ALMA ACA study of the H2_2S/OCS ratio in low-mass protostars

The identification of the main sulfur reservoir on its way from the diffuse interstellar medium to the cold dense star-forming cores and eventually to protostars is a long-standing problem. Despite sulfur's astrochemical relevance, the abundance of S-bearing molecules in dense cores and regions around protostars is still insufficiently constrained. The goal of this investigation is to derive the gas-phase H$_2$S/OCS ratio for several low-mass protostars, which could provide crucial information about the physical and chemical conditions in the birth cloud of Sun-like stars. Using ALMA ACA Band 6 observations, H$_2$S, OCS, and their isotopologs are searched for in 10 Class 0/I protostars with different source properties such as age, mass, and environmental conditions. An LTE model is used to fit synthetic spectra to the detected lines and to derive the column densities based solely on optically thin lines. The H$_2$S and OCS column densities span four orders of magnitude across the sample. The H$_2$S/OCS ratio is found to be in the range from 0.2 to above 9.7. IRAS 16293-2422 A and Ser-SMM3 have the lowest ratio, while BHR71-IRS1 has the highest. Only the H$_2$S/OCS ratio of BHR71-IRS1 agress within uncertainties with the ratio in comet 67P/C$-$G. The determined gas-phase H$_2$S/OCS ratios can be below the upper limits on the solid-state ratios by as much as an order of magnitude. The H$_2$S/OCS ratio depends significantly on the environment of the birth cloud, such as UV-irradiation and heating received prior to the formation of a protostar. The highly isolated birth environment of BHR71-IRS1 is hypothesized to be the reason for its high gaseous H$_2$S/OCS ratio due to lower rates of photoreactions and more efficient hydrogenation reactions under such dark, cold conditions. The gaseous inventory of S-bearing molecules in BHR71-IRS1 appears to be most similar to that of interstellar ices.Comment: Accepted for publication in A&A; 32 pages, 24 figures, 18 table

ALMA ACA study of the H2S/OCS ratio in low-mass protostars

Context. The identification of the main sulfur reservoir on its way from the diffuse interstellar medium to the cold dense star-forming cores and, ultimately, to protostars is a long-standing problem. Despite sulfur’s astrochemical relevance, the abundance of S-bearing molecules in dense cores and regions around protostars is still insufficiently constrained. Aims. The goal of this investigation is to derive the gas-phase H2S/OCS ratio for several low-mass protostars, which could provide crucial information about the physical and chemical conditions in the birth cloud of Sun-like stars. This may also shed new light onto the main sulfur reservoir in low-mass star-forming systems. Methods. Using Atacama Large Millimeter/submillimeter Array (ALMA) Atacama Compact Array (ACA) Band 6 observations, we searched for H2S, OCS, and their isotopologs in ten Class 0/I protostars with different source properties such as age, mass, and environmental conditions. The sample contains IRAS 16293-2422 A, IRAS 16293-2422 B, NGC 1333-IRAS 4A, RCrA IRS7B, Per-B1-c, BHR71-IRS1, Per-emb-25, NGC 1333-IRAS4B, Ser-SMM3, and TMC1. A local thermal equilibrium (LTE) model is used to fit synthetic spectra to the detected lines and to derive the column densities based solely on optically thin lines. Results. The H2S and OCS column densities span four orders of magnitude across the sample. The H2S/OCS ratio is found to be in the range from 0.2 to above 9.7. IRAS 16293-2422 A and Ser-SMM3 have the lowest ratio, while BHR71-IRS1 has the highest. Only the H2S/OCS ratio of BHR71-IRS1 is in agreement with the ratio in comet 67P/Churyumov–Gerasimenko within the uncertainties. Conclusions. The determined gas-phase H2S/OCS ratios can be below the upper limits on the solid-state ratios by as much as one order of magnitude. The H2S/OCS ratio depends in great measure on the environment of the birth cloud, such as UV-irradiation and heating received prior to the formation of a protostar. The highly isolated birth environment (a Bok globule) of BHR71-IRS1 is hypothesized as the reason for its high gaseous H2S/OCS ratio that is due to lower rates of photoreactions and more efficient hydrogenation reactions under such dark, cold conditions. The gaseous inventory of S-bearing molecules in BHR71-IRS1 appears to be the most similar to that of interstellar ices

