Context. Hydrogenation reactions of CO in inter-and circumstellar ices are regarded as an important starting point in the formation of more complex species. Previous laboratory measurements by two groups of the hydrogenation of CO ices provided controversial results about the formation rate of methanol. Aims. Our aim is to resolve this controversy by an independent investigation of the reaction scheme for a range of H-atom fluxes and different ice temperatures and thicknesses. To fully understand the laboratory data, the results are interpreted theoretically by means of continuous-time, random-walk Monte Carlo simulations. Methods. Reaction rates are determined by using a state-of-the-art ultra high vacuum experimental setup to bombard an interstellar CO ice analog with H atoms at room temperature. The reaction of CO + H into H 2 CO and subsequently CH 3 OH is monitored by a Fourier transform infrared spectrometer in a reflection absorption mode. In addition, after each completed measurement, a temperature programmed desorption experiment is performed to identify the produced species according to their mass spectra and to determine their abundance. Different H-atom fluxes, morphologies, and ice thicknesses are tested. The experimental results are interpreted using Monte Carlo simulations. This technique takes into account the layered structure of CO ice. Results. The formation of both formaldehyde and methanol via CO hydrogenation is confirmed at low temperature (T = 12−20 K). We confirm that the discrepancy between the two Japanese studies is caused mainly by a difference in the applied hydrogen atom flux, as proposed by Hidaka and coworkers. The production rate of formaldehyde is found to decrease and the penetration column to increase with temperature. Temperature-dependent reaction barriers and diffusion rates are inferred using a Monte Carlo physical chemical model. The model is extended to interstellar conditions to compare with observational H 2 CO/CH 3 OH data.

Aims. We study the chemical origin of a set of complex organic molecules thought to be produced by grain surface chemistry in high mass young stellar objects (YSOs). Methods. A partial submillimeter line-survey was performed toward 7 high-mass YSOs aimed at detecting H 2 CO, CH 3 OH, CH 2 CO, CH 3 CHO, C 2 H 5 OH, HCOOH, HNCO and NH 2 CHO. In addition, lines of CH 3 CN, C 2 H 5 CN, CH 3 CCH, HCOOCH 3 , and CH 3 OCH 3 were observed. Rotation temperatures and beam-averaged column densities are determined. To correct for beam dilution and determine abundances for hot gas, the radius and H 2 column densities of gas at temperatures >100 K are computed using 850 µm dust continuum data and source luminosity.Results. Based on their rotation diagrams, molecules can be classified as either cold (<100 K) or hot (>100 K). This implies that complex organics are present in at least two distinct regions. Furthermore, the abundances of the hot oxygen-bearing species are correlated, as are those of HNCO and NH 2 CHO. This is suggestive of chemical relationships within, but not between, those two groups of molecules. Conclusions. The most likely explanation for the observed correlations of the various hot molecules is that they are "first generation" species that originate from solid-state chemistry. This includes H 2 CO, CH 3 OH, C 2 H 5 OH, HCOOCH 3 , CH 3 OCH 3 , HNCO, NH 2 CHO, and possibly CH 3 CN, and C 2 H 5 CN. The correlations between sources implies very similar conditions during their formation or very similar doses of energetic processing. Cold species such as CH 2 CO, CH 3 CHO, and HCOOH, some of which are seen as ices along the same lines of sight, are probably formed in the solid state as well, but appear to be destroyed at higher temperatures. A low level of non-thermal desorption by cosmic rays can explain their low rotation temperatures and relatively low abundances in the gas phase compared to the solid state. The CH 3 CCH abundances can be fully explained by low temperature gas phase chemistry. No cold N-containing molecules are found.

