The ALMA-PILS survey: isotopic composition of oxygen-containing complex organic molecules toward IRAS 16293–2422B

Context. One of the important questions of astrochemistry is how complex organic molecules, including potential prebiotic species, are formed in the envelopes around embedded protostars. The abundances of minor isotopologues of a molecule, in particular the D- and 13C-bearing variants, are sensitive to the densities, temperatures and timescales characteristic of the environment in which they form, and can therefore provide important constraints on the formation routes and conditions of individual species. Aims. The aim of this paper is to systematically survey the deuteration and the 13C content of a variety of oxygen-bearing complex organic molecules on solar system scales toward the “B component” of the protostellar binary IRAS16293–2422. Methods. We have used the data from an unbiased molecular line survey of the protostellar binary IRAS16293−2422 between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The data probe scales of 60 AU (diameter) where most of the organic molecules are expected to have sublimated off dust grains and be present in the gas phase. The deuterated and 13C isotopic species of ketene, acetaldehyde and formic acid, as well as deuterated ethanol, are detected unambiguously for the first time in the interstellar medium. These species are analysed together with the 13C isotopic species of ethanol, dimethyl ether and methyl formate along with mono-deuterated methanol, dimethyl ether and methyl formate. Results. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of ≈2% and the other, the more complex species, D/H ratios of 4–8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short timescale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 and 300 K. This likely reflects the binding energies of the individual species, in good agreement with what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. Tentative identifications suggest that the same may apply for 13C isotopologues of methyl formate and ethanol. If confirmed, this may be a clue to their formation at the late prestellar or early protostellar phases with an enhancement of the available 13C relative to 12C related to small differences in binding energies for CO isotopologues or the impact of FUV irradiation by the central protostar. Conclusions. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species.

Download Full-text

The ALMA-PILS survey: inventory of complex organic molecules towards IRAS 16293–2422 A

Astronomy and Astrophysics ◽

10.1051/0004-6361/201936299 ◽

2020 ◽

Vol 635 ◽

pp. A48 ◽

Cited By ~ 13

Author(s):

S. Manigand ◽

J. K. Jørgensen ◽

H. Calcutt ◽

H. S. P. Müller ◽

N. F. W. Ligterink ◽

...

Keyword(s):

Spatial Distribution ◽

Organic Molecules ◽

Rotational Temperature ◽

Line Strength ◽

Spatial Differentiation ◽

Complex Species ◽

Ethyl Methyl ◽

Compact Region ◽

Many Sources ◽

Complex Organic

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.

Download Full-text

Organic Molecules: Is It Possible to Distinguish Aromatics from Aliphatics Collected by Space Missions in High-Speed Impacts?

Sci ◽

10.3390/sci2020041 ◽

2020 ◽

Vol 2 (2) ◽

pp. 41

Author(s):

Mark Burchell ◽

Kathryn Harriss

Keyword(s):

High Speed ◽

Organic Molecules ◽

Chemical Structures ◽

Surface Ocean ◽

Life Itself ◽

Organic Particles ◽

Open Question ◽

The Impact ◽

The Relationship ◽

Complex Organic

A prime site of astrobiological interest within the Solar System is the interior ocean of Enceladus. This ocean has already been shown to contain organic molecules, and is thought to have the conditions necessary for more complex organic biomolecules to emerge and potentially even life itself. This sub-surface ocean has been accessed by Cassini, an unmanned spacecraft that interacted with the water plumes ejected naturally from Enceladus. The encounter speed with these plumes and their contents, was between 5 and 15 km s−1. Encounters at such speeds allow analysis of vapourised material from submicron-sized particles within the plume, but sampling micron-sized particles remains an open question. The latter particles can impact metal targets exposed on the exterior of future spacecraft, producing impact craters lined with impactor residue, which can then be analysed. Although there is considerable literature on how mineral grains behave in such high-speed impacts, and also on the relationship between the crater residue and the original grain composition, far less is known regarding the behaviour of organic particles. Here we consider a deceptively simple yet fundamental scientific question: for impacts at speeds of around 5–6 kms−1 would the impactor residue alone be sufficient to enable us to recognise the signature conferred by organic particles? Furthermore, would it be possible to identify the organic molecules involved, or at least distinguish between aromatic and aliphatic chemical structures? For polystyrene (aromatic-rich) and poly(methyl methacrylate) (solely aliphatic) latex particles impinging at around 5 km s−1 onto metal targets, we find that sufficient residue is retained at the impact site to permit identification of a carbon-rich projectile, but not of the particular molecules involved, nor is it currently possible to discriminate between aromatic-rich and solely aliphatic particles. This suggests that an alternative analytical method to simple impacts on metal targets is required to enable successful collection of organic samples in a fly-by Enceladus mission, or, alternatively, a lower encounter speed is required.

