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Planet formation is strongly influenced by the composition and distribution of volatiles within protoplanetary disks. With JWST, it is now possible to obtain direct observational constraints on disk ices, as recently demonstrated by the detection of ice absorption features towards the edge-on HH 48 NE disk as part of the Ice Age Early Release Science program. Here, we introduce a new radiative transfer modeling framework designed to retrieve the composition and mixing status of disk ices using their band profiles, and apply it to interpret the H2O, CO2, and CO ice bands observed towards the HH 48 NE disk. We show that the ices are largely present as mixtures, with strong evidence for CO trapping in both H2O and CO2 ice. The HH 48 NE disk ice composition (pure vs. polar vs. apolar fractions) is markedly different from earlier protostellar stages, implying thermal and/or chemical reprocessing during the formation or evolution of the disk. We infer low ice-phase C/O ratios around 0.1 throughout the disk, and also demonstrate that the mixing and entrapment of disk ices can dramatically affect the radial dependence of the C/O ratio. It is therefore imperative that realistic disk ice compositions are considered when comparing planetary compositions with potential formation scenarios, which will fortunately be possible for an increasing number of disks with JWST., Comment: Accepted to ApJ. 24 pages, 15 figures

A unique bistable transition has been identified in granular/colloidal gel-composites, resulting from shear-induced phase separation of the gel phase into dense blobs. In energy applications, it is critical to understand how this transition influences electrical performance. Mixing conductive colloids with conductive inclusions, we find the conductivity and elasticity move in concert, both decreasing in the collapsed phase-separated state. Surprisingly, with insulating inclusions these properties can become decoupled, with the conductivity instead increasing despite the collapse of the gel structure.

Whilst multi-principal element alloys (MPEAs) remain a promising class of materials owing to several attractive mechanical properties, their corrosion performance is also unique. In this concise review, we present an emerging overview of some of the general features related to MPEA corrosion, following a decade of work in the field. This includes highlighting some of the key aspects related to the electrochemical phenomena in MPEA corrosion, and the relevant future works required for a holistic mechanistic understanding. In addition, a comprehensive database of the reported corrosion performance of MPEAs is presented, based on works reported to date. The database is assembled to also allow users to undertake machine learning or their own data analysis, with a parsed representation of alloy composition, test electrolyte, and corrosion related parameters.

Cement is an essential construction material due to its ability to flow before later setting, however the rheological properties must be tightly controlled. Despite this, much understanding remains empirical. Using a combination of continuous and oscillatory shear flow, we compare fresh Portland cement suspensions to previous measurements on model non-Brownian suspensions to gain a micro-physical understanding. Comparing steady and small-amplitude oscillatory shear, we reveal two distinct jamming concentrations, $\phi_{\mu}$ and $\phi_{\rm rcp}$, where the respective yield stresses diverge. As in model suspensions, the steady-shear jamming point is notably below the oscillatory jamming point, $\phi_{\mu} < \phi_{\rm rcp}$, suggesting that it is tied to frictional particle contacts. These results indicate that recently established models for the rheology of frictional, adhesive non-Brownian suspensions can be applied to fresh cement pastes, offering a new framework to understand the role of additives and fillers. Such micro-physical understanding can guide formulation changes to improve performance and reduce environmental impact., Comment: 10 pages, 8 figures

The ability to manipulate rheological and electrical properties of colloidal carbon black gels makes them attractive in composites for energy applications such as batteries and fuel cells, where they conduct electricity and prevent sedimentation of `granular' active components. While it is commonly assumed that granular fillers have a simple additive effect on the composite properties, new phenomena can emerge unexpectedly, with some composites exhibiting a unique rheological bi-stability between solid-like and liquid-like states. Here we report such bi-stability in suspensions of non-Brownian graphite and colloidal carbon black in oil, a model system to mimic composite suspensions for energy applications. Steady shear below a critical stress elicits a transition to a persistent mechanically weak and poorly conducting state, which must be `rejuvenated' using high-stress shear to recover a stronger, high-conductivity state. Our findings highlight the highly tunable nature of binary granular/gel composite suspensions, and present new possibilities for optimizing mixing and processing conditions for Li-ion battery slurries.

