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Ice-coated dust grains provide the main reservoir of volatiles that play an important role in planet formation processes and may become incorporated into planetary atmospheres. However, due to observational challenges, the ice abundance distribution in protoplanetary disks is not well constrained. We present JWST/MIRI observations of the edge-on disk HH 48 NE carried out as part of the IRS program Ice Age. We detect CO$_2$, NH$_3$, H$_2$O and tentatively CH$_4$ and NH$_4^+$. Radiative transfer models suggest that ice absorption features are produced predominantly in the 50-100 au region of the disk. The CO$_2$ feature at 15 micron probes a region closer to the midplane (z/r = 0.1-0.15) than the corresponding feature at 4.3 micron (z/r = 0.2-0.6), but all observations trace regions significantly above the midplane reservoirs where we expect the bulk of the ice mass to be located. Ices must reach a high scale height (z/r ~ 0.6; corresponding to modeled dust extinction Av ~ 0.1), in order to be consistent with the observed vertical distribution of the peak ice optical depths. The weakness of the CO$_2$ feature at 15 micron relative to the 4.3 micron feature and the red emission wing of the 4.3 micron CO$_2$ feature are both consistent with ices being located at high elevation in the disk. The retrieved NH$_3$ abundance and the upper limit on the CH$_3$OH abundance relative to H$_2$O are significantly lower than those in the interstellar medium (ISM), but consistent with cometary observations. Full wavelength coverage is required to properly study the abundance distribution of ices in disks. To explain the presence of ices at high disk altitudes, we propose two possible scenarios: a disk wind that entrains sufficient amounts of dust, thus blocking part of the stellar UV radiation, or vertical mixing that cycles enough ices into the upper disk layers to balance ice photodesorption., Comment: 16 pages, 11 figures, accepted in A&A

With two directly detected protoplanets, the PDS 70 system is a unique source in which to study the complex interplay between forming planets and their natal environment. The large dust cavity carved by the two giant planets can affect the disk chemistry, and therefore the molecular emission morphology. On the other hand, chemical properties of the gas component of the disk are expected to leave an imprint on the planetary atmospheres. In this work, we reconstruct the emission morphology of a rich inventory of molecular tracers in the PDS 70 disk, and we look for possible chemical signatures of the two actively accreting protoplanets, PDS b and c. We leverage Atacama Large Millimeter/submillimeter Array (ALMA) band 6 high-angular-resolution and deep-sensitivity line emission observations, together with image and $uv$-plane techniques, to boost the detection of faint lines. We robustly detect ring-shaped emission from $^{12}$CO, $^{13}$CO, C$^{18}$O, H$^{13}$CN, HC$^{15}$N, DCN, H$_2$CO, CS, C$_2$H, and H$^{13}$CO$^{+}$ lines in unprecedented detail. Most of the molecular tracers show a peak of the emission inside the millimeter dust peak. We interpret this as the direct impact of the effective irradiation of the cavity wall, as a result of the planet formation process. Moreover, we have found evidence of an O-poor gas reservoir in the outer disk, which is supported by the observations of bright C-rich molecules, the non-detection of SO, and a lower limit on the $\mathrm{CS/SO}$ ratio of $\sim1$. Eventually, we provide the first detection of the c-C$_3$H$_2$ transitions at 218.73 GHz, and the marginal detection of an azimuthal asymmetry in the higher-energy H$_2$CO (3$_{2,1}$-2$_{2,0}$) line, which could be due to accretion heating near PDS 70b., Comment: 25 pages, 10 figures, 3 tables, 8 figures and one table in appendix. Accepted for publication in A&A

Ices are the main carriers of volatiles in protoplanetary disks and are crucial to our understanding of the chemistry that ultimately sets the organic composition of planets. The ERS program Ice Age on the JWST follows the ice evolution through all stages of star and planet formation. JWST/NIRSpec observations of the edge-on Class II protoplanetary disk HH~48~NE reveal spatially resolved absorption features of the major ice components H$_2$O, CO$_2$, CO, and multiple weaker signatures from less abundant ices NH$_3$, OCN$^-$, and OCS. Isotopologue $^{13}$CO$_2$ ice has been detected for the first time in a protoplanetary disk. Since multiple complex light paths contribute to the observed flux, the ice absorption features are filled in by ice-free scattered light. The $^{12}$CO$_2$/$^{13}$CO$_2$ ratio of 14 implies that the $^{12}$CO$_2$ feature is saturated, without the flux approaching 0, indicative of a very high CO$_2$ column density on the line of sight, and a corresponding abundance with respect to hydrogen that is higher than ISM values by a factor of at least a few. Observations of rare isotopologues are crucial, as we show that the $^{13}$CO$_2$ observation allows us to determine the column density of CO$_2$ to be at an order of magnitude higher than the lower limit directly inferred from the observed optical depth. Radial variations in ice abundance, e.g., snowlines, are significantly modified since all observed photons have passed through the full radial extent of the disk. CO ice is observed at perplexing heights in the disk, extending to the top of the CO-emitting gas layer. We argue that the most likely interpretation is that we observe some CO ice at high temperatures, trapped in less volatile ices like H$_2$O and CO$_2$. Future radiative transfer models will be required to constrain the implications on our current understanding of disk physics and chemistry., Comment: 16 pages, 8 figures, accepted for publication in A&A