Download Full-text

Abundances of Organic Molecules in Molecular Cloud Cores

Symposium - International Astronomical Union ◽

10.1017/s0074180900193210 ◽

2004 ◽

Vol 213 ◽

pp. 173-176

Author(s):

Edmund C. Sutton ◽

Andrej M. Sobolev

Keyword(s):

Dimethyl Ether ◽

Spatial Resolution ◽

Molecular Cloud ◽

Organic Molecules ◽

Methyl Formate ◽

High Spatial Resolution ◽

Independent Method ◽

The Status ◽

Cloud Cores

Molecular cloud cores are often found to contain regions with high abundances of organic molecules such as formaldehyde, methanol, ethanol, dimethyl ether, and methyl formate. First we will review the status of observations of these molecules in a number of sources and discuss some of the limitations of present techniques. Then we will discuss systematic factors involved in the conversion of column densities into fractional abundances and introduce an independent method of calibrating that conversion. Finally we will present recent results from high spatial resolution observations of W3(OH).

Download Full-text

Laboratory data in support of JWST observations of interstellar ices

Proceedings of the International Astronomical Union ◽

10.1017/s1743921319009827 ◽

2019 ◽

Vol 15 (S350) ◽

pp. 420-421

Author(s):

Marina G. Rachid ◽

Jeroen Terwisscha van Scheltinga ◽

Daniël Koletzki ◽

Giulia Marcandalli ◽

Ewine F. van Dishoeck ◽

...

Keyword(s):

Solid State ◽

Gas Phase ◽

Organic Molecules ◽

Methyl Formate ◽

Laboratory Data ◽

Protoplanetary Disks ◽

Theoretical Studies ◽

James Webb Space Telescope ◽

Complex Organic ◽

Experimental And Theoretical Studies

AbstractExperimental and theoretical studies have shown that Complex Organic Molecules (COMs) can be formed on icy dusty grains in molecular clouds and protoplanetary disks. The number of astronomical detections of solid COMs, however, is very limited. With the upcoming launch of the James Webb Space Telescope (JWST) this should change, but in order to identify solid state features of COMs, accurate laboratory data are needed. Here we present high resolution (0.5 cm–1) infrared ice spectra of acetone (C3H6O) and methyl formate (HCOOCH3), two molecules already identified in astronomical gas phase surveys, whose interstellar synthesis is expected to follow solid state pathways.

Download Full-text

Organic Molecules: Is It Possible To Distinguish Aromatics From Aliphatics Collected By Space Missions in High-Speed Impacts

Sci ◽

10.3390/sci2010012 ◽

2020 ◽

Vol 2 (1) ◽

pp. 12

Author(s):

Mark Burchell ◽

Kathryn Harriss

Keyword(s):

High Speed ◽

Organic Molecules ◽

Chemical Structures ◽

Surface Ocean ◽

Life Itself ◽

Organic Particles ◽

Open Question ◽

The Impact ◽

The Relationship ◽

Complex Organic

A prime site of astrobiological interest within the Solar System is the interior ocean of Enceladus. This ocean has already been shown to contain organic molecules, and is thought to have the conditions necessary for more complex organic biomolecules to emerge and potentially even life itself. This sub-surface ocean has been accessed by Cassini, an unmanned spacecraft that interacted with the water plumes ejected naturally from Enceladus. The encounter speed with these plumes and their contents, was 5 km s−1 and above. Encounters at such speeds allow analysis of vapourised material from submicron-sized particles within the plume, but sampling micron-sized particles remains an open question. The latter particles can impact metal targets exposed on the exterior of future spacecraft, producing impact craters lined with impactor residue, which can then be analysed. Although there is considerable literature on how mineral grains behave in such high-speed impacts, and also on the relationship between the crater residue and the original grain composition, far less is known regarding the behaviour of organic particles. Here we consider a deceptively simple yet fundamental scientific question: for impacts at speeds of around 5−6 kms−1 would the impactor residue alone be sufficient to enable us to recognise the signature conferred by organic particles? Furthermore, would it be possible to identify the organic molecules involved, or at least distinguish between aromatic and aliphatic chemical structures? For polystyrene (aromatic-rich) and poly(methyl methacrylate) (solely aliphatic) latex particles impinging at around 5 km s-1 onto metal targets, we find that sufficient residue is retained at the impact site to permit identification of a carbon-rich projectile, but not of the particular molecules involved, nor is it currently possible to discriminate between aromatic-rich and solely aliphatic particles. This suggests that an alternative analytical method to simple impacts on metal targets is required to enable successful collection of organic samples in a fly-by Enceladus mission, or, alternatively, a lower encounter speed is required.