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

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

We present an experimental instrument that performs laboratory-based gas-phase Terahertz Desorption Emission Spectroscopy (THz-DES) experiments in support of astrochemistry. The measurement system combines a terahertz heterodyne radiometer that uses room temperature semiconductor mixer diode technology previously developed for the purposes of Earth observation, with a high-vacuum desorption gas cell and high-speed digital sampling circuitry to enable high spectral and temporal resolution spectroscopy of molecular species with thermal discrimination. During use, molecules are condensed onto a liquid nitrogen cooled metal finger to emulate ice structures that may be present in space. Following deposition, thermal desorption is controlled and initiated by means of a heater and monitored via a temperature sensor. The 'rest frequency' spectral signatures of molecules released into the vacuum cell environment are detected by the heterodyne radiometer in real-time and characterised with high spectral resolution. To demonstrate the viability of the instrument, we have studied Nitrous Oxide (N2O). This molecule strongly emits within the terahertz (sub-millimetre wavelength) range and provide a suitable test gas and we compare the results obtained with more traditional techniques such as quadrupole mass spectrometry. The results obtained allow us to fully characterize the measurement method and we discuss its potential use as a laboratory tool in support of astrochemical observations of molecular species in the interstellar medium and the Solar System., Comment: 12 pages, 12 figures. Accepted for publication in MNRAS

Dust grains play an important role in the synthesis of molecules in the interstellar medium, from the simplest species to complex organic molecules. How some of these solid-state molecules are converted into gas-phase species is still a matter of debate. Our aim is to directly compare ice and gas abundances of methanol (CH$_3$OH) and CO, and to investigate the relationship between ice and gas in low-mass protostellar envelopes. We present Submillimeter Array and Atacama Pathfinder EXperiment observations of gas-phase CH$_3$OH and CO towards the multiple protostellar system IRAS05417+0907 located in the B35A cloud. We use archival AKARI ice data toward the same target to calculate CH$_3$OH and CO gas-to-ice ratios. The CO isotopologues emissions are extended, whereas the CH$_3$OH emission is compact and traces the giant outflow emanating from IRAS05417+0907. A discrepancy between submillimeter dust emission and H$_2$O ice column density is found for B35A$-$4 and B35A$-$5, similar to what has previously been reported. B35A$-$2 and B35A$-$3 are located where the submillimeter dust emission peaks and show H$_2$O column densities lower than for B35A$-$4. The difference between the submillimeter continuum emission and the infrared H$_2$O ice observations suggests that the distributions of dust and H$_2$O ice differ around the young stellar objects in this dense cloud. The reason for this may be that the sources are located in different environments resolved by the interferometric observations: B35A$-$2, B35A$-$3 and in particular B35A$-$5 are situated in a shocked region plausibly affected by sputtering and heating impacting the submillimeter dust emission pattern, while B35A$-$4 is situated in a more quiescent part of the cloud. Gas and ice maps are essential to connect small-scale variations in the ice composition with large-scale astrophysical phenomena probed by gas observations., Comment: 18 pages, 15 figures, accepted for publication in Astronomy & Astrophysics

The interaction between dust, ice, and gas during the formation of stars produces complex organic molecules. While observations indicate that several species are formed on ice-covered dust grains and are released into the gas phase, the exact chemical interplay between solid and gas phases and their relative importance remain unclear. Our goal is to study the interplay in regions of low-mass star formation through ice- and gas-mapping and by directly measuring gas-to-ice ratios. This provides constraints on the routes that lead to the chemical complexity that is observed in both phases. We present observations of gas-phase methanol (CH$_3$OH) and carbon monoxide at 1.3 mm towards ten low-mass young protostars in the Serpens SVS4 cluster from the SubMillimeter Array and the Atacama Pathfinder EXperiment telescope. We used archival data from the Very Large Telescope to derive abundances of ice H$_2$O, CO, and CH$_3$OH towards the same region. Finally, we constructed gas-ice maps of SVS4 and directly measured CO and CH$_3$OH gas-to-ice ratios. The CH$_3$OH gas-to-ice ratio agrees with values that were previously reported for embedded Class 0/I low-mass protostars. The CO gas-maps trace an extended gaseous component that is not sensitive to the effect of freeze-out. We find that there is no straightforward correlation between CO and CH$_3$OH gas with their ice counterparts in the cluster. This is likely related to the complex morphology of SVS4: the Class 0 protostar SMM4 and its envelope lie in the vicinity, and the outflow associated with SMM4 intersects the cluster. This study serves as a pathfinder for future observations with ALMA and the James Webb Space Telescope that will provide high-sensitivity gas-ice maps of molecules more complex than methanol. Such comparative maps will be essential to constrain the chemical routes that regulate the chemical complexity in star-forming regions., Comment: 25 pages, 20 figures, accepted for publication by A&A

