Search

Young low-mass protostars often possess hot corinos, compact, hot and dense regions bright in interstellar Complex Organic Molecules (iCOMs). Besides of their prebiotic role, iCOMs can be used as a powerful tool to characterize the chemical and physical properties of hot corinos. Using ALMA/FAUST data we aim to explore the iCOMs emission at < 50 au scale around the Class 0 prototypical hot corino IRAS 4A2. We imaged IRAS 4A2 in six abundant, common iCOMs (CH$_3$OH, HCOOCH$_3$, CH$_3$CHO, CH$_3$CH$_2$OH, CH$_2$OHCHO, and NH$_2$CHO), and derived their emitting size. The column density and gas temperature for each species were derived at 1$\sigma$ from a multi-line analysis by applying a non-LTE approach for CH$_3$OH, and LTE population or rotational diagram analysis for the other iCOMs. Thanks to the unique estimates of the absorption from foreground millimeter dust toward IRAS 4A2, we derived for the first time unbiased gas temperatures and column densities. We resolved the IRAS 4A2 hot corino finding evidence for a chemical spatial distribution in the inner 50 au, with the outer emitting radius increasing from ~ 22-23 au for NH$_2$CHO and CH$_2$OHCHO, followed by CH$_3$CH$_2$OH (~ 27 au), CH$_3$CHO (~ 28 au), HCOOCH$_3$ (~ 36 au), and out to ~ 40 au for CH$_3$OH. Combining our estimate of the gas temperature probed by each iCOM with their beam-deconvolved emission sizes, we inferred the gas temperature profile of the hot corino on scales of 20-50 au in radius, finding a power-law index $q$ of approximately -1. We observed, for the first time, a chemical segregation in iCOMs of the IRAS 4A2 hot corino, and derived the gas temperature profile of its inner envelope. The derived profile is steeper than when considering a simple spherical collapsing and optically-thin envelope, hinting at a partially optically-thick envelope or a gravitationally unstable disk-like structure., Comment: 21 pages, 16 figures, 4 tables. Accepted in A&A

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

46P/Wirtanen is a Jupiter-family comet, probably originating from the Solar System's Kuiper belt, that now resides on a 5.4 year elliptical orbit. During its 2018 apparition, comet 46P passed unusually close to the Earth (within 0.08 au), presenting an outstanding opportunity for close-up observations of its inner coma. Here we present observations of HCN, H$^{13}$CN and HC$^{15}$N emission from 46P using the Atacama Compact Array (ACA). The data were analyzed using the SUBLIME non-LTE radiative transfer code to derive $^{12}$C/$^{13}$C and $^{14}$N/$^{15}$N ratios. The HCN/H$^{13}$CN ratio is found to be consistent with a lack of significant $^{13}$C fractionation, whereas the HCN/HC$^{15}$N ratio of $68\pm27$ (using our most conservative $1\sigma$ uncertainties), indicates a strong enhancement in $^{15}$N compared with the solar and terrestrial values. The observed $^{14}$N/$^{15}$N ratio is also significantly lower than the values of $\sim140$ found in previous comets, implying a strong $^{15}$N enrichment in 46P's HCN. This indicates that the nitrogen in Jupiter-family comets could reach larger isotopic enrichments than previously thought, with implications for the diversity of $^{14}$N/$^{15}$N ratios imprinted into icy bodies at the birth of the Solar System., Comment: Accepted for publication in PSJ, September 2024

Recent observations suggest that planets formation starts early, in protostellar disks of $\le10^5$ yrs, which are characterized by strong interactions with the environment, e.g., through accretion streamers and molecular outflows. To investigate the impact of such phenomena on disk physical and chemical properties it is key to understand what chemistry planets inherit from their natal environment. In the context of the ALMA Large Program Fifty AU STudy of the chemistry in the disk/envelope system of Solar-like protostars (FAUST), we present observations on scales from ~1500 au to ~60 au of H$_2$CO, HDCO, and D$_2$CO towards the young planet-forming disk IRS~63. H$_2$CO probes the gas in the disk as well as in a large scale streamer (~1500 au) impacting onto the South-East (SE) disk side. We detect for the first time deuterated formaldehyde, HDCO and D$_2$CO, in a planet-forming disk, and HDCO in the streamer that is feeding it. This allows us to estimate the deuterium fractionation of H$_2$CO in the disk: [HDCO]/[H$_2$CO]$\sim0.1-0.3$ and [D$_2$CO]/[H$_2$CO]$\sim0.1$. Interestingly, while HDCO follows the H$_2$CO distribution in the disk and in the streamer, the distribution of D$_2$CO is highly asymmetric, with a peak of the emission (and [D]/[H] ratio) in the SE disk side, where the streamer crashes onto the disk. In addition, D$_2$CO is detected in two spots along the blue- and red-shifted outflow. This suggests that: (i) in the disk, HDCO formation is dominated by gas-phase reactions similarly to H$_2$CO, while (ii) D$_2$CO was mainly formed on the grain mantles during the prestellar phase and/or in the disk itself, and is at present released in the gas-phase in the shocks driven by the streamer and the outflow. These findings testify on the key role of streamers in the build-up of the disk both concerning the final mass available for planet formation and its chemical composition., Comment: 12 pages, 10 figures, accepted for publication on A&A

The subsurface ocean of Europa is a high priority target in the search for extraterrestrial life, but direct investigations are hindered by the presence of a thick, exterior ice shell. Here we present spectral line and continuum maps of Europa obtained over four epochs in May-June 2021 using the Atacama Large Millimeter/submillimeter Array (ALMA), to search for molecular emission from atmospheric plumes, with the aim of investigating subsurface processes. Using a 3D physical model, we obtained upper limits for the plume abundances of HCN, H$_2$CO, SO$_2$ and CH$_3$OH. If active plume(s) were present, they contained very low abundances of these molecules. Assuming a total gas production rate of $10^{29}$ s$^{-1}$, our H$_2$CO abundance upper limit of $<0.016$\% is more than an order of magnitude less than measured in the Enceladus plume by the Cassini spacecraft, implying a possible chemical difference between the plume source materials for these two icy moons., Comment: Submitted to IAU Symposium 383 conference proceedings --- Astrochemistry VIII: From the First Galaxies to the Formation of Habitable Worlds

The temperature structure of Titan's upper atmosphere exhibits large variability resulting from numerous spatially and temporally irregular external energy sources, seasonal changes, and the influence of molecular species produced via photochemistry. In particular, Titan's relatively abundant HCN is thought to provide substantial cooling to the upper atmosphere through rotational emission, balancing UV/EUV heating and thermal conduction. Here, we present the analysis of ALMA observations of Titan from 2012, 2014, 2015, and 2017, corresponding to planetocentric solar longitudes of ~34-89$^{\circ}$, including vertical HCN and temperature profiles retrieved from the lower mesosphere through the thermosphere (~350-1200 km; $3\times10^{-2}$-$2\times10^{-8}$ mbar). Throughout the atmosphere, temperature profiles differ by 10 to 30 K between observations approximately one Earth year apart, particularly from 600-900 km. We find evidence for a large imbalance in Titan's upper atmospheric energy budget between 2014 and 2015, where the mesospheric thermal structure changes significantly and marks the transition between a mesopause located at ~600 km ($2\times10^{-4}$ mbar) and at ~800 km ($3\times10^{-6}$ mbar). The retrieved HCN abundances vary dramatically during the 2012 to 2017 time period as well, showing close to 2 orders of magnitude difference in abundance at 1000 km. However, the change in HCN abundance does not appear to fully account for the variation in mesospheric temperatures over the $L_S\sim$34-89$^{\circ}$ period. These measurements provide additional insight into the variability of Titan's mesospheric composition and thermal structure following its 2009 vernal equinox, and motivate continued investigation of the origins of such rapid changes in Titan's atmosphere throughout its seasonal cycle., Comment: Published in the Planetary Science Journal. 25 pages, 11 figures, 1 table

