Deuterium enrichment of ammonia produced by surface N+H/D addition reactions at low temperature

The surface formation of NH3 and its deuterated isotopologues – NH_2D, NHD_2, and ND_3 – is investigated at low temperatures through the simultaneous addition of hydrogen and deuterium atoms to nitrogen atoms in CO-rich interstellar ice analogues. The formation of all four ammonia isotopologues is only observed up to 15 K, and drops below the detection limit for higher temperatures. Differences between hydrogenation and deuteration yields result in a clear deviation from a statistical distribution in favour of deuterium enriched species. The data analysis suggests that this is due to a higher sticking probability of D atoms to the cold surface, a property that may generally apply to molecules that are formed in low temperature surface reactions. The results found here are used to interpret ammonia–deuterium fractionation as observed in pre-protostellar cores

Solid CO_2 in low-mass young stellar objects: Comparison between Spitzer and laboratory spectra

Context. Solid interstellar CO_2 is an abundant component of ice dust mantles. Its ubiquity towards quiescent molecular clouds, as well as protostellar envelopes, has recently been confirmed by the IRS (InfraRed Spectrograph) aboard the Spitzer Space Telescope. Although it has been shown that CO_2 cannot be efficiently formed in the gas phase, the CO_2 surface formation pathway is still unclear. To date several CO_2 surface formation mechanisms induced by energetic (e.g., UV photolysis and cosmic ray irradiation) and non-energetic (e.g., cold atom addition) input have been proposed. Aims. Our aim is to investigate the contribution of cosmic ray irradiation to the formation of CO_2 in different regions of the interstellar medium (ISM). To achieve this goal we compared quantitatively laboratory data with the CO_2 bending mode band profile observed towards several young stellar objects (YSOs) and a field star by the Spitzer Space Telescope. Methods. All the experiments presented here were performed at the Laboratory for Experimental Astrophysics in Catania (Italy). The interstellar relevant samples were all irradiated with fast ions (30−200 keV) and subsequently annealed in a stainless steel high vacuum chamber (P < 10^(-7) mbar). Chemical and structural modifications of the ice samples were monitored by means of infrared spectroscopy. Laboratory spectra were then used to fit some thirty observational spectra. Results. A qualitative analysis shows that a good fit can be obtained with a minimum of two components. The choice of the laboratory components is based on the chemical-physical condition of each source. A quantitative analysis of the sources with known visual extinction (A_V) and methanol abundances highlights that the solid carbon dioxide can be efficiently and abundantly formed after ion irradiation of interstellar ices in all the selected YSOs in a time compatible with cloud lifetimes (3 × 10^7 years). Only in the case of field stars can the expected CO_2 column density formed upon energetic input not explain the observed abundances. This result, to be confirmed along the line of sight to different quiescent clouds, gives an indirect indication that CO_2 can also be formed in an early cloud stage through surface reactions induced by non-energetic mechanisms. In a later stage, when ices are exposed to higher UV and cosmic ray doses, the CO_2 total abundance is strongly affected by energetic formation mechanisms. Conclusions. Our results indicate that energetic processing of icy grain mantles significantly contribute to the formation of solid phase interstellar CO_2

Water formation at low temperatures by surface O2 hydrogenation I: characterization of ice penetration

Water is the main component of interstellar ice mantles, is abundant in the solar system and is a crucial ingredient for life. The formation of this molecule in the interstellar medium cannot be explained by gas-phase chemistry only and its surface hydrogenation formation routes at low temperatures (O, O2, O3 channels) are still unclear and most likely incomplete. In a previous paper we discussed an unexpected zeroth-order H2O production behavior in O2 ice hydrogenation experiments compared to the first-order H2CO and CH3OH production behavior found in former studies on hydrogenation of CO ice. In this paper we experimentally investigate in detail how the structure of O2 ice leads to this rare behavior in reaction order and production yield. In our experiments H atoms are added to a thick O2 ice under fully controlled conditions, while the changes are followed by means of reflection absorption infrared spectroscopy (RAIRS). The H-atom penetration mechanism is systematically studied by varying the temperature, thickness and structure of the O2 ice. We conclude that the competition between reaction and diffusion of the H atoms into the O2 ice explains the unexpected H2O and H2O2 formation behavior. In addition, we show that the proposed O2 hydrogenation scheme is incomplete, suggesting that additional surface reactions should be considered. Indeed, the detection of newly formed O3 in the ice upon H-atom exposure proves that the O2 channel is not an isolated route. Furthermore, the addition of H2 molecules is found not to have a measurable effect on the O2 reaction channel.Comment: 1 page, 1 figur

Relevance of the H_2 + O reaction pathway for the surface formation of interstellar water. Combined experimental and modeling study