We present the first release of the data and compact-source catalogue for the JCMT Large Program SCUBA-2 Continuum Observations of Pre-protostellar Evolution (SCOPE). SCOPE consists of 850-um continuum observations of 1235 Planck Galactic Cold Clumps (PGCCs) made with the Submillimetre Common-User Bolometer Array 2 on the James Clerk Maxwell Telescope. These data are at an angular resolution of 14.4 arcsec, significantly improving upon the 353-GHz resolution of Planck at 5 arcmin, and allowing for a catalogue of 3528 compact sources in 558 PGCCs. We find that the detected PGCCs have significant sub-structure, with 61 per cent of detected PGCCs having 3 or more compact sources, with filamentary structure also prevalent within the sample. A detection rate of 45 per cent is found across the survey, which is 95 per cent complete to Planck column densities of $N_{H_{2}}$ $>$ 5 $\times$ 10$^{21}$ cm$^{-2}$. By positionally associating the SCOPE compact sources with YSOs, the star formation efficiency, as measured by the ratio of luminosity to mass, in nearby clouds is found to be similar to that in the more distant Galactic Plane, with the column density distributions also indistinguishable from each other., Comment: 16 pages, 13 figures, 1 table. Accepted for publication in MNRAS

Saturn's moon Enceladus has vents emerging from a sub-surface ocean, offering unique probes into the liquid environment. These vents drain into the larger neutral torus in orbit around Saturn. We present a methanol (CH3OH) detection observed with IRAM 30-m from 2008 along the line-of-sight through Saturn's E-ring. Additionally, we also present supporting observations from the Herschel public archive of water (ortho-H2O; 1669.9 GHz) from 2012 at a similar elongation and line-of-sight. The CH3OH 5(1,1)-4(1,1) transition was detected at 5.9 sigma confidence. The line has 0.43 km/s width and is offset by +8.1 km/s in the moon's reference frame. Radiative transfer models allow for gas cloud dimensions from 1750 km up to the telescope beam diameter ~73000 km. Taking into account the CH3OH lifetime against solar photodissociation and the redshifted line velocity, there are two possible explanations for the CH3OH emission: methanol is primarily a secondary product of chemical interactions within the neutral torus that (1) spreads outward throughout the E-ring or (2) originates from a compact, confined gas cloud lagging Enceladus by several km/s. We find either scenario to be consistent with significant redshifted H2O emission (4 sigma) measured from the Herschel public archive. The measured CH3OH:H2O abundance (> 0.5 per cent) significantly exceeds the observed abundance in the direct vicinity of the vents (~0.01 per cent), suggesting CH3OH is likely chemically processed within the gas cloud with methane (CH4) as its parent species., Comment: 16 pages, 4 figures, accepted for publication in the International Journal of Astrobiology (IJA)

We present maps of the column densities of H$_2$O, CO$_2$, and CO ices towards the molecular cores B~35A, DC~274.2-00.4, BHR~59, and DC~300.7-01.0. These ice maps, probing spatial distances in molecular cores as low as 2200~AU, challenge the traditional hypothesis that the denser the region observed, the more ice is present, providing evidence that the relationships between solid molecular species are more varied than the generic picture we often adopt to model gas-grain chemical processes and explain feedback between solid phase processes and gas phase abundances. We present the first combined solid-gas maps of a single molecular species, based upon observations of both CO ice and gas phase C$^{18}$O towards B~35A, a star-forming dense core in Orion. We conclude that molecular species in the solid phase are powerful tracers of "small scale" chemical diversity, prior to the onset of star formation. With a component analysis approach, we can probe the solid phase chemistry of a region at a level of detail greater than that provided by statistical analyses or generic conclusions drawn from single pointing line-of-sight observations alone., Comment: 10 pages, 5 figures, accepted for publication in MNRAS

