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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 in this paper mid-infrared (5-8~$\mu$m) spectroscopy toward the massive young binary W3~IRS~5, using the EXES spectrometer in high-resolution mode ($R\sim$50,000) from the NASA Stratospheric Observatory for Infrared Astronomy (SOFIA). Many ($\sim$180) $\nu_2$=1--0 and ($\sim$90) $\nu_2$=2-1 absorption rovibrational transitions are identified. Two hot components over 500 K and one warm component of 190 K are identified through Gaussian fittings and rotation diagram analysis. Each component is linked to a CO component identified in the IRTF/iSHELL observations ($R$=88,100) through their kinematic and temperature characteristics. Revealed by the large scatter in the rotation diagram, opacity effects are important, and we adopt two curve-of-growth analyses, resulting in column densities of $\sim10^{19}$ cm$^{-2}$. In one analysis, the model assumes a foreground slab. The other assumes a circumstellar disk with an outward-decreasing temperature in the vertical direction. The disk model is favored because fewer geometry constraints are needed, although this model faces challenges as the internal heating source is unknown. We discuss the chemical abundances along the line of sight based on the CO-to-H$_2$O connection. In the hot gas, all oxygen not locked in CO resides in water. In the cold gas, we observe a substantial shortfall of oxygen and suggest that the potential carrier could be organics in solid ice., Comment: Accepted for publication in ApJ. 34 pages, 13 figures, and 14 tables. Comments are more than welcome!

The properties of dust change during the transition from diffuse to dense clouds as a result of ice formation and dust coagulation, but much is still unclear about this transformation. We present 2-20 micron spectra of 49 field stars behind the Perseus and Serpens Molecular Clouds and establish relationships between the near-infrared continuum extinction (AK) and the depths of the 9.7 micron silicate (tau97) and 3.0 micron H2O ice (tau30) absorption bands. The tau97/AK ratio varies from large, diffuse interstellar medium-like values (~0.55), to much lower ratios (~0.26). Above extinctions of AK~1.2 (AV~10; Perseus, Lupus, dense cores) and ~2.0 (AV~17; Serpens), the tau97/AK ratio is lowest. The tau97/AK reduction from diffuse to dense clouds is consistent with a moderate degree of grain growth (sizes up to ~0.5 micron), increasing the near-infrared color excess (and thus AK), but not affecting ice and silicate band profiles. This grain growth process seems to be related to the ice column densities and dense core formation thresholds, highlighting the importance of density. After correction for Serpens foreground extinction, the H2O ice formation threshold is in the range of AK=0.31-0.40 (AV=2.6-3.4) for all clouds, and thus grain growth takes place after the ices are formed. Finally, abundant CH3OH ice (~21% relative to H2O) is reported for 2MASSJ18285266+0028242 (Serpens), a factor of >4 larger than for the other targets., Comment: 29 pages+17 pages appendix. Published in The Astrophysical Journal, 930, 2, 2022

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

This paper presents spectra in the 2 to 20 micron range of quiescent cloud material located in the IC 5146 cloud complex. The spectra were obtained with NASA's Infrared Telescope Facility (IRTF) SpeX instrument and the Spitzer Space Telescope's Infrared Spectrometer. We use these spectra to investigate dust and ice absorption features in pristine regions of the cloud that are unaltered by embedded stars. We find that the H2O-ice threshold extinction is 4.03+/-0.05 mag. Once foreground extinction is taken into account, however, the threshold drops to 3.2 mag, equivalent to that found for the Taurus dark cloud, generally assumed to be the touchstone quiescent cloud against which all other dense cloud and embedded young stellar object observations are compared. Substructure in the trough of the silicate band for two sources is attributed to CH3OH and NH3 in the ices, present at the ~2% and ~5% levels, respectively, relative to H2O-ice. The correlation of the silicate feature with the E(J-K) color excess is found to follow a much shallower slope relative to lines of sight that probe diffuse clouds, supporting the previous results by Chiar et al. (2007)., Comment: 13 pages, 13 figures with multiple parts, accepted for publication in Astrophysical Journal, Feb. 2011

