, near-monochromatic mid-IR (MIR) free-electron-laser radiation using the LISA end-station at the FELIX free electron laser facility to selectively excite the species. Changes to the ice are monitored by means of reflection-absorption IR spectroscopy combined with quadrupole mass-spectrometry. These methods also allowed us to characterize the photodesorption efficiency. Results. The dissipation of vibrational energy is observed to be highly dependent on the excited mode and the chemical environment of the ice. All amorphous ices undergo some degree of restructuring towards a more organized configuration upon on-resonance irradiation. Moreover, IR-induced photodesorption is observed to occur for both pure CO and CH3OH ices, with interstellar photodesorption efficiencies on the order of 10 molecules cm−2 s−1. This result is comparable to or higher than what is found for UV-induced counterparts. An indirect photodesorption of CO upon vibrational excitation of CH3OH in ice mixtures is also observed to occur, particularly in environments that are rich in methanol. Here, we discuss the astrochemical implications of these IR-induced phenomena.

On a radiolytic origin of red organics at the surface of the Arrokoth Trans-Neptunian Object

The classical Kuiper Belt Object (KBO) Arrokoth was surveyed by the New Horizons spacecraft on 1st January 2019, revealing a small bilobed object with a red surface, whose spectral slope lies in the average of the whole KBOs population. This red color has been assigned to reddish organic materials, either inherited from the protosolar disk during accretion, or formed through radiolytic processes in the surface due to exposure to solar or interstellar photons, Solar Wind, Solar Energetic Particles or Galactic Cosmic Rays. We report here a study investigating the radiolytic scenario, based on numerical calculations and experimental simulations run with swift heavy ions (74.8 MeV 136Xe19+ and 33.06 MeV 58Ni9+), and low-energy 105 keV 18O6+ ions on CH3OH ice, the only molecule identified at Arrokoth’s surface. Calculations show that sputtering is essentially controlled by Solar Wind (H and He), and that the sputtering rate depends on the nature of the material: erosion thickness over 4.55 Gyr are a few micrometers for amorphous carbon (as an analog of red organics) and a ∼240μm to around ∼10 mm for H2O and CO ice, respectively. Chemistry within the subsurface is essentially controlled by Galactic Cosmic rays (H and He), which penetrate deep down to several tens of meters and deliver an electronic dose higher than 1 eV.atom−1 in the first meter. The electronic and elastic doses delivered by Solar Wind ions are limited to the first 10s nm of the top surface, but Solar Energetic Particles deliver high electronic doses in the first 100μm of the surface (up to 200 eV.atom−1). Experimental simulations show that irradiating methanol ice with a dose consistent with that in planetary conditions, results in the formation of reddish organic materials made of aliphatic, conjugated and unconjugated olefinic, acetylinic, carbonyl and hydroxyl groups. A similarity with irradiated simple polymers (e.g. polyethyleneglycol) and materials formed through cold plasma experiments (tholins) is observed. There is little dependence with the nature and energy of the ion. The residue recovered at room temperature was analyzed with High Resolution Mass Spectrometry (Orbitrap), revealing a complex composition with around 6596 chemical formulas and likely several tens of thousands of molecules. Altogether, these analyses support active polymerization mechanisms similar to those observed in irradiated polymers, as bond-breaking, cross-linking or formation of olefinic bonds through recombination of radicals in adjacent carbon atoms. Considering both sputtering and radiolysis, as well as material ablation due to dust bombardment reported in literature, a scenario is taking shape as the production of reddish organics deep in the subsurface, and the settling of an organic crust at the top surface through volatiles removal. The presence of methanol and absence of water, inconsistent with sputtering fractionation, remains unexplained.