Context: Understanding the collisional properties of ice is important for understanding both the early stages of planet formation and the evolution of planetary ring systems. Simple chemicals such as methanol and formic acid are known to be present in cold protostellar regions alongside the dominant water ice; they are also likely to be incorporated into planets which form in protoplanetary disks, and planetary ring systems. However, the effect of the chemical composition of the ice on its collisional properties has not yet been studied. Aims: Collisions of 1.5 cm ice spheres composed of pure crystalline water ice, water with 5% methanol, and water with 5% formic acid were investigated to determine the effect of the ice composition on the collisional outcomes. Methods: The collisions were conducted in a dedicated experimental instrument, operated under microgravity conditions, at relative particle impact velocities between 0.01 and 0.19 m s^-1, temperatures between 131 and 160 K and a pressure of around 10^-5 mbar. Results: A range of coefficients of restitution were found, with no correlation between this and the chemical composition, relative impact velocity, or temperature. Conclusions: We conclude that the chemical composition of the ice (at the level of 95% water ice and 5% methanol or formic acid) does not affect the collisional properties at these temperatures and pressures due to the inability of surface wetting to take place. At a level of 5% methanol or formic acid, the structure is likely to be dominated by crystalline water ice, leading to no change in collisional properties. The surface roughness of the particles is the dominant factor in explaining the range of coefficients of restitution.

Planetisimals are thought to be formed from the solid material of a protoplanetary disk by a process of dust aggregation. It is not known how growth proceeds to kilometre sizes, but it has been proposed that water ice beyond the snowline might affect this process. To better understand collisional processes in protoplanetary disks leading to planet formation, the individual low velocity collisions of small ice particles were investigated. The particles were collided under microgravity conditions on a parabolic flight campaign using a purpose-built, cryogenically cooled experimental setup. The setup was capable of colliding pairs of small ice particles (between 4.7 and 10.8 mm in diameter) together at relative collision velocities of between 0.27 and 0.51 m s ^-1 at temperatures between 131 and 160 K. Two types of ice particle were used: ice spheres and irregularly shaped ice fragments. Bouncing was observed in the majority of cases with a few cases of fragmentation. A full range of normalised impact parameters (b/R = 0.0-1.0) was realised with this apparatus. Coefficients of restitution were evenly spread between 0.08 and 0.65 with an average value of 0.36, leading to a minimum of 58% of translational energy being lost in the collision. The range of coefficients of restitution is attributed to the surface roughness of the particles used in the study. Analysis of particle rotation shows that up to 17% of the energy of the particles before the collision was converted into rotational energy. Temperature did not affect the coefficients of restitution over the range studied.

Enceladus, a small icy moon of Saturn, is one of the most remarkable bodies in the solar system. This moon is a geologically active object, and despite the lower temperatures on most of its surface, the geothermally heated south polar region presents geysers that spouts a plume made of water (approximately ninety percent), carbon dioxide, methane, ammonia, and methanol, among other molecules. Most of the upward-moving particles do not have the velocity to escape from the gravitational influence of the moon and fall back to the surface. The molecules in the ice are continuously exposed to ionizing radiation, such as UV and X-rays photons, cosmic rays, and electrons. Over time, the ionizing radiation promotes molecular bond rupture, destroying and also forming molecules, radicals, and fragments. We analyse the processing of an ice mixture analogue to the Enceladus fallout ice in cold resurfaced areas (north pole) by 1 keV electrons. The main goal is to search for complex species that have not yet been detected in this moon, and to determine relevant physico-chemical parameters, such as destruction and formation cross-sections and the half-life of the studied molecules in the ice. The experiment consisted of the electron irradiation of an Enceladus-like ice mixture (H2O,CO2,CH4,NH3, and CH3OH) in an ultra-high vacuum chamber at 20 K. The analysis was made by infrared spectrometry in the mid-infrared region (4000-800 cm-1 or 2.5-12.5 microns).The absolute dissociation cross-sections of the parent molecules, the formation cross-section of daughter species, and the half-life of the parental species in a simulated Enceladus irradiation scenario were determined. Among the produced species, CO (carbon monoxide), OCN- (cyanate anion), HCONH2 (formamide), and H2CO (formaldehyde) were tentatively detected.

