Isotopic fractionation of carbon, deuterium and nitrogen : a full chemical study

Context. The increased sensitivity and high spectral resolution of millimeter telescopes allow the detection of an increasing number of isotopically substituted molecules in the interstellar medium. The 14N/ 15N ratio is difficult to measure directly for carbon containing molecules. Aims. We want to check the underlying hypothesis that the 13C/ 12C ratio of nitriles and isonitriles is equal to the elemental value via a chemical time dependent gas phase chemical model. Methods. We have built a chemical network containing D, 13C and 15N molecular species after a careful check of the possible fractionation reactions at work in the gas phase. Results. Model results obtained for 2 different physical conditions corresponding respectively to a moderately dense cloud in an early evolutionary stage and a dense depleted pre-stellar core tend to show that ammonia and its singly deuterated form are somewhat enriched in 15N, in agreement with observations. The 14N/ 15N ratio in N2H+ is found to be close to the elemental value, in contrast to previous models which obtain a significant enrichment, as we found that the fractionation reaction between 15N and N2H+ has a barrier in the entrance channel. The large values of the N2H+/15NNH+ and N2H+/ N15NH+ ratios derived in L1544 cannot be reproduced in our model. Finally we find that nitriles and isonitriles are in fact significantly depleted in 13C, questioning previous interpretations of observed C15N, HC15N and H15NC abundances from 13C containing isotopologues.Comment: 21 pages, 9 figures in the text, 3 Figures in the appendices. 7 tables in the text, 4 tables in the appendices. Accepted for publication by Astronomy Astrophysic

Rate constants and Arrhenius parameters for the reactions of OH radicals and Cl atoms with CF3CH2OCHF2, CF3CHClOCHF2 and CF3CH2OCClF2, using the discharge-flow/resonance fluorescence method

Rate constants have been determined for the reactions of OH radicals and Cl atoms with the three partially halogenated methyl-ethyl ethers, CF$_3$CH$_2$OCHF$_2$, CF$_3$CHClOCHF$_2$ and CF$_3$CH$_2$OCClF$_2$, using discharge-flow techniques to generate the OH radicals and the Cl atoms and resonance fluorescence to observe changes in their relative concentrations in the presence of added ether. For each combination of radical and ether, experiments were carried out at three temperatures between 292 and 410 K, yielding the following Arrhenius expressions for the rate constants within this range of temperature: OH + CF$_3$CH$_2$OCHF$_2$: $k$ = (2.0$\pm$0.8) $\times$ 10$^{-11}$ exp( – 2110 $\pm$ 150 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CHClOCHF$_2$: $k$ = (4.5 $\pm$ 1.3) $\times$ 10$^{-13}$ exp( – 940 $\pm$ 100 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ OH + CF$_3$CH$_2$OCClF$_2$: $k$ = (1.6 $\pm$ 0.6) $\times$ 10$^{-12}$ exp( – 1100 $\pm$ 125 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCHF$_2$: $k$ = (6.1 $\pm$ 1.4) $\times$ 10$^{-12}$ exp( – 1830 $\pm$ 90 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CHClOCHF$_2$: $k$ = (7.8 $\pm$ 2.6) $\times$ 10$^{-11}$ exp( – 2980 $\pm$ 130 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ Cl + CF$_3$CH$_2$OCClF$_2$: $k$ = (2.2 $\pm$ 0.2) $\times$ 10$^{-11}$ exp( – 2700 $\pm$ 40 K / T) cm$^3$ molecule$^{-1}$ s$^{-1}$ The results are compared with those obtained previously for the same and related reactions of OH radicals and Cl atoms, and the atmospheric implications of the results are considered briefly

A Kinetic Study of the Gas-Phase O( 1 D) + CH3OH and O( 1 D) + CH3CN Reactions. Low Temperature Rate Constants and Atomic Hydrogen Product Yields