AGB stars are major contributors to the chemical enrichment of the ISM through nucleosynthesis and extensive mass loss. Most of our current knowledge of AGB atmospheric and circumstellar chemistry, in particular in a C-rich environment, is based on observations of the carbon star IRC+10216. We aim to obtain a more generalised understanding of the chemistry in C-rich AGB CSEs by studying a sample of three carbon stars, IRAS15194-5115, IRAS15082-4808, and IRAS07454-7112, and test the archetypal status often attributed to IRC+10216. We performed spatially resolved, unbiased spectral surveys in ALMA Band 3. We identify a total of 132 rotational transitions from 49 molecular species. There are two main morphologies of the brightness distributions: centrally-peaked (e.g. HCN) and shell-like (e.g. C$_2$H). We estimated the sizes of the molecular emitting regions using azimuthally-averaged radial profiles of the line brightness distributions, and derived abundance estimates. Of the shell distributions, the cyanopolyynes peak at slightly smaller radii than the hydrocarbons, and CN and HNC show the most extended emission. The emitting regions for each species are the smallest for IRAS07454-7112. We find that, within the uncertainties of the analysis, the three stars present similar abundances for most species, also compared to IRC+10216. We find that SiO is more abundant in our three stars compared to IRC+10216. Our estimated isotopic ratios match well the literature values for the sources. The observed circumstellar chemistry appears very similar across our sample and compared to that of IRC+10216, both in terms of the relative location of the emitting regions and molecular abundances. This implies that, to a first approximation, the chemical models tailored to IRC+10216 are able to reproduce the observed chemistry in C-rich envelopes across roughly an order of magnitude in wind density., Comment: 21 pages. 13 figures and 8 tables in the main text. 5 appendices contain additional figures and tables. Appendix tables are available in electronic form at the CDS, along with the reprocessed ALMA cubes and spectra, at http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/ or via anonymous ftp to cdsarc.u-strasbg.fr(130.79.128.5). Accepted for publication in Astronomy & Astrophysics

During the journey from the cloud to the disc, the chemical composition of the protostellar envelope material can be either preserved or processed to varying degrees depending on the surrounding physical environment. This works aims to constrain the interplay of solid (ice) and gaseous methanol (CH$_3$OH) in the outer regions of protostellar envelopes located in the Coronet cluster in Corona Australis (CrA), and assess the importance of irradiation by the Herbig Ae/Be star R CrA. CH$_3$OH is a prime test-case as it predominantly forms as a consequence of the solid-gas interplay (hydrogenation of condensed CO molecules onto the grain surfaces) and it plays an important role in future complex molecular processing. We present 1.3 mm Submillimeter Array (SMA) and Atacama Pathfinder Experiment (APEX) observations towards the envelopes of four low-mass protostars in the Coronet. Eighteen molecular transitions of seven species are identified. We calculate CH$_3$OH gas-to-ice ratios in this strongly irradiated cluster and compare them with ratios determined towards protostars located in less irradiated regions such as the Serpens SVS 4 cluster in Serpens Main and the Barnard 35A cloud in the $\lambda$ Orionis region. The CH$_3$OH gas-to-ice ratios in the Coronet vary by one order of magnitude (from 1.2$\times$10$^{-4}$ to 3.1$\times$10$^{-3}$) which is similar to less irradiated regions as found in previous studies. We find that the CH$_3$OH gas-to-ice ratios estimated in these three regions are remarkably similar despite the different UV radiation field intensities and formation histories. This result suggests that the overall CH$_3$OH chemistry in the outer regions of low-mass envelopes is relatively independent of variations in the physical conditions and hence that it is set during the prestellar stage., Comment: 20 pages, 17 figures, accepted for publication in Astronomy & Astrophysics

Gas-phase molecules in cometary atmospheres (comae) originate primarily from (1) outgassing by the nucleus, (2) sublimation of icy grains in the near-nucleus coma, and (3) coma (photo-)chemical processes. However, the majority of cometary gases observed at radio wavelengths have yet to be mapped, so their production/release mechanisms remain uncertain. Here we present observations of six molecular species towards comet 46P/Wirtanen, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) during the comet's unusually close (~0.1 au) approach to Earth in December 2018. Interferometric maps of HCN, CH3OH, CH3CN, H2CO, CS and HNC were obtained at an unprecedented sky-projected spatial resolution of up to 25 km, enabling the nucleus and coma sources of these molecules to be accurately quantified. The HCN, CH3OH and CH3CN spatial distributions are consistent with production by direct outgassing from (or very near to) the nucleus, with a significant proportion of the observed CH3OH originating from sublimation of icy grains in the near-nucleus coma (at a scale-length $L_p=36\pm7$ km). On the other hand, H2CO, CS and HNC originate primarily from distributed coma sources (with $L_p$ values in the range 550-16,000 km), the identities of which remain to be established. The HCN, CH3OH and HNC abundances in 46P are consistent with the average values previously observed in comets, whereas the H2CO, CH3CN and CS abundances are relatively low., Comment: Accepted for publication in the Astrophysical Journal on 2023-06-17

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

The presence of phosphine (PH$_3$) in the atmosphere of Venus was reported by Greaves et al. (2021a), based on observations of the J=1-0 transition at 267 GHz using ground-based, millimeter-wave spectroscopy. This unexpected discovery presents a challenge for our understanding of Venus's atmosphere, and has led to a reappraisal of the possible sources and sinks of atmospheric phosphorous-bearing gases. Here we present results from a search for PH$_3$ on Venus using the GREAT instrument aboard the SOFIA aircraft, over three flights conducted in November 2021. Multiple PH$_3$ transitions were targeted at frequencies centered on 533 GHz and 1067 GHz, but no evidence for atmospheric PH$_3$ was detected. Through radiative transfer modeling, we derived a disk-averaged upper limit on the PH$_3$ abundance of 0.8 ppb in the altitude range 75-110 km, which is more stringent than previous ground-based studies., Comment: Accepted for publication in Geophysical Research Letters

Isotopic ratios provide a powerful tool for understanding the origins of materials, including the volatile and refractory matter within solar system bodies. Recent high sensitivity observations of molecular isotopologues, in particular with ALMA, have brought us new information on isotopic ratios of hydrogen, carbon, nitrogen and oxygen in star and planet forming regions as well as the solar system objects. Solar system exploration missions, such as Rosetta and Cassini, have given us further new insights. Meanwhile, the recent development of sophisticated models for isotope chemistry including detailed gas-phase and grain surface reaction network has made it possible to discuss how isotope fractionation in star and planet forming regions is imprinted into the icy mantles of dust grains, preserving a record of the initial isotopic state of solar system materials. This chapter reviews recent progress in observations of molecular isotopologues in extra-solar planet forming regions, prestellar/protostellar cores and protoplanetary disks, as well as objects in our solar system -- comets, meteorites, and planetary/satellite atmospheres -- and discusses their connection by means of isotope chemical models., Comment: To appear in Protostars and Planets VII, University of Arizona Press, eds. Shu-ichiro Inutsuka, Yuri Aikawa, Takayuki Muto, Kengo Tomida, and Motohide Tamura