We present near infrared spectroscopic observations of 19 molecular clouds made using the AKARI satellite, and the data reduction pipeline written to analyse those observations. The 2.5 --~5 $\mu$m spectra of 30 objects -- 22 field stars behind quiescent molecular clouds and eight low mass YSOs in cores -- were successfully extracted using the pipeline. Those spectra are further analysed to calculate the column densities of key solid phase molecular species, including H$_2$O, CO$_2$, CO, and OCN$^-$. The profile of the H$_2$O ice band is seen to vary across the objects observed and we suggest that the extended red wing may be an evolutionary indicator of both dust and ice mantle properties. The observation of 22 spectra with fluxes as low as $<$~5 mJy towards background stars, including 15 where the column densities of H$_2$O, CO and CO$_2$ were calculated, provides valuable data that could help to benchmark the initial conditions in star-forming regions prior to the onset of star formation., Comment: Accepted for publication in ApJ

To investigate the composition and evolution of circumstellar ice around low-mass YSOs, we observed ice absorption bands in the near infrared (NIR) towards eight YSOs ranging from class 0 to class II, among which seven are associated with edge-on disks. We performed slit-less spectroscopic observations using the grism mode of the Infrared Camera (IRC) on board AKARI, which enables us to obtain full NIR spectra from 2.5 $\mu$m to 5 $\mu$m. The spectra were fitted with polynomial baselines to derive the absorption spectra. The molecular absorption bands were then fitted with the laboratory database of ice absorption bands, considering the instrumental line profile and the spectral resolution of the grism dispersion element. Towards the class 0-I sources (L1527, IRC-L1041-2, and IRAS04302), absorption bands of H$_2$O, CO$_2$, CO, and XCN are clearly detected. Column density ratios of CO$_2$ ice and CO ice relative to H$_2$O ice are 21-28% and 13-46%, respectively. If XCN is OCN$^-$, its column density is as high as 2-6% relative to H$_2$O ice. The HDO ice feature at 4.1 $\mu$m is tentatively detected towards the class 0-I sources and HV Tau. Non-detections of the CH-stretching mode features around 3.5 $\mu$m provide upper limits to the CH$_3$OH abundance of 26% (L1527) and 42% (IRAS04302) relative to H$_2$O. We tentatively detect OCS ice absorption towards IRC-L1041-2. Towards class 0-I sources, the detected features should mostly originate in the cold envelope, while CO gas and OCN$^-$ could originate in the region close to the protostar, where there are warm temperatures and UV radiation. We detect H$_2$O ice band towards ASR41 and 2MASSJ1628137-243139, which are edge-on class II disks. We also detect H$_2$O ice and CO$_2$ ice towards HV Tau, HK Tau, and UY Aur, and tentatively detect CO gas features towards HK Tau and UY Aur., Comment: Accepted to A&A

The desorption characteristics of molecules on interstellar dust grains are important for modelling the behaviour of molecules in icy mantles and, critically, in describing the solid-gas interface. In this study, a series of laboratory experiments exploring the desorption of three small molecules from three astrophysically relevant surfaces are presented. The desorption of CO, O2 and CO2 at both sub-monolayer and multilayer coverages was investigated from non-porous water, crystalline water and silicate surfaces. Experimental data was modelled using the Polanyi-Wigner equation to produce a mathematical description of the desorption of each molecular species from each type of surface, uniquely describing both the monolayer and multilayer desorption in a single combined model. The implications of desorption behaviour over astrophysically relevant timescales are discussed., Comment: 13 pages, 5 figures, accepted for publication in Monthly Notices of the Royal Astronomical Society Main Journal

We discuss the design, operation, and performance of a vacuum setup constructed for use in zero (or reduced) gravity conditions to initiate collisions of fragile millimeter-sized particles at low velocity and temperature. Such particles are typically found in many astronomical settings and in regions of planet formation. The instrument has participated in four parabolic flight campaigns to date, operating for a total of 2.4 hours in reduced gravity conditions and successfully recording over 300 separate collisions of loosely packed dust aggregates and ice samples. The imparted particle velocities achieved range from 0.03-0.28 m s^-1 and a high-speed, high-resolution camera captures the events at 107 frames per second from two viewing angles separated by either 48.8 or 60.0 degrees. The particles can be stored inside the experiment vacuum chamber at temperatures of 80-300 K for several uninterrupted hours using a built-in thermal accumulation system. The copper structure allows cooling down to cryogenic temperatures before commencement of the experiments. Throughout the parabolic flight campaigns, add-ons and modifications have been made, illustrating the instrument flexibility in the study of small particle collisions., Comment: D. M. Salter, D. Hei{\ss}elmann, G. Chaparro, G. van der Wolk, P. Rei{\ss}aus, A. G. Borst, R. W. Dawson, E. de Kuyper, G. Drinkwater, K. Gebauer, M. Hutcheon, H. Linnartz, F. J. Molster, B. Stoll, P. C. van der Tuijn, H. J. Fraser, and J. Blum

