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Estimating uncertainties associated with the predictions of Machine Learning (ML) models is of crucial importance to assess their robustness and predictive power. In this submission, we introduce MAPIE (Model Agnostic Prediction Interval Estimator), an open-source Python library that quantifies the uncertainties of ML models for single-output regression and multi-class classification tasks. MAPIE implements conformal prediction methods, allowing the user to easily compute uncertainties with strong theoretical guarantees on the marginal coverages and with mild assumptions on the model or on the underlying data distribution. MAPIE is hosted on scikit-learn-contrib and is fully "scikit-learn-compatible". As such, it accepts any type of regressor or classifier coming with a scikit-learn API. The library is available at: https://github.com/scikit-learn-contrib/MAPIE/., Comment: Submitted to the 2022 ICML workshop "Distribution-free uncertainty quantification"

We report a study of the low-mass Class-0 multiple system VLA 1623AB in the Ophiuchus star-forming region, using H$^{13}$CO$^+$ ($J=3-2$), CS ($J=5-4$), and CCH ($N=3-2$) lines as part of the ALMA Large Program FAUST. The analysis of the velocity fields revealed the rotation motion in the envelope and the velocity gradients in the outflows (about 2000 au down to 50 au). We further investigated the rotation of the circum-binary VLA 1623A disk as well as the VLA 1623B disk. We found that the minor axis of the circum-binary disk of VLA 1623A is misaligned by about 12 degrees with respect to the large-scale outflow and the rotation axis of the envelope. In contrast, the minor axis of the circum-binary disk is parallel to the large-scale magnetic field according to previous dust polarization observations, suggesting that the misalignment may be caused by the different directions of the envelope rotation and the magnetic field. If the velocity gradient of the outflow is caused by rotation, the outflow has a constant angular momentum and the launching radius is estimated to be $5-16$ au, although it cannot be ruled out that the velocity gradient is driven by entrainments of the two high-velocity outflows. Furthermore, we detected for the first time a velocity gradient associated with rotation toward the VLA 16293B disk. The velocity gradient is opposite to the one from the large-scale envelope, outflow, and circum-binary disk. The origin of its opposite gradient is also discussed., Comment: 27 pages, 21 figures, 2 Tables, Accepted for publication in ApJ

We have observed the very low-mass Class 0 protostar IRAS 15398-3359 at scales ranging from 50 au to 1800 au, as part of the ALMA Large Program FAUST. We uncover a linear feature, visible in H2CO, SO, and C18O line emission, which extends from the source along a direction almost perpendicular to the known active outflow. Molecular line emission from H2CO, SO, SiO, and CH3OH further reveals an arc-like structure connected to the outer end of the linear feature and separated from the protostar, IRAS 15398-3359, by 1200 au. The arc-like structure is blue-shifted with respect to the systemic velocity. A velocity gradient of 1.2 km/s over 1200 au along the linear feature seen in the H2CO emission connects the protostar and the arc-like structure kinematically. SO, SiO, and CH3OH are known to trace shocks, and we interpret the arc-like structure as a relic shock region produced by an outflow previously launched by IRAS 15398-3359. The velocity gradient along the linear structure can be explained as relic outflow motion. The origins of the newly observed arc-like structure and extended linear feature are discussed in relation to turbulent motions within the protostellar core and episodic accretion events during the earliest stage of protostellar evolution.

After almost 20 years of hunting, only about a dozen hot corinos, hot regions enriched in interstellar complex organic molecules (iCOMs), are known. Of them, many are binary systems with the two components showing drastically different molecular spectra. Two obvious questions arise. Why are hot corinos so difficult to find and why do their binary components seem chemically different? The answer to both questions could be a high dust opacity that would hide the molecular lines. To test this hypothesis, we observed methanol lines at centimeter wavelengths, where dust opacity is negligible, using the Very Large Array interferometer. We targeted the NGC 1333 IRAS 4A binary system, for which one of the two components, 4A1, has a spectrum deprived of iCOMs lines when observed at millimeter wavelengths, while the other component, 4A2, is very rich in iCOMs. We found that centimeter methanol lines are similarly bright toward 4A1 and 4A2. Their non-LTE analysis indicates gas density and temperature ($\geq2\times10^6$ cm$^{-3}$ and 100--190 K), methanol column density ($\sim10^{19}$ cm$^{-2}$) and extent ($\sim$35 au in radius) similar in 4A1 and 4A2, proving that both are hot corinos. Furthermore, the comparison with previous methanol line millimeter observations allows us to estimate the optical depth of the dust in front of 4A1 and 4A2, respectively. The obtained values explain the absence of iCOMs line emission toward 4A1 at millimeter wavelengths and indicate that the abundances toward 4A2 are underestimated by $\sim$30\%. Therefore, centimeter observations are crucial for the correct study of hot corinos, their census, and their molecular abundances., Comment: 9 pages, 3 figures, 2 Tables - Published in ApJ Letters

