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To study the demographics of interstellar ices in the Central Molecular Zone (CMZ) of the Milky Way, we obtain near-infrared spectra of $109$ red point sources using NASA IRTF/SpeX at Maunakea. We select the sample from near- and mid-infrared photometry, including $12$ objects in the previous paper of this series, to ensure that these sources trace a large amount of absorption through clouds in each line of sight. We find that most of the sample ($100$ objects) show CO band-head absorption at $2.3\ \mu$m, tagging them as red (super-) giants. Despite the photospheric signature, however, a fraction of the sample with $L$-band spectra ($9/82=0.11$) exhibit large H$_2$O ice column densities ($N > 2\times10^{18}\ {\rm cm}^{-2}$), and six of them also reveal CH$_3$OH ice absorption. As one of such objects is identified as a young stellar object (YSO) in our previous work, these ice-rich sight lines are likely associated with background stars in projection to an extended envelope of a YSO or a dense cloud core. The low frequency of such objects in the early stage of stellar evolution implies a low star-formation rate ($<0.02\ M_\odot$ yr$^{-1}$), reinforcing the previous claim on the suppressed star-formation activity in the CMZ. Our data also indicate that the strong "shoulder" CO$_2$ ice absorption at $15.4\ \mu$m observed in YSO candidates in the previous paper arises from CH$_3$OH-rich ice grains having a large CO$_2$ concentration [$N {\rm (CO_2)} / N {\rm (CH_3OH)} \approx 1/3$]., Comment: 28 pages, 12 figures, 3 tables. Accepted for publication in the Astrophysical Journal

Isolated dense molecular cores are investigated to study the onset of complex organic molecule formation in interstellar ice. Sampling three cores with ongoing formation of low-mass stars (B59, B335, and L483) and one starless core (L694-2) we sample lines of sight to nine background stars and five young stellar objects (YSOs; A_K ~0.5 - 4.7). Spectra of these stars from 2-5 $\mu$m with NASA's Infrared Telescope Facility (IRTF) simultaneously display signatures from the cores of H$_2$O (3.0 $\mu$m), CH$_3$OH (C-H stretching mode, 3.53 $\mu$m) and CO (4.67 $\mu$m) ices. The CO ice is traced by nine stars in which five show a long wavelength wing due to a mixture of CO with polar ice (CO$_r$), presumably CH$_3$OH. Two of these sight lines also show independent detections of CH$_3$OH. For these we find the ratio of the CH$_3$OH:CO$_r$ is 0.55$\pm$0.06 and 0.73$\pm$0.07 from L483 and L694-2, respectively. The detections of both CO and CH$_3$OH for the first time through lines of sight toward background stars observationally constrains the conversion of CO into CH$_3$OH ice. Along the lines of sight most of the CO exists in the gas phase and $\leq$15% of the CO is frozen out. However, CH$_3$OH ice is abundant with respect to CO (~50%) and exists mainly as a CH$_3$OH-rich CO ice layer. Only a small fraction of the lines of sight contains CH$_3$OH ice, presumably that with the highest density. The high conversion of CO to CH$_3$OH can explain the abundances of CH$_3$OH ice found in later stage Class 1 low mass YSO envelopes (CH$_3$OH:CO$_r$ ~ 0.5-0.6). For high mass YSOs and one Class 0 YSO this ratio varies significantly implying local variations can affect the ice formation. The large CH$_3$OH ice abundance indicates that the formation of complex organic molecules is likely during the pre-stellar phase in cold environments without higher energy particle interactions (e.g. cosmic rays)., Comment: 26 pages, 7 figures, Accepted for publication by ApJ