With the goal to study the physical and chemical evolution of ices in solar-mass systems, a spectral survey is conducted of a sample of 41 low luminosity YSOs using 3-38 um Spitzer and ground-based spectra. The long-known 6.0 and 6.85 um bands are detected toward all sources, with the Class 0-type YSOs showing the deepest bands ever observed. In almost all sources the 6.0 um band is deeper than expected from the bending mode of pure solid H2O. The depth and shape variations of the remaining 5-7 um absorption indicate that it consists of 5 independent components, which, by comparison to laboratory studies, must be from at least 8 different carriers. Simple species are responsible for much of the absorption in the 5-7 um region, at abundances of 1-30% for CH3OH, 3-8% for NH3, 1-5% for HCOOH, ~6% for H2CO, and ~0.3% for HCOO- with respect to solid H2O. The 6.85 um band likely consists of one or two carriers, of which one is less volatile than H2O because its abundance relative to H2O is enhanced at lower H2O/tau_9.7 ratios. It does not survive in the diffuse interstellar medium (ISM), however. The similarity of the 6.85 um bands for YSOs and background stars indicates that its carrier(s) must be formed early in the molecular cloud evolution. If an NH4+ salt is the carrier its abundance with respect to solid H2O is typically 7%, and low temperature acid-base chemistry or cosmic ray induced reactions must have been involved in its formation. Possible origins are discussed for the carrier of an enigmatic, very broad absorption between 5 and 8 um. Finally, all the phenomena observed for ices toward massive YSOs are also observed toward low mass YSOs, indicating that processing of the ices by internal ultraviolet radiation fields is a minor factor in the early chemical evolution of the ices. [abridged], Comment: Accepted for publication in ApJ. 22 pages, 18 b&w figures

We present experimental measurements of photodesorption from ices of astrophysical relevance. Layers of benzene and water ice were irradiated with a laser tuned to an electronic transition in the benzene molecule. The translational energy of desorbed molecules was measured by time-of-flight (ToF) mass spectrometry. Three distinct photodesorption processes were identified - a direct adsorbate-mediated desorption producing benzene molecules with a translational temperature of around 1200 K, an indirect adsorbate-mediated desorption resulting in water molecules with a translational temperature of around 450 K, and a substrate-mediated desorption of both benzene and water producing molecules with translational temperatures of around 530 K and 450 K respectively. The translational temperature of each population of desorbed molecules is well above the temperature of the ice matrix. The implications for gas-phase chemistry in the interstellar medium are discussed., Comment: 23 pages, including 4 figures; submitted to ApJ

Solid O2 has been proposed as a possible reservoir for oxygen in dense clouds through freeze-out processes. The aim of this work is to characterize quantitatively the physical processes that are involved in the desorption kinetics of CO-O2 ices by interpreting laboratory temperature programmed desorption (TPD) data. This information is used to simulate the behavior of CO-O2 ices under astrophysical conditions. The TPD spectra have been recorded under ultra high vacuum conditions for pure, layered and mixed morphologies for different thicknesses, temperatures and mixing ratios. An empirical kinetic model is used to interpret the results and to provide input parameters for astrophysical models. Binding energies are determined for different ice morphologies. Independent of the ice morphology, the desorption of O2 is found to follow 0th-order kinetics. Binding energies and temperature-dependent sticking probabilities for CO-CO, O2-O2 and CO-O2 are determined. O2 is slightly less volatile than CO, with binding energies of 912+-15 versus 858+-15 K for pure ices. In mixed and layered ices, CO does not co-desorb with O2 but its binding energies are slightly increased compared with pure ice whereas those for O2 are slightly decreased. Lower limits to the sticking probabilities of CO and O2 are 0.9 and 0.85, respectively, at temperatures below 20K. The balance between accretion and desorption is studied for O2 and CO in astrophysically relevant scenarios. Only minor differences are found between the two species, i.e., both desorb between 16 and 18K in typical environments around young stars. Thus, clouds with significant abundances of gaseous CO are unlikely to have large amounts of solid O2., Comment: 8 pages + 2 pages online material, 8 figures (1 online), accepted by A&A