The relation between ices in the envelopes and disks surrounding YSOs and those in the quiescent interstellar medium is investigated. For a sample of 31 stars behind isolated dense cores, ground-based and Spitzer spectra and photometry in the 1-25 um wavelength range are combined. The baseline for the broad and overlapping ice features is modeled, using calculated spectra of giants, H2O ice and silicates. The adopted extinction curve is derived empirically. Its high resolution allows for the separation of continuum and feature extinction. The extinction between 13-25 um is ~50% relative to that at 2.2 um. The strengths of the 6.0 and 6.85 um absorption bands are in line with those of YSOs. Thus, their carriers, which, besides H2O and CH3OH, may include NH4+, HCOOH, H2CO and NH3, are readily formed in the dense core phase, before stars form. The 3.53 um C-H stretching mode of solid CH3OH was discovered. The CH3OH/H2O abundance ratios of 5-12% are larger than upper limits in the Taurus molecular cloud. The initial ice composition, before star formation occurs, therefore depends on the environment. Signs of thermal and energetic processing that were found toward some YSOs are absent in the ices toward background stars. Finally, the peak optical depth of the 9.7 um band of silicates relative to the continuum extinction at 2.2 um is significantly shallower than in the diffuse interstellar medium. This extends the results of Chiar et al. (2007) to a larger sample and higher extinctions., Comment: Accepted for publication in The Astrophysical Journal

Studying the composition of dust in the interstellar medium (ISM) is crucial in understanding the cycle of dust in our galaxy. The mid-infrared spectral signature of amorphous silicates, the most abundant dust species in the ISM, is studied in different lines-of-sight through the Galactic plane, thus probing different conditions in the ISM. We have analysed 10 spectra from the Spitzer archive, of which 6 lines-of-sight probe diffuse interstellar medium material and 4 probe molecular cloud material. The 9.7 um silicate absorption features in 7 of these spectra were studied in terms of their shape and strength. In addition, the shape of the 18 um silicate absorption features in 4 of the diffuse sightline spectra were analysed. The 9.7 um silicate absorption bands in the diffuse sightlines show a strikingly similar band shape. This is also the case for all but one of the 18 um silicate absorption bands observed in diffuse lines-of-sight. The 9.7 um bands in the 4 molecular sightlines show small variations in shape. These modest variations in the band shape are inconsistent with the interpretation of the large variations in {\tau}_9.7/E(J-K) between diffuse and molecular sightlines in terms of silicate grain growth. Instead, we suggest that the large changes in {\tau}_9.7 / E(J-K) must be due to changes in E(J-K)., Comment: 14 pages, 19 figures, accepted for publication in A&A

The properties of the ices that form in dense molecular clouds represent an important set of initial conditions in the evolution of interstellar and preplanetary matter in regions of active star formation. Of the various spectral features available for study, the bending mode of solid CO2 near 15 microns has proven to be a particularly sensitive probe of physical conditions, especially temperature. We present new observations of this absorption feature in the spectrum of Q21-1, a background field star located behind a dark filament in the Cocoon Nebula (IC5146). We show the profile of the feature be consistent with a two-component (polar + nonpolar) model for the ices, based on spectra of laboratory analogs with temperatures in the range 10-20K. The polar component accounts for 85% of the CO2 in the line of sight. We compare for the first time 15 micron profiles in three widely separated dark clouds (Taurus, Serpens and IC5146), and show that they are indistinguishable to within observational scatter. Systematic differences in the observed CO2/H2O ratio in the three clouds have little or no effect on the 15 micron profile. The abundance of elemental oxygen in the ices appears to be a unifying factor, displaying consistent behavior in the three clouds. We conclude that the ice formation process is robust and uniformly efficient, notwithstanding compositional variations arising from differences in how the O is distributed between the primary species (H2O, CO2 and CO) in the ices.

We have examined the relationship between the optical depth of the 9.7 micron silicate absorption feature (tau_9.7) and the near-infrared color excess, E(J-Ks) in the Serpens, Taurus, IC 5146, Chameleon I, Barnard 59, and Barnard 68 dense clouds/cores. Our data set, based largely on Spitzer IRS spectra, spans E(J-Ks)=0.3 to 10 mag (corresponding to visual extinction between about 2 and 60 mag.). All lines of sight show the 9.7 micron silicate feature. Unlike in the diffuse ISM where a tight linear correlation between the 9.7 micron silicate feature optical depth and the extinction (Av) is observed, we find that the silicate feature in dense clouds does not show a monotonic increase with extinction. Thus, in dense clouds, tau_9.7 is not a good measure of total dust column density. With few exceptions, the measured tau_9.7 values fall well below the diffuse ISM correlation line for E(J-Ks) > 2 mag (Av >12 mag). Grain growth via coagulation is a likely cause of this effect., Comment: 11 pages including 2 figures, 1 table. Accepted for publication in ApJ Letters, 23 July 2007