Context. Low-mass protostars drive powerful molecular outflows that can be observed with mm and sub-mm telescopes. Various sulfuretted species are known to be bright in shocks and could be used to infer the physical and chemical conditions throughout the observed outflows. Aims. The evolution of sulfur chemistry is studied along the outflows driven by the NGC1333-IRAS4A protobinary system located in the Perseus cloud to constrain the physical and chemical processes at work in shocks. Methods. We observed various transitions from OCS, CS, SO, and SO$_2$ towards NGC1333-IRAS4A in the 1.3, 2, and 3mm bands using the IRAM NOEMA array and we interpreted the observations through the use of the Paris-Durham shock model. Results. The targeted species clearly show different spatial emission along the two outflows driven by IRAS4A. OCS is brighter on small and large scales along the south outflow driven by IRAS4A1, whereas SO$_2$ is detected rather along the outflow driven by IRAS4A2 that is extended along the north east - south west (NE-SW) direction. Column density ratio maps estimated from a rotational diagram analysis allowed us to confirm a clear gradient of the OCS/SO$_2$ column density ratio between the IRAS4A1 and IRAS4A2 outflows. SO is detected at extremely high radial velocity up to 25 km/s relative to the source velocity, clearly allowing us to distinguish the two outflows on small scales. Conclusions. The observed chemical differentiation between the two outflows of the IRAS4A system could be explained by a different chemical history. The outflow driven by IRAS4A1 is likely younger and more enriched in species initially formed in interstellar ices, such as OCS, and recently sputtered into the shock gas. In contrast, the longer and likely older outflow triggered by IRAS4A2 is more enriched in species that have a gas phase origin, such as SO$_2$., Comment: Accepted for publication in A&A

Methanol is a key species in astrochemistry since it is the most abundant organic molecule in the ISM and is thought to be the mother molecule of many complex organic species. Estimating the deuteration of methanol around young protostars is of crucial importance because it highly depends on its formation mechanisms and the physical conditions during its moment of formation. We analyse dozens of transitions from deuterated methanol isotopologues coming from various existing observational datasets from the IRAM-PdBI and ALMA sub-mm interferometers to estimate the methanol deuteration surrounding three low-mass protostars on Solar System scales. A population diagram analysis allows us to derive a [CH$_2$DOH]/[CH$_3$OH] abundance ratio of 3-6 % and a [CH$_3$OD]/[CH$_3$OH] ratio of 0.4-1.6 % in the warm inner protostellar regions. These values are ten times lower than those derived with previous single-dish observations towards these sources but they are 10-100 times higher than the methanol deuteration measured in massive hot cores. Dust temperature maps obtained from Herschel and Planck observations show that massive hot cores are located in warmer molecular clouds than low-mass sources, with temperature differences of $\sim$10 K. Comparison with the predictions of the gas-grain astrochemical model GRAINOBLE shows that such a temperature difference is sufficient to explain the different deuteration observed in low- to high-mass sources, suggesting that the physical conditions of the molecular cloud at the origin of the protostars mostly govern the present observed deuteration of methanol. The methanol deuteration measured in this work is higher by a factor of 5 than the upper limit in methanol deuteration estimated in comet Hale-Bopp, implying that an important reprocessing of the organic material would have occurred in the solar nebula during the formation of the Solar System., Comment: 16 pages, 10 figures, accepted for publication in Astronomy & Astrophysics

The Large and Small Magellanic Clouds (LMC and SMC), gas-rich dwarf companions of the Milky Way, are the nearest laboratories for detailed studies on the formation and survival of complex organic molecules (COMs) under metal poor conditions. To date, only methanol, methyl formate, and dimethyl ether have been detected in these galaxies - all three toward two hot cores in the N113 star-forming region in the LMC, the only extragalactic sources exhibiting complex hot core chemistry. We describe a small and diverse sample of the LMC and SMC sources associated with COMs or hot core chemistry, and compare the observations to theoretical model predictions. Theoretical models accounting for the physical conditions and metallicity of hot molecular cores in the Magellanic Clouds have been able to broadly account for the existing observations, but fail to reproduce the dimethyl ether abundance by more than an order of magnitude. We discuss future prospects for research in the field of complex chemistry in the low-metallicity environment. The detection of COMs in the Magellanic Clouds has important implications for astrobiology. The metallicity of the Magellanic Clouds is similar to galaxies in the earlier epochs of the Universe, thus the presence of COMs in the LMC and SMC indicates that a similar prebiotic chemistry leading to the emergence of life, as it happened on Earth, is possible in low-metallicity systems in the earlier Universe., Comment: This document is unedited Author's version of a Submitted Work that was subsequently accepted for publication in ACS Earth and Space Chemistry, copyright American Chemical Society, after peer review. To access the final edited and published work, see https://pubs.acs.org/articlesonrequest/AOR-mPUVfkWhtGmqXI5KbiR7