We present Temperature Programmed Desorption (TPD) experiments of CO and N2 ices in pure, layered and mixed morphologies at various ice "thicknesses" and abundance ratios as well as simultaneously taken Reflection Absorption Infrared Spectra (RAIRS) of CO. A kinetic model has been developed to constrain the binding energies of CO and N2 in both pure and mixed environments and to derive the kinetics for desorption, mixing and segregation. For mixed ices N2 desorption occurs in a single step whereas for layered ices it proceeds in two steps, one corresponding to N2 desorption from a pure N2 ice environment and one corresponding to desorption from a mixed ice environment. The latter is dominant for astrophysically relevant ice "thicknesses". The ratio of the binding energies, Rbe, for pure N2 and CO is found to be 0.936 +/- 0.03, and to be close to 1 for mixed ice fractions. The model is applied to astrophysically relevant conditions for cold pre-stellar cores and for protostars which start to heat their surroundings. The importance of treating CO desorption with zeroth rather than first order kinetics is shown. The experiments also provide lower limits of 0.87 +/- 0.05 for the sticking probabilities of CO-CO, N2-CO and N2-N2 ices at 14 K. The combined results from the desorption experiments, the kinetic model, and the sticking probability data lead to the conclusion that these solid-state processes of CO and N2 are very similar under astrophysically relevant conditions. This conclusion affects the explanations for the observed anti-correlations of gaseous CO and N2H+ in pre-stellar and protostellar cores., Comment: 13 pages, 7 figures, plus appendix of 2 pages containing 2 figures, Accepted by A&A

We performed a spectroscopic survey toward five intermediate-mass class I YSOs located in the Southern Vela molecular cloud in the L and M bands at resolving powers 600-800 up to 10,000, using the Infrared Spectrometer and Array Camera mounted on the VLT-ANTU. Lower mass companion objects were observed simultaneously in both bands. Solid H2O at 3 micron is detected in all sources, including the companion objects. CO ice at 4.67 micron is detected in a few main targets and one companion object. One object (LLN 19) shows little CO ice but strong gas-phase CO ro-vibrational lines in absorption. The CO ice profiles are different from source to source. The amount of water ice and CO ice trapped in a water-rich mantle may correlate with the flux ratio at 12 and 25 micron. The abundance of H2O-rich CO likely correlates with that of water ice. A weak feature at 3.54 mu attributed to solid CH3OH and a broad feature near 4.62 mu are observed toward LLN17, but not toward the other sources. The derived abundances of solid CH3OH and OCN- are ~10% and ~1% of the H2O ice abundance respectively. The H2O optical depths do not show an increase with envelope mass, nor do they show lower values for the companion objects compared with the main protostar. The line-of-sight CO ice abundance does not correlate with the source bolometric luminosity. Comparison of the solid CO profile toward LLN17, which shows an extremely broad CO ice feature, and that of its lower mass companion at a few thousand AU, which exhibits a narrow profile, together with the detection of OCN- toward LLN17 provide direct evidences for local thermal processing of the ice., Comment: Replace wrong files. Accepted by A&A, 22 pages, 18 figures

The spectra of pure, mixed and layered CO and CO2 ices have been studied systematically under laboratory conditions using infrared spectroscopy. This work provides improved resolution spectra (0.5 cm-1) of the CO2 bending and asymmetric stretching mode, as well as the CO stretching mode, extending the existing Leiden database of laboratory spectra to match the spectral resolution reached by modern telescopes and to support the interpretation of the most recent data from Spitzer. It is shown that mixed and layered CO and CO2 ices exhibit very different spectral characteristics, which depend critically on thermal annealing and can be used to distinguish between mixed, layered and thermally annealed CO-CO2 ices. CO only affects the CO2 bending mode spectra in mixed ices below 50K under the current experimental conditions, where it exhibits a single asymmetric band profile in intimate mixtures. In all other ice morphologies the CO2 bending mode shows a double peaked profile, similar to that observed for pure solid CO2. Conversely, CO2 induces a blue-shift in the peak-position of the CO stretching vibration, to a maximum of 2142 cm-1 in mixed ices, and 2140-2146 cm-1 in layered ices. As such, the CO2 bending mode puts clear constraints on the ice morphology below 50K, whereas beyond this temperature the CO2 stretching vibration can distinguish between initially mixed and layered ices. This is illustrated for the low-mass YSO HH46, where the laboratory spectra are used to analyse the observed CO and CO2 band profiles and try to constrain the formation scenarios of CO2., Comment: Accepted in A&A

