Karin I. Öberg

The Spitzer Ice Legacy: Ice Evolution from Cores to Protostars

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 Legacy 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 H_(2)O:CO:CO_2:CH_(3)OH:NH_3:CH_4: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 H_(2)O of CH_4, NH_3, and the component of CO_2 mixed with H_(2)O typically vary by <25%, indicative of co-formation with H_(2)O. In contrast, some CO and CO_2 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 an H_(2)O-dominated ice. At later prestellar times, CO freezes out and variations in CO freezeout 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 the formation of complex organic molecules. The distribution of cometary ice abundances is consistent with the idea that most cometary ices have a protostellar origin.

Formation rates of complex organics in UV irradiated CH3OH-rich ices I: Experiments

Context. Gas-phase complex organic molecules are commonly detected in the warm inner regions of protostellar envelopes, so-called hot cores. Recent models show that photochemistry in ices followed by desorption may explain the observed abundances. There is, however, a general lack of quantitative data on UV-induced complex chemistry in ices. Aims. This study aims to experimentally quantify the UV-induced production rates of complex organics in CH3OH-rich ices under a variety of astrophysically relevant conditions. Methods. The ices are irradiated with a broad-band UV hydrogen microwave-discharge lamp under ultra-high vacuum conditions, at 20–70 K, and then heated to 200 K. The reaction products are identified by reflection-absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD), through comparison with RAIRS and TPD curves of pure complex species, and through the observed effects of isotopic substitution and enhancement of specific functional groups, such as CH3, in the ice. Results. Complex organics are readily formed in all experiments, both during irradiation and during the slow warm-up of the ices after the UV lamp is turned off. The relative abundances of photoproducts depend on the UV fluence, the ice temperature, and whether pure CH3OH ice or CH3OH:CH4/CO ice mixtures are used. C2H6 ,C H 3CHO, CH3CH2OH, CH3OCH3, HCOOCH3, HOCH2CHO and (CH2OH)2 are all detected in at least one experiment. Varying the ice thickness and the UV flux does not affect the chemistry. The derived product-formation yields and their dependences on different experimental parameters, such as the initial ice composition, are used to estimate the CH3OH photodissociation branching ratios in ice and the relative diffusion barriers of the formed radicals. At 20 K, the pure CH3OH photodesorption yield is 2.1(±1.0) × 10 −3 per incident UV photon, the photo-destruction cross section 2.6(±0.9) × 10 −18 cm 2 . Conclusions. Photochemistry in CH3OH ices is efficient enough to explain the observed abundances of complex organics around protostars. Some complex molecules, such as CH3CH2OH and CH3OCH3, form with a constant ratio in our ices and this can can be used to test whether complex gas-phase molecules in astrophysical settings have an ice-photochemistry origin. Other molecular ratios, e.g. HCO-bearing molecules versus (CH2OH)2, depend on the initial ice composition and temperature and can thus be used to investigate when and where complex ice molecules form.

PHOTODESORPTION OF ICES. II. H2O AND D2O

Gaseous H2O has been detected in several cold astrophysical environments, where the observed abundances cannot be explained by thermal desorption of H2O ice or by H2O gas-phase formation. These observations hence suggest an efficient nonthermal ice desorption mechanism. Here, we present experimentally determined UV photodesorption yields of H2O and D2O ices and deduce their photodesorption mechanism. The ice photodesorption is studied under ultrahigh vacuum conditions and at astrochemically relevant temperatures (18–100 K) using a hydrogen discharge lamp (7–10.5 eV), which simulates the interstellar UV field. The ice desorption during irradiation is monitored using reflection absorption infrared spectroscopy of the ice and simultaneous mass spectrometry of the desorbed species. The photodesorption yield per incident photon, Ypd( T, x), is identical for H2O and D2O and its dependence on ice thickness and temperature is described empirically by Ypd( T, x) = Ypd( T, x > 8)(1 − e −x/ l(T ) ), where x is the ice thickness in monolayers (MLs) and l(T )i s a temperature-dependent ice diffusion parameter that varies between ∼1.3 ML at 30 K and 3.0 ML at 100 K. For thick ices, the yield is linearly dependent on temperature due to increased diffusion of ice species such that Ypd( T, x >8) = 10 −3 (1. 3+0 .032 × T ) UV photon −1 , with a 60% uncertainty for the absolute yield. The increased diffusion also results in an increasing H2O:OH desorption product ratio with temperature from 0.7:1.0 at 20 K to 2.0:1.2 at 100 K. The yield does not depend on the substrate, the UV photon flux, or the UV fluence. The yield is also independent of the initial ice structure since UV photons efficiently amorphize H2O ice. The results are consistent with theoretical predictions of H2O photodesorption at low temperatures and partly in agreement with a previous experimental study. Applying the experimentally determined yield to a Herbig Ae/Be star+disk model provides an estimate of the amount of gas-phase H2O that may be observed by, e.g., Herschel in an example astrophysical environment. The model shows that UV photodesorption of ices increases the H2O content by orders of magnitude in the disk surface region compared to models where nonthermal desorption is ignored.