We present 5 deg^2 (~250 pc^2) HCN, HNC, HCO+, and CO J=1-0 maps of the Orion B GMC, complemented with existing wide-field [CI] 492 GHz maps, as well as new pointed observations of rotationally excited HCN, HNC, H13CN, and HN13C lines. We detect anomalous HCN J=1-0 hyperfine structure line emission almost everywhere in the cloud. About 70% of the total HCN J=1-0 luminosity arises from gas at A_V < 8 mag. The HCN/CO J=1-0 line intensity ratio shows a bimodal behavior with an inflection point at A_V < 3 mag typical of translucent gas and UV-illuminated cloud edges. We find that most of the HCN J=1-0 emission arises from extended gas with n(H2) ~< 10^4 cm^-3, even lower density gas if the ionization fraction is > 10^-5 and electron excitation dominates. This result explains the low-A_V branch of the HCN/CO J=1-0 intensity ratio distribution. Indeed, the highest HCN/CO ratios (~0.1) at A_V < 3 mag correspond to regions of high [CI] 492 GHz/CO J=1-0 intensity ratios (>1) characteristic of low-density PDRs. Enhanced FUV radiation favors the formation and excitation of HCN on large scales, not only in dense star-forming clumps. The low surface brightness HCN and HCO+ J=1-0 emission scale with I_FIR (a proxy of the stellar FUV radiation field) in a similar way. Together with CO J=1-0, these lines respond to increasing I_FIR up to G0~20. On the other hand, the bright HCN J=1-0 emission from dense gas in star-forming clumps weakly responds to I_FIR once the FUV radiation field becomes too intense (G0>1500). The different power law scalings (produced by different chemistries, densities, and line excitation regimes) in a single but spatially resolved GMC resemble the variety of Kennicutt-Schmidt law indexes found in galaxy averages. As a corollary for extragalactic studies, we conclude that high HCN/CO J=1-0 line intensity ratios do not always imply the presence of dense gas., Comment: accepted for publication in A&A. 24 pages, 18 figures, plus Appendix. Abridged Abstract

Embedded planets are potentially the cause of substructures like gaps and cavities observed in several protoplanetary disks. Thus, the substructures observed in the continuum and in line emission encode information about the presence of planets in the system and how they interact with the natal disk. The pre-transitional disk around the star PDS 70 is the first case of two young planets imaged within a dust depleted gap that was likely carved by themselves. We aim to determine the spatial distribution of the gas and dust components in the PDS 70 disk. The axisymmetric substructures observed in the resulting profiles are interpreted in the context of planet-disk interactions. We develop a thermo-chemical forward model for an axisymmetric disk to explain a subset of the Atacama Large Millimeter/Submillimeter Array (ALMA) band 6 observations of three CO isotopologues plus the continuum towards PDS 70. Combining the inferred gas and dust distributions, the model results in a variable gas-to-dust ratio profile throughout the disk that spans two orders of magnitude within the first $130$ au and shows a step gradient towards the outer disk, which is consistent with the presence of a pressure maxima driven by planet-disk interactions. We find a gas density drop factor of ${\sim} 19$ at the location of the planet PDS 70 c with respect to the peak gas density at $75$ au. Combining this value with literature results on the hydrodynamics of planet-disk interactions, we find this gas gap depth to be consistent with independent planet mass estimates from infrared observations. Our findings point towards gas stirring processes taking place in the common gap due to the gravitational perturbation of both planets., Comment: Accepted for publication in A&A