The chemical composition of high-mass protostars reflects the physical evolution associated with different stages of star formation. In this study, the molecular inventory of the forming high-mass star AFGL 4176 is studied in detail at high angular resolution (~0.35 arcsec) using ALMA. This high resolution makes it possible to separate the emission associated with the inner hot envelope and disk around the forming star from that of its cool outer envelope. In addition, the high sensitivity of ALMA makes it possible to identify weak and optically thin lines and allows for many isotopologues to be detected, providing a more complete and accurate inventory of the source. A total of 23 different molecular species and their isotopologues are detected in the spectrum towards AFGL 4176. The most abundant species is methanol (CH3OH), remaining species are present at levels between 0.003 % and 15 % with respect to CH3OH. Hints that N-bearing species peak slightly closer to the location of the peak continuum emission than the O-bearing species are seen. AFGL 4176 comprises a rich chemical inventory including many complex species present on disk-scales. On average, the derived column density ratios with respect to methanol of O-bearing species are higher than those derived for N-bearing species by a factor of three. This may indicate that AFGL 4176 is a relatively young source since nitrogen chemistry generally takes longer to evolve in the gas-phase. Taking methanol as a reference, the composition of AFGL 4176 more closely resembles that of the low-mass protostar IRAS 16293-2422B than that of high-mass star-forming regions located near the Galactic centre. This similarity hints that the chemical composition of complex species is already set in the cold cloud stage and implies that AFGL 4176 is a young source whose chemical composition has not yet been strongly processed by the central protostar., Comment: Accepted for publication in Astronomy & Astrophysics

Interstellar formamide (NH2CHO) has recently attracted significant attention due to its potential role as a molecular building block in the formation of precursor biomolecules relevant for the origin of life. Its formation, whether on the surfaces of the interstellar grains or in the gas phase, is currently debated. The present article presents new theoretical quantum chemical computations on possible NH2CHO formation routes in water-rich amorphous ices, simulated by a 33-H2O-molecule cluster. We have considered three possible routes. The first one refers to a scenario used in several current astrochemical models, that is, the radical-radical association reaction between NH2 and HCO. Our calculations show that formamide can indeed be formed, but in competition with formation of NH3 and CO through a direct H transfer process. The final outcome of the NH2 + HCO reactivity depends on the relative orientation of the two radicals on the ice surface. We then analyzed two other possibilities, suggested here for the first time: reaction of either HCN or CN with water molecules of the ice mantle. The reaction with HCN has been found to be characterized by large energy barriers and, therefore, cannot occur under the interstellar ice conditions. On the contrary, the reaction with the CN radical can occur, possibly leading through multiple steps to the formation of NH2CHO. For this reaction, water molecules of the ice act as catalytic active sites since they help the H transfers involved in the process, thus reducing the energy barriers (compared to the gas-phase analogous reaction). Additionally, we apply a statistical model to estimate the reaction rate coefficient when considering the cluster of 33-H2O-molecules as an isolated moiety with respect to the surrounding environment, i.e., the rest of the ice.

The formation of asteroids, comets and planets occurs in the interior of protoplanetary disks during the early phase of star formation. Consequently, the chemical composition of the disk might shape the properties of the emerging planetary system. In this context, it is crucial to understand whether and what organic molecules are synthesized in the disk. In this Letter, we report the first detection of formic acid (HCOOH) towards the TW Hydrae protoplanetary disk. The observations of the trans-HCOOH 6$_{(1,6)-5(1,5)}$ transition were carried out at 129~GHz with ALMA. We measured a disk-averaged gas-phase t-HCOOH column density of $\sim$ (2-4)$\times$10$^{12}$~cm$^{-2}$, namely as large as that of methanol. HCOOH is the first organic molecules containing two oxygen atoms detected in a protoplanetary disk, a proof that organic chemistry is very active even though difficult to observe in these objects. Specifically, this simplest acid stands as the basis for synthesis of more complex carboxylic acids used by life on Earth., Comment: 9 pages, 4 figures, 1 table, published online in ApJL on 16th July 2018

Recent measurements carried out at comet 67P/C-G with the ${\it Rosetta}$ probe revealed that molecular oxygen, O$_2$, is the fourth most abundant molecule in comets. Models show that O$_2$ is likely of primordial nature, coming from the interstellar cloud from which our Solar System was formed. However, gaseous O$_2$ is an elusive molecule in the interstellar medium with only one detection towards quiescent molecular clouds, in the $\rho$ Oph A core. We perform a deep search for molecular oxygen, through the $2_1 - 0_1$ rotational transition at 234 GHz of its $^{16}$O$^{18}$O isotopologue, towards the warm compact gas surrounding the nearby Class 0 protostar IRAS 16293--2422 B with the ALMA interferometer. The targeted $^{16}$O$^{18}$O transition is surrounded by two brighter transitions at $\pm 1$ km s$^{-1}$ relative to the expected $^{16}$O$^{18}$O transition frequency. After subtraction of these two transitions, residual emission at a 3$\sigma$ level remains, but with a velocity offset of $0.3 - 0.5$ km s$^{-1}$ relative to the source velocity, rendering the detection "tentative". We derive the O$_2$ column density for two excitation temperatures $T_{\rm ex}$ of 125 and 300 K, as indicated by other molecules, in order to compare the O$_2$ abundance between IRAS16293 and comet 67P/C-G. Assuming that $^{16}$O$^{18}$O is not detected and using methanol CH$_3$OH as a reference species, we obtain a [O$_2$]/[CH$_3$OH] abundance ratio lower than $2-5$, depending on the assumed $T_{\rm ex}$, a three to four times lower abundance than the [O$_2$]/[CH$_3$OH] ratio of $5-15$ found in comet 67P/C-G. Such a low O$_2$ abundance could be explained by the lower temperature of the dense cloud precursor of IRAS16293 with respect to the one at the origin of our Solar System that prevented an efficient formation of O$_2$ in interstellar ices., Comment: 12 pages, 3 figures, accepted for publication in Astronomy & Astrophysics