Survey of Ices toward Massive Young Stellar Objects. I. OCS, CO, OCN−, and CH3OH

An important tracer of the origin and evolution of cometary ices is the comparison with ices found in dense clouds and toward young stellar objects (YSOs). We present a survey of ices in the 2–5 μm spectra of 23 massive YSOs, taken with the NASA InfraRed Telescope Facility SpeX spectrometer. The 4.90 μm absorption band of OCS ice is detected in 20 sight lines, more than 5 times the previously known detections. The absorption profile shows little variation and is consistent with OCS embedded in CH3OH-rich ices, and proton-irradiated H2S or SO2-containing ices. The OCS column densities correlate well with those of CH3OH and OCN−, but not with H2O and apolar CO ice. This association of OCS with CH3OH and OCN− firmly establishes their formation location deep inside dense clouds or protostellar envelopes. The median composition of this ice phase toward massive YSOs, as a percentage of H2O, is CO:CH3OH:OCN−:OCS = 24:20:1.53:0.15. CS, due to its low abundance, is likely not the main precursor to OCS. Sulfurization of CO is likely needed, although the source of this sulfur is not well constrained. Compared to massive YSOs, low-mass YSOs and dense clouds have similar or somewhat lower CO and CH3OH ice abundances, but less OCN− and more apolar CO, while OCS awaits detection. Comets tend to be underabundant in carbon-bearing species, but this does not appear to be the case for OCS, perhaps signalling OCS production in protoplanetary disks.

Massive Young Stellar Objects in the Galactic Center. II. Seeing Through the Ice-rich Envelopes

To study the demographics of interstellar ices in the Central Molecular Zone (CMZ) of the Milky Way, we obtain near-infrared spectra of 109 red point sources using NASA IRTF/SpeX at Maunakea. We select the sample from near- and mid-infrared photometry, including 12 objects in the previous paper of this series, to ensure that these sources trace a large amount of absorption through clouds in each line of sight. We find that most of the sample (100 objects) show CO band-head absorption at 2.3 μm, tagging them as red (super-) giants. Despite the photospheric signature, however, a fraction of the sample with L-band spectra (9/82 = 0.11) exhibit large H2O ice column densities (N > 2 × 1018 cm−2), and six of them also reveal CH3OH ice absorption. As one of such objects is identified as a young stellar object (YSO) in our previous work, these ice-rich sight lines are likely associated with background stars in projection to an extended envelope of a YSO or a dense cloud core. The low frequency of such objects in the early stage of stellar evolution implies a low star-formation rate (≲0.02 M ⊙ yr−1), reinforcing the previous claim on the suppressed star-formation activity in the CMZ. Our data also indicate that the strong “shoulder” CO2 ice absorption at 15.4 μm observed in YSO candidates in the previous paper arises from CH3OH-rich ice grains having a large CO2 concentration [N(CO2)/N(CH3OH) ≈ 1/3].

Infrared Spectroscopic Survey of the Quiescent Medium of Nearby Clouds. II. Ice Formation and Grain Growth in Perseus and Serpens

The properties of dust change during the transition from diffuse to dense clouds as a result of ice formation and dust coagulation, but much is still unclear about this transformation. We present 2–20 μm spectra of 49 field stars behind the Perseus and Serpens Molecular Clouds and establish relationships between the near-infrared continuum extinction (A K) and the depths of the 9.7 μm silicate (τ 9.7) and 3.0 μm H2O ice (τ 3.0) absorption bands. The τ 9.7/A K ratio varies from large, diffuse interstellar medium-like values (∼0.55), to much lower ratios (∼0.26). Above extinctions of A K ∼ 1.2 (A V ∼ 10; Perseus, Lupus, dense cores) and ∼2.0 (A V ∼ 17; Serpens), the τ 9.7/A K ratio is lowest. The τ 9.7/A K reduction from diffuse to dense clouds is consistent with a moderate degree of grain growth (sizes up to ∼0.5 μm), increasing the near-infrared color excess (and thus A K), but not affecting the ice and silicate band profiles. This grain growth process seems to be related to the ice column densities and dense core formation thresholds, highlighting the importance of density. After correction for Serpens foreground extinction, the H2O ice formation threshold is in the range of A K = 0.31–0.40 (A V = 2.6–3.4) for all clouds, and thus grain growth takes place after the ices are formed. Finally, abundant CH3OH ice (∼21% relative to H2O) is reported for 2MASSJ18285266+0028242 (Serpens), a factor of >4 larger than for the other targets.