The abundance and distribution of ice in protoplanetary disks (PPD) is critical to understand the linkage between the composition of circumstellar matter and the composition of exoplanets. Edge-on PPDs are a useful tool to constrain such ice composition and its location in the disk, as ice spectral signatures can be observed in absorption against the continuum emission arising from the warmer central disk regions. The aim of this work is to model ice absorption features in PPDs and determine how well the abundance of the main ice species across the disk can be determined within the uncertainty of the physical parameter space. The edge-on PPD around HH 48 NE, a target of the JWST ERS program IceAge, is used as a reference system. We use RADMC-3D to raytrace the mid-infrared continuum. Using a constant parameterized ice abundance, ice opacities are added to the dust opacity in regions wherever the disk is cold enough for the main carbon, oxygen and nitrogen carriers to freeze out. The global abundance of the main ice carriers in HH 48 NE can be determined within a factor of 3, when taking the uncertainty of the physical parameters into account. Ice features in PPDs can be saturated at an optical depth <1, due to local saturation. Spatially observed ice optical depths cannot be directly related to column densities due to radiative transfer effects. Vertical snowlines will not be a clear transition due to the radially increasing height of the snowsurface, but their location may be constrained from observations using radiative transfer modeling. Radial snowlines are not really accesible. Not only the ice abundance, but also inclination, settling, grain size distribution and disk mass have strong impact on the observed ice absorption features in disks. Relative changes in ice abundance can be inferred from observations only if the source structure is well constrained, Comment: 18 pages, 12 figures, accepted for publication in Astronomy & Astrophysics

Context. Observations of edge-on disks are an important tool for constraining general protoplanetary disk properties that cannot be determined in any other way. However, most radiative transfer models cannot simultaneously reproduce the spectral energy distributions (SEDs) and resolved scattered light and submillimeter observations of these systems, due to the differences in geometry and dust properties at different wavelengths. Aims. We simultaneously constrain the geometry of the edge-on protoplanetary disk HH 48 NE and the characteristics of the host star. HH 48 NE is part of the JWST early release science program Ice Age. This work serves as a stepping stone towards a better understanding of the disk physical structure and icy chemistry in this particular source. This kind of modeling lays the groundwork for studying other edge-on sources to be observed with the JWST. Methods. We fit a parameterized dust model to HH 48 NE by coupling the radiative transfer code RADMC-3D and an MCMC framework. The dust structure was fitted independently to a compiled SED, a scattered light image at 0.8 ${\mu}$m and an ALMA dust continuum observation at 890 ${\mu}$m. Results. We find that 90% of the dust mass in HH 48 NE is settled to the disk midplane, less than in average disks, and that the atmospheric layers of the disk contain exclusively large grains (0.3-10 ${\mu}$m). The exclusion of small grains in the upper atmosphere likely has important consequences for the chemistry due to the deep penetration of high-energy photons. The addition of a relatively large cavity (ca. 50 au in radius) is necessary to explain the strong mid-infrared emission, and to fit the scattered light and continuum observations simultaneously., Comment: 16 pages, 8 figures, accepted for publication in Astronomy & Astrophysics

Planetary systems such as our own are formed after a long process where matter condenses from diffuse clouds to stars, planets, asteroids, comets and residual dust, undergoing dramatic changes in physical and chemical state in less than a few million years. Several studies have shown that the chemical composition during the early formation of a Solar-type planetary system is a powerful diagnostic to track the history of the system itself. Among the approximately 270 molecules so far detected in the ISM, the so-called interstellar complex organic molecules (iCOMs) are of particular interest both because of their evolutionary diagnostic power and because they might be potential precursors of biomolecules, which are at the basis of terrestrial life. This Chapter focuses on the evolution of organic molecules during the early stages of a Solar-type planetary system, represented by the prestellar, Class 0/I and protoplanetary disk phases, and compares them with what is observed presently in Solar System comets. Our twofold goal is to review the processes at the base of organic chemistry during Solar-type star formation and, in addition, to possibly provide constraints on the early history of our own planetary system., Comment: Chapter for Protostars & Planets VII