The abundance of deuterated molecules in a star-forming region is sensitive to the environment in which they are formed. Deuteration fractions therefore provide a powerful tool for studying the physical and chemical evolution of a star-forming system. While local low-mass star-forming regions show very high deuteration ratios, much lower fractions are observed towards Orion and the Galactic Centre. We derive methanol deuteration fractions at a number of locations towards the high-mass star-forming region NGC 6334I, located at a mean distance of 1.3 kpc, and discuss how these can shed light on the conditions prevailing during its formation. We use high sensitivity, high spatial and spectral resolution observations obtained with ALMA to study transitions of the less abundant, optically thin, methanol-isotopologues: (13)CH3OH, CH3(18)OH, CH2DOH and CH3OD, detected towards NGC 6334I. Assuming LTE and excitation temperatures of 120-330 K, we derive column densities for each of the species and use these to infer CH2DOH/CH3OH and CH3OD/CH3OH fractions. Interestingly, the column densities of CH3OD are consistently higher than those of CH2DOH throughout the region. All regions studied in this work show CH2DOH/CH3OH as well as CH2DOH/CH3OD ratios that are considerably lower than those derived towards low-mass star-forming regions and slightly lower than those derived for the high-mass star-forming regions in Orion and the Galactic Centre. The low ratios indicate a grain surface temperature during formation ~30 K, for which the efficiency of the formation of deuterated species is significantly reduced., Comment: Accepted for publication in Astronomy & Astrophysics

In dense molecular clouds, interstellar grains are covered by mantles of iced molecules. The formation of the grain mantles has two important consequences: it removes species from the gas phase and promotes the synthesis of new molecules on the grain surfaces. The composition of the mantle is a strong function of the environment which the cloud belongs to. Therefore, clouds in high-zeta galaxies, where conditions -like temperature, metallicity and cosmic rays flux- are different from those in the Milky Way, will have different grain mantles. In the last years, several authors have suggested that silicate grains might grow by accretion of silicon bearing species on smaller seeds. This would occur simultaneously to the formation of the iced mantles and be greatly affected by its composition as a function of time. In this work, we present a numerical study of the grain mantle formation in high-zeta galaxies and we quantitatively address the possibility of silicate growth. We find that the mantle thickness decreases with increasing redshift, from about 120 to 20 layers for z varying from 0 to 8. Furthermore, the mantle composition is also a strong function of the cloud redshift, with the relative importance of CO, CO2, ammonia, methane and methanol highly varying with z. Finally, being Si-bearing species always a very minor component of the mantle, the formation of silicates in molecular clouds is practically impossible., Comment: MNRAS in press

Towards the pre-stellar core L1544, the methanol (CH$_3$OH) emission forms an asymmetric ring around the core centre, where CH$_3$OH is mostly in solid form, with a clear peak 4000~au to the north-east of the dust continuum peak. As part of the NOEMA Large Project SOLIS (Seeds of Life in Space), the CH$_3$OH peak has been spatially resolved to study its kinematics and physical structure and to investigate the cause behind the local enhancement. We find that methanol emission is distributed in a ridge parallel to the main axis of the dense core. The centroid velocity increases by about 0.2~km~s$^{-1}$ and the velocity dispersion increases from subsonic to transonic towards the central zone of the core, where the velocity field also shows complex structure. This could be indication of gentle accretion of material onto the core or interaction of two filaments, producing a slow shock. We measure the rotational temperature and show that methanol is in local thermodynamic equilibrium (LTE) only close to the dust peak, where it is significantly depleted. The CH$_3$OH column density, $N_{tot}({\rm CH_3OH})$, profile has been derived with non-LTE radiative transfer modelling and compared with chemical models of a static core. The measured $N_{tot}({\rm CH_3OH})$ profile is consistent with model predictions, but the total column densities are one order of magnitude lower than those predicted by models, suggesting that the efficiency of reactive desorption or atomic hydrogen tunnelling adopted in the model may be overestimated; or that an evolutionary model is needed to better reproduce methanol abundance., Comment: 19 pages, 18 figures. Accepted by ApJ