The formation of interstellar water is commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10–20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H_2 + O has been proposed to contribute significantly to the formation of water as well. However, gas-phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature-programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H_2 and O. These reactants were brought together in a matrix of CO_2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The water detected with the quadrupole mass spectrometer upon TPD was found to originate mainly from contamination in the chamber itself. However, if water is produced in small quantities on the surface through H_2 + O, this can only be explained by a combined classical and tunneled reaction mechanism. An absolutely conservative upper limit for the reaction rate was derived with a microscopic kinetic Monte Carlo model that converts the upper limit into the highest possible reaction rate. Incorporating this rate into simulation runs for astrochemically relevant parameters shows that the upper limit to the contribution of the reaction H_2 + O in OH, and hence water formation, is 11% in dense interstellar clouds. Our combined experimental and theoretical results indicate, however, that this contribution is most likely much lower

Water formation at low temperatures by surface O2 hydrogenation II: the reaction network

Water is abundantly present in the Universe. It is the main component of interstellar ice mantles and a key ingredient for life. Water in space is mainly formed through surface reactions. Three formation routes have been proposed in the past: hydrogenation of surface O, O2, and O3. In a previous paper [Ioppolo et al., Astrophys. J., 2008, 686, 1474] we discussed an unexpected non-standard zeroth-order H2O2 production behaviour in O2 hydrogenation experiments, which suggests that the proposed reaction network is not complete, and that the reaction channels are probably more interconnected than previously thought. In this paper we aim to derive the full reaction scheme for O2 surface hydrogenation and to constrain the rates of the individual reactions. This is achieved through simultaneous H-atom and O2 deposition under ultra-high vacuum conditions for astronomically relevant temperatures. Different H/O2 ratios are used to trace different stages in the hydrogenation network. The chemical changes in the forming ice are followed by means of reflection absorption infrared spectroscopy (RAIRS). New reaction paths are revealed as compared to previous experiments. Several reaction steps prove to be much more efficient (H + O2) or less efficient (H + OH and H2 + OH) than originally thought. These are the main conclusions of this work and the extended network concluded here will have profound implications for models that describe the formation of water in space.Comment: 1 page, 1 figur

SURFRESIDE2: An ultrahigh vacuum system for the investigation of surface reaction routes of interstellar interest

A new ultrahigh vacuum experiment is described to study atom and radical addition reactions in interstellar ice analogues for astronomically relevant temperatures. The new setup – SURFace REaction SImulation DEvice (SURFRESIDE2) – allows a systematic investigation of solid state pathways resulting in the formation of molecules of astrophysical interest. The implementation of a double beam line makes it possible to expose deposited ice molecules to different atoms and/or radicals sequentially or at the same time. Special efforts are made to perform experiments under fully controlled laboratory conditions, including precise atom flux determinations, in order to characterize reaction channels quantitatively. In this way, we can compare and combine different surface reaction channels with the aim to unravel the solid state processes at play in space. Results are constrained in situ by means of a Fourier transform infrared spectrometer and a quadrupole mass spectrometer using reflection absorption infrared spectroscopy and temperature programmed desorption, respectively. The performance of the new setup is demonstrated on the example of carbon dioxide formation by comparing the efficiency through two different solid state channels (CO + OH → CO_2 + H and CO + O → CO_2) for which different addition products are needed. The potential of SURFRESIDE2 to study complex molecule formation, including nitrogen containing (prebiotic) compounds, is discussed

Water formation on bare grains: When the chemistry on dust impacts interstellar gas

Context. Water together with O2 are important gas phase ingredients to cool dense gas in order to form stars. On dust grains, H2 O is an important constituent of the icy mantle in which a complex chemistry is taking place, as revealed by hot core observations. The formation of water can occur on dust grain surfaces, and can impact gas phase composition. Aims. The formation of molecules such as OH, H2 O, HO2, H2 O2, as well as their deuterated forms and O2 and O3 is studied in order to assess how the chemistry varies in different astrophysical environments, and how the gas phase is affected by grain surface chemistry. Methods. We use Monte Carlo simulations to follow the formation of molecules on bare grains as well as the fraction of molecules released into the gas phase. We consider a surface reaction network, based on gas phase reactions, as well as UV photo-dissociation of the chemical species. Results. We show that grain surface chemistry has a strong impact on gas phase chemistry, and that this chemistry is very different for different dust grain temperatures. Low temperatures favor hydrogenation, while higher temperatures favor oxygenation. Also, UV photons dissociate the molecules on the surface, that can reform subsequently. The formation-destruction cycle increases the amount of species released into the gas phase. We also determine the time scales to form ices in diffuse and dense clouds, and show that ices are formed only in shielded environments, as supported by observations.Comment: Accepted in A&