Previous radio observations revealed widespread gas-phase methanol (CH$_3$OH) in the Central Molecular Zone (CMZ) at the Galactic center (GC), but its origin remains unclear. Here, we report the discovery of CH$_3$OH ice toward a star in the CMZ, based on a Subaru $3.4$-$4.0\ \mu$m spectrum, aided by NASA/IRTF $L'$ imaging and $2$-$4\ \mu$m spectra. The star lies $\sim8000$ au away in projection from a massive young stellar object (MYSO). Its observed high CH$_3$OH ice abundance ($17\%\pm3\%$ relative to H$_2$O ice) suggests that the $3.535\ \mu$m CH$_3$OH ice absorption likely arises in the MYSO's extended envelope. However, it is also possible that CH$_3$OH ice forms with a higher abundance in dense clouds within the CMZ, compared to within the disk. Either way, our result implies that gas-phase CH$_3$OH in the CMZ can be largely produced by desorption from icy grains. The high solid CH$_3$OH abundance confirms the prominent $15.4\ \mu$m shoulder absorption observed toward GC MYSOs arises from CO$_2$ ice mixed with CH$_3$OH., Comment: Accepted for publication in the Astrophysical Journal Letters

We present an analysis of CO emission lines from a sample of T Tauri, Herbig Ae/Be, and transitional disks with known inclinations, in order to study the structure of inner disk molecular gas. We calculate CO inner radii by fitting line profiles with a simple parameterized model. We find that, for optically thick disks, CO inner radii are strongly correlated with the total system luminosity (stellar plus accretion), and consistent with the dust sublimation radius. Transitional disk inner radii show the same trend with luminosity, but are systematically larger. Using rotation diagram fits, we derive, for classical T Tauri disks, emitting areas consistent with a ring of width ~0.15 AU located at the CO inner radius; emitting areas for transitional disks are systematically smaller. We also measure lower rotational temperatures for transitional disks, and disks around Herbig Ae/Be stars, than for those around T Tauri stars. Finally, we find that rotational temperatures are similar to, or slightly lower than, the expected temperature of blackbody grains located at the CO inner radius, in contrast to expectations of thermal decoupling between gas and dust., Comment: Accepted for publication in the Astrophysical Journal

Icy grain mantles are commonly observed through infrared spectroscopy toward dense clouds, cloud cores, protostellar envelopes and protoplanetary disks. Up to 80% of the available oxygen, carbon and nitrogen are found in such ices; the most common ice constituents - H2O, CO2 and CO - are second in abundance only to H2 in many star forming regions. In addition to being a molecular reservoir, ice chemistry is responsible for much of the chemical evolution from H2O to complex, prebiotic molecules. Combining the existing ISO, Spitzer, VLT and Keck ice data results in a large sample of ice sources (\sime80) that span all stages of star formation and a large range of protostellar luminosities (<0.1-105 L\odot). Here we summarize the different techniques that have been applied to mine this ice data set on information on typical ice compositions in different environments and what this implies about how ices form and evolve during star and planet formation. The focus is on how to maximize the use of empirical constraints from ice observations, followed by the application of information from experiments and models. This strategy is used to identify ice bands and to constrain which ices form early during cloud formation, which form later in the prestellar core and which require protostellar heat and/or UV radiation to form. The utility of statistical tests, survival analysis and ice maps is highlighted; the latter directly reveals that the prestellar ice formation takes place in two phases, associated with H2O and CO ice formation, respectively, and that most protostellar ice variation can be explained by differences in the prestellar CO ice formation stage. Finally, special attention is paid to the difficulty of observing complex ices directly and how gas observations, experiments and models help in constraining this ice chemistry stage., Comment: 14 pages, including 13 figures. To appear in the proceedings of IAU Symposium 280: "The Molecular Universe"