The 4.62$\mu$m (2164.5 cm$^{-1}$) `XCN' band has been detected in the $M$-band spectra of 34 deeply embedded young stellar objects (YSO's), observed with high signal-to-noise and high spectral resolution with the VLT-ISAAC spectrometer, providing the first opportunity to study the solid OCN$^-$ abundance toward a large number of low-mass YSO's. It is shown unequivocally that at least two components, centred at 2165.7 cm$^{-1}$ (FWHM = 26 cm$^{-1}$) and 2175.4 cm$^{-1}$ (FWHM = 15 cm$^{-1}$), underlie the XCN band. Only the 2165.7-component can be ascribed to OCN$^-$, embedded in a strongly hydrogen-bonding, and possibly thermally annealed, ice environment based on laboratory OCN$^-$ spectra. In order to correct for the contribution of the 2175.4-component to the XCN band, a phenomenological decomposition into the 2165.7- and the 2175.4-components is used to fit the full band profile and derive the OCN$^-$ abundance for each line-of-sight. The same analysis is performed for 5 high-mass YSO's taken from the ISO-SWS data archive. Inferred OCN$^-$ abundances are $\leq$ 0.85 % toward low-mass YSO's and $\leq$ 1 % toward high-mass YSO's, except for W33 A. Abundances are found to vary by at least a factor of 10--20 and large source-to-source abundance variations are observed within the same star-forming cloud complex on scales down to 400 AU, indicating that the OCN$^-$ formation mechanism is sensitive to local conditions. The inferred abundances allow quantitatively for photochemical formation of OCN$^-$, but the large abundance variations are not easily explained in this scenario unless local radiation sources or special geometries are invoked. Surface chemistry should therefore be considered as an alternative formation mechanism.

Medium resolution (lambda/Delta lambda = 5000-10000) VLT-ISAAC M-band spectra are presented of 39 young stellar objects in nearby low-mass star forming clouds showing the 4.67 micron stretching vibration mode of solid CO. By taking advantage of the unprecedentedly large sample, high S/N ratio and high spectral resolution, similarities in the ice profiles from source to source are identified. It is found that excellent fits to all the spectra can be obtained using a phenomenological decomposition of the CO stretching vibration profile at 4.67 micron into 3 components. All observed interstellar CO profiles can thus be uniquely described by a model depending on only 3 linear fit parameters, indicating that a maximum of 3 specific molecular environments of solid CO exist under astrophysical conditions. A simple physical model of the CO ice is presented, which shows that the 2139.9 cm-1 component is indistinguishable from pure CO ice. It is concluded, that in the majority of the observed lines of sight, 60-90% of the CO is in a nearly pure form. In the same model the 2143.7 cm-1 component can possibly be explained by the longitudinal optical (LO) component of the vibrational transition in pure crystalline CO ice which appears when the background source is linearly polarised. Furthermore the absorption band from solid 13CO at 2092 cm-1 is detected towards IRS 51 in the Rho Ophiuchi cloud complex and an isotopic ratio of 12CO/13CO=68+/-10 is derived. It is shown that all the observed solid 12CO profiles, along with the solid 13CO profile, are consistent with grains with an irregularly shaped CO ice mantle simulated by a Continuous Distribution of Ellipsoids (CDE), but inconsistent with the commonly used models of spherical grains in the Rayleigh limit. [Abstract abridged], Comment: 30 pages, accepted for publication in Astronomy & Astrophysics. Preprint w. high res figures available at http://www.strw.leidenuniv.nl/~pontoppi/ms3823.pdf

General results from a 3-5 micron spectroscopic survey of nearby low-mass young stellar objects are presented. L and M-band spectra have been obtained of \~50 low mass embedded young stars using the ISAAC spectrometer mounted on UT1-Antu at Paranal Observatory. For the first time, a consistent census of the CO, H2O ices and the minor ice species CH3OH and OCN- and warm CO gas present around young stars is obtained, using large number statistics and resolving powers of up to R=10000. The molecular structure of circumstellar CO ices, the depletion of gaseous CO onto grains in protoplanetary disks, the presence of hot gas in the inner parts of circumstellar disks and in outflows and infalls are studied. Furthermore, the importance of scattering effects for the interpretation of the spectra have been addressed., Comment: To appear in the proceedings of the conference "Chemistry as a Diagnostic of Star Formation", University of Waterloo, Canada, 21-23 August 2002