Comparative electron irradiations of amorphous and crystalline astrophysical ice analogues.

Laboratory studies of the radiation chemistry occurring in astrophysical ices have demonstrated the dependence of this chemistry on a number of experimental parameters. One experimental parameter which has received significantly less attention is that of the phase of the solid ice under investigation. In this present study, we have performed systematic 2 keV electron irradiations of the amorphous and crystalline phases of pure CH3OH and N2O astrophysical ice analogues. Radiation-induced decay of these ices and the concomitant formation of products were monitored in situ using FT-IR spectroscopy. A direct comparison between the irradiated amorphous and crystalline CH3OH ices revealed a more rapid decay of the former compared to the latter. Interestingly, a significantly lesser difference was observed when comparing the decay rates of the amorphous and crystalline N2O ices. These observations have been rationalised in terms of the strength and extent of the intermolecular forces present in each ice. The strong and extensive hydrogen-bonding network that exists in crystalline CH3OH (but not in the amorphous phase) is suggested to significantly stabilise this phase against radiation-induced decay. Conversely, although alignment of the dipole moment of N2O is anticipated to be more extensive in the crystalline structure, its weak attractive potential does not significantly stabilise the crystalline phase against radiation-induced decay, hence explaining the smaller difference in decay rates between the amorphous and crystalline phases of N2O compared to those of CH3OH. Our results are relevant to the astrochemistry of interstellar ices and icy Solar System objects, which may experience phase changes due to thermally-induced crystallisation or space radiation-induced amorphisation.

Simulating Observations of Ices in Protoplanetary Disks

Abstract Ices are an important constituent of protoplanetary disks. New observational facilities, notably the James Webb Space Telescope (JWST), will greatly enhance our view of disk ices by measuring their infrared spectral features. We present a suite of models to complement these upcoming observations. Our models use a kinetics-based gas–grain chemical evolution code to simulate the distribution of ices in a disk, followed by a radiative transfer code using a subset of key ice species to simulate the observations. We present models reflecting both molecular inheritance and chemical reset initial conditions. We find that near-to-mid-IR absorption features of H2O, CO2, and CH3OH are readily observable in disk-integrated spectra of highly inclined disks while CO, NH3, and CH4 ice do not show prominent features. CH3OH ice has low abundance and is not observable in the reset model, making this species an excellent diagnostic of initial chemical conditions. CO2 ice features exhibit the greatest change over disk lifetime, decreasing and increasing for the inheritance and reset models, respectively. Spatially resolved spectra of edge-on disks, possible with JWST's integral field unit observing modes, are ideal for constraining the vertical distribution of ices and may be able to isolate features from ices closer to the midplane (e.g., CO) given sufficient sensitivity. Spatially resolved spectra of face-on disks can trace scattered-light features from H2O, CO2, and CH3OH, plus CO and CH4 from the outermost regions. We additionally simulate far-IR H2O ice emission features and find they are strongest for disks viewed face-on.

Spectroscopic measurements of CH3OH in layered and mixed interstellar ice analogues