The coma of comet C/2016 R2 (PanSTARRS) is one of the most chemically peculiar ever observed, in particular due to its extremely high CO/H2O and N2+/H2O ratios}, and unusual trace volatile abundances. However, the complex shape of its CO emission lines, as well as uncertainties in the coma structure and excitation, has lead to ambiguities in the total CO production rate. We performed high resolution, spatially, spectrally and temporally resolved CO observations using the James Clerk Maxwell Telescope (JCMT) and Submillimeter Array (SMA) to elucidate the outgassing behaviour of C/2016 R2. Results are analyzed using a new, time-dependent, three dimensional radiative transfer code (SUBLIME), incorporating for the first time, accurate state-to-state collisional rate coefficients for the CO--CO system. The total CO production rate was found to be in the range $(3.8-7.6)\times10^{28}$ s$^{-1}$ between 2018-01-13 and 2018-02-01, with a mean value of $(5.3\pm0.6)\times10^{28}$ s$^{-1}$ at r_H = 2.8-2.9 au. The emission is concentrated in a near-sunward jet, with an outflow velocity $0.51\pm0.01$ km/s, compared to $0.25\pm0.01$ km/s in the ambient (and night-side) coma. Evidence was also found for an extended source of CO emission, possibly due to icy grain sublimation around $1.2\times10^5$ km from the nucleus. Based on the coma molecular abundances, we propose that the nucleus ices of C/2016 R2 can be divided into a rapidly sublimating apolar phase, rich in CO, CO2, N2 and CH3OH, and a predominantly frozen (or less abundant), polar phase containing more H2O, CH4, H2CO and HCN., Comment: Accepted for publication in ApJ

Similar to Earth, Saturn's largest moon, Titan, possesses a system of high-altitude zonal winds (or jets) that encircle the globe. Using the Atacama Large Millimeter/submillimeter Array (ALMA) in August 2016, Lellouch et al. (2019) discovered an equatorial jet at much higher altitudes than previously known, with a surprisingly fast speed of up to ~340 m/s, but the origin of such high velocities is not yet understood. We obtained spectrally and spatially resolved ALMA observations in May 2017 to map Titan's 3D global wind field and compare our results with a reanalysis of the August 2016 data. Doppler wind velocity maps were derived in the altitude range ~300-1000 km (from the upper stratosphere to the thermosphere). At the highest, thermospheric altitudes, a 47% reduction in the equatorial zonal wind speed was measured over the 9-month period (corresponding to L_s = 82-90 degrees on Titan). This is interpreted as due to a dramatic slowing and loss of confinement (broadening) of the recently-discovered thermospheric equatorial jet, as a result of dynamical instability. These unexpectedly-rapid changes in the upper-atmospheric dynamics are consistent with strong variability of the jet's primary driving mechanism.

The chemical pathways linking the small organic molecules commonly observed in molecular clouds to the large, complex, polycyclic species long-suspected to be carriers of the ubiquitous unidentified infrared emission bands remain unclear. To investigate whether the formation of mono- and poly-cyclic molecules observed in cold cores could form via the bottom-up reaction of ubiquitous carbon-chain species with, e.g. atomic hydrogen, a search is made for possible intermediates in data taken as part of the GOTHAM (GBT Observations of TMC-1 Hunting for Aromatic Molecules) project. Markov-Chain Monte Carlo (MCMC) Source Models were run to obtain column densities and excitation temperatures. Astrochemical models were run to examine possible formation routes, including a novel grain-surface pathway involving the hydrogenation of C$_6$N and HC$_6$N, as well as purely gas-phase reactions between C$_3$N and both propyne (CH$_3$CCH) and allene (CH$_2$CCH$_2$), as well as via the reaction CN + H$_2$CCCHCCH. We report the first detection of cyanoacetyleneallene (H$_2$CCCHC$_3$N) in space toward the TMC-1 cold cloud using the Robert C. Byrd 100 m Green Bank Telescope (GBT). Cyanoacetyleneallene may represent an intermediate between less-saturated carbon-chains, such as the cyanopolyynes, that are characteristic of cold cores and the more recently-discovered cyclic species like cyanocyclopentadiene. Results from our models show that the gas-phase allene-based formation route in particular produces abundances of H$_2$CCCHC$_3$N that match the column density of $2\times10^{11}$ cm$^{-2}$ obtained from the MCMC Source Model, and that the grain-surface route yields large abundances on ices that could potentially be important as precursors for cyclic molecules., Comment: Accepted in A&A Letters

Remote and in-situ observations of cometary gases have revealed the presence of a wealth of complex organic molecules, including carbon chains, alcohols, imines and the amino acid glycine. Such chemical complexity in cometary material implies that impacts by comets could have supplied reagents for prebiotic chemistry to young planetary surfaces. However, the assumption that some of the molecules observed in cometary comae at millimetre wavelengths originate from ices stored inside the nucleus has not yet been proven. In fact, the comae of moderately-active comets reach sufficient densities within a few thousand kilometers of the nucleus for an active (solar radiation-driven) photochemistry to ensue. Here we present results from our latest chemical-hydrodynamic models incorporating an updated reaction network, and show that the commonly-observed HC3N (cyanoacetylene) and NH2CHO (formamide) molecules can be efficiently produced in cometary comae as a result of two-body, neutral-neutral, gas-phase reactions involving well-known coma gases. In the presence of a near-nucleus distributed source of CN (similar to that observed by the Rosetta spacecraft at comet 67P), we find that sufficient HC$_3$N and NH2CHO can be synthesized to match the abundances of these molecules in previous observations of Oort Cloud comets. The precise origin of these (and other) complex organic molecules in cometary comae can be verified through interferometric mapping observations, for example, using the Atacama Large Millimeter/submillimeter Array (ALMA)., Comment: Accepted for publication in MNRAS, April 15th 2021

The origin of bistable solutions in the kinetic equations describing the chemistry of dense interstellar clouds is explained as being due to the autocatalysis and feedback of oxygen nuclei from the oxygen dimer (O2). We identify four autocatalytic processes that can operate in dense molecular clouds, driven respectively by reactions of H+, He+, C+, and S+ with O2. We show that these processes can produce the bistable solutions found in previous studies, as well as the dependence on various model parameters such as the helium ionization rate, the sulfur depletion and the {{{H}}}3+ electron recombination rate. We also show that ion-grain neutralizations are unlikely to affect the occurrence of bistability in dense clouds. It is pointed out that many chemical models of astronomical sources should have the potential to show bistable solutions.

Titan harbors a dense, organic-rich atmosphere primarily composed of N$_2$ and CH$_4$, with lesser amounts of hydrocarbons and nitrogen-bearing species. As a result of high sensitivity observations by the Atacama Large Millimeter/submillimeter Array (ALMA) in Band 6 ($\sim$230-272 GHz), we obtained the first spectroscopic detection of CH$_3$C$_3$N (methylcyanoacetylene or cyanopropyne) in Titan's atmosphere through the observation of seven transitions in the $J = 64\rightarrow63$ and $J = 62\rightarrow61$ rotational bands. The presence of CH$_3$C$_3$N on Titan was suggested by the Cassini Ion and Neutral Mass Spectrometer detection of its protonated form: C$_4$H$_3$NH$^+$, but the atmospheric abundance of the associated (deprotonated) neutral product is not well constrained due to the lack of appropriate laboratory reaction data. Here, we derive the column density of CH$_3$C$_3$N to be (3.8-5.7)$\times10^{12}$ cm$^{-2}$ based on radiative transfer models sensitive to altitudes above 400 km Titan's middle atmosphere. When compared with laboratory and photochemical model results, the detection of methylcyanoacetylene provides important constraints for the determination of the associated production pathways (such as those involving CN, CCN, and hydrocarbons), and reaction rate coefficients. These results also further demonstrate the importance of ALMA and (sub)millimeter spectroscopy for future investigations of Titan's organic inventory and atmospheric chemistry, as CH$_3$C$_3$N marks the heaviest polar molecule detected spectroscopically in Titan's atmosphere to date., Comment: 17 pages, 6 figures, 2 tables. Accepted in ApJ Letters

