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

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

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

Bombardment of CO ice by cosmic rays: I. Experimental insights into the microphysics of molecule destruction and sputtering

We present a dedicated experimental study of microscopic mechanisms controlling radiolysis and sputtering of astrophysical ices due to their bombardment by cosmic ray ions. Such ions are slowed down due to inelastic collisions with bound electrons, resulting in ionization and excitation of ice molecules. In experiments on CO ice irradiation, we show that the relative contribution of these two mechanisms of energy loss to molecule destruction and sputtering can be probed by selecting ion energies near the peak of the electronic stopping power. We have observed a significant asymmetry, both in the destruction cross section and the sputtering yield, for pairs of ion energies corresponding to same values of the stopping power on either side of the peak. This implies that the stopping power does not solely control these processes, as usually assumed in the literature. Our results suggest that electronic excitations represent a significantly more efficient channel for radiolysis and, possibly, also for sputtering of CO ice. We also show that the charge state of incident ions as well as the rate for CO$^+$ production in the ice have negligible effect on these processes.Comment: Accepted for publication in Ap

Laboratory evidence for efficient water formation in interstellar ices

Even though water is the main constituent in interstellar icy mantles, its chemical origin is not well understood. Three different formation routes have been proposed following hydrogenation of O, O2, or O3, but experimental evidence is largely lacking. We present a solid state astrochemical laboratory study in which one of these routes is tested. For this purpose O2 ice is bombarded by H- or D-atoms under ultra high vacuum conditions at astronomically relevant temperatures ranging from 12 to 28 K. The use of reflection absorption infrared spectroscopy (RAIRS) permits derivation of reaction rates and shows efficient formation of H2O (D2O) with a rate that is surprisingly independent of temperature. This formation route converts O2 into H2O via H2O2 and is found to be orders of magnitude more efficient than previously assumed. It should therefore be considered as an important channel for interstellar water ice formation as illustrated by astrochemical model calculations.Comment: 15 pages, 4 figures. ApJ, in pres

Grain Surface Models and Data for Astrochemistry

AbstractThe cross-disciplinary field of astrochemistry exists to understand the formation, destruction, and survival of molecules in astrophysical environments. Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. A broad consensus has been reached in the astrochemistry community on how to suitably treat gas-phase processes in models, and also on how to present the necessary reaction data in databases; however, no such consensus has yet been reached for grain-surface processes. A team of ∼25 experts covering observational, laboratory and theoretical (astro)chemistry met in summer of 2014 at the Lorentz Center in Leiden with the aim to provide solutions for this problem and to review the current state-of-the-art of grain surface models, both in terms of technical implementation into models as well as the most up-to-date information available from experiments and chemical computations. This review builds on the results of this workshop and gives an outlook for future directions

Recovery and genotyping ancient Sicilian monumental olive trees

The long-lived and evergreen olive tree dominates the Mediterranean landscape, representing an agroecological and cultural symbol and a genetic heritage of inestimable value. Sicily, for historical, geographical, and cultural reasons, has a very rich and distinctive olive germplasm. In this work, a large survey was conducted to discover, collect, and characterize the genetic diversity of centennial monumental olive trees from historical sites, such as the Greek Temple Valley (Agrigento), ancient gardens, or farmland present in the western part of the island. Trees were chosen based on their height, trunk, stump size, and presumed age; particularly, only olive trees with an age estimated at more than 400 years old were taken into consideration. For the morphological characterization, the leaf, fruit, and endocarp traits were analyzed. For the molecular characterization, 11 polymorphic microsatellite markers largely used for fingerprinting analysis were used. Reference cultivars were included in the analysis for comparison. Nuclear DNA was extracted from different parts of the plant (young leaves of shoots taken from the canopy and young leaves taken from suckers, which arose from the basal part of the tree) to check if the trees were grafted and to explore their diversity. Most of the monumental trees have been grafted at least one time during their long life, and some genotypes showed unique genetic profiles combined with peculiar phenotypic traits. Suckers (rootstock of the trees) showed a strict genetic relationship with an ancient monumental oleaster tree, also included in the study. “Patriarch” (original mother plants) trees of local cultivars were also identified. This research revealed a high level of the still unexplored genetic diversity of the Sicilian olive germplasm and highlighted its importance as a gene reservoir, which could support new breeding programs for the evaluation and possible selection of traits linked to putative resilience to abiotic and biotic stresses (particularly Xylella fastidiosa subsp. pauca ST53 or soil- borne diseases or insects). The results will be useful for improving the conservation process, enriching existing collections of olive genetic resources, and supporting on-farm conservation projects

Ozone Production in Electron Irradiated CO2:O2 Ices

The detection of ozone (O3) in the surface ices of Ganymede, Jupiter's largest moon, and of the Saturnian moons Rhea and Dione, has motivated several studies on the route of formation of this species. Previous studies have successfully quantified trends in the production of O3 as a result of the irradiation of pure molecular ices using ultraviolet photons and charged particles (i.e., ions and electrons), such as the abundances of O3 formed after irradiation at different temperatures or using different charged particles. In this study, we extend such results by quantifying the abundance of O3 as a result of the 1 keV electron irradiation of a series of 14 stoichiometrically distinct CO2:O2 astrophysical ice analogues at 20 K. By using mid-infrared spectroscopy as our primary analytical tool, we have also been able to perform a spectral analysis of the asymmetric stretching mode of solid O3 and the variation in its observed shape and profile among the investigated ice mixtures. Our results are important in the context of better understanding the surface composition and chemistry of icy outer Solar System objects, and may thus be of use to future interplanetary space missions such as the ESA Jupiter Icy Moons Explorer and the NASA Europa Clipper missions, as well as the recently launched NASA James Webb Space Telescope