Context. The molecular composition of interstellar ice mantles is defined by gas-grain processes in molecular clouds, with the main components being H2O, CO, and CO2. Methanol (CH3OH) ice is detected towards the denser pre-stellar cores and star-forming regions, where large amounts of CO molecules freeze out and get hydrogenated on top of the icy grains. The thermal heating from nearby protostars can further change the ice structure and composition. Despite the several observations of icy features carried out towards molecular clouds and along the line of site of protostars, it is not yet clear if interstellar ices are mixed or if they have a layered structure. Aims. We aim to examine the effect of mixed and layered ice growth in dust grain mantle analogues, with specific focus on the position and shape of methanol infrared bands, so dedicated future observations could shed light on the structure of interstellar ices in different environments. Methods. Mixed and layered ice samples were deposited on a cold substrate kept at a temperature of 10 K using a closed-cycle cryostat placed in a vacuum chamber. The spectroscopic features were analysed by Fourier transform infrared spectroscopy. Different proportions of the most abundant four molecular species in ice mantles, namely H2O, CO, CO2, and CH3OH, were investigated, with a special attention placed on the analysis of the CH3OH bands. Results. We measure changes in the position and shape of the CH and CO stretching bands of CH3OH depending on the mixed or layered nature of the ice sample. Spectroscopic features of methanol are also found to change due to heating. Conclusions. A layered ice structure best reproduces the CH3OH band position recently observed towards a pre-stellar core and in star-forming regions. Based on our experimental results, we conclude that observations of CH3OH ice features in space can provide information about the structure of interstellar ices, and we expect the James Webb Space Telescope to put stringent constraints on the layered or mixed nature of ices in different interstellar environments, from molecular clouds to pre-stellar cores to protostars and protoplanetary discs.

Linking ice and gas in the λ Orionis Barnard 35A cloud

Context. Dust grains play an important role in the synthesis of molecules in the interstellar medium, from the simplest species, such as H2, to complex organic molecules. How some of these solid-state molecules are converted into gas-phase species is still a matter of debate. Aims. Our aim is to directly compare ice and gas abundances of methanol (CH3OH) and carbon monoxide (CO) obtained from near-infrared (2.5−5 μm) and millimetre (1.3 mm) observations and to investigate the relationship between ice, dust, and gas in low-mass protostellar envelopes. Methods. We present Submillimeter Array (SMA) and Atacama Pathfinder EXperiment (APEX) observations of gas-phase CH3OH (JK = 5K−4K), 13CO, and C18O (J = 2−1) towards the multiple protostellar system IRAS 05417+0907, which is located in the B35A cloud, λ Orionis region. We use archival IRAM 30 m data and AKARI H2O, CO, and CH3OH ice observations towards the same target to compare ice and gas abundances and directly calculate CH3OH and CO gas-to-ice ratios. Results. The CO isotopologue emissions are extended, whereas the CH3OH emission is compact and traces the giant molecular outflow emanating from IRAS 05417+0907. A discrepancy between sub-millimetre dust emission and H2O ice column density is found for B35A−4 and B35A−5, similar to what has previously been reported. B35A−2 and B35A−3 are located where the sub-millimetre dust emission peaks and show H2O column densities lower than that of B35A−4. Conclusions. The difference between the sub-millimetre continuum emission and the infrared H2O ice observations suggests that the distributions of dust and H2O ice differ around the young stellar objects in this dense cloud. The reason for this may be that the four sources are located in different environments resolved by the interferometric observations: B35A−2, B35A−3, and, in particular, B35A−5 are situated in a shocked region that is plausibly affected by sputtering and heating, which in turn impacts the sub-millimetre dust emission pattern, while B35A−4 is situated in a more quiescent part of the cloud. Gas and ice maps are essential for connecting small-scale variations in the ice composition with the large-scale astrophysical phenomena probed by gas observations.

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices

Context.Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices.Aims.We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from binary mixed ices:13CO:CH3OH ice and H2O:CH3OH ice.Methods.We irradiated these ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.Results.For13CO:CH3OH ice, CH3OH X-ray photodesorption yield is estimated to be ∼10−2molecule/photon at 564 eV. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is detected with a yield of ∼10−3molecule/photon. When methanol is mixed with water, X-ray photodesorption of methanol and of the previous COMs is not detected. X-ray induced chemistry, dominated by low-energy secondary electrons, is found to be the main mechanism that explains these results. We also provide desorption yields that are applicable to protoplanetary disk environments for astrochemical models.Conclusions.The X-ray emission from YSOs should participate in the enrichment of the protoplanetary disk gas phase with COMs such as methanol in the cold and X-ray dominated regions because of X-ray photodesorption from methanol-containing ices.