Post-treatment follow-up study of abdominal cystic echinococcosis in Tibetan communities of northwest Sichuan Province, China

Background: Human cystic echinococcosis (CE), caused by the larval stage of Echinococcus granulosus, with the liver as the most frequently affected organ, is known to be highly endemic in Tibetan communities of northwest Sichuan Province. Antiparasitic treatment with albendazole remains the primary choice for the great majority of patients in this resource-poor remote area, though surgery is the most common approach for CE therapy that has the potential to remove cysts and lead to complete cure. The current prospective study aimed to assess the effectiveness of community based use of cyclic albendazole treatment in Tibetan CE cases, and concurrently monitor the changes of serum specific antibody levels during treatment. Methodology/Principal Findings: Ultrasonography was applied for diagnosis and follow-up of CE cases after cyclic albendazole treatment in Tibetan communities of Sichuan Province during 2006 to 2008, and serum specific IgG antibody levels against Echinococcus granulosus recombinant antigen B in ELISA was concurrently monitored in these cases. A total of 196 CE cases were identified by ultrasound, of which 37 (18.9%) showed evidence of spontaneous healing/involution of hepatic cyst(s) with CE4 or CE5 presentations. Of 49 enrolled CE cases for treatment follow-up, 32.7% (16) were considered to be cured based on B-ultrasound after 6 months to 30 months regular albendazole treatment, 49.0% (24) were improved, 14.3% (7) remained unchanged, and 4.1% (2) became aggravated. In general, patients with CE2 type cysts (daughter cysts present) needed a longer treatment course for cure (26.4 months), compared to cases with CE1 (univesicular cysts) (20.4 months) or CE3 type (detached cyst membrane or partial degeneration of daughter cysts) (9 months). In addition, the curative duration was longer in patients with large (.10 cm) cysts (22.3 months), compared to cases with medium (5– 10 cm) cysts (17.3 months) or patients with small (,5 cm) cysts (6 months). At diagnosis, seven (53.8%) of 13 cases with CE1 type cysts without any previous intervention showed negative specific IgG antibody response to E. granulosus recombinant antigen B (rAgB). However, following 3 months to 18 months albendazole therapy, six of these 7 initially seronegative CE1 cases sero-converted to be specific IgG antibody positive, and concurrently ultrasound scan showed that cysts changed to CE3a from CE1 type in all the six CE cases. Two major profiles of serum specific IgG antibody dynamics during albendazole treatment were apparent in CE cases: (i) presenting as initial elevation followed by subsequent decline, or (ii) a persistent decline. Despite a decline, however, specific antibody levels remained positive in most improved or cured CE cases. Conclusions: This was the first attempt to follow up community-screened cystic echinococcosis patients after albendazole therapy using ultrasonography and serology in an endemic Tibetan region. Cyclic albendazole treatment proved to be effective in the great majority of CE cases in this resource-poor area, but periodic abdominal ultrasound examination was necessary to guide appropriate treatment. Oral albendazole for over 18 months was more likely to result in CE cure. Poor drug compliance resulted in less good outcomes. Serology with recombinant antigen B could provide additional limited information about the effectiveness of albendazole in CE cases. Post-treatment positive specific IgG antibody seroconversion, in initially seronegative, CE1 patients was considered a good indication for positive therapeutic efficacy of albendazole

Ice chemistry in embedded young stellar objects in the Large Magellanic Cloud

We present spectroscopic observations of a sample of 15 embedded young stellar objects (YSOs) in the Large Magellanic Cloud (LMC). These observations were obtained with the Spitzer Infrared Spectrograph (IRS) as part of the SAGE-Spec Legacy program. We analyze the two prominent ice bands in the IRS spectral range: the bending mode of CO_2 ice at 15.2 micron and the ice band between 5 and 7 micron that includes contributions from the bending mode of water ice at 6 micron amongst other ice species. The 5-7 micron band is difficult to identify in our LMC sample due to the conspicuous presence of PAH emission superimposed onto the ice spectra. We identify water ice in the spectra of two sources; the spectrum of one of those sources also exhibits the 6.8 micron ice feature attributed to ammonium and methanol. We model the CO_2 band in detail, using the combination of laboratory ice profiles available in the literature. We find that a significant fraction (> 50%) of CO_2 ice is locked in a water-rich component, consistent with what is observed for Galactic sources. The majority of the sources in the LMC also require a pure-CO_2 contribution to the ice profile, evidence of thermal processing. There is a suggestion that CO_2 production might be enhanced in the LMC, but the size of the available sample precludes firmer conclusions. We place our results in the context of the star formation environment in the LMC.Comment: Minor corrections to Table 2. Accepted for publication in ApJ, 66 pages, 9 figures (some in color), 4 table