Methanol (CH$_3$OH) is at the root of organic ice chemistry in protoplanetary disks. However, its weak emission has made detections difficult. To date, gas-phase CH$_3$OH has been detected in only one Class II disk, TW Hya. We use the Atacama Large Millimeter/submillimeter Array (ALMA) to search for a total of four CH$_3$OH emission lines in bands 6 and 7 toward the disk around the young Herbig Ae star HD 163296. The disk-averaged column density of methanol and its related species formaldehyde (H$_2$CO) are estimated assuming optically thin emission in local thermodynamic equilibrium. We compare these results to the gas-phase column densities of the TW Hya disk. No targeted methanol lines were detected individually nor after line stacking. The 3$\sigma$ disk-integrated intensity upper limits are $< 51$ mJy km s$^{-1}$ for the band 6 lines and $< 26$ mJy km s$^{-1}$ for the band 7 lines. The band 7 lines provide the strictest 3$\sigma$ upper limit on disk-averaged column density with $N_{\mathrm{avg}} < 5.0 \times 10^{11}$ cm$^{-2}$. The methanol-to-formaldehyde ratio is CH$_3$OH/H$_2$CO $< 0.24$ in the HD 163296 disk compared to a ratio of $1.27$ in the TW Hya disk. Differences in the stellar irradiation of Herbig disks compared to T Tauri disks likely influence the gaseous methanol and formaldehyde content. Possible reasons for the lower HD 163296 methanol-to-formaldehyde ratio include: a higher than expected gas-phase formation of H$_2$CO in the HD 163296 disk, uncertainties in the grain surface formation efficiency of CH$_3$OH and H$_2$CO, and differences in the disk structure and/or CH$_3$OH and H$_2$CO desorption processes that release the molecules from ice mantles back into the gas phase. These results provide observational evidence that the gas-phase chemical complexity found in disks may be strongly influenced by the spectral type of the host star., Comment: Accepted to Astronomy & Astrophysics, 11 pages, 3 figures

This paper presents a systematic survey of the deuterated and 13C isotopologues of a variety of oxygen-bearing complex organic molecules on Solar System scales toward the protostar IRAS 16293-2422B. We use the data from an unbiased molecular line survey between 329 and 363 GHz from the Atacama Large Millimeter/submillimeter Array (ALMA). The observations probe scales of 60 AU where most of the organic molecules have sublimated off dust grains and are present in the gas-phase. The complex organic molecules can be divided into two groups with one group, the simpler species, showing a D/H ratio of approximately 2% and the other, the more complex species, D/H ratios of 4-8%. This division may reflect the formation time of each species in the ices before or during warm-up/infall of material through the protostellar envelope. No significant differences are seen in the deuteration of different functional groups for individual species, possibly a result of the short time-scale for infall through the innermost warm regions where exchange reactions between different species may be taking place. The species show differences in excitation temperatures between 125 K and 300 K. This likely reflects the binding energies/sublimation temperatures of the individual species, in good agreement to what has previously been found for high-mass sources. For dimethyl ether, the 12C/13C ratio is found to be lower by up to a factor of 2 compared to typical ISM values similar to what has previously been inferred for glycolaldehyde. The results point to the importance of ice surface chemistry for the formation of these complex organic molecules at different stages in the evolution of embedded protostars and demonstrate the use of accurate isotope measurements for understanding the history of individual species., Comment: Accepted for publication in A&A. Abstract abridged

We present a suite of ALMA interferometric molecular line and continuum images that elucidate, on linear size scales of $\sim$30--40 AU, the chemical structure of the nearby, evolved, protoplanetary disk orbiting the close binary system V4046 Sgr. The observations were undertaken in the 1.1--1.4 mm wavelength range (ALMA Bands 6 and 7) with antenna configurations involving maximum baselines of several hundred meters, yielding subarcsecond-resolution images in more than a dozen molecular species and isotopologues. Isotopologues of CO and HCN display centrally peaked morphologies of integrated emission line intensity, whereas the line emission from complex nitrile group molecules (HC$_3$N, CH$_3$CN), deuterated molecules (DCN, DCO$^+$), hydrocarbons (as traced by C$_2$H), and potential CO ice line tracers (N$_2$H$^+$, and H$_2$CO) appears as a sequence of sharp and diffuse rings. The dimensions and morphologies of HC$_3$N and CH$_3$CN emission are suggestive of photodesorption of organic ices from the surfaces of dust grains, while the sequence of increasing radius of peak intensity represented by DCN (smallest), DCO$^+$, N$_2$H$^+$, and H$_2$CO (largest) is qualitatively consistent with the expected decline of midplane gas temperature with increasing disk radius. Empirical modeling indicates that the sharp-edged C$_2$H emission ring lies at relatively deep disk layers, leaving open the question of the origin of C$_2$H abundance enhancements in evolved disks. This study of the "molecular anatomy" of V4046 Sgr should serve as motivation for additional subarcsecond ALMA molecular line imaging surveys of nearby, evolved protoplanetary disks aimed at addressing major uncertainties in protoplanetary disk physical and chemical structure and molecular production pathways., Comment: 32 pages, 10 figures; accepted 26 June 2018 by The Astrophysical Journal