Download Full-text

Infrared spectra of complex organic molecules in astronomically relevant ice matrices

Astronomy and Astrophysics ◽

10.1051/0004-6361/201731998 ◽

2018 ◽

Vol 611 ◽

pp. A35 ◽

Cited By ~ 9

Author(s):

J. Terwisscha van Scheltinga ◽

N. F. W. Ligterink ◽

A. C. A. Boogert ◽

E. F. van Dishoeck ◽

H. Linnartz

Keyword(s):

Gas Phase ◽

Dimethyl Ether ◽

Organic Molecules ◽

Laboratory Data ◽

Laboratory Studies ◽

Astronomical Data ◽

Astronomical Observations ◽

Circumstellar Gas ◽

Complex Organic ◽

Recent Laboratory

Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking.Aim. This work provides infrared reference spectra of acetaldehyde (CH3CHO), ethanol (CH3CH2OH), and dimethyl ether (CH3OCH3) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations.Methods. Fourier transform transmission spectroscopy (500–4000 cm−1/20–2.5 μm, 1.0 cm−1 resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15 K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed.Results. We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 μm bands are recommended, for ethanol the 11.36 and 7.240 μm bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 μm can be used. All spectra are publicly available in the Leiden Database for Ice.

Download Full-text

Infrared spectra of complex organic molecules in astronomically relevant ice mixtures

Astronomy and Astrophysics ◽

10.1051/0004-6361/202037497 ◽

2020 ◽

Vol 639 ◽

pp. A4

Author(s):

M. G. Rachid ◽

J. Terwisscha van Scheltinga ◽

D. Koletzki ◽

H. Linnartz

Keyword(s):

Ir Spectra ◽

Infrared Spectra ◽

Organic Molecules ◽

Solid Phase ◽

High Vacuum ◽

Peak Position ◽

Large Set ◽

Complex Species ◽

Asymmetric Stretch ◽

Complex Organic

Context. Complex organic molecules (COMs) have been largely identified through their characteristic rotational transitions in the gas of interstellar and circumstellar regions. Although these species are formed in the icy mantles that cover dust grains, the most complex species that has been unambiguously identified in the solid-phase to date is methanol (CH3OH). With the upcoming launch of the James Webb Space Telescope (JWST), this situation may change. The higher sensitivity, spectral and spatial resolution of the JWST will allow for the probing of the chemical inventory of ices in star-forming regions. In order to identify features of solid-state molecules in astronomical spectra, laboratory infrared spectra of COMs within astronomically relevant conditions are required. This paper is part of a series of laboratory studies focusing on the infrared spectra of frozen COMs embedded in ice matrices. These reflect the environmental conditions in which COMs are thought to be found. Aims. This work is aimed at characterizing the infrared features of acetone mixed in ice matrices containing H2O, CO2, CO, CH4, and CH3OH for temperatures ranging between 15 K and 160 K. Changes in the band positions and shapes due to variations in the temperature, ice composition, and morphology are reported. This work also points out the IR features that are considered the best promising tracers when searching for interstellar acetone-containing ices. Methods. Acetone-containing ices were grown at 15 K under high-vacuum conditions and infrared (IR) spectra (500–4000 cm−1/20–2.5 μm, 0.5 cm−1 resolution) in transmission mode were recorded using a Fourier transform infrared spectrometer. Spectra of the ices at higher temperatures are acquired during the heating of the sample (at a rate of 25 K h−1) up to 160 K. The changes in the infrared features for varying conditions were analyzed. Results. A large set of IR spectra of acetone-containing ices is presented and made available as a basis for interpreting current and future infrared astronomical spectra. The peak position and full width at half maximum of selected acetone bands have been measured for different ice mixtures and temperatures. The bands that are best suitable for acetone identification in astronomical spectra are: the C=O stretch mode, around 1710.3 cm−1 (5.847 μm), that lies in the 1715–1695 cm−1 (5.83–5.90 μm) range in the mixed ices; the CH3 symmetric deformation, around 1363.4 cm−1 (7.335 μm) that lies in the 1353–1373 cm−1 (7.28–7.39 μm) range in the mixed ices; and the CCC asymmetric stretch, around 1228.4 cm−1 (8.141 μm), that lies in the 1224–1245 cm−1 (8.16–8.03 μm) range in the mixed ices. The CCC asymmetric stretch band also exhibits potential as a remote probe of the ice temperature and composition; this feature is the superposition of two components that respond differently to temperature and the presence of CH3OH. All the spectra are available through the Leiden Ice Database.