Comets spend most of their lives at large distances from any star, during which time their interior compositions remain relatively unaltered. Cometary observations can therefore provide direct insight into the chemistry that occurred during their birth at the time of planet formation. To-date, there have been no confirmed observations of parent volatiles (gases released directly from the nucleus) of a comet from any planetary system other than our own. Here we present high-resolution, interferometric observations of 2I/Borisov, the first confirmed interstellar comet, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 15th-16th December 2019. Our observations reveal emission from hydrogen cyanide (HCN), and carbon monoxide (CO), coincident with the expected position of 2I/Borisov's nucleus, with production rates Q(HCN)=$(7.0\pm1.1)\times10^{23}$ s$^{-1}$ and Q(CO)=$(4.4\pm0.7)\times10^{26}$ s$^{-1}$. While the HCN abundance relative to water (0.06-0.16%) appears similar to that of typical, previously observed comets in our Solar System, the abundance of CO (35-105%) is among the highest observed in any comet within 2 au of the Sun. This shows that 2I/Borisov must have formed in a relatively CO-rich environment - probably beyond the CO ice-line in the very cold, outer regions of a distant protoplanetary accretion disk, as part of a population of small, icy bodies analogous to our Solar System's own proto-Kuiper Belt.

The Cassini mission performed 127 targeted flybys of Titan during its 13-year mission to Saturn, culminating in the Grand Finale between April-September 2017. Here we demonstrate the use of the Atacama Large Millimeter/submillimeter Array (ALMA) to continue Cassini's legacy for chemical and climatological studies of Titan's atmosphere. Whole-hemisphere, interferometric spectral maps of HCN, HNC, HC3N, CH3CN, C2H3CN, C2H5CN and C3H8 were obtained using ALMA in May 2017 at moderate (~0.2'', or 1300 km) spatial resolution, revealing the effects of seasonally-variable chemistry and dynamics on the distribution of each species. The ALMA sub-mm observations of HCN and HC3N are consistent with Cassini infrared data on these species, obtained in the same month. Chemical/dynamical lifetimes of a few years are inferred for C2H3CN and C2H5CN, in reasonably close agreement with the latest chemical models incorporating sticking of C2H5CN to stratospheric aerosol particles. ALMA radial limb flux profiles provide column density information as a function of altitude, revealing maximum abundances in the thermosphere (above 600 km) for HCN, HNC, HC3N and C2H5CN. This constitutes the first detailed measurement of the spatial distribution of HNC, which is found to be confined predominantly to altitudes above 730 $\pm$ 60 km. The HNC emission map shows an east-west hemispheric asymmetry of (13$\pm$3)%. These results are consistent with very rapid production (and loss) of HNC in Titan's uppermost atmosphere, making this molecule an effective probe of short-timescale (diurnal) ionospheric processes., Comment: AJ; submitted March 2019; accepted for publication June 2019

Recent advances in laboratory spectroscopy lead to the claim of ionized Buckminsterfullerene (C60+) as the carrier of two diffuse interstellar bands (DIBs) in the near-infrared. However, irrefutable identification of interstellar C60+ requires a match between the wavelengths and the expected strengths of all absorption features detectable in the laboratory and in space. Here we present Hubble Space Telescope (HST) spectra of the region covering the C60+ 9348, 9365, 9428 and 9577 {\AA} absorption bands toward seven heavily-reddened stars. We focus in particular on searching for the weaker laboratory C60+ bands, the very presence of which has been a matter for recent debate. Using the novel STIS-scanning technique to obtain ultra-high signal-to-noise spectra without contamination from telluric absorption that afflicted previous ground-based observations, we obtained reliable detections of the (weak) 9365, 9428 {\AA} and (strong) 9577 {\AA} C60+ bands. The band wavelengths and strength ratios are sufficiently similar to those determined in the latest laboratory experiments that we consider this the first robust identification of the 9428 {\AA} band, and a conclusive confirmation of interstellar C60+., Comment: Published in ApJ Letters, April 2019, 875, L28

The Atacama Large Millimeter/submillimeter Array (ALMA) is a powerful tool for high-resolution mapping of comets, but the main interferometer (comprised of 50x12-m antennas) is insensitive to the largest coma scales due to a lack of very short baselines. In this work, we present a new technique employing ALMA autocorrelation data (obtained simultaneously with the interferometric observations), effectively treating the entire 12-m array as a collection of single-dish telescopes. Using combined autocorrelation spectra from 28 active antennas, we recovered extended HCN coma emission from comet C/2012 S1 (ISON), resulting in a fourteen-fold increase in detected line brightness compared with the interferometer. This resulted in the first detection of rotational emission from H^13CN in this comet. Using a detailed coma radiative transfer model accounting for optical depth and non-LTE excitation effects, we obtained an H^12CN/H^13CN ratio of 88+-18, which matches the terrestrial value of 89, consistent with a lack of isotopic fractionation in HCN during comet formation in the protosolar accretion disk. The possibility of future discoveries in extended sources using autocorrelation spectroscopy from the main ALMA array is thus demonstrated.

Submillimeter emission lines of carbon monoxide (CO) in Titan's atmosphere provide excellent probes of atmospheric temperature due to the molecule's long chemical lifetime and stable, well constrained volume mixing ratio. Here we present the analysis of 4 datasets obtained with the Atacama Large Millimeter/Submillimeter Array (ALMA) from 2012 to 2015 that contain strong CO rotational transitions. Utilizing ALMA's high spatial resolution in the 2012, 2014, and 2015 observations, we extract spectra from 3 separate regions on Titan's disk using datasets with beam sizes of ~0.3''. Temperature profiles retrieved by the NEMESIS radiative transfer code are compared to Cassini Composite Infrared Spectrometer (CIRS) and radio occultation science results from similar latitude regions. Small seasonal variations in atmospheric temperature are present from 2012 to 2015 in the stratosphere and mesosphere (~100-500 km) of spatially resolved regions. We measure the stratopause (320 km) to increase in temperature by 5 K in northern latitudes from 2012-2015, while temperatures rise throughout the stratosphere at lower latitudes. While retrieved temperature profiles cover a range of latitudes in these observations, deviations from CIRS nadir maps and radio occultation measurements convolved with the ALMA beam-footprint are not found to be statistically significant, and discrepancies are often found to be less than 5 K throughout the atmosphere. ALMA's excellent sensitivity in the lower stratosphere (60-300 km) provides a highly complementary dataset to contemporary CIRS and radio science observations. The demonstrated utility of CO emission lines in the submillimeter as a tracer of Titan's atmospheric temperature lays the groundwork for future studies of other molecular species, as temperature profiles are found to consistently vary with latitude in all three years by up to 15 K., Comment: 11 pages, 9 figures, 3 tables

Previous investigations have employed more than 100 close observations of Titan by the Cassini orbiter to elucidate connections between the production and distribution of Titan's vast, organic-rich chemical inventory and its atmospheric dynamics. However, as Titan transitions into northern summer, the lack of incoming data from the Cassini orbiter presents a potential barrier to the continued study of seasonal changes in Titan's atmosphere. In our previous work (Thelen et al., 2018), we demonstrated that the Atacama Large Millimeter/submillimeter Array (ALMA) is well suited for measurements of Titan's atmosphere in the stratosphere and lower mesosphere (~100-500 km) through the use of spatially resolved (beam sizes <1'') flux calibration observations of Titan. Here, we derive vertical abundance profiles of four of Titan's trace atmospheric species from the same 3 independent spatial regions across Titan's disk during the same epoch (2012 to 2015): HCN, HC$_3$N, C$_3$H$_4$, and CH$_3$CN. We find that Titan's minor constituents exhibit large latitudinal variations, with enhanced abundances at high latitudes compared to equatorial measurements; this includes CH$_3$CN, which eluded previous detection by Cassini in the stratosphere, and thus spatially resolved abundance measurements were unattainable. Even over the short 3-year period, vertical profiles and integrated emission maps of these molecules allow us to observe temporal changes in Titan's atmospheric circulation during northern spring. Our derived abundance profiles are comparable to contemporary measurements from Cassini infrared observations, and we find additional evidence for subsidence of enriched air onto Titan's south pole during this time period. Continued observations of Titan with ALMA beyond the summer solstice will enable further study of how Titan's atmospheric composition and dynamics respond to seasonal changes., Comment: 15 pages, 16 figures, 2 tables. Accepted for publication in Icarus, September 2018