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices

Context.Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. This Paper I focuses on the case of X-ray photodesorption from pure methanol ices.Aims.We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from pure CH3OH ices, and to shed light on the mechanisms responsible for the desorption process.Methods.We irradiated methanol ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.Results.Under our experimental conditions, the CH3OH X-ray photodesorption yield from pure methanol ice is ~10−2molecule/photon at 564 eV. Photo-products such as CH4, H2CO, H2O, CO2, and CO also desorb at increasing efficiency. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is also detected. The physical mechanisms at play are discussed and must likely involve the thermalization of Auger electrons in the ice, thus indicating that its composition plays an important role. Finally, we provide desorption yields applicable to protoplanetary disk environments for astrochemical models.Conclusions.The X-rays are shown to be a potential candidate to explain gas-phase abundances of methanol in disks. However, more relevant desorption yields derived from experiments on mixed ices are mandatory to properly support the role played by X-rays in nonthermal desorption of methanol (see Paper II).

Observations of the Onset of Complex Organic Molecule Formation in Interstellar Ices

Abstract Isolated dense molecular cores are investigated to study the onset of complex organic molecule formation in interstellar ice. Sampling three cores with ongoing formation of low-mass stars (B59, B335, and L483) and one starless core (L694-2), we sample lines of sight to nine background stars and five young stellar objects (YSOs; A K ∼ 0.5–4.7). Spectra of these stars from 2 to 5 μm with NASA’s Infrared Telescope Facility (IRTF) simultaneously display signatures from the cores of H2O (3.0 μm), CH3OH (C–H stretching mode, 3.53 μm), and CO (4.67 μm) ices. The CO ice is traced by nine stars, in which five show a long-wavelength wing due to a mixture of CO with polar ice (CO r ), presumably CH3OH. Two of these sightlines also show independent detections of CH3OH. For these we find the ratio of the CH3OH:CO r is 0.55 ± 0.06 and 0.73 ± 0.07 from L483 and L694-2, respectively. The detections of both CO and CH3OH for the first time through lines of sight toward background stars observationally constrains the conversion of CO into CH3OH ice. Along the lines of sight, most of the CO exists in the gas phase and ≤15% of the CO is frozen out. However, CH3OH ice is abundant with respect to CO (∼50%) and exists mainly as a CH3OH-rich CO ice layer. Only a small fraction of the lines of sight contains CH3OH ice, presumably those with the highest density. The high conversion of CO to CH3OH can explain the abundances of CH3OH ice found in later stage Class 1 low-mass YSO envelopes (CH3OH:CO r ∼ 0.5–0.6). For high-mass YSOs and one Class 0 YSO, this ratio varies significantly, implying local variations can affect ice formation. The large CH3OH ice abundance indicates that the formation of complex organic molecules is likely during the prestellar phase in cold environments without higher energy particle interactions (e.g., cosmic rays).