Ices regulate much of the chemistry during star formation and account for up to 80% of the available oxygen and carbon. In this paper, we use the Spitzer c2d ice survey, complimented with data sets on ices in cloud cores and high-mass protostars, to determine standard ice abundances and to present a coherent picture of the evolution of ices during low- and high-mass star formation. The median ice composition H2O:CO:CO2:CH3OH:NH3:CH4:XCN is 100:29:29:3:5:5:0.3 and 100:13:13:4:5:2:0.6 toward low- and high-mass protostars, respectively, and 100:31:38:4:-:-:- in cloud cores. In the low-mass sample, the ice abundances with respect to H2O of CH4, NH3, and the component of CO2 mixed with H2O typically vary by <25%, indicative of co-formation with H2O. In contrast, some CO and CO2 ice components, XCN and CH3OH vary by factors 2-10 between the lower and upper quartile. The XCN band correlates with CO, consistent with its OCN- identification. The origin(s) of the different levels of ice abundance variations are constrained by comparing ice inventories toward different types of protostars and background stars, through ice mapping, analysis of cloud-to-cloud variations, and ice (anti-)correlations. Based on the analysis, the first ice formation phase is driven by hydrogenation of atoms, which results in a H2O-dominated ice. At later prestellar times, CO freezes out and variations in CO freeze-out levels and the subsequent CO-based chemistry can explain most of the observed ice abundance variations. The last important ice evolution stage is thermal and UV processing around protostars, resulting in CO desorption, ice segregation and formation of complex organic molecules. The distribution of cometary ice abundances are consistent with with the idea that most cometary ices have a protostellar origin., Comment: 48 pages, including 19 figures. Accepted for publication in ApJ

We present results from our spectroscopic study, using the Infrared Spectrograph (IRS) onboard the Spitzer Space Telescope, designed to identify massive young stellar objects (YSOs) in the Galactic Center (GC). Our sample of 107 YSO candidates was selected based on IRAC colors from the high spatial resolution, high sensitivity Spitzer/IRAC images in the Central Molecular Zone (CMZ), which spans the central ~300 pc region of the Milky Way Galaxy. We obtained IRS spectra over 5um to 35um using both high- and low-resolution IRS modules. We spectroscopically identify massive YSOs by the presence of a 15.4um shoulder on the absorption profile of 15um CO2 ice, suggestive of CO2 ice mixed with CH3OH ice on grains. This 15.4um shoulder is clearly observed in 16 sources and possibly observed in an additional 19 sources. We show that 9 massive YSOs also reveal molecular gas-phase absorption from CO2, C2H2, and/or HCN, which traces warm and dense gas in YSOs. Our results provide the first spectroscopic census of the massive YSO population in the GC. We fit YSO models to the observed spectral energy distributions and find YSO masses of 8 - 23 Msun, which generally agree with the masses derived from observed radio continuum emission. We find that about 50% of photometrically identified YSOs are confirmed with our spectroscopic study. This implies a preliminary star formation rate of ~0.07 Msun/yr at the GC., Comment: Accepted for publication in ApJ

NH3 and CH3OH are key molecules in astrochemical networks leading to the formation of more complex N- and O-bearing molecules, such as CH3CN and HCOOCH3. Despite a number of recent studies, little is known about their abundances in the solid state. (...) In this work, we investigate the ~ 8-10 micron region in the Spitzer IRS (InfraRed Spectrograph) spectra of 41 low-mass young stellar objects (YSOs). These data are part of a survey of interstellar ices in a sample of low-mass YSOs studied in earlier papers in this series. We used both an empirical and a local continuum method to correct for the contribution from the 10 micron silicate absorption in the recorded spectra. In addition, we conducted a systematic laboratory study of NH3- and CH3OH-containing ices to help interpret the astronomical spectra. We clearly detect a feature at ~9 micron in 24 low-mass YSOs. Within the uncertainty in continuum determination, we identify this feature with the NH3 nu_2 umbrella mode, and derive abundances with respect to water between ~2 and 15%. Simultaneously, we also revisited the case of CH3OH ice by studying the nu_4 C-O stretch mode of this molecule at ~9.7 micron in 16 objects, yielding abundances consistent with those derived by Boogert et al. 2008 (hereafter paper I) based on a simultaneous 9.75 and 3.53 micron data analysis. Our study indicates that NH3 is present primarily in H2O-rich ices, but that in some cases, such ices are insufficient to explain the observed narrow FWHM. The laboratory data point to CH3OH being in an almost pure methanol ice, or mixed mainly with CO or CO2, consistent with its formation through hydrogenation on grains. Finally, we use our derived NH3 abundances in combination with previously published abundances of other solid N-bearing species to find that up to 10-20 % of nitrogen is locked up in known ices., Comment: 31 pages, 15 figures, accepted for publication in ApJ