Aliphatic hydrocarbons exhibit an absorption feature at 3.4 micron observed toward sources that sample diffuse regions of the interstellar medium. The absorbers responsible for this feature are assumed to reside in some component of interstellar dust, but the physical nature of the particles (size, shape, structure, etc.) is uncertain. Observations of interstellar polarization provide discrimination. Since the grains that carry the silicate absorption feature are known to be aligned, polarization across the 3.4 micron hydrocarbon feature can be used to test the silicate core-organic refractory mantle grain theory. Although the 3.4 micron feature has been observed to be devoid of polarization for one line of sight toward the Galactic center, a corresponding silicate polarization measurement for the same line of sight was not available. Here, we present spectropolarimetric observations toward GCS 3-II and GCS 3-IV toward the Galactic center, where the 9.7 micron silicate polarization has been previously observed. We show that polarization is not detected across the 3.4 micron feature to a limit of 0.06 +/- 0.13% (GCS 3-II) and 0.15 +/- 0.31% (GCS 3-IV), well below the lowest available prediction of polarization on the basis of the core-mantle model. We conclude that the hydrocarbons in the diffuse ISM do not reside on the same grains as the silicates and likely form a separate population of small grains., Comment: 11 pages, 1 figure. To appear in ApJ Oct. 20, 2006, volume 650

We have analyzed the 9.7 and ``18'' micron interstellar silicate absorption features along the line of sight toward four heavily extincted galactic WC-type Wolf-Rayet (WR) stars. We construct two interstellar extinction curves from 1.25 to 25 micron using near-IR extinction measurements from the literature along with the silicate profiles of WR 98a (representing the local ISM) and GCS 3 (representing the Galactic Center). We have investigated the mineralogy of the interstellar silicates by comparing extinction profiles for amorphous silicates with olivine and pyroxene stochiometry to the 9.7 and ``18'' micron absorption features in the WR 98a spectrum. In this analysis, we have considered solid and porous spheres and a continuous distribution of ellipsoids. While it is not possible to simultaneously provide a perfect match to both profiles, we find the best match requires a mixture of these two types of compounds. We also consider iron oxides, aluminosilicates and silicate carbide (SiC) as grain components. Iron oxides cannot be accommodated in the observed spectrum, while the amount of Si in SiC is limited to <4%. Finally, we discuss the cosmic elemental abundance constraints on the silicate mineralogy, grain shape and porosity., Comment: 34 pages, 8 figures, 7 tables

We report the detection of strong absorption and weak emission features in the 4--27 micron Spitzer-IRS spectrum of the distant ultraluminous infrared galaxy (ULIRG) IRAS F00183--7111 (z=0.327). The absorption features of CO2 and CO gas, water ice, hydrocarbons and silicates are indicative of a strongly obscured (A[9.6]>=5.4; A[V]>=90) and complex line of sight through both hot diffuse ISM and shielded cold molecular clouds towards the nuclear power source. From the profile of the 4.67 micron CO fundamental vibration mode we deduce that the absorbing gas is dense (n~10^6 cm^-3) and warm (720 K) and has a CO column density of ~10^19.5 cm^-2, equivalent to N[H]~10^23.5 cm^-2. The high temperature and density, as well as the small infered size (<0.03pc), locates this absorbing gas close to the power source of this region. Weak emission features of molecular hydrogen, PAHs and Ne+, likely associated with star formation, are detected against the 9.7 micron silicate feature, indicating an origin away from the absorbing region. Based on the 11.2 micron PAH flux, we estimate the star formation component to be responsible for up to 30% of the IR luminosity of the system. While our mid-infrared spectrum shows no tell-tale signs of AGN activity, the similarities to the mid-infrared spectra of deeply obscured sources (e.g. NGC4418) and AGN hot dust (e.g. NGC1068), as well as evidence from other wavelength regions, suggest that the power source hiding behind the optically thick dust screen may well be a buried AGN., Comment: 5 pages, 3 figures. Accepted for publication in ApJS Spitzer Special Issue. Also available at http://isc.astro.cornell.edu/~spoon/publications.html