Download Full-text

The ALMA-PILS survey: the first detection of doubly deuterated methyl formate (CHD2OCHO) in the ISM

Astronomy and Astrophysics ◽

10.1051/0004-6361/201832844 ◽

2019 ◽

Vol 623 ◽

pp. A69 ◽

Cited By ~ 16

Author(s):

S. Manigand ◽

H. Calcutt ◽

J. K. Jørgensen ◽

V. Taquet ◽

H. S. P. Müller ◽

...

Keyword(s):

Star Formation ◽

Organic Molecules ◽

Methyl Formate ◽

Local Thermal Equilibrium ◽

Organic Species ◽

Physical Conditions ◽

Methyl Cyanide ◽

Model Tracing ◽

Star Formation Regions ◽

Complex Organic

Studies of deuterated isotopologues of complex organic molecules can provide important constraints on their origin in star formation regions. In particular, the abundances of deuterated species are very sensitive to the physical conditions in the environment where they form. Because the temperatures in star formation regions are low, these isotopologues are enhanced to significant levels, which enables the detection of multiply deuterated species. However, for complex organic species, so far only the multiply deuterated variants of methanol and methyl cyanide have been reported. The aim of this paper is to initiate the characterisation of multiply deuterated variants of complex organic species with the first detection of doubly deuterated methyl formate, CHD2OCHO. We use ALMA observations from the Protostellar Interferometric Line Survey (PILS) of the protostellar binary IRAS 16293–2422 in the spectral range of 329.1 GHz to 362.9 GHz. Spectra towards each of the two protostars are extracted and analysed using a local thermal equilibrium model in order to derive the abundances of methyl formate and its deuterated variants. We report the first detection of doubly deuterated methyl formate CHD2OCHO in the ISM. The D-to-H ratio (D/H ratio) of CHD2OCHO is found to be 2–3 times higher than the D/H ratio of CH2DOCHO for both sources, similar to the results for formaldehyde from the same dataset. The observations are compared to a gas-grain chemical network coupled to a dynamical physical model, tracing the evolution of a molecular cloud until the end of the Class 0 protostellar stage. The overall D/H ratio enhancements found in the observations are of about the same magnitude as the predictions from the model for the early stages of Class 0 protostars. However, that the D/H ratio of CHD2OCHO is higher than that of CH2DOCHO is still not predicted by the model. This suggests that a mechanism enhances the D/H ratio of singly and doubly deuterated methyl formate that is not in the model, for instance, mechanisms for H–D substitutions. This new detection provides an important constraint on the formation routes of methyl formate and outlines a path forward in terms of using these ratios to determine the formation of organic molecules through observations of differently deuterated isotopologues towards embedded protostars.

Download Full-text

Organic Molecules: Is It Possible to Distinguish Aromatics from Aliphatics Collected by Space Missions in High-Speed Impacts?

Sci ◽

10.3390/sci2030056 ◽

2020 ◽

Vol 2 (3) ◽

pp. 56

Author(s):

Mark Burchell ◽

Kathryn Harriss

Keyword(s):