Linking ice and gas in the Serpens low-mass star-forming region

Context. The interaction between dust, ice, and gas during the formation of stars produces complex organic molecules. While observations indicate that several species are formed on ice-covered dust grains and are released into the gas phase, the exact chemical interplay between solid and gas phases and their relative importance remain unclear. Aims. Our goal is to study the interplay between dust, ice, and gas in regions of low-mass star formation through ice- and gas-mapping and by directly measuring gas-to-ice ratios. This provides constraints on the routes that lead to the chemical complexity that is observed in solid and gas phases. Methods. We present observations of gas-phase methanol (CH3OH) and carbon monoxide (13CO and C18O) at 1.3 mm towards ten low-mass young protostars in the Serpens SVS 4 cluster from the SubMillimeter Array (SMA) and the Atacama Pathfinder EXperiment (APEX) telescope. We used archival data from the Very Large Telescope (VLT) to derive abundances of ice H2O, CO, and CH3OH towards the same region. Finally, we constructed gas-ice maps of SVS 4 and directly measured CO and CH3OH gas-to-ice ratios. Results. The SVS 4 cluster is characterised by a global temperature of 15 ± 5 K. At this temperature, the chemical behaviours of CH3OH and CO are anti-correlated: larger variations are observed for CH3OH gas than for CH3OH ice, whereas the opposite is seen for CO. The gas-to-ice ratios (Ngas/Nice) range from 1–6 for CO and 1.4 × 10−4–3.7 × 10−3 for CH3OH. The CO gas-maps trace an extended gaseous component that is not sensitive to the effect of freeze-out. Because of temperature variations and dust heating around 20 K, the frozen CO is efficiently desorbed. The CH3OH gas-maps, in contrast, probe regions where methanol is predominantly formed and present in ices and is released into the gas phase through non-thermal desorption mechanisms. Conclusions. Combining gas- and ice-mapping techniques, we measure gas-to-ice ratios of CO and CH3OH in the SVS 4 cluster. The CH3OH gas-to-ice ratio agrees with values that were previously reported for embedded Class 0/I low-mass protostars. We find that there is no straightforward correlation between CO and CH3OH gas with their ice counterparts in the cluster. This is likely related to the complex morphology of SVS 4: the Class 0 protostar SMM 4 and its envelope lie in the vicinity, and the outflow associated with SMM 4 intersects the cluster. This study serves as a pathfinder for future observations with ALMA and the James Webb Space Telescope (JWST) that will provide high-sensitivity gas-ice maps of molecules more complex than methanol. Such comparative maps will be essential to constrain the chemical routes that regulate the chemical complexity in star-forming regions.

On the origin & thermal stability of Arrokoth's and Pluto's ices

In this paper we discuss in a thermodynamic, geologically empirical way the long-term nature of the stable majority ices that could be present in Kuiper Belt object (KBO) 2014 MU69 (also called Arrokoth; hereafter “MU69”) after its 4.6 Gyr residence in the Edgeworth-Kuiper belt (EKB) as a cold classical object. We compare the upper bounds for the gas production rate (~1024 molecules/s) measured by the New Horizons (NH) spacecraft flyby on 01 Jan 2019 to estimates for the outgassing flux rates from a suite of common cometary and KBO ices at the average ~ 40 K sunlit surface temperature of MU69, but do not find the upper limit very constraining except for the most volatile of species (e.g. CO, N2, CH4). More constraining is the stability versus sublimation into vacuum requirement over Myr to Gyr, and from this we find only 3 common ices that are truly refractory: HCN, CH3OH, and H2O (in order of increasing stability), while NH3 and H2CO ices are marginally stable and may be removed by any positive temperature excursions in the EKB, as produced every 108–109 years by nearby supernovae and passing O/B stars. To date the NH team has reported the presence of abundant CH3OH and H2O on MU69's surface (Stern et al., 2019; Grundy et al., 2020). NH3 has been searched for, but not found. We predict that future absorption feature detections, if any are ever derived from higher signal-to-noise ratio spectra, will be due to an HCN or poly-H2CO based species. Consideration of the conditions present in the EKB region during the formation era of MU69 lead us to state that it is highly likely that it “formed in the dark”, in an optically thick mid-plane, unable to see the nascent, variable, highly luminous Young Stellar Object (YSO)/TTauri Sun, and that KBOs contain HCN and CH3OH ice phases in addition to the H2O ice phases found in their short period (SP) comet descendants. Finally, when we apply our ice thermal stability analysis to bodies/populations related to MU69, we find that methanol ice is likely ubiquitous in the outer solar system; that if Pluto isn't a fully differentiated body, then it must have gained its hypervolatile ices from proto-planetary disk (PPD) sources in the first few Myr of the solar system's existence; and that hypervolatile rich, highly primordial comet C/2016 R2 was placed onto an Oort Cloud orbit on a similar few Myr timescale.