Atomic oxygen in its first excited singlet state, O(1 D), is an important species in the photochemistry of several planetary atmospheres and has been predicted to be a potentially important reactive species on interstellar ices. Here, we report the results of a kinetic study of the reactions of O(1 D) with methanol, CH3OH, and acetonitrile, CH3CN, over the 50-296 K temperature range. A continuous supersonic flow reactor was used to attain these low temperatures coupled with pulsed laser photolysis and pulsed laser induced fluorescence to generate and monitor O(1 D) atoms respectively. Secondary experiments examining the atomic hydrogen product channels of these reactions were also performed, through laser induced fluorescence measurements of H(2 S) atom formation. On the kinetics side, the rate constants for these reactions were seen to be large (> 2 x 10-10 cm 3 s-1) and consistent with barrierless reactions, although they display contrasting dependences as a function of temperature. On the product formation side, both reactions are seen to yield non-negligible quantities of atomic hydrogen. For the O(1 D) + CH3OH reaction, the derived yields are in good agreement with the conclusions of previous experimental and theoretical work. For the O(1 D) + CH3CN reaction, whose H-atom formation channels had not previously been investigated, electronic structure calculations of several new product formation channels were performed to explain the observed H-atom yields. These calculations demonstrate the barrierless and exothermic nature of the relevant exit channels, confirming that atomic hydrogen is also an important product of the O(1 D) + CH3CN reaction

Discrimination of hot versus cold avalanche deposits: Implications for hazard assessment at Mount Meager, B.C.

The surficial deposits surrounding the Mount Meager volcanic complex include numerous avalanche deposits. These deposits share many attributes: (a) they are nearly monolithologic and comprise mainly intermediate volcanic rock clasts, (b) they lack internal structure, and (c) they are very poorly sorted. Despite these similarities, the avalanche deposits represent two distinct processes. Mass wasting of the Mount Meager volcanic edifice has produced cold rock avalanche deposits, whereas gravitational collapse of active lava domes and flows has produced hot block and ash avalanche deposits. The ability to discriminate between these "hot" and "cold" avalanche deposits is a critical component in the assessment of hazards in volcanic terranes. Hot block and ash avalanche deposits can be distinguished by the presence of radially-oriented joints, breadcrust textures, and incipient welding, which are features indicative of high emplacement temperatures. Conversely, rock avalanche deposits resulting from mass wasting events may be distinguished by the presence of clasts that preserve pre-depositional weathering and jointing surfaces. Volcanic avalanches are mechanically similar to rock avalanches but pose a greater hazard due to high temperatures, increased fluidization from degassing and the potential to decouple highly mobile elutriated ash clouds. The increasing use of hazardous regions such as the Lillooet River valley requires more reliable risk assessment in order to minimize losses from future hazardous events

The Nuclear Activity of the Galaxies in the Hickson Compact Groups

In order to investigate the nuclear activity of galaxies residing in compact groups of galaxies, we present results of our optical spectroscopic program made at Okayama Astrophysical Observatory. We have performed optical spectroscopy of 69 galaxies which belong to 31 Hickson Compact Groups (HCGs) of Galaxies. Among them, three galaxies have discordant redshifts. Further, spectral quality is too poor to classify other three galaxies. Therefore, we describe our results for the remaining 63 galaxies. Our main results are summarized below. (1) We have found in our sample; 28 AGN, 16 HII nuclei, and 19 normal galaxies which show no emission line. We used this HCG sample for statistical analyses. (2) Comparing the frequency distributions of activity types between the HCGs and the field galaxies whose data are taken from Ho, Filippenko, & Sargent (382 field galaxies), we find that the frequency of HII nuclei in the HCGs is significantly less than that in the field. However, this difference may be due to selection bias that our HCG sample contains more early-type galaxies than the field, because it is known that HII nuclei are rarer in early-type galaxies than in later ones. (3) Applying correction this morphological bias to the HCG sample, we find that there is no statistically significant difference in the frequency of occurrence of emission-line galaxies between the HCGs and the field. This implies that the dense galaxy environment in the HCGs does not affect triggering both the AGN activity and the nuclear starburst. We discuss some implications on the nuclear activity in the HCG galaxies.Comment: 33 pages (3 aasms4 LaTeX files), 5 figures (5 Postscript files: excluded Figure 1), Accepted for publication in The Astronomical Journa