Snowlines are key ingredients for planet formation. Providing observational constraints on the locations of the major snowlines is therefore crucial for fully connecting planet compositions to their formation mechanism. Unfortunately, the most important snowline, that of water, is very difficult to observe directly in protoplanetary disks due to its close proximity to the central star. Based on chemical considerations, HCO$^+$ is predicted to be a good chemical tracer of the water snowline, because it is particularly abundant in dense clouds when water is frozen out. This work maps the optically thin isotopologue H$^{13}$CO$^+$ ($J=3-2$) toward the envelope of the low-mass protostar NGC1333-IRAS2A (observed with NOEMA at ~0.9" resolution), where the snowline is at larger distance from the star than in disks. The H$^{13}$CO$^+$ emission peaks ~2" northeast of the continuum peak, whereas the previously observed H$_2^{18}$O shows compact emission on source. Quantitative modeling shows that a decrease in H$^{13}$CO$^+$ abundance by at least a factor of six is needed in the inner ~360 AU to reproduce the observed emission profile. Chemical modeling predicts indeed a steep increase in HCO$^+$ just outside the water snowline; the 50% decrease in gaseous H$_2$O at the snowline is not enough to allow HCO$^+$ to be abundant. This places the water snowline at 225 AU, further away from the star than expected based on the 1D envelope temperature structure for NGC1333-IRAS2A. In contrast, DCO$^+$ observations show that the CO snowline is at the expected location, making an outburst scenario unlikely. The spatial anticorrelation of the H$^{13}$CO$^+$ and H$_2^{18}$O emission provide a proof of concept that H$^{13}$CO$^+$ can be used as a tracer of the water snowline., Comment: 10 pages, 8 figures, 3 tables. Accepted for publication in A&A

Molecular oxygen, O$_2$, was recently detected in comet 67P by the ROSINA instrument on board the Rosetta spacecraft with a surprisingly high abundance of 4 % relative to H$_2$O, making O$_2$ the fourth most abundant in comet 67P. Other volatile species with similar volatility, such as molecular nitrogen N$_2$, were also detected by Rosetta, but with much lower abundances and much weaker correlations with water. Here, we investigate the chemical and physical origin of O$_2$ and other volatile species using the new constraints provided by Rosetta. We follow the chemical evolution during star formation with state-of-the-art astrochemical models applied to dynamical physical models by considering three origins: i) in dark clouds, ii) during forming protostellar disks, and iii) during luminosity outbursts in disks. The models presented here favour a dark cloud (or "primordial") grain surface chemistry origin for volatile species in comets, albeit for dark clouds which are slightly warmer and denser than those usually considered as solar system progenitors., Comment: To appear in "Astrochemistry VII -- Through the Cosmos from Galaxies to Planets", proceedings of the IAU Symposium No. 332, 2017, Puerto Varas, Chile. M. Cunningham, T. Millar and Y. Aikawa, eds. (9 pages, 2 figures)

Cold gas-phase water has recently been detected in a cold dark cloud, Barnard 5 located in the Perseus complex, by targeting methanol peaks as signposts for ice mantle evaporation. Observed morphology and abundances of methanol and water are consistent with a transient non-thermal evaporation process only affecting the outermost ice mantle layers, possibly triggering a more complex chemistry. We present the detection of the Complex Organic Molecules (COMs) acetaldehyde and methyl formate as well as formic acid and ketene, and the tentative detection of di-methyl ether towards the methanol hotspot of Barnard 5 located between two dense cores using the single dish OSO 20m, IRAM 30m, and NRO 45m telescopes. The high energy cis- conformer of formic acid is detected, suggesting that formic acid is mostly formed at the surface of interstellar grains and then evaporated. The detection of multiple transitions for each species allows us to constrain their abundances through LTE and non-LTE methods. All the considered COMs show similar abundances between $\sim 1$ and $\sim 10$ % relative to methanol depending on the assumed excitation temperature. The non-detection of glycolaldehyde, an isomer of methyl formate, with a [glycolaldehyde]/[methyl formate] abundance ratio lower than 6 %, favours gas phase formation pathways triggered by methanol evaporation. According to their excitation temperatures derived in massive hot cores, formic acid, ketene, and acetaldehyde have been designated as "lukewarm" COMs whereas methyl formate and di-methyl ether were defined as "warm" species. Comparison with previous observations of other types of sources confirms that "lukewarm" and "warm" COMs show similar abundances in low-density cold gas whereas the "warm" COMs tend to be more abundant than the "lukewarm" species in warm protostellar cores., Comment: Accepted for publication in Astronomy and Astrophysics

Molecular oxygen has been confirmed as the fourth most abundant molecule in cometary material O$_2$/H$_2$O $\sim 4$ %) and is thought to have a primordial nature, i.e., coming from the interstellar cloud from which our solar system was formed. However, interstellar O$_2$ gas is notoriously difficult to detect and has only been observed in one potential precursor of a solar-like system. Here, the chemical and physical origin of O$_2$ in comets is investigated using sophisticated astrochemical models. Three origins are considered: i) in dark clouds, ii) during forming protostellar disks, and iii) during luminosity outbursts in disks. The dark cloud models show that reproduction of the observed abundance of O$_2$ and related species in comet 67P/C-G requires a low H/O ratio facilitated by a high total density ($\geq 10^5$ cm$^{-3}$), and a moderate cosmic ray ionisation rate ($\leq 10^{-16}$ s$^{-1}$) while a temperature of 20 K, slightly higher than the typical temperatures found in dark clouds, also enhances the production of O$_2$. Disk models show that O$_2$ can only be formed in the gas phase in intermediate disk layers, and cannot explain the strong correlation between O$_2$ and H$_2$O in comet 67P/C-G together with the weak correlation between other volatiles and H$_2$O. However, primordial O$_2$ ice can survive transport into the comet-forming regions of disks. Taken together, these models favour a dark cloud (or "primordial") origin for O$_2$ in comets, albeit for dark clouds which are warmer and denser than those usually considered as solar system progenitors., Comment: Accepted for publication in MNRAS. 20 pages, 13 figures, 2 tables