Resolved observations of millimetre-sized dust, tracing larger planetesimals, have pinpointed the location of 26 Edgeworth-Kuiper belt analogs. We report that a belt's distance $R$ to its host star correlates with the star's luminosity $L_{\star}$, following $R\propto L^{0.19}_{\star}$ with a low intrinsic scatter of $\sim$17%. Remarkably, our Edgeworth-Kuiper belt in the Solar System and the two CO snow lines imaged in protoplanetary disks lie close to this $R$-$L_{\star}$ relation, suggestive of an intrinsic relationship between protoplanetary disk structures and belt locations. To test the effect of bias on the relation, we use a Monte Carlo approach and simulate uncorrelated model populations of belts. We find that observational bias could produce the slope and intercept of the $R$-$L_{\star}$ relation, but is unable to reproduce its low scatter. We then repeat the simulation taking into account the collisional evolution of belts, following the steady state model that fits the belt population as observed through infrared excesses. This significantly improves the fit by lowering the scatter of the simulated $R$-$L_{\star}$ relation; however, this scatter remains only marginally consistent with the one observed. The inability of observational bias and collisional evolution alone to reproduce the tight relationship between belt radius and stellar luminosity could indicate that planetesimal belts form at preferential locations within protoplanetary disks. The similar trend for CO snow line locations would then indicate that the formation of planetesimals and/or planets in the outer regions of planetary systems is linked to the volatility of their building blocks, as postulated by planet formation models., Comment: Accepted for publication in ApJ. 23 pages, 9 figures

The exocometary origin of CO gas has been confirmed in several extrasolar Kuiper belts, with CO ice abundances consistent with Solar System comets. We here present a molecular survey of the $\beta$ Pictoris belt with the Submillimeter Array (SMA), reporting upper limits for CN, HCN, HCO$^+$, N$_2$H$^+$ and H$_2$CO, as well as for H$_2$S, CH$_3$OH, SiO and DCN from archival ALMA data. Non-detections can be attributed to rapid molecular photodissociation due to the A-star's strong UV flux. CN is the longest-lasting and most easily detectable molecule after CO in this environment. We update our NLTE excitation model to include UV fluorescence, finding it plays a key role in CO and CN excitation, and use it to turn the SMA CN/CO flux ratio constraint into an upper limit of $<2.5$% on the HCN/(CO+CO$_2$) ratio of outgassing rates. This value is consistent with, but at the low end of, the broad range observed in Solar System comets. If sublimation dominates outgassing, then this low value may be caused by decreased outgassing for the less volatile molecule HCN compared to CO. If instead UV photodesorption or collisional vaporization of unbound grains dominates outgassing, then this low ratio of rates would imply a low ice abundance ratio, which would in turn indicate a variation in cometary cyanide abundances across planetary systems. To conclude, we make predictions for future molecular surveys and show that CN and HCN should be readily detectable with ALMA around $\beta$ Pictoris for Solar-System-like exocometary compositions., Comment: Accepted for publication in ApJ. 19 pages, 7 figures

The formation pathways of deuterated species trace different regions of protoplanetary disks and may shed light into their physical structure. We aim to constrain the radial extent of main deuterated species; we are particularly interested in spatially characterizing the high and low temperature pathways for enhancing deuteration of these species. We observed the disk surrounding the Herbig Ae star HD 163296 using ALMA in Band 6 and obtained resolved spectral imaging data of DCO$^+$ ($J$=3-2), DCN ($J$=3-2) and N$_2$D$^+$ ($J$=3-2). We model the radial emission profiles of DCO$^+$, DCN and N$_2$D$^+$, assuming their emission is optically thin, using a parametric model of their abundances and radial excitation temperature estimates. DCO$^+$ can be described by a three-region model, with constant-abundance rings centered at 70 AU, 150 AU and 260 AU. The DCN radial profile peaks at about ~60 AU and N$_2$D$^+$ is seen in a ring at ~160 AU. Simple models of both molecules using constant abundances reproduce the data. Assuming reasonable average excitation temperatures for the whole disk, their disk-averaged column densities (and deuterium fractionation ratios) are 1.6-2.6$\times 10^{12}$ cm$^{-2}$ (0.04-0.07), 2.9-5.2$\times 10^{12}$ cm$^{-2}$ ($\sim$0.02) and 1.6-2.5 $\times 10^{11}$ cm$^{-2}$ (0.34-0.45) for DCO$^+$, DCN and N$_2$D$^+$, respectively. Our simple best-fit models show a correlation between the radial location of the first two rings in DCO$^+$ and the DCN and N$_2$D$^+$ abundance distributions that can be interpreted as the high and low temperature deuteration pathways regimes. The origin of the third DCO$^+$ ring at 260 AU is unknown but may be due to a local decrease of ultraviolet opacity allowing the photodesorption of CO or due to thermal desorption of CO as a consequence of radial drift and settlement of dust grains.