We discuss the composition of dust and ice along the line of sight to the Galactic Center (GC) based on analysis of mid-infrared spectra (2.4-13 micron) from the Short Wavelength Spectrometer on the Infrared Space Observatory (ISO). We have analyzed dust absorption features arising in the molecular cloud material and the diffuse interstellar medium along the lines of sight toward Sagittarius A* and the Quintuplet sources, GCS3 and GCS4. It is evident from the depth of the 3.0 micron H2O and the 4.27 micron CO2 ice features that there is more molecular cloud material along the line of sight toward Sgr A* than GCS3 and 4. In fact, Sgr A* has a rich infrared ice spectrum with evidence for the presence of solid CH4, NH3, and possibly HCOOH. Hydrocarbon dust in the diffuse interstellar medium along the line of sight to the GC is characterized by absorption features centered at 3.4, 6.85, and 7.25 micron. Ground-based studies have identified the 3.4 micron feature with aliphatic hydrocarbons, and ISO has given us the first meaningful observations of the corresponding modes at longer wavelengths. The integrated strengths of these three features suggest that hydrogenated amorphous carbon is their carrier. We attribute an absorption feature centered at 3.28 micron in the GCS3 spectrum to the C-H stretch in aromatic hydrocarbons. This feature is not detected, and its C-C stretch counterpart appears to be weaker, in the SgrA* spectrum. One of the key questions which now arises is whether aromatics are a widespread component of the diffuse interstellar medium, analogous to aliphatic hydrocarbons., Comment: 37 pages, including 14 figures and 6 tables. Accepted to Astrophys. J., to appear V. 537, Jul. 10, 2000

Interstellar silicates are likely to be a part of all grains responsible for visual extinction (Av) in the diffuse interstellar medium (ISM) and dense clouds. A correlation between Av and the depth of the 9.7 micron silicate feature (measured as optical depth, tau(9.7)) is expected if the dust species are well 'mixed. In the di&se ISM, such a correlation is observed for lines of sight in the solar neighborhood. A previous study of the silicate absorption feature in the Taurus dark cloud showed a tendency for the correlation to break down at high Av (Whittet et al. 1988, MNRAS, 233,321), but the scatter was large. We have acquired Spitzer Infrared Spectrograph data of several lines of sight in the IC 5 146, Barnard 68, Chameleon I and Serpens dense clouds. Our data set spans an Av range between 2 and 35 magnitudes. All lines of sight show the 9.7 micron silicate feature. The Serpens data appear to follow the diffuse ISM correlation line whereas the data for the other clouds show a non-linear correlation between the depth of the silicate feature relative to Av, much like the trend observed in the Taurus data. In fact, it appears that for visual extinctions greater than about 10 mag, tau(9.7) begins to level off. This decrease in the growth of the depth of the 9.7 micron feature with increasing Av could indicate the effects of grain growth in dense clouds. In this poster, we explore the possibility that grain growth causes an increase in opacity (Av) without causing a corresponding increase in tau(9.7).

A new 2.8-3.8 micrometers spectrum of the carbon-rich protoplanetary nebula CRL 618 confirms the previous detection of a circumstellar 3.4 micrometers absorption feature in this object (Lequeux & Jourdain de Muizon). The high resolution and high signal-to-noise ratio of our spectrum allow us to derive the detailed profile of this absorption feature, which is very similar to that observed in the spectrum of the Galactic center and also resembles the strong 3.4 micrometers emission feature in some post-asymptotic giant branch stars. A weak 3.3 micrometers unidentified infrared band, marginally detected in the CRL 618 spectrum of Lequeux & Jourdain de Muizon, is present in our spectrum. The existence of the 3.4 micrometers feature implies the presence of relatively short-chained, aliphatic hydrocarbon materials (-CH2-/-CH3 approximately = 2-2.5) in the circumstellar environment around CRL 618. It also implies that the carriers of the interstellar 3.4 micrometers feature are produced at least in part in circumstellar material, and it calls into question whether any are produced by the processing of interstellar ices in dense interstellar clouds, as has been previously proposed. Other features in the spectrum are recombination lines of hydrogen, rotational and vibration-rotation lines of molecular hydrogen, and a broad absorption probably due to a blend of HCN and C2H2 bands.