During the formation of stars, the accretion of the surrounding material toward the central object is thought to undergo strong luminosity outbursts, followed by long periods of relative quiescence, even at the early stages of star formation when the protostar is still embedded in a large envelope. We investigated the gas phase formation and the recondensation of the complex organic molecules (COMs) di-methyl ether and methyl formate, induced by sudden ice evaporation processes occurring during luminosity outbursts of different amplitudes in protostellar envelopes. For this purpose, we updated a gas phase chemical network forming complex organic molecules in which ammonia plays a key role. The model calculations presented here demonstrate that ion-molecule reactions alone could account for the observed presence of di-methyl ether and methyl formate in a large fraction of protostellar cores, without recourse to grain-surface chemistry, although they depend on uncertain ice abundances and gas phase reaction branching ratios. In spite of the short outburst timescales of about one hundred years, abundance ratios of the considered species with respect to methanol higher than 10 % are predicted during outbursts due to their low binding energies relative to water and methanol that delay their recondensation during the cooling. Although the current luminosity of most embedded protostars would be too low to produce these complex species in hot core regions that can be observable with current sub-millimetric interferometers, previous luminosity outburst events would induce a formation of COMs in extended regions of protostellar envelopes with sizes increasing by up to one order of magnitude., Comment: 12 pages and 7 figures. Accepted for publication in The Astrophysical Journal

Water is an important molecule in the chemical and thermal balance of dense molecular gas, but knowing its history through-out the various stages of the star formation is a fundamental problem. Its molecular deuteration provides us with a crucial clue to its formation history. H$_2$O has recently been detected for the first time towards the prestellar core L1544 with the Herschel Space Observatory with a high spectral resolution (HIFI instrument). Prestellar cores provide the original reservoir of material from which future planetary systems are built, but few observational constraints exist on the formation of water and none on its deuteration before the collapse starts and a protostar forms at the centre. We report on new APEX observations of the ground state 1$_{0,1}$-0$_{0,0}$ HDO transition at 464 GHz towards the prestellar core L1544. The line is undetected, and we present an extensive study of the conditions for its detectability in cold and dense cloud cores. The water and deuterated water abundances have been estimated using an advanced chemical model simplified for the limited number of reactions or processes that are active in cold regions (< 15 K). We use the LIME radiative transfer code to compute the expected intensity and profile of both H$_2$O and HDO lines and compare them with the observations. We present several ad hoc profiles that best-fit the observations and compare the profiles with results from an astrochemical modelling, coupling gas phase and grain surface chemistry. Our comparison between observations, radiative transfer, and chemical modelling shows the limits of detectability for singly deuterated water, through the ground-state transitions 1$_{0,1}$-0$_{0,0}$ and 1$_{1,1}$-0$_{0,0}$ at 464.9 and 893.6 GHz, respectively, with both single-dish telescope and interferometric observations., Comment: 8 pages, 6 figures

The high abundances of Complex Organic Molecules (COMs) with respect to methanol, the most abundant COM, detected towards low-mass protostars, tend to be underpredicted by astrochemical models. This discrepancy might come from the large beam of the single-dish telescopes, encompassing several components of the studied protostar, commonly used to detect COMs. To address this issue, we have carried out multi-line observations of methanol and several COMs towards the two low-mass protostars NGC1333-IRAS2A and -IRAS4A with the Plateau de Bure interferometer at an angular resolution of 2 arcsec, resulting in the first multi-line detection of the O-bearing species glycolaldehyde and ethanol and of the N-bearing species ethyl cyanide towards low-mass protostars other than IRAS 16293. The high number of detected transitions from COMs (more than 40 methanol transitions for instance) allowed us to accurately derive the source size of their emission and the COMs column densities. The COMs abundances with respect to methanol derived towards IRAS2A and IRAS4A are slightly, but not substantitally, lower than those derived from previous single-dish observations. The COMs abundance ratios do not vary significantly with the protostellar luminosity, over five orders of magnitude, implying that low-mass hot corinos are quite chemically rich as high-mass hot cores. Astrochemical models still underpredict the abundances of key COMs, such as methyl formate or di-methyl ether, suggesting that our understanding of their formation remains incomplete., Comment: 60 pages, 10 figures, 17 tables. Accepted for publication in ApJ

While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain surface and gas phase chemistry. We propose here a new model to form DME and MF with gas phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthetized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairy well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry., Comment: MNRAS, accepted