High Speed ◽

Organic Molecules ◽

Chemical Structures ◽

Surface Ocean ◽

Life Itself ◽

Organic Particles ◽

Open Question ◽

The Impact ◽

The Relationship ◽

Complex Organic

A prime site of astrobiological interest within the Solar System is the interior ocean of Enceladus. This ocean has already been shown to contain organic molecules, and is thought to have the conditions necessary for more complex organic biomolecules to emerge and potentially even life itself. This sub-surface ocean has been accessed by Cassini, an unmanned spacecraft that interacted with the water plumes ejected naturally from Enceladus. The encounter speed with these plumes and their contents, was between 5 and 15 km s−1. Encounters at such speeds allow analysis of vapourised material from submicron-sized particles within the plume, but sampling micron-sized particles remains an open question. The latter particles can impact metal targets exposed on the exterior of future spacecraft, producing impact craters lined with impactor residue, which can then be analysed. Although there is considerable literature on how mineral grains behave in such high-speed impacts, and also on the relationship between the crater residue and the original grain composition, far less is known regarding the behaviour of organic particles. Here we consider a deceptively simple yet fundamental scientific question: for impacts at speeds of around 5−6 kms−1 would the impactor residue alone be sufficient to enable us to recognise the signature conferred by organic particles? Furthermore, would it be possible to identify the organic molecules involved, or at least distinguish between aromatic and aliphatic chemical structures? For polystyrene (aromatic-rich) and polymethylmethacrylate (solely aliphatic) latex particles impinging at around 5 km s−1 onto metal targets, we find that sufficient residue is retained at the impact site to permit identification of a carbon-rich projectile, but not of the particular molecules involved, nor is it currently possible to discriminate between aromatic-rich and solely aliphatic particles. This suggests that an alternative analytical method to simple impacts on metal targets is required to enable successful collection of organic samples in a fly-by Enceladus mission, or, alternatively, a lower encounter speed is required.

Download Full-text

The GUAPOS project: G31.41+0.31 Unbiased ALMA sPectral Observational Survey

Astronomy and Astrophysics ◽

10.1051/0004-6361/202038966 ◽

2020 ◽

Vol 644 ◽

pp. A84

Author(s):

C. Mininni ◽

M. T. Beltrán ◽

V. M. Rivilla ◽

A. Sánchez-Monge ◽

F. Fontani ◽

...

Keyword(s):

Acetic Acid ◽

Gas Phase ◽

Organic Molecules ◽

Methyl Formate ◽

Galactic Center ◽

Physical Parameters ◽

Star Forming ◽

Grain Surface ◽

Spectral Survey ◽

Complex Organic

Context. One of the goals of astrochemistry is to understand the degree of chemical complexity that can be reached in star-forming regions, along with the identification of precursors of the building blocks of life in the interstellar medium. To answer such questions, unbiased spectral surveys with large bandwidth and high spectral resolution are needed, in particular, to resolve line blending in chemically rich sources and identify each molecule (especially for complex organic molecules). These kinds of observations have already been successfully carried out, primarily towards the Galactic Center, a region that shows peculiar environmental conditions. Aims. We present an unbiased spectral survey of one of the most chemically rich hot molecular cores located outside the Galactic Center, in the high-mass star-forming region G31.41+0.31. The aim of this 3mm spectral survey is to identify and characterize the physical parameters of the gas emission in different molecular species, focusing on complex organic molecules. In this first paper, we present the survey and discuss the detection and relative abundances of the three isomers of C2H4O2: methyl formate, glycolaldehyde, and acetic acid. Methods. Observations were carried out with the ALMA interferometer, covering all of band 3 from 84 to 116 GHz (~32 GHz bandwidth) with an angular resolution of 1.2′′ × 1.2′′ (~ 4400 au × 4400 au) and a spectral resolution of ~0.488 MHz (~1.3−1.7 km s−1). The transitions of the three molecules have been analyzed with the software XCLASS to determine the physical parameters of the emitted gas. Results. All three isomers were detected with abundances of (2 ± 0.6) × 10−7, (4.3−8) × 10−8, and (5.0 ± 1.4) × 10−9 for methyl formate, acetic acid, and glycolaldehyde, respectively. Methyl formate and acetic acid abundances are the highest detected up to now, if compared to sources in the literature. The size of the emission varies among the three isomers with acetic acid showing the most compact emission while methyl formate exhibits the most extended emission. Different chemical pathways, involving both grain-surface chemistry and cold or hot gas-phase reactions, have been proposed for the formation of these molecules, but the small number of detections, especially of acetic acid and glycolaldehyde, have made it very difficult to confirm or discard the predictions of the models. The comparison with chemical models in literature suggests the necessity of grain-surface routes for the formation of methyl formate in G31, while for glycolaldehyde both scenarios could be feasible. The proposed grain-surface reaction for acetic acid is not capable of reproducing the observed abundance in this work, while the gas-phase scenario should be further tested, given the large uncertainties involved.

Download Full-text