We have obtained CO absorption profiles of several young stellar objects (YSOs), spanning a range of mass and luminosity, in order to investigate their ice mantle composition. We present the first detection of CO toward the class I YSO L1489 IRS in the Taurus dark cloud. In general, the CO profiles for YSOs show evidence for both processed and pristine ices in the same line of sight, strong indirect evidence for CO, is suggested in R CrA IRS 7, L1489 IRS, Elias 18, and GL 961E. Toward other sources (R CrA IRS 1, IRS 2, W33A, NGC 7538 IRS 9, Mon R2 IRS 2) CO is present in (nearly) pure form. We propose an evolutionary scenario to explain the chemical diversity of the icy mantles toward these objects.

The 4.5-4.8 micron spectral region provides two potential diagnostics of radiative or thermal processing of interstellar ices in the environs of embedded stars in molecular clouds. A broad absorption feature centered at 4.62 micron is seen in the spectra of several young stellar objects (YSO's) and attributed to C-N triple bonds in a nitrile or isonitrile. As CN-bearing solids in the laboratory are produced by energetic radiative processing of ices containing nitrogen, detection of this feature in YSO's is taken as evidence for (1) the presence of nitrogen in the unprocessed cloud ices, and (2) evolution of the ice in the vicinity of the embedded source. The adjacent feature at 4.67 micron, identified with solid CO, provides not only quantitative information on CO itself but also indirect evidence for the presence of other species; its position and profile are sensitive to the molecular environment of the CO molecules in the ice mantle, and may be used to constrain both the composition and thermal/radiative history of the ice. One important example is the possibility to detect CO2, which is produced easily in the laboratory by UV irradiation of CO-rich or CH3OH-rich ices. CO embedded in a CO2 matrix gives a characteristic spectral signature distinct from other CO-bearing mixtures investigated to date. We have obtained CO absorption profiles of three young stellar objects in order to investigate their ice mantle composition.

Field stars provide an important means for probing undisturbed regions of molecular clouds where icy mantles are most likely to form. Combining observation of field stars with those of protostars provides a comparison of the extent of grain processing in photostellar environments. The Taurus dark cloud provides an ideal environment for the formation of icy mantles as it is free from shocks and bright internal sources of ultraviolet (UV) radiation. Earlier low-resolution observations of the Taurus cloud done by Whittet et al. (1989) showed that about 30 percent of the available CO is depleted on to the grains.

The 4.67 micrometer absorption feature of solid CO is an important signature of grain mantles in molecular clouds. This paper presents new observations of solid CO absorption in the spectra of four infrared sources in and behind the Serpens dark cloud. We also present supplementary 2.0-2.5 micrometer spectra which clarify the nature of selected sources. Solid CO profiles are compared with models based on laboratory data. In common with previous studies of other clouds, we find that the observed profiles are consistent with the presence of two distinct phases of CO-bearing ice, one dominated either by CO itself or by CO mixed with absorption relative to that of the water-ice feature at 3.1 micrometers is unusually high in Serpens: we deduce column densities for CO and H2O in solid form and conclude that the mean CO abundance in dust is 40% of the H2O abundance, compared with values in the range 0%-30% typical of other molecular clouds. On the basis of its 2.0-2.5 micrometer spectrum and near-infrared colors, we deduce the infrared source CK 2 to be a K5-M0 III field star situated behind the Serpens cloud and suffering 40-50 mag of visual extinction. Assuming empirical correlations between extinction and total (gas + dust) CO column density, we estimate the CO depletion (i.e., the fraction of interstellar CO in the line of sight tied up in grains) to be approximately 40% in the intracloud medium of the Serpens cloud, comparable with previous estimates for the Taurus dark cloud, and much higher than that found in the environments of protostellar objects.

HR 3126 is a unique M giant star embedded in the bipolar reflection nebula IC 2220. In this paper we present new photometric and spectroscopic observations of HR 3126 and combine them with existing data from the literature in an extensive reappraisal of the star's properties at infrared wavelengths. The spectral energy distribution is consistent with an optical classification of M0-3 II with infrared excess. The dust shell cannot be fitted by a single-temperature blackbody: at least three components are required, with temperatures in the range 35-1300 K. On the basis of spectroscopy at 1-4 and 7-25 microns, combined with an assessment of various color-color diagrams, we are able to reject the hypothesis that HR 3126 is carbon-rich. Weak silicate emission features are detected at 10 and 19 microns, and a previous report of silicon carbide emission at 11.2 microns is not substantiated. It seems likely that HR 2136 is in a phase of advanced and rapid postmain-sequence evolution, possibly beginning its ascent of the asymptotic giant branch.