Three formaldehyde lines were observed (H$_2$CO 3$_{03}$--2$_{02}$, H$_2$CO 3$_{22}$--2$_{21}$, and H$_2$CO 3$_{21}$--2$_{20}$) in the protoplanetary disk around the Herbig Ae star HD 163296 with ALMA at 0.5 arcsecond (60 AU) spatial resolution. H$_2$CO 3$_{03}$--2$_{02}$ was readily detected via imaging, while the weaker H$_2$CO 3$_{22}$--2$_{21}$ and H$_2$CO 3$_{21}$--2$_{20}$ lines required matched filter analysis to detect. H$_2$CO is present throughout most of the gaseous disk, extending out to 550 AU. An apparent 50 AU inner radius of the H$_2$CO emission is likely caused by an optically thick dust continuum. The H$_2$CO radial intensity profile shows a peak at 100 AU and a secondary bump at around 300 AU, suggesting increased production in the outer disk. Different parameterizations of the H$_2$CO abundance were compared to the observed visibilities with $\chi^2$ minimization, using either a characteristic temperature, a characteristic radius or a radial power law index to describe the H$_2$CO chemistry. Similar models were applied to ALMA Science Verification data of C$^{18}$O. In all modeling scenarios, fits to the H$_2$CO data show an increased abundance in the outer disk. The overall best-fit H$_2$CO model shows a factor of two enhancement beyond a radius of 270$\pm$20 AU, with an inner abundance of $2\!-\!5 \times 10^{-12}$. The H$_2$CO emitting region has a lower limit on the kinetic temperature of $T > 20$ K. The C$^{18}$O modeling suggests an order of magnitude depletion in the outer disk and an abundance of $4\!-\!12 \times 10^{-8}$ in the inner disk. The increase in H$_2$CO outer disk emission could be a result of hydrogenation of CO ices on dust grains that are then sublimated via thermal desorption or UV photodesorption, or more efficient gas-phase production beyond about 300 AU if CO is photodisocciated in this region.

Nitrogen fractionation is commonly used to assess the thermal history of Solar System volatiles. With ALMA it is for the first time possible to directly measure 14N/15N ratios in common molecules during the assembly of planetary systems. We present ALMA observations of the H13CN and HC15N J=3-2 lines at 0".5 angular resolution, toward a sample of six protoplanetary disks, selected to span a range of stellar and disk structure properties. Adopting a typical 12C/13C ratio of 70, we find comet-like 14N/15N ratios of 80-160 in 5/6 of the disks (3 T Tauri and 2 Herbig Ae disks) and lack constraints for one of the T Tauri disks (IM Lup). There are no systematic differences between T Tauri and Herbig Ae disks, or between full and transition disks within the sample. In addition, no correlation is observed between disk-averaged D/H and 14N/15N ratios in the sample. One of the disks, V4046 Sgr, presents unusually bright HCN isotopologue emission, enabling us to model the radial profiles of H13CN and HC15N. We find tentative evidence of an increasing 14N/15N ratio with radius, indicating that selective photodissociation in the inner disk is important in setting the 14N/15N ratio during planet formation., Comment: Accepted for publication in ApJ; 16 pages, 14 figures, 5 tables