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 (L $ 0:1Y10 L ) using 3Y38 m Spitzer and ground-based spectra. The sample is complemented with previously published Spitzer spectra of background stars and with ISO spectra of well-studied massive YSOs (L $ 10 5 L ). The long-known 6.0 and 6.85 m bands are detected toward all sources, with the Class 0Y type YSOs showing the deepest bands ever observed. The 6.0 m band is often deeper than expected from the bending mode of pure solid H 2 O. The additional 5Y7 m absorption consists of five independent components, which, by comparison to laboratory studies, must be from at least eight different carriers. Much of this absorption is due to simple species likely formed by grain surface chemistry, at abundances of 1%Y30% for CH 3 OH, 3%Y8% for NH 3 , 1%Y5% for HCOOH, $6% for H 2 CO, and $0.3% for HCOO À relative to solid H 2 O. The 6.85 m band has one or two carriers, of which one may be less volatile than H 2 O. Its carrier(s) formed early in the molecular cloud evolution and do not survive in the diffuse ISM. If an NH þ 4 -containing salt is the carrier, its abundance relative to solid H 2 O is $7%, demonstrating the efficiency of low-temperature acid-base chemistry or cosmic-rayYinduced reactions. Possible origins are discussed for enigmatic, very broad absorption between 5 and 8 m. Finally, the same ices are observed toward massive and low-mass YSOs, indicating that processing by internal UV radiation fields is a minor factor in their early chemical evolution.

Abstract. Medium resolution (λ/∆λ = 5000−10 000) VLT-ISAAC M-band spectra are presented of 39 young stellar objects in nearby low-mass star forming clouds showing the 4.67 µm 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 µm into 3 components, centered on 2143.7 cm −1 , 2139.9 cm −1 and 2136.5 cm −1 with fixed widths of 3.0, 3.5 and 10.6 cm −1 , respectively. 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. The model therefore predicts the polarisation fraction at 4.67 µm, which can be confirmed by imaging polarimetry. The 2152 cm −1 feature characteristic of CO on or in an unprocessed water matrix is not detected toward any source and stringent upper limits are given. When this is taken into account, the 2136.5 cm −1 component is not consistent with the available water-rich laboratory mixtures and we suggest that the carrier is not yet fully understood. A shallow absorption band centered between 2165 cm −1 and 2180 cm −1 is detected towards 30 sources. For low-mass stars, this band is correlated with the CO component at 2136.5 cm −1 , suggesting the presence of a carrier different from XCN at 2175 cm −1 . Furthermore the absorption band from solid 13 CO at 2092 cm −1 is detected towards IRS 51 in the ρ Ophiuchi cloud complex and an isotopic ratio of 12 CO/ 13 CO = 68 ± 10 is derived. It is shown that all the observed solid 12 CO profiles, along with the solid 13 CO 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.

Glycolaldehyde (HCOCH 2 OH) is the simplest sugar and an important intermediate in the path toward forming more complex biologically relevant molecules. In this paper we present the first detection of 13 transitions of glycolaldehyde around a solar-type young star, through Atacama Large Millimeter Array (ALMA) observations of the Class 0 protostellar binary IRAS 16293-2422 at 220 GHz (6 transitions) and 690 GHz (7 transitions). The glycolaldehyde lines have their origin in warm (200-300 K) gas close to the individual components of the binary. Glycolaldehyde co-exists with its isomer, methyl formate (HCOOCH 3 ), which is a factor 10-15 more abundant toward the two sources. The data also show a tentative detection of ethylene glycol, the reduced alcohol of glycolaldehyde. In the 690 GHz data, the seven transitions predicted to have the highest optical depths based on modeling of the 220 GHz lines all show red-shifted absorption profiles toward one of the components in the binary (IRAS16293B) indicative of infall and emission at the systemic velocity offset from this by about 0.2 ′′ (25 AU). We discuss the constraints on the chemical formation of glycolaldehyde and other organic species -in particular, in the context of laboratory experiments of photochemistry of methanolcontaining ices. The relative abundances appear to be consistent with UV photochemistry of a CH 3 OH-CO mixed ice that has undergone mild heating. The order of magnitude increase in line density in these early ALMA data illustrate its huge potential to reveal the full chemical complexity associated with the formation of solar system analogs.