We report the detection of several molecular gas-phase and ice absorption features in three photometrically-selected young stellar object (YSO) candidates in the central 280 pc of the Milky Way. Our spectra, obtained with the Infrared Spectrograph (IRS) onboard the Spitzer Space Telescope, reveal gas-phase absorption from CO2 (15.0um), C2H2 (13.7um) and HCN (14.0um). We attribute this absorption to warm, dense gas in massive YSOs. We also detect strong and broad 15um CO2 ice absorption features, with a remarkable double-peaked structure. The prominent long-wavelength peak is due to CH3OH-rich ice grains, and is similar to those found in other known massive YSOs. Our IRS observations demonstrate the youth of these objects, and provide the first spectroscopic identification of massive YSOs in the Galactic Center., Comment: Accepted for publication in ApJ Letters

CH4 is proposed to be the starting point of a rich organic chemistry. Solid CH4 abundances have previously been determined mostly toward high mass star forming regions. Spitzer/IRS now provides a unique opportunity to probe solid CH4 toward low mass star forming regions as well. Infrared spectra from the Spitzer Space Telescope are presented to determine the solid CH4 abundance toward a large sample of low mass young stellar objects. 25 out of 52 ice sources in the $c2d$ (cores to disks) legacy have an absorption feature at 7.7 um, attributed to the bending mode of solid CH4. The solid CH4 / H2O abundances are 2-8%, except for three sources with abundances as high as 11-13%. These latter sources have relatively large uncertainties due to small total ice column densities. Toward sources with H2O column densities above 2E18 cm-2, the CH4 abundances (20 out of 25) are nearly constant at 4.7+/-1.6%. Correlation plots with solid H2O, CH3OH, CO2 and CO column densities and abundances relative to H2O reveal a closer relationship of solid CH4 with CO2 and H2O than with solid CO and CH3OH. The inferred solid CH4 abundances are consistent with models where CH4 is formed through sequential hydrogenation of C on grain surfaces. Finally the equal or higher abundances toward low mass young stellar objects compared with high mass objects and the correlation studies support this formation pathway as well, but not the two competing theories: formation from CH3OH and formation in gas phase with subsequent freeze-out., Comment: 27 pages, 7 figures, accepted by ApJ

Infrared images of the dark cloud core B59 were obtained with the Spitzer Space Telescope as part of the "Cores to Disks" Legacy Science project. Photometry from 3.6-70 microns indicates at least 20 candidate low-mass young stars near the core, more than doubling the previously known population. Out of this group, 13 are located within about 0.1 pc in projection of the molecular gas peak, where a new embedded source is detected. Spectral energy distributions span the range from small excesses above photospheric levels to rising in the mid-infrared. One other embedded object, probably associated with the millimeter source B59-MMS1, with a bolometric luminosity L(bol) roughly 2 L(sun), has extended structure at 3.6 and 4.5 microns, possibly tracing the edges of an outflow cavity. The measured extinction through the central part of the core is A(V) greater than of order 45 mag. The B59 core is producing young stars with a high efficiency.