We present the first maps of cyanoacetylene isotopologues in Titan's atmosphere, including H$^{13}$CCCN and HCCC$^{15}$N, detected in the 0.9 mm band using the Atacama Large Millimeter/submillimeter array (ALMA) around the time of Titan's (southern winter) solstice in May 2017. The first high-resolution map of HC$_3$N in its $v_7=1$ vibrationally excited state is also presented, revealing a unique snapshot of the global HC$_3$N distribution, free from the strong optical depth effects that adversely impact the ground-state ($v=0$) map. The HC$_3$N emission is found to be strongly enhanced over Titan's south pole (by a factor of 5.7 compared to the north pole), consistent with rapid photochemical loss of HC$_3$N from the summer hemisphere combined with production and transport to the winter pole since the April 2015 ALMA observations. The H$^{13}$CCCN/HCCC$^{15}$N flux ratio is derived at the southern HC$_3$N peak, and implies an HC$_3$N/HCCC$^{15}$N ratio of $67\pm14$. This represents a significant enrichment in $^{15}$N compared with Titan's main molecular nitrogen reservoir, which has a $^{14}$N/$^{15}$N ratio of 167, and confirms the importance of photochemistry in determining the nitrogen isotopic ratio in Titan's organic inventory., Comment: Accepted for publication in ApJL, May 2018

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of $^{15}$N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised $^{15}$N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirstr\"{o}m et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included $^{15}$N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing $^{15}$N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching $^{14}$N/$^{15}$N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the $^{14}$N/$^{15}$N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk $^{15}$N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed., Comment: Accepted for publication in MNRAS, 3 figures

Comet composition provides critical information on the chemical and physical processes that took place during the formation of the Solar system. We report here on millimetre spectroscopic observations of the long-period bright comet C/2014 Q2 (Lovejoy) using the Atacama Pathfinder Experiment (APEX) band 1 receiver between 2015 January UT 16.948 to 18.120, when the comet was at heliocentric distance of 1.30 AU and geocentric distance of 0.53 AU. Bright comets allow for sensitive observations of gaseous volatiles that sublimate in their coma. These observations allowed us to detect HCN, CH3OH (multiple transitions), H2CO and CO, and to measure precise molecular production rates. Additionally, sensitive upper limits were derived on the complex molecules acetaldehyde (CH3CHO) and formamide (NH2CHO) based on the average of the strongest lines in the targeted spectral range to improve the signal-to-noise ratio. Gas production rates are derived using a non-LTE molecular excitation calculation involving collisions with H2O and radiative pumping that becomes important in the outer coma due to solar radiation. We find a depletion of CO in C/2014 Q2 (Lovejoy) with a production rate relative to water of 2 per cent, and relatively low abundances of Q(HCN)/Q(H2O), 0.1 per cent, and Q(H2CO)/Q(H2O), 0.2 per cent. In contrast the CH3OH relative abundance Q(CH3OH)/Q(H2O), 2.2 per cent, is close to the mean value observed in other comets. The measured production rates are consistent with values derived for this object from other facilities at similar wavelengths taking into account the difference in the fields of view. Based on the observed mixing ratios of organic molecules in four bright comets including C/2014 Q2, we find some support for atom addition reactions on cold dust being the origin of some of the molecules., Comment: 10 pages, 7 figures, to be published in MNRAS

The 100 m Robert C. Byrd Green Bank Telescope K-band (KFPA) receiver was used to perform a high-sensitivity search for rotational emission lines from complex organic molecules in the cold interstellar medium towards TMC-1 (cyanopolyyne peak), focussing on the identification of new carbon-chain-bearing species as well as molecules of possible prebiotic relevance. We report a detection of the carbon-chain oxide species HC$_7$O and derive a column density of $(7.8\pm0.9)\times10^{11}$~cm$^{-2}$. This species is theorized to form as a result of associative electron detachment reactions between oxygen atoms and C$_7$H$^-$, and/or reaction of C$_6$H$_2$$^+$ with CO (followed by dissociative electron recombination). Upper limits are given for the related HC$_6$O, C$_6$O and C$_7$O molecules. In addition, we obtained the first detections of emission from individual $^{13}$C isotopologues of HC$_7$N, and derive abundance ratios HC$_7$N/HCCC$^{13}$CCCCN = $110\pm16$ and HC$_7$N/HCCCC$^{13}$CCCN = $96\pm 11$, indicative of significant $^{13}$C depletion in this species relative to the local interstellar elemental $^{12}$C/$^{13}$C ratio of 60-70. The observed spectral region covered two transitions of HC$_{11}$N, but emission from this species was not detected, and the corresponding column density upper limit is $7.4\times10^{10}$ cm$^{-2}$ (at 95% confidence). This is significantly lower than the value of $2.8\times10^{11}$ cm$^{-2}$ previously claimed by Bell et al. (1997) and confirms the recent non-detection of HC$_{11}$N in TMC-1 by Loomis et al. (2016). Upper limits were also obtained for the column densities of malononitrile and the nitrogen heterocycles quinoline, isoquinoline and pyrimidine., Comment: Accepted for publication in ApJ

Vinyl cyanide (C$_2$H$_3$CN) is theorized to form in Titan's atmosphere via high-altitude photochemistry and is of interest regarding the astrobiology of cold planetary surfaces due to its predicted ability to form cell membrane-like structures (azotosomes) in liquid methane. In this work, we follow up on the initial spectroscopic detection of C$_2$H$_3$CN on Titan by Palmer et al. (2017) with the detection of three new C$_2$H$_3$CN rotational emission lines at submillimeter frequencies. These new, high-resolution detections have allowed for the first spatial distribution mapping of C$_2$H$_3$CN on Titan. We present simultaneous observations of C$_2$H$_5$CN, HC$_3$N, and CH$_3$CN emission, and obtain the first (tentative) detection of C$_3$H$_8$ (propane) at radio wavelengths. We present disk-averaged vertical abundance profiles, two-dimensional spatial maps, and latitudinal flux profiles for the observed nitriles. Similarly to HC$_3$N and C$_2$H$_5$CN, which are theorized to be short-lived in Titan's atmosphere, C$_2$H$_3$CN is most abundant over the southern (winter) pole, whereas the longer-lived CH$_3$CN is more concentrated in the north. This abundance pattern is consistent with the combined effects of high-altitude photochemical production, poleward advection, and the subsequent reversal of Titan's atmospheric circulation system following the recent transition from northern to southern winter. We confirm that C$_2$H$_3$CN and C$_2$H$_5$CN are most abundant at altitudes above 200 km. Using a 300 km step model, the average abundance of C$_2$H$_3$CN is found to be $3.03\pm0.29$ ppb, with a C$_2$H$_5$CN/C$_2$H$_3$CN abundance ratio of $2.43\pm0.26$. Our HC$_3$N and CH$_3$CN spectra can be accurately modeled using abundance gradients above the tropopause, with fractional scale-heights of $2.05\pm0.16$ and $1.63\pm0.02$, respectively., Comment: Accepted for publication in the Astronomical Journal