The effects of snowlines on C/O in planetary atmospheres

The C/O ratio is predicted to regulate the atmospheric chemistry in hot Jupiters. Recent observations suggest that some exoplanets, e.g., Wasp 12-b, have atmospheric C/O ratios substantially different from the solar value of 0.54. In this Letter, we present a mechanism that can produce such atmospheric deviations from the stellar C/O ratio. In protoplanetary disks, different snowlines of oxygen- and carbon-rich ices, especially water and carbon monoxide, will result in systematic variations in the C/O ratio both in the gas and in the condensed phases. In particular, between the H2O and CO snowlines most oxygen is present in icy grains—the building blocks of planetary cores in the core accretion model—while most carbon remains in the gas phase. This region is coincidental with the giant-planet-forming zone for a range of observed protoplanetary disks. Based on standard core accretion models of planet formation, gas giants that sweep up most of their atmospheres from disk gas outside of the water snowline will have a C/O ~ 1, while atmospheres significantly contaminated by evaporating planetesimals will have a stellar or substellar C/O when formed at the same disk radius. The overall metallicity will also depend on the atmosphere formation mechanism, and exoplanetary atmospheric compositions may therefore provide constraints on where and how a specific planet formed.

Photodesorption of ices I: CO, N₂, and CO₂

Context. A longstanding problem in astrochemistry is how molecules can be maintained in the gas phase in dense inter- and circumstellar regions at temperatures well below their thermal desorption values. Photodesorption is a non-thermal desorption mechanism, which may explain the small amounts of observed cold gas in cloud cores and disk mid-planes. Aims. This study aims to determine the UV photodesorption yields and to constrain the photodesorption mechanisms of three astrochemically relevant ices: CO, N2 and CO2. In addition, the possibility of co-desorption in mixed and layered CO:N2 ices is explored. Methods. The UV photodesorption of ices is studied experimentally under ultra high vacuum conditions and at astrochemically relevant temperatures (15–60 K) using a hydrogen discharge lamp (7–10.5 eV). The ice desorption is monitored by reflection absorption infrared spectroscopy of the ice and simultaneous mass spectrometry of the desorbed molecules. Results. Both the UV photodesorption yield per incident photon and the photodesorption mechanism are highly molecule specific. The CO photodesorbs without dissociation from the surface layer of the ice, and N2, which lacks a dipole allowed electronic transition in the wavelength range of the lamp, has a photodesorption yield that is more than an order of magnitude lower. This yield increases significantly due to co-desorption when N2 is mixed in with, or layered on top of, CO ice. CO2 photodesorbs through dissociation and subsequent recombination from the top 10 layers of the ice. At low temperatures (15–18 K), the derived photodesorption yields are 2.7(±1.3) × 10 −3 and <2 × 10 −4 molecules photon −1 for pure CO and N2, respectively. The CO2 photodesorption yield is 1.2(±0.7)×10 −3 ×(1−e −(x/2.9(±1.1)) )+1.1(±0.7)×10 −3 ×(1−e −(x/4.6(±2.2) )) molecules photon −1 ,w herex is the ice thickness in monolayers and the two parts of the expression represent a CO2 and a CO photodesorption pathway, respectively. At higher temperatures, the CO ice photodesorption yield decreases, while that of CO2 increases.

Distribution and levels of brominated flame retardants in sewage sludge.

One hundred and sixteen sewage sludge samples from 22 municipal wastewater treatment plants in Sweden were analysed for brominated flame retardants. Polybrominated diphenyl ethers (PBDEs) were in the range n.d.-450 ng/g wet weight, tetrabromobisphenol A (TBBPA) varied between n.d. and 220 ng/g wet weight, 2,4,6-tribromophenol was in the range n.d.-0.9 ng/g wet weight and polybrominated biphenyls were not detected (except for a possible analytical interference). There was a significant variation in the samples among plants. Influence from industries and other local sources can therefore be assumed. The correlation pattern indicated contribution from three different types of technical products; composed of either low-brominated PBDEs, decaBDE or TBBPA.