H2O is the most abundant component of astrophysical ices. In most lines of sight it is not possible to fit both the H2O 3 um stretching, the 6 um bending and the 13 um libration band intensities with a single pure H2O spectrum. Recent Spitzer observations have revealed CO2 ice in high abundances and it has been suggested that CO2 mixed into H2O ice can affect relative strengths of the 3 um and 6 um bands. We used laboratory infrared transmission spectroscopy of H2O:CO2 ice mixtures to investigate the effects of CO2 on H2O ice spectral features at 15-135 K. We find that the H2O peak profiles and band strengths are significantly different in H2O:CO2 ice mixtures compared to pure H2O ice. In all H2O:CO2 mixtures, a strong free-OH stretching band appears around 2.73 um, which can be used to put an upper limit on the CO2 concentration in the H2O ice. The H2O bending mode profile also changes drastically with CO2 concentration; the broad pure H2O band gives way to two narrow bands as the CO2 concentration is increased. This makes it crucial to constrain the environment of H2O ice to enable correct assignments of other species contributing to the interstellar 6 um absorption band. The amount of CO2 present in the H2O ice of B5:IRS1 is estimated by simultaneously comparing the H2O stretching and bending regions and the CO2 bending mode to laboratory spectra of H2O, CO2, H2O:CO2 and HCOOH., Comment: 12 pages, 11 figures, accepted by A&A

We present mid-infrared Spitzer-IRS spectra of the well-known UX Orionis star VV Ser. We combine the Spitzer data with interferometric and spectroscopic data from the literature covering UV to submillimeter wavelengths. The full set of data are modeled by a two-dimensional axisymmetric Monte Carlo radiative transfer code. The model is used to test the prediction of (Dullemond et al. 2003) that disks around UX Orionis stars must have a self-shadowed shape, and that these disks are seen nearly edge-on, looking just over the edge of a puffed-up inner rim, formed roughly at the dust sublimation radius. We find that a single, relatively simple model is consistent with all the available observational constraints spanning 4 orders of magnitude in wavelength and spatial scales, providing strong support for this interpretation of UX Orionis stars. The grains in the upper layers of the puffed-up inner rim must be small (0.01-0.4 micron) to reproduce the colors (R_V ~ 3.6) of the extinction events, while the shape and strength of the mid-infrared silicate emission features indicate that grains in the outer disk (> 1-2 AU) are somewhat larger (0.3-3.0 micron). From the model fit, the location of the puffed-up inner rim is estimated to be at a dust temperature of 1500 K or at 0.7-0.8 AU for small grains. This is almost twice the rim radius estimated from near-infrared interferometry. A best fitting model for the inner rim in which large grains in the disk mid-plane reach to within 0.25 AU of the star, while small grains in the disk surface create a puffed-up inner rim at ~0.7-0.8 AU, is able to reproduce all the data, including the near-infrared visibilities. [Abstract abridged], Comment: 12 pages, accepted for publication in ApJ

We present results from our spectroscopic study, using the Infrared Spectrograph (IRS) onboard the Spitzer Space Telescope, designed to identify massive young stellar objects (YSOs) in the Galactic Center (GC). Our sample of 107 YSO candidates was selected based on IRAC colors from the high spatial resolution, high sensitivity Spitzer/IRAC images in the Central Molecular Zone (CMZ), which spans the central approximately 300 pc region of the Milky Way Galaxy. We obtained IRS spectra over 5 micron to 35 micron using both high- and low-resolution IRS modules. We spectroscopically identify massive YSOs by the presence of a 15.4 micron shoulder on the absorption profile of 15 micron CO2 ice, suggestive of CO2 ice mixed with CH30H ice on grains. This 15.4 micron shoulder is clearly observed in 16 sources and possibly observed in an additional 19 sources. We show that 9 massive YSOs also reveal molecular gas-phase absorption from C02, C2H2, and/or HCN, which traces warm and dense gas in YSOs. Our results provide the first spectroscopic census of the massive YSO population in the GC. We fit YSO models to the observed spectral energy distributions and find YSO masses of 8 - 23 solar Mass, which generally agree with the masses derived from observed radio continuum emission. We find that about 50% of photometrically identified YSOs are confirmed with our spectroscopic study. This implies a preliminary star formation rate of approximately 0.07 solar mass/yr at the GC.