Due to recent advances in laboratory spectroscopy, the first optical detection of a very large molecule has been claimed in the diffuse interstellar medium (ISM): C60+ (ionized Buckminsterfullerene). Confirming the presence of this molecule would have significant implications regarding the carbon budget and chemical complexity of the ISM. Here we present results from a new method for ultra-high signal-to-noise (S/N) spectroscopy of background stars in the near infrared (at wavelengths 0.9-1 micron), using the Hubble Space Telescope Imaging Spectrograph (STIS) in a previously untested `STIS scan' mode. The use of HST provides the crucial benefit of eliminating the need for error-prone telluric correction methods in the part of the spectrum where the C60+ bands lie, and terrestrial water vapor contamination is severe. Our STIS spectrum of the heavily-reddened B0 star BD63\,1964 reaches an unprecedented S/N for this instrument ($\sim600-800$), allowing the detection of the diffuse interstellar band (DIB) at 9577 \AA\ attributed to C60+ as well as new DIBs in the near-IR. Unfortunately, the presence of overlapping stellar lines, and the unexpected weakness of the C60+ bands in this sightline, prevents conclusive detection of the weaker C60+ bands. A probable correlation between the 9577 \AA\ DIB strength and interstellar radiation field is identified, which suggests that more strongly-irradiated interstellar sightlines will provide the optimal targets for future C60+ searches., Comment: Accepted for publication in ApJL, June 2017

Observations of the sungrazing comet C/2012 S1 (ISON) were carried out using the Atacama Large Millimeter/submillimeter Array (ALMA) at a heliocentric distance of 0.58-0.54 AU (pre-perihelion) on 2013 November 16-17. Temporally resolved measurements of the coma distributions of HNC, CH$_3$OH, H$_2$CO and dust were obtained over the course of about an hour on each day. During the period UT 10:10-11:00 on Nov. 16, the comet displayed a remarkable drop in activity, manifested as a $>42$% decline in the molecular line and continuum fluxes. The H$_2$CO observations are consistent with an abrupt, $\approx50$% reduction in the cometary gas production rate soon after the start of our observations. On Nov. 17, the total observed fluxes remained relatively constant during a similar period, but strong variations in the morphology of the HNC distribution were detected as a function of time, indicative of a clumpy, intermittent outflow for this species. Our observations suggest that at least part of the detected HNC originated from degradation of nitrogen-rich organic refractory material, released intermittently from confined regions of the nucleus. By contrast, the distributions of CH$_3$OH and H$_2$CO during the Nov. 17 observations were relatively uniform, consistent with isotropic outflow and stable activity levels for these species. These results highlight a large degree of variability in the production of gas and dust from comet ISON during its pre-perihelion outburst, consistent with repeated disruption of the nucleus interspersed with periods of relative quiescence., Comment: 9 pages. Accepted for publication in ApJ, February 2017

We present spatially and spectrally-resolved observations of CH$_3$OH emission from comet C/2012 K1 (PanSTARRS) using The Atacama Large Millimeter/submillimeter Array (ALMA) on 2014 June 28-29. Two-dimensional maps of the line-of-sight average rotational temperature ($T_{rot}$) were derived, covering spatial scales $0.3''-1.8''$ (corresponding to sky-projected distances $\rho\sim500$-2500 km). The CH$_3$OH column density distributions are consistent with isotropic, uniform outflow from the nucleus, with no evidence for extended sources of CH$_3$OH in the coma. The $T_{rot}(\rho)$ radial profiles show a significant drop within a few thousand kilometers of the nucleus, falling from about 60 K to 20 K between $\rho=0$ and 2500 km on June 28, whereas on June 29, $T_{rot}$ fell from about 120 K to 40 K between $\rho=$ 0 km and 1000 km. The observed $T_{rot}$ behavior is interpreted primarily as a result of variations in the coma kinetic temperature due to adiabatic cooling of the outflowing gas, as well as radiative cooling of the CH$_3$OH rotational levels. Our excitation model shows that radiative cooling is more important for the $J=7-6$ transitions (at 338 GHz) than for the $K=3-2$ transitions (at 252 GHz), resulting in a strongly sub-thermal distribution of levels in the $J=7-6$ band at $\rho\gtrsim1000$ km. For both bands, the observed temperature drop with distance is less steep than predicted by standard coma theoretical models, which suggests the presence of a significant source of heating in addition to the photolytic heat sources usually considered., Comment: Accepted for publication in ApJ, January 2017

IRAS 19312+1950 is a peculiar object that has eluded firm characterization since its discovery, with combined maser properties similar to an evolved star and a young stellar object (YSO). To help determine its true nature, we obtained infrared spectra of IRAS 19312+1950 in the range 5-550 $\mu$m using the Herschel and Spitzer space observatories. The Herschel PACS maps exhibit a compact, slightly asymmetric continuum source at 170 $\mu$m, indicative of a large, dusty circumstellar envelope. The far-IR CO emission line spectrum reveals two gas temperature components: $\approx0.22M_{\odot}$ of material at $280\pm18$ K, and $\approx1.6M_{\odot}$ of material at $157\pm3$ K. The OI 63 $\mu$m line is detected on-source but no significant emission from atomic ions was found. The HIFI observations display shocked, high-velocity gas with outflow speeds up to 90 km s$^{-1}$ along the line of sight. From Spitzer spectroscopy, we identify ice absorption bands due to H$_2$O at 5.8 $\mu$m and CO$_2$ at 15 $\mu$m. The spectral energy distribution is consistent with a massive, luminous ($\sim2\times10^4L_{\odot}$) central source surrounded by a dense, warm circumstellar disk and envelope of total mass $\sim500$-$700M_{\odot}$, with large bipolar outflow cavities. The combination of distinctive far-IR spectral features suggest that IRAS 19312+1950 should be classified as an accreting high-mass YSO rather than an evolved star. In light of this reclassification, IRAS 19312+1950 becomes only the 5th high-mass protostar known to exhibit SiO maser activity, and demonstrates that 18 cm OH maser line ratios may not be reliable observational discriminators between evolved stars and YSOs., Comment: 16 pages. Accepted for publication in ApJ

The Atacama Large Millimeter/submillimeter Array (ALMA) was used to obtain measurements of spatially and spectrally resolved CH$_3$OH emission from comet C/2012 K1 (PanSTARRS) on 28-29 June 2014. Detection of 12-14 emission lines of CH$_3$OH on each day permitted the derivation of spatially-resolved rotational temperature profiles (averaged along the line of sight), for the innermost 5000 km of the coma. On each day, the CH$_3$OH distribution was centrally peaked and approximately consistent with spherically symmetric, uniform outflow. The azimuthally-averaged CH$_3$OH rotational temperature ($T_{rot}$) as a function of sky-projected nucleocentric distance ($\rho$), fell by about 40 K between $\rho=0$ and 2500 km on 28 June, whereas on 29 June, $T_{rot}$ fell by about 50 K between $\rho=$0 km and 1500 km. A remarkable ($\sim50$ K) rise in $T_{rot}$ at $\rho=$1500-2500 km on 29 June was not present on 28 June. The observed variations in CH$_3$OH rotational temperature are interpreted primarily as a result of variations in the coma kinetic temperature due to adiabatic cooling, and heating through Solar irradiation, but collisional and radiative non-LTE excitation processes also play a role., Comment: Submitted to Astronomy in Focus, Volume 1. Based on work presented at the XXIXth IAU General Assembly, August 2015