Imaging of the CO Snow Line in a Solar Nebula Analog

Solar Snow Lines Models of the formation of our solar system have suggested that condensation lines, or snow lines—the distance from a star beyond which a gas or a liquid can condense into the solid phase—are favorable locations for planet formation. Taking advantage of the increase of N2H+ abundance in cold regions where CO condenses out of the gas phase, Qi et al. (p. 630, published online 18 July) used the Atacama Large Millimeter/Submillimeter Array to image the CO snow line in the disk around TW Hya, an analog of the solar nebula from which the solar system formed. This disks snow line corresponds to Neptunes orbit in our solar system. Millimeter-wavelength observations locate the carbon monoxide condensation line within the disk around a young planet-forming star. Planets form in the disks around young stars. Their formation efficiency and composition are intimately linked to the protoplanetary disk locations of “snow lines” of abundant volatiles. We present chemical imaging of the carbon monoxide (CO) snow line in the disk around TW Hya, an analog of the solar nebula, using high spatial and spectral resolution Atacama Large Millimeter/Submillimeter Array observations of diazenylium (N2H+), a reactive ion present in large abundance only where CO is frozen out. The N2H+ emission is distributed in a large ring, with an inner radius that matches CO snow line model predictions. The extracted CO snow line radius of ∼30 astronomical units helps to assess models of the formation dynamics of the solar system, when combined with measurements of the bulk composition of planets and comets.

An Old Disk Still Capable of Forming a Planetary System

From the masses of the planets orbiting the Sun, and the abundance of elements relative to hydrogen, it is estimated that when the Solar System formed, the circumstellar disk must have had a minimum mass of around 0.01 solar masses within about 100 astronomical units of the star. (One astronomical unit is the Earth–Sun distance.) The main constituent of the disk, gaseous molecular hydrogen, does not efficiently emit radiation from the disk mass reservoir, and so the most common measure of the disk mass is dust thermal emission and lines of gaseous carbon monoxide. Carbon monoxide emission generally indicates properties of the disk surface, and the conversion from dust emission to gas mass requires knowledge of the grain properties and the gas-to-dust mass ratio, which probably differ from their interstellar values. As a result, mass estimates vary by orders of magnitude, as exemplified by the relatively old (3–10 million years) star TW Hydrae, for which the range is 0.0005–0.06 solar masses. Here we report the detection of the fundamental rotational transition of hydrogen deuteride from the direction of TW Hydrae. Hydrogen deuteride is a good tracer of disk gas because it follows the distribution of molecular hydrogen and its emission is sensitive to the total mass. The detection of hydrogen deuteride, combined with existing observations and detailed models, implies a disk mass of more than 0.05 solar masses, which is enough to form a planetary system like our own.

Photodesorption of CO Ice

At the high densities and low temperatures found in star forming regions, all molecules other than H2 should stick on dust grains on timescales shorter than the cloud lifetimes. Yet these clouds are detected in the millimeter lines of gaseous CO. At these temperatures, thermal desorption is negligible and hence a non-thermal desorption mechanism is necessary to maintain molecules in the gas phase. Here, the first laboratory study of the photodesorption of pure CO ice under ultra high vacuum is presented, which gives a desorption rate of 3 × 10 3 CO molecules per UV (7–10.5 eV) photon at 15 K. This rate is factors of 10 2 -10 5 larger than previously estimated and is comparable to estimates of other non-thermal desorption rates. The experiments constrains the mechanism to a single photon desorption process of ice surface molecules. The measured efficiency of this process shows that the role of CO photodesorption in preventing total removal of molecules in the gas has been underestimated. Subject headings: Molecular data — Molecular processes — ISM: abundances — Physical Data and Processes: astrochemistry — ISM: molecules

RINGED SUBSTRUCTURE AND A GAP AT 1 au IN THE NEAREST PROTOPLANETARY DISK

We present long-baseline Atacama Large Millimeter/submillimeter Array (ALMA) observations of the 870 micron continuum emission from the nearest gas-rich protoplanetary disk, around TW Hya, that trace millimeter-sized particles down to spatial scales as small as 1 AU (20 mas). These data reveal a series of concentric ring-shaped substructures in the form of bright zones and narrow dark annuli (1-6 AU) with modest contrasts (5-30%). We associate these features with concentrations of solids that have had their inward radial drift slowed or stopped, presumably at local gas pressure maxima. No significant non-axisymmetric structures are detected. Some of the observed features occur near temperatures that may be associated with the condensation fronts of major volatile species, but the relatively small brightness contrasts may also be a consequence of magnetized disk evolution (the so-called zonal flows). Other features, particularly a narrow dark annulus located only 1 AU from the star, could indicate interactions between the disk and young planets. These data signal that ordered substructures on ~AU scales can be common, fundamental factors in disk evolution, and that high resolution microwave imaging can help characterize them during the epoch of planet formation.