One of the open questions in astrochemistry is how complex organic and prebiotic molecules are formed. Aims. Our aim is to start the process of compiling an inventory of oxygen-bearing complex organic molecules toward the solar-type Class 0 protostellar binary IRAS16293-2422 from an unbiased spectral survey with ALMA (PILS). Here we focus on the new detections of ethylene oxide (c-C$_2$H$_4$O), acetone (CH$_3$COCH$_3$), and propanal (C$_2$H$_5$CHO). Methods. With ALMA, we surveyed the spectral range from 329 to 363 GHz at 0.5$"$ (60 AU diameter) resolution. Using a simple model for the molecular emission in LTE, the excitation temperatures and column densities of each species were constrained. Results. We successfully detect propanal (44 lines), ethylene oxide (20 lines) and acetone (186 lines) toward one component of the protostellar binary, IRAS16293B. The high resolution maps demonstrate that the emission for all investigated species originates from the compact central region close to the protostar. This, along with a derived common excitation temperature of $\sim$ 125 K, is consistent with a coexistence of these molecules in the same gas. Conclusions. The observations mark the first detections of acetone, propanal and ethylene oxide toward a low-mass protostar. The relative abundance ratios of the two sets of isomers (CH$_3$COCH$_3$/C$_2$H$_5$CHO $\sim$ 8 and CH$_3$CHO/c-C$_2$H$_4$O $\sim$ 12) are comparable to previous observations toward high-mass protostars. The majority of observed abundance ratios from these results as well as those measured toward high-mass protostars are up to an order of magnitude above the predictions from chemical models. This may reflect either missing reactions or uncertain rates in the chemical networks. The physical conditions, such as temperatures or densities, used in the models, may not be applicable to solar-type protostars either., Comment: Accepted in A&A

The inner regions of the envelopes surrounding young protostars are characterised by a complex chemistry, with prebiotic molecules present on the scales where protoplanetary disks eventually may form. This paper introduces a systematic survey, "Protostellar Interferometric Line Survey (PILS)" of the Class 0 protostellar binary IRAS 16293-2422 using the Atacama Large Millimeter/submillimeter Array (ALMA). The survey covers the full frequency range from 329 to 363 GHz (0.8 mm) with additional targeted observations at 3.0 and 1.3 mm. More than 10,000 features are detected toward one component in the protostellar binary. Glycolaldehyde, its isomers, methyl formate and acetic acid, and its reduced alcohol, ethylene glycol, are clearly detected. For ethylene glycol both lowest state conformers, aGg' and gGg', are detected, the latter for the first time in the ISM. The abundance of glycolaldehyde is comparable to or slightly larger than that of ethylene glycol. In comparison to the Galactic Center, these two species are over-abundant relative to methanol, possibly an indication of formation at low temperatures in CO-rich ices. Both 13C and deuterated isotopologues of glycolaldehyde are detected, also for the first time ever in the ISM. For the deuterated species, a D/H ratio of approximately 5% is found with no differences between the deuteration in the different functional groups of glycolaldehyde. Measurements of the 13C-species lead to a 12C:13C ratio of approximately 30, lower than the typical ISM value. This low ratio may reflect an enhancement of 13CO in the ice due to either ion-molecule reactions in the gas before freeze-out or differences in the temperatures where 12CO and 13CO ices sublimate. The results reinforce the importance of low-temperature grain surface chemistry for the formation of prebiotic molecules seen here in the gas after sublimation of the entire ice mantle., Comment: Accepted for publication in A&A. Abstract abridged

Formamide (NH$_2$CHO) has previously been detected in several star-forming regions and is thought to be a precursor for different prebiotic molecules. Its formation mechanism is still debated, however. Observations of formamide, related species and their isopotologues may provide useful clues to the chemical pathways leading to their formation. The Protostellar Interferometric Line Survey (PILS) represents an unbiased high angular resolution and sensitivity spectral survey of the low-mass protostellar binary IRAS 16293-2422 with the Atacama Large Millimeter/submillimeter Array (ALMA). We detect for the first time the three singly deuterated forms of NH$_2$CHO (NH$_2$CDO, cis- and trans-NHDCHO) as well as DNCO towards the component B of this binary source. The images reveal that the different isotopologues are all present in the same region. Based on observations of the $^{13}$C isotopologues of formamide and a standard $^{12}$C/$^{13}$C ratio, the deuterium fractionation is found to be similar for the three different forms with a value of about 2%. The DNCO/HNCO ratio is also comparable to the D/H ratio of formamide ($\sim$1%). These results are in agreement with the hypothesis that NH$_2$CHO and HNCO are chemically related through grain surface formation., Comment: Accepted in A&A Letters