Conditions in the protosolar nebula have left their mark in the composition of cometary volatiles, thought to be some of the most pristine material in the solar system. Cometary compositions represent the end point of processing that began in the parent molecular cloud core and continued through the collapse of that core to form the protosun and the solar nebula, and finally during the evolution of the solar nebula itself as the cometary bodies were accreting. Disentangling the effects of the various epochs on the final composition of a comet is complicated. But comets are not the only source of information about the solar nebula. Protostellar disks around young stars similar to the protosun provide a way of investigating the evolution of disks similar to the solar nebula while they are in the process of evolving to form their own solar systems. In this way we can learn about the physical and chemical conditions under which comets formed, and about the types of dynamical processing that shaped the solar system we see today. This paper summarizes some recent contributions to our understanding of both cometary volatiles and the composition, structure and evolution of protostellar disks., Comment: To appear in Space Science Reviews. The final publication is available at Springer via http://dx.doi.org/10.1007/s11214-015-0167-6

We report the first spectroscopic detection of ethyl cyanide (C$_2$H$_5$CN) in Titan's atmosphere, obtained using spectrally and spatially resolved observations of multiple emission lines with the Atacama Large Millimeter/submillimeter array (ALMA). The presence of C$_2$H$_5$CN in Titan's ionosphere was previously inferred from Cassini ion mass spectrometry measurements of C$_2$H$_5$CNH$^+$. Here we report the detection of 27 rotational lines from C$_2$H$_5$CN (in 19 separate emission features detected at $>3\sigma$ confidence), in the frequency range 222-241 GHz. Simultaneous detections of multiple emission lines from HC$_3$N, CH$_3$CN and CH$_3$CCH were also obtained. In contrast to HC$_3$N, CH$_3$CN and CH$_3$CCH, which peak in Titan's northern (spring) hemisphere, the emission from C$_2$H$_5$CN is found to be concentrated in the southern (autumn) hemisphere, suggesting a distinctly different chemistry for this species, consistent with a relatively short chemical lifetime for C$_2$H$_5$CN. Radiative transfer models show that most of the C$_2$H$_5$CN is concentrated at altitudes 300-600 km, suggesting production predominantly in the mesosphere and above. Vertical column densities are found to be in the range (2-5)$\times10^{14}$ cm$^{-2}$., Comment: Published in 2015, ApJL, 800, L14

We present spectrally and spatially-resolved maps of HNC and HC$_3$N emission from Titan's atmosphere, obtained using the Atacama Large Millimeter/submillimeter Array (ALMA) on 2013 November 17. These maps show anisotropic spatial distributions for both molecules, with resolved emission peaks in Titan's northern and southern hemispheres. The HC$_3$N maps indicate enhanced concentrations of this molecule over the poles, consistent with previous studies of Titan's photochemistry and atmospheric circulation. Differences between the spectrally-integrated flux distributions of HNC and HC$_3$N show that these species are not co-spatial. The observed spectral line shapes are consistent with HNC being concentrated predominantly in the mesosphere and above (at altitudes $z\gtrsim 400$ km), whereas HC$_3$N is abundant at a broader range of altitudes ($z\approx70$-600 km). From spatial variations in the HC$_3$N line profile, the locations of the HC$_3$N emission peaks are shown to be variable as a function of altitude. The peaks in the integrated emission from HNC and the line core (upper-atmosphere) component of HC$_3$N (at $z\gtrsim300$ km) are found to be asymmetric with respect to Titan's polar axis, indicating that the mesosphere may be more longitudinally-variable than previously thought. The spatially-integrated HNC and HC$_3$N spectra are modeled using the NEMESIS planetary atmosphere code and the resulting best-fitting disk-averaged vertical mixing ratio (VMR) profiles are found to be in reasonable agreement with previous measurements for these species. Vertical column densities of the best-fitting gradient models for HNC and HC$_3$N are $1.9\times10^{13}$ cm$^{-2}$ and $2.3\times10^{14}$ cm$^{-2}$, respectively., Comment: Accepted for publication in ApJ Letters

Results are presented from the first cometary observations using the Atacama Large Millimeter/Submillimeter Array (ALMA), including measurements of the spatially-resolved distributions of HCN, HNC, H$_2$CO and dust within the comae of two comets: C/2012 F6 (Lemmon) and C/2012 S1 (ISON), observed at heliocentric distances of 1.5 AU and 0.54 AU, respectively. These observations (with angular resolution $\approx0.5''$), reveal an unprecedented level of detail in the distributions of these fundamental cometary molecules, and demonstrate the power of ALMA for quantitative measurements of the distributions of molecules and dust in the inner comae of typical bright comets. In both comets, HCN is found to originate from (or within a few hundred km of) the nucleus, with a spatial distribution largely consistent with spherically-symmetric, uniform outflow. By contrast, the HNC distributions are clumpy and asymmetrical, with peaks at cometocentric radii $\sim$500-1000~km, consistent with release of HNC in collimated outflow(s). Compared to HCN, the H$_2$CO distribution in comet Lemmon is very extended. The interferometric visibility amplitudes are consistent with coma production of H$_2$CO and HNC from unidentified precursor material(s) in both comets. Adopting a Haser model, the H$_2$CO parent scale-length is found to be a few thousand km in Lemmon and only a few hundred km in ISON, consistent with destruction of the precursor by photolysis or thermal degradation at a rate which scales in proportion to the Solar radiation flux.

The Jupiter-family comet 103P/Hartley 2 (103P) was the target of the NASA EPOXI mission. In support of this mission, we conducted observations from radio to submillimeter wavelengths of comet 103P in the three weeks preceding the spacecraft rendezvous on UT 2010 November 4.58. This time period included the passage at perihelion and the closest approach of the comet to the Earth. Here we report detections of HCN, H2CO, CS, and OH and upper limits for HNC and DCN towards 103P, using the Arizona Radio Observatory Kitt Peak 12m telescope (ARO 12m) and submillimeter telescope (SMT), the James Clerk Maxwell Telescope (JCMT) and the Greenbank Telescope (GBT). The water production rate, QH2O = (0.67 - 1.07) x 10^28 s^-1, was determined from the GBT OH data. From the average abundance ratios of HCN and H2CO relative to water (0.13 +/- 0.03 % and 0.14 +/- 0.03 %, respectively), we conclude that H2CO is depleted and HCN is normal with respect to typically-observed cometary mixing ratios. However, the abundance ratio of HCN with water shows a large diversity with time. Using the JCMT data we measured an upper limit for the DCN/HCN ratio <0.01. Consecutive observations of ortho- H2CO and para-H2CO on November 2 (from data obtained at the JCMT), allowed us to derive an ortho : para ratio (OPR) ~ 2.12 +/- 0.59 (1sigma), corresponding to Tspin > 8 K (2sigma)., Comment: Accepted for publication in the Astrophysical Journal (July 2, 2014) - ApJ95151R1

After more than 30 years of investigations, the nature of gas-grain interactions at low temperatures remains an unresolved issue in astrochemistry. Water ice is the dominant ice found in cold molecular clouds, however, there is only one region where cold (~10 K) water vapor has been detected - L1544. This study aims to shed light on ice desorption mechanisms under cold cloud conditions by expanding the sample. The clumpy distribution of methanol in dark clouds testifies to transient desorption processes at work -- likely to also disrupt water ice mantles. Therefore, the Herschel HIFI instrument was used to search for cold water in a small sample of prominent methanol emission peaks. We report detections of the ground-state transition of o-H2O (J = 1_10 - 1_01) at 556.9360 GHz toward two positions in the cold molecular cloud Barnard 5. The relative abundances of methanol and water gas support a desorption mechanism which disrupts the outer ice mantle layers, rather than causing complete mantle removal., Comment: 10 pages, 2 figures