Water plays a crucial role both in the interstellar medium and on Earth. To constrain its formation mechanisms and its evolution through the star formation process, the determination of the water deuterium fractionation ratios is particularly suitable. Previous studies derived HDO/H$_2$O ratios in the warm inner regions of low-mass protostars. We here report a detection of the D$_2$O 1$_{1,0}$-1$_{0,1}$ transition toward the low-mass protostar NGC1333 IRAS2A with the Plateau de Bure interferometer: this represents the first interferometric detection of D$_2$O - and only the second solar-type protostar for which this isotopologue is detected. Using the observations of the HDO 5$_{4,2}$-6$_{3,3}$ transition simultaneously detected and three other HDO lines previously observed, we show that the HDO line fluxes are well reproduced with a single excitation temperature of 218$\pm$21 K and a source size of $\sim$0.5 arcsec. The D$_2$O/HDO ratio is $\sim$(1.2$\pm$0.5) $\times$ 10$^{-2}$, while the use of previous H$_2^{18}$O observations give an HDO/H$_2$O ratio of $\sim$(1.7$\pm$0.8) $\times$ 10$^{-3}$, i.e. a factor of 7 lower than the D$_2$O/HDO ratio. These results contradict the predictions of current grain surface chemical models and indicate that either the surface deuteration processes are poorly understood or that both sublimation of grain mantles and water formation at high temperatures ($\gtrsim$230 K) take place in the inner regions of this source. In the second scenario, the thermal desorption of the grain mantles would explain the high D$_2$O/HDO ratio, while water formation at high temperature would explain significant extra production of H$_2$O leading to a decrease of the HDO/H$_2$O ratio., Comment: Accepted for publication in ApJ Letters; 12 pages, 2 figures

Extremely large deuteration of several molecules has been observed towards prestellar cores and low-mass protostars for a decade. New observations performed towards low-mass protostars suggest that water presents a lower deuteration in the warm inner gas than in the cold external envelope. We coupled a gas-grain astrochemical model with a one-dimension model of collapsing core to properly follow the formation and the deuteration of interstellar ices as well as their subsequent evaporation in the low-mass protostellar envelopes with the aim of interpreting the spatial and temporal evolutions of their deuteration. The astrochemical model follows the formation and the evaporation of ices with a multilayer approach and also includes a state-of-the-art deuterated chemical network by taking the spin states of H$_2$ and light ions into account. Because of their slow formation, interstellar ices are chemically heterogeneous and show an increase of their deuterium fractionation towards the surface. The differentiation of the deuteration in ices induces an evolution of the deuteration within protostellar envelopes. The warm inner region is poorly deuterated because it includes the whole molecular content of ices while the deuteration predicted in the cold external envelope scales with the highly deuterated surface of ices. We are able to reproduce the observed evolution of water deuteration within protostellar envelopes but we are still unable to predict the super-high deuteration observed for formaldehyde and methanol. Finally, the extension of this study to the deuteration of complex organics (COMs), important for the prebiotic chemistry, shows a good agreement with the observations, suggesting that we can use the deuteration to retrace their mechanisms and their moments of formation., Comment: 22 pages, 11 figures. Accepted for publication in The Astrophysical Journal

The [HDO]/[H2O] ratio is a crucial parameter for probing the history of water formation. So far, it has been measured for only three solar type protostars and yielded different results, possibly pointing to a substantially different history in their formation. In the present work, we report new interferometric observations of the HDO 4 2,2 - 4 2,3 line for two solar type protostars, IRAS2A and IRAS4A, located in the NGC1333 region. In both sources, the detected HDO emission originates from a central compact unresolved region. Comparison with previously published interferometric observations of the H218$O 3 1,3 - 2 2,0 line shows that the HDO and H$_2$O lines mostly come from the same region. A non-LTE LVG analysis of the HDO and H218$O line emissions, combined with published observations, provides a [HDO]/[H2O] ratio of 0.3 - 8 % in IRAS2A and 0.5 - 3 % in IRAS4A. First, the water fractionation is lower than that of other molecules such as formaldehyde and methanol in the same sources. Second, it is similar to that measured in the solar type protostar prototype, IRAS16293-2422, and, surprisingly enough, larger than that measured in NGC1333 IRAS4B. {The comparison of the measured values towards IRAS2A and IRAS4A with the predictions of our gas-grain model GRAINOBLE gives similar conclusions to those for IRAS 16293, arguing that these protostars {share} a similar chemical history, although they are located in different clouds., Comment: Accepted for publication to ApJL. 6 pages, 2 figures