HCN is a commonly observed molecule in Solar System bodies and in interstellar environments. Its abundance with respect to CN is a proposed tracer of UV exposure. HCN is also frequently used to probe the thermal history of objects, by measuring its degree of nitrogen fractionation. To address the utility of HCN as a probe of disks, we present ALMA observations of CN, HCN, H13CN and HC15N toward the protoplanetary disk around Herbig Ae star MWC480, and of CN and HCN toward the disk around T Tauri star DM Tau. Emission from all molecules is clearly detected and spatially resolved, including the first detection of HC15N in a disk. Toward MWC 480, CN emission extends radially more than 1" exterior to the observed cut-off of HCN emission. Quantitative modeling further reveals very different radial abundance profiles for CN and HCN, with best-fit outer cut-off radii of >300 AU and 110+-10 AU, respectively. This result is in agreement with model predictions of efficient HCN photodissociation into CN in the outer-part of the disk where the vertical gas and dust column densities are low. No such difference in CN and HCN emission profiles are observed toward DM Tau, suggestive of different photochemical structures in Herbig Ae and T Tauri disks. We use the HCN isotopologue data toward the MWC 480 disk to provide the first measurement of the 14N/15N ratio in a disk. We find a low disk averaged 14N/15N ratio of 200+-100, comparable to what is observed in cloud cores and comets, demonstrating interstellar inheritance and/or efficient nitrogen fractionation in this disk., Comment: 7 pages, 9 figures

Core accretion models of massive star formation require the existence of stable massive starless cores, but robust observational examples of such objects have proven elusive. We report subarcsecond-resolution SMA 1.3 mm, 1.1 mm, and 0.88 mm and VLA 1.3 cm observations of an excellent massive starless core candidate, G11.92-0.61-MM2, initially identified in the course of studies of GLIMPSE Extended Green Objects (EGOs). Separated by ~7.2" from the nearby MM1 protostellar hot core, MM2 is a strong, compact dust continuum source (submillimeter spectral index alpha=2.6+/-0.1), but is devoid of star formation indicators. In contrast to MM1, MM2 has no masers, no centimeter continuum, and no (sub)millimeter wavelength line emission in ~24 GHz of bandwidth observed with the SMA, including N2H+(3-2), HCO+(3-2), and HCN(3-2). Additionally, there is no evidence for an outflow driven by MM2. The (sub)millimeter spectral energy distribution (SED) of MM2 is best fit with a dust temperature of ~17-19 K and luminosity of ~5-7 L_sun. The combined physical properties of MM2, as inferred from its dust continuum emission, are extreme: M>30 M_sun within a radius<1000 AU, N(H2)>10^25 cm^-2 and n(H2)>10^9 cm^-3. Comparison of the molecular abundance limits derived from our SMA observations with gas-grain chemical models indicates that extremely dense (n(H)>>10^8 cm^-3), cold (<20 K) conditions are required to explain the lack of observed (sub)millimeter line emission, consistent with the dust continuum results. Our data suggest that G11.92-0.61-MM2 is the best candidate for a bonafide massive prestellar core found to date, and a promising target for future, higher-sensitivity observations., Comment: ApJ Letters, accepted. 19 pages including 3 figures and 2 tables

Infrared photometry and spectroscopy (1-25 um) of background stars reddened by the Lupus molecular cloud complex are used to determine the properties of the grains and the composition of the ices before they are incorporated into circumstellar envelopes and disks. H2O ices form at extinctions of Ak=0.25+/-0.07 mag (Av=2.1+/-0.6). Such a low ice formation threshold is consistent with the absence of nearby hot stars. Overall, the Lupus clouds are in an early chemical phase. The abundance of H2O ice (2.3+/-0.1*10^-5 relative to Nh) is typical for quiescent regions, but lower by a factor of 3-4 compared to dense envelopes of YSOs. The low solid CH3OH abundance (<3-8% relative to H2O) indicates a low gas phase H/CO ratio, which is consistent with the observed incomplete CO freeze out. Furthermore it is found that the grains in Lupus experienced growth by coagulation. The mid-infrared (>5 um) continuum extinction relative to Ak increases as a function of Ak. Most Lupus lines of sight are well fitted with empirically derived extinction curves corresponding to Rv~ 3.5 (Ak=0.71) and Rv~5.0 (Ak=1.47). For lines of sight with Ak>1.0 mag, the tau9.7/Ak ratio is a factor of 2 lower compared to the diffuse medium. Below 1.0 mag, values scatter between the dense and diffuse medium ratios. The absence of a gradual transition between diffuse and dense medium-type dust indicates that local conditions matter in the process that sets the tau9.7/Ak ratio. This process is likely related to grain growth by coagulation, as traced by the A7.4/Ak continuum extinction ratio, but not to ice mantle formation. Conversely, grains acquire ice mantles before the process of coagulation starts., Comment: Accepted for publication in the ApJ on 29 August 2013