Low NH3_{3}/H2_{2}O ratio in comet C/2020 F3 (NEOWISE) at 0.7 au from the Sun

A lower-than-solar elemental nitrogen content has been demonstrated for several comets, including 1P/Halley and 67P/C-G with independent in situ measurements of volatile and refractory budgets. The recently discovered semi-refractory ammonium salts in 67P/C-G are thought to be the missing nitrogen reservoir in comets. The thermal desorption of ammonium salts from cometary dust particles leads to their decomposition into ammonia and a corresponding acid. The NH$_{3}$/H$_{2}$O ratio is expected to increase with decreasing heliocentric distance with evidence for this in near-infrared observations. NH$_{3}$ has been claimed to be more extended than expected for a nuclear source. Here, the aim is to constrain the NH$_{3}$/H$_{2}$O ratio in comet C/2020 F3 (NEOWISE) during its July 2020 passage. OH emission from comet C/2020 F3 (NEOWISE) was monitored for 2 months with NRT and observed from GBT on 24 July and 11 August 2020. Contemporaneously with the 24 July 2020 OH observations, the NH$_{3}$ hyperfine lines were targeted with GBT. The concurrent GBT and NRT observations allowed the OH quenching radius to be determined at $\left(5.96\pm0.10\right)\times10^{4}$ km on 24 July 2020, which is important for accurately deriving $Q(\text{OH})$. C/2020 F3 (NEOWISE) was a highly active comet with $Q(\text{H}_{2}\text{O}) \approx 2\times10^{30}$ molec s$^{-1}$ one day before perihelion. The $3\sigma$ upper limit for $Q_{\text{NH}_{3}}/Q_{\text{H}_{2}\text{O}}$ is $<0.29\%$ at $0.7$ au from the Sun. The obtained NH$_{3}$/H$_{2}$O ratio is a factor of a few lower than measurements for other comets at such heliocentric distances. The abundance of NH$_{3}$ may vary strongly with time depending on the amount of water-poor dust in the coma. Lifted dust can be heated, fragmented, and super-heated; whereby, ammonium salts, if present, can rapidly thermally disintegrate and modify the NH$_{3}$/H$_{2}$O ratio.Comment: Accepted for publication in A&A; 18 pages, 8 figures, 6 table

Prestellar grain-surface origins of deuterated methanol in comet 67P/Churyumov-Gerasimenko

Deuterated methanol is one of the most robust windows astrochemists have on the individual chemical reactions forming deuterium-bearing molecules and the physicochemical history of the regions where they reside. The first-time detection of mono- and di-deuterated methanol in a cometary coma is presented for comet 67P/Churyumov-Gerasimenko using Rosetta-ROSINA data. D-methanol (CH3OD and CH2DOH combined) and D2-methanol (CH2DOD and CHD2OH combined) have an abundance of 5.5+/-0.46 and 0.00069+/-0.00014 per cent relative to normal methanol. The data span a methanol deuteration fraction (D/H ratio) in the 0.71-6.6 per cent range, accounting for statistical corrections for the location of D in the molecule and including statistical error propagation in the ROSINA measurements. It is argued that cometary CH2DOH forms from CO hydrogenation to CH3OH and subsequent H-D substitution reactions in CH3-R. CHD2OH is likely produced from deuterated formaldehyde. Meanwhile, CH3OD and CH2DOD, could form via H-D exchange reactions in OH-R in the presence of deuterated water ice. Methanol formation and deuteration is argued to occur at the same epoch as D2O formation from HDO, with formation of mono-deuterated water, hydrogen sulfide, and ammonia occurring prior to that. The cometary D-methanol/methanol ratio is demonstrated to agree most closely with that in prestellar cores and low-mass protostellar regions. The results suggest that cometary methanol stems from the innate cold (10-20 K) prestellar core that birthed our Solar System. Cometary volatiles individually reflect the evolutionary phases of star formation from cloud to core to protostar.Comment: Accepted for publication in MNRAS; 29 pages, 8 figures, 4 table

Azimuthal C/O variations in a planet-forming disk

The elemental carbon-to-oxygen ratio (C/O) in the atmosphere of a giant planet is a promising diagnostic of that planet’s formation history in a protoplanetary disk. Alongside efforts in the exoplanet community to measure the C/O ratio in planetary atmospheres, observational and theoretical studies of disks are increasingly focused on understanding how the gas-phase C/O ratio varies both with radial location and between disks. This is mostly tied to the icelines of major volatile carriers such as CO and H2O. Using ALMA observations of CS and SO, we have found evidence for an entirely unexpected type of C/O variation in the protoplanetary disk around HD 100546: an azimuthal variation from a typical, oxygen-dominated ratio (C/O ≈ 0.5) to a carbon-dominated ratio (C/O ≳ 1.0). We show that the spatial distribution and peculiar line kinematics of both CS and SO molecules can be well explained by azimuthal variations in the C/O ratio. We propose a shadowing mechanism that could lead to such a chemical dichotomy. Our results imply that tracing the formation history of giant exoplanets using their atmospheric C/O ratios will need to take into account time-dependent azimuthal C/O variations in a planet’s accretion zone

The complex chemistry of outflow cavity walls exposed: the case of low-mass protostars