Context. Millimetric observations have measured high degrees of molecular deuteration in several species seen around low-mass protostars. The Herschel Space Telescope, launched in 2009, is now providing new measures of the deuterium fractionation of water, the main constituent of interstellar ices. Aims. We aim at theoretically studying the formation and the deuteration of water, which is believed to be formed on interstellar grain surfaces in molecular clouds. Methods. We used our gas-grain astrochemical model GRAINOBLE, which considers the multilayer formation of interstellar ices. We varied several input parameters to study their impact on water deuteration. We included the treatment of ortho- and para-states of key species, including H2, which affects the deuterium fractionation of all molecules. The model also includes relevant laboratory and theoretical works on the water formation and deuteration on grain surfaces. In particular, we computed the transmission probabilities of surface reactions using the Eckart model, and we considered ice photodissociation following molecular dynamics simulations. Results. The use of a multilayer approach allowed us to study the influence of various parameters on the abundance and the deuteration of water. Deuteration of water is found to be very sensitive to the ortho-to-para ratio of H2 and to the total density, but it also depends on the gas/grain temperatures and the visual extinction of the cloud. Since the deuteration is very sensitive to the physical conditions, the comparison with sub-millimetric observation towards the low-mass protostar IRAS 16293 allows us to suggest that water ice is formed together with CO2 in molecular clouds with limited density, whilst formaldehyde and methanol are mainly formed in a later phase, where the condensation becomes denser and colder., Comment: Accepted for publication to A&A. 24 pages, 10 figures

Extremely high deuteration of several molecules have been observed around low mass protostars since a decade. Among them, formaldehyde and methanol present particularly high deuteration, with observations of abundant doubly and triply deuterated forms. Both species are thought to be mainly formed on interstellar grains during the low temperature and dense pre-collapse phase by H and D atom additions on the iced CO. We present here a theoretical study of the formaldehyde and methanol deuteration obtained with our gas-grain model, GRAINOBLE. This model takes into account the multilayer nature of the mantle and explores the robustness of the results against the uncertainties of poorly constrained chemical and surface model parameters. The comparison of the model predictions with the observations leads to two major results: i) the observed high deuteration is obtained during the last phase of the pre-collapse stage, when the density reaches 5 10^6 cm^-3, and this phase is fast, lasting only several thousands years. ii) D and H abstraction and substitution reactions are crucial in making up the observed deuteration ratios; This work shows the power of chemical composition as a tool to reconstruct the past history of protostars., Comment: 7 pages and 4 figures, accepted in The Astrophysical Journal Letters (14th February 2012)

Mantles of iced water, mixed with CO, H2CO, and CH3OH are formed during the so called prestellar core phase. In addition, radicals are also thought to be formed on the grain surfaces, and to react to form complex organic molecules later on, during the warm-up phase of the protostellar evolution. We aim to study the formation of the grain mantles during the prestellar core phase and the abundance of H2CO, CH3OH, and radicals trapped in them. We have developed a macrosopic statistic multilayer model that follows the formation of grain mantles with time and that includes two effects that may increase the number of radicals trapped in the mantles: i) at each time of the mantle formation, only the surface layer is chemically active rather than the entire bulk, and ii) the porous structure of grains allows to trap reactive particles. The model considers a network of H, O and CO forming neutral species such as water, CO, formaldehyde, and methanol, plus several radicals. We run a large grid of models to study the impact of the mantle multilayer nature and grain porous structure. In addition, we explored the influence of the uncertainty of other key parameters on the mantle composition. Our model predicts relatively large abundances of radicals. In addition, the multilayer approach makes it possible to follow the chemical differentiation within the grain mantle, showing that the mantles are far from being uniform. For example, methanol is mostly present in the outer layers of the mantles whereas CO and other reactive species are trapped in the inner layers. The overall mantle composition depends on the density and age of the prestellar core, and on some microscopic parameters. Comparison with observations allows us to constrain the value of few parameters and provide some indications on the physical conditions during the formation of the ices., Comment: 20 pages and 19 figures. Accepted in Astronomy & Astrophysics

We utilize a chemical equilibrium code in order to study the condensation process which occurs in protoplanetary discs during the formation of the first solids. The model specifically focuses on the thermodynamic behaviour on the solid species assuming the regular solution model. For each solution, we establish the relationship between the activity of the species, the composition and the temperature using experimental data from the literature. We then apply the Gibbs free energy minimization method and study the resulting condensation sequence for a range of temperatures and pressures within a protoplanetary disc. Our results using the regular solution model show that grains condense over a large temperature range and therefore throughout a large portion of the disc. In the high temperature region (T > 1400 K) Ca-Al compounds dominate and the formation of corundum is sensitive to the pressure. The mid-temperature region is dominated by Fe(s) and silicates such as Mg2SiO4 and MgSiO3 . The chemistry of forsterite and enstatite are strictly related, and our simulations show a sequence of forsterite-enstatite-forsterite with decreasing temperature. In the low temperature regions (T < 600 K) a range of iron compounds and sulfides form. We also run simulations using the ideal solution model and see clear differences in the resulting condensation sequences with changing solution model In particular, we find that the turning point in which forsterite replaces enstatite in the low temperature region is sensitive to the solution model. Our results show that the ideal solution model is often a poor approximation to experimental data at most temperatures important in protoplanetary discs. We find some important differences in the resulting condensation sequences when using the regular solution model, and suggest that this model should provide a more realistic condensation sequence., Comment: MNRAS: Accepted 2011 February 16. Received 2011 February 14; in original form 2010 July 22