HCl and HF are expected to be the main reservoirs of fluorine and chlorine wherever hydrogen is predominantly molecular. They are found to be strongly depleted in dense molecular clouds, suggesting freeze-out onto grains in such cold environments. We can then expect that HCl and HF were also the major carriers of Cl and F in the gas and icy phases of the outer solar nebula, and were incorporated into comets. We aimed to measure the HCl and HF abundances in cometary ices as they can provide insights on the halogen chemistry in the early solar nebula. We searched for the J(1-0) lines of HCl and HF at 626 and 1232 GHz, respectively, using the HIFI instrument on board the Herschel Space Observatory. HCl was searched for in comets 103P/Hartley 2 and C/2009 P1 (Garradd), whereas observations of HF were conducted in comet C/2009 P1. In addition, observations of H$_2$O and H$_2^{18}$O lines were performed in C/2009 P1 to measure the H$_2$O production rate. Three lines of CH$_3$OH were serendipitously observed in the HCl receiver setting. HCl is not detected, whereas a marginal (3.6-$\sigma$) detection of HF is obtained. The upper limits for the HCl abundance relative to water are 0.011% and 0.022%, for 103P and C/2009 P1, respectively, showing that HCl is depleted with respect to the solar Cl/O abundance by a factor more than 6$^{+6}_{-3}$ in 103P, where the error is related to the uncertainty in the chlorine solar abundance. The marginal HF detection obtained in C/2009 P1 corresponds to an HF abundance relative to water of (1.8$\pm$0.5) $\times$ 10$^{-4}$, which is approximately consistent with a solar photospheric F/O abundance. The observed depletion of HCl suggests that HCl was not the main reservoir of chlorine in the regions of the solar nebula where these comets formed. HF was possibly the main fluorine compound in the gas phase of the outer solar nebula., Comment: Accepted for publication in Astronomy & Astrophysics

Results are presented from a survey for molecular anions in seven nearby Galactic star-forming cores and molecular clouds. The hydrocarbon anion C6H- is detected in all seven target sources, including four sources where no anions have been previously detected: L1172, L1389, L1495B and TMC-1C. The C6H-/C6H column density ratio is greater than about 1.0% in every source, with a mean value of 3.0% (and standard deviation 0.92%). Combined with previous detections, our results show that anions are ubiquitous in dense clouds wherever C6H is present. The C6H-/C6H ratio is found to show a positive correlation with molecular hydrogen number density, and with the apparent age of the cloud. We also report the first detection of C4H- in TMC-1 (at 4.8-sigma confidence), and derive an anion-to-neutral ratio C4H-/C4H = (1.2 +- 0.4) x 10^-5 (= 0.0012 +- 0.0004%). Such a low value compared with C6H- highlights the need for a revised radiative electron attachment rate for C4H. Chemical model calculations show that the observed C4H- could be produced as a result of reactions of oxygen atoms with C5H- and C6H-.

Organic material found in meteorites and interplanetary dust particles is enriched in D and 15N. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and 15N and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large 15N enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, 15N enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both 15N and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest 15N enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that Solar System 15N and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model., Comment: Submitted to ApJL

Long-chain hydrocarbon anions CnH- (n=4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n_{H_2} >~ 10^5 cm^{-3}). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H- anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally-stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment.

We report the detection of microwave emission lines from the hydrocarbon anion C6H- and its parent neutral C6H in the star-forming region L1251A (in Cepheus), and the pre-stellar core L1512 (in Auriga). The carbon-chain-bearing species C4H, HC3N, HC5N, HC7N and C3S are also detected in large abundances. The observations of L1251A constitute the first detections of anions and long-chain polyynes and cyanopolyynes (with more than 5 carbon atoms) in the Cepheus Flare star-forming region, and the first detection of anions in the vicinity of a protostar outside of the Taurus molecular cloud complex, highlighting a wider importance for anions in the chemistry of star formation. Rotational excitation temperatures have been derived from the HC3N hyperfine structure lines, and are found to be 6.2 K for L1251A and 8.7 K for L1512. The anion-to-neutral ratios are 3.6% and 4.1%, respectively, which are within the range of values previously observed in the interstellar medium, and suggest a relative uniformity in the processes governing anion abundances in different dense interstellar clouds. This research contributes towards the growing body of evidence that carbon chain anions are relatively abundant in interstellar clouds throughout the Galaxy, but especially in the regions of relatively high density and high depletion surrounding pre-stellar cores and young, embedded protostars.

We discuss the connection between the chemistry of dense interstellar clouds and those characteristics of cometary matter that could be remnants of it. The chemical evolution observed to occur in molecular clouds is summarized and a model for dense core collapse that can plausibly account for the isotopic fractionation of hydrogen, nitrogen, oxygen and carbon measured in primitive solar system materials is presented., Comment: to be published in Advances in Geosciences

We report new calculations of interstellar 15N fractionation. Previously, we have shown that large enhancements of 15N/14N can occur in cold, dense gas where CO is frozen out, but that the existence of an NH + N channel in the dissociative recombination of N2H+ severely curtails the fractionation. In the light of recent experimental evidence that this channel is in fact negligible, we have reassessed the 15N chemistry in dense cloud cores. We consider the effects of temperatures below 10 K, and of the presence of large amounts of atomic nitrogen. We also show how the temporal evolution of gas-phase isotope ratios is preserved as spatial heterogeneity in ammonia ice mantles, as monolayers deposited at different times have different isotopic compositions. We demonstrate that the upper layers of this ice may have 15N/14N ratios an order of magnitude larger than the underlying elemental value. Converting our ratios to delta-values, we obtain delta(15N) > 3,000 per mil in the uppermost layer, with values as high as 10,000 per mil in some models. We suggest that this material is the precursor to the 15N `hotspots' recently discovered in meteorites and IDPs, Comment: accepted by MNRAS

We present a sensitive 3-sigma upper limit of 1.1% for the HNC/HCN abundance ratio in comet 73P/Schwassmann-Wachmann (Fragment B), obtained on May 10-11, 2006 using Caltech Submillimeter Observatory (CSO). This limit is a factor of ~7 lower than the values measured previously in moderately active comets at 1 AU from the Sun. Comet 73P/Schwassmann-Wachmann was depleted in most volatile species, except of HCN. The low HNC/HCN ratio thus argues against HNC production from polymers produced from HCN. However, thermal degradation of macromolecules, or polymers, produced from ammonia and carbon compounds, such as acetylene, methane, or ethane appears a plausible explanation for the observed variations of the HNC/HCN ratio in moderately active comets, including the very low ratio in comet 73P/Schwassmann-Wachmann reported here. Similar polymers have been invoked previously to explain anomalous 14N/15N ratios measured in cometary CN., Comment: 6 pages, 5 figures, 2 tables

We demonstrate how the observed H2O ice column densities toward three dense globules in the Southern Coalsack could be used to constrain the ages of these sources. We derive ages of ~10^5 yr, in agreement with dynamical studies of these objects. We have modelled the chemical evolution of the globules, and show how the molecular abundances are controlled by both the gas density and the initial chemical conditions as the globules formed. Based on our derived ages, we predict the column densities of several species of interest. These predictions should be straightforward to test by performing molecular line observations, Comment: 10 pages, 4 figures, in press at MNRAS

We have extensively mapped a sample of dense molecular clouds (L1512, TMC-1C, L1262, Per 7, L1389, L1251E) in lines of HC3N, CH3OH, SO and C^{18}O. We demonstrate that a high degree of chemical differentiation is present in all of the observed clouds. We analyse the molecular maps for each cloud, demonstrating a systematic chemical differentiation across the sample, which we relate to the evolutionary state of the cloud. We relate our observations to the cloud physical, kinematical and evolutionary properties, and also compare them to the predictions of simple chemical models. The implications of this work for understanding the origin of the clumpy structures and chemical differentiation observed in dense clouds are discussed., Comment: 20 pages, 7 figures. Higher quality figures appear in the published journal article