Complex organic molecules are ubiquitous companions of young low-mass protostars. Recent observations suggest that their emission stems, not only from the traditional hot corino, but also from offset positions. In this work, 2D physicochemical modelling of an envelope-cavity system is carried out. Wavelength-dependent radiative transfer calculations are performed and a comprehensive gas-grain chemical network is used to simulate the physical and chemical structure. The morphology of the system delineates three distinct regions: the cavity wall layer with time-dependent and species-variant enhancements; a torus rich in complex organic ices, but not reflected in gas-phase abundances and the remaining outer envelope abundant in simpler solid and gaseous molecules. Strongly irradiated regions, such as the cavity wall layer, are subject to frequent photodissociation in the solid phase. Subsequent recombination of the photoproducts leads to frequent reactive desorption, causing gas-phase enhancements of several orders of magnitude. This mechanism remains to be quantified with laboratory experiments. Direct photodesorption is found to be relatively inefficient. If radicals are not produced directly in the icy mantle, the formation of complex organics is impeded. For efficiency, a sufficient number of FUV photons needs to penetrate the envelope, and elevated cool dust temperatures need to enable grain-surface radical mobility. As a result, a high stellar luminosity and a sufficiently wide cavity favour chemical complexity. Furthermore within this paradigm, complex organics are demonstrated to have unique lifetimes and be grouped into early (formaldehyde, ketene, methanol, formic acid, methyl formate, acetic acid and glycolaldehyde) and late (acetaldehyde, dimethyl ether and ethanol) species

Methanol along the path from envelope to protoplanetary disc

Interstellar methanol is considered to be a parent species of larger, more complex organic molecules. A physicochemical simulation of infalling parcels of matter is performed for a low-mass star-forming system to trace the chemical evolution from cloud to disc. An axisymmetric 2D semi-analytic model generates the time-dependent density and velocity distributions, and full continuum radiative transfer is performed to calculate the dust temperature and the UV radiation field at each position as a function of time. A comprehensive gas–grain chemical network is employed to compute the chemical abundances along infall trajectories. Two physical scenarios are studied, one in which the dominant disc growth mechanism is viscous spreading, and another in which continuous infall of matter prevails. The results show that the infall path influences the abundance of methanol entering each type of disc, ranging from complete loss of methanol to an enhancement by a factor of >1 relative to the prestellar phase. Critical chemical processes and parameters for the methanol chemistry under different physical conditions are identified. The exact abundance and distribution of methanol is important for the budget of complex organic molecules in discs, which will be incorporated into forming planetary system objects such as protoplanets and comets. These simulations show that the comet-forming zone contains less methanol than in the precollapse phase, which is dominantly of prestellar origin, but also with additional layers built up in the envelope during infall. Such intriguing links will soon be tested by upcoming data from the Rosetta mission

Physicochemical models: source-tailored or generic?

Physicochemical models can be powerful tools to trace the chemical evolution of a protostellar system and allow to constrain its physical conditions at formation. The aim of this work is to assess whether source-tailored modelling is needed to explain the observed molecular abundances around young, low-mass protostars or if, and to what extent, generic models can improve our understanding of the chemistry in the earliest stages of star formation. The physical conditions and the abundances of simple, most abundant molecules based on three models are compared. After establishing the discrepancies between the calculated chemical output, the calculations are redone with the same chemical model for all three sets of physical input parameters. With the differences arising from the chemical models eliminated, the output is compared based on the influence of the physical model. Results suggest that the impact of the chemical model is small compared to the influence of the physical conditions, with considered time-scales having the most drastic effect. Source-tailored models may be simpler by design; however, likely do not sufficiently constrain the physical and chemical parameters within the global picture of star-forming regions. Generic models with more comprehensive physics may not provide the optimal match to observations of a particular protostellar system, but allow a source to be studied in perspective of other star-forming regions

Volatile Species in Comet 67P/Churyumov-Gerasimenko: Investigating the Link from the ISM to the Terrestrial Planets

Comets contain abundant amounts of organic and inorganic species. Many of the volatile molecules in comets have also been observed in the interstellar medium and some of them even with similar relative abundances, indicating formation under similar conditions or even sharing a common chemical pathway. There is a growing amount of evidence that suggests comets inherit and preserve substantial fractions of materials inherited from previous evolutionary phases, potentially indicating that commonplace processes occurred throughout comet-forming regions. Through impacts, part of this material has also been transported to the inner planetary system, including the terrestrial planets. While comets have been ruled out as a major contributor to terrestrial ocean water, substantial delivery of volatile species to the Earth’s atmosphere, and as a consequence also organic molecules to its biomass, appears more likely. Comets contain many species of prebiotic relevance and molecules that are related to biological processes on Earth, and have hence been proposed as potential indicators for the presence of biological processes in the search of extraterrestrial life. Although the delivery of cometary material to Earth may have played a crucial role in the emergence of life, the presence of such alleged biosignature molecules in the abiotical environment of comets complicates the detection of life elsewhere in the universe