Infrared emission from compact groups of galaxies

A search of the IRAS Point Source Catalog, Version 2 has revealed infrared sources within 1 arcmin of the optical centers of 54 gal axies in Hickson's catalog of compact groups of galaxies. The 60μm luminosity function for these galaxies has the same shape as the luminosity function of the IRAS bright galaxy sample. The space density of IRAS galaxies in compact groups is 60 times smaller than the space density of IRAS bright galaxies, indicating that of order 1% of all bright IRAS galaxies are in compact groups. The infrared emission from these galaxies is compared with the emission from samples of isolated galaxies by Keel et aI. and cluster galaxies studied by Bicay and Giovanelli . The fractional distribution of the ratio of far-infrared to optical luminosity of compact group galaxies is significantly larger than that of the isolated galaxies and comparable to that of the cluster galaxies. These results indicate that infrared emission is enhanced in the compact group galaxies, probably because of interactions. We also report an upper limit to the 2-10 keV X-ray flux of compact groups in our sample of 3χ 1041h-2 ergs-1, from the HEAO I A-2 experiment

A Dynamical Study of Galaxies in the Hickson Compact Groups

In order to investigate dynamical properties of spiral galaxies in the Hickson compact groups (HCGs), we present rotation curves of 30 galaxies in 20 HCGs. We found as follows. 1) There is not significant relation between dynamical peculiarity and morphological peculiarity in HCG spirals. 2) There is no significant relation between the dynamical properties and the frequency distribution of nuclear activities in HCG spirals. 3) There are no significant correlations between the dynamical properties of HCG spirals and any group properties (i.e., the size, the velocity dispersion, the galaxy number density, and the crossing time). 4) Asymmetric and peculiar rotation curves are more frequently seen in the HCG spirals than in field spirals and in cluster ones. However, this tendency is more obviously seen in late-type HCG spirals. These results suggest that the dynamical properties of HCG spirals do not strongly correlate with the morphology, the nuclear activity, and the group properties. Our results also suggest that more frequent galaxy collisions occur in the HCGs than in the field and in the clusters.Comment: 24 pages test (aasms4 LaTeX), 50 page tables (aasms4 LaTeX), and 16 Postscript figures, Accepted for The Astronomical Journa

Dietary supplement use and nosebleeds in hereditary haemorrhagic telangiectasia - an observational study.

Understanding potential provocations of haemorrhage is important in a range of clinical settings, and particularly for people with abnormal vasculature. Patients with hereditary haemorrhagic telangiectasia (HHT) can report haemorrhage from nasal telangiectasia in real time, and suggested dietary factors may precipitate nosebleeds. To examine further, nosebleed severity, dietary supplement use, and blood indices were evaluated in an unselected group of 50 HHT patients recruited from a specialist UK service. Using the validated Epistaxis Severity Score, nosebleed severity ranged from 0 to 9.1 out of 10 (median 3.9). Using a Food Frequency Questionnaire, 24/50 (48%) participants reported use of dietary supplements in the previous year. A third (18/50; 36%) had used self prescribed, non-iron containing dietary supplements, ingesting between 1 and 3 different supplements each day. Eight (16%) used fish oils. Despite having more severe epistaxis (p = 0.012), the 12 iron supplement users had higher serum iron concentrations, and were able to maintain their red blood cell indices. In contrast, there was no evident benefit for the participants using non iron supplements. Furthermore, platelet counts and serum fibrinogen tended to be lower in fish oil/supplement users, and one fish oil user demonstrated reduced in vitro platelet aggregation. In conclusion, in this small study, a third of HHT patients used non-iron dietary supplements, and one in six ingested fish oils, unaware of their known anti-platelet activity. The scale of use, and potential of these "natural health supplements" to exacerbate nosebleeds has not been appreciated previously in HHT

How Can eHealth Meet the Hearing and Communication Needs of Adults With Hearing Impairment and their Significant Others? A Group Concept Mapping Study

Objectives: To seek the perspectives of key stakeholders regarding: (1) how eHealth could help meet the hearing and communication needs of adults with hearing impairment and their significant others; and (2) how helpful each aspect of eHealth would be to key stakeholders personally. / Design: Group concept mapping, a mixed-methods participatory research method, was used to seek the perspectives of key stakeholders: adults with hearing impairment (n = 39), significant others (n = 28), and hearing care professionals (n = 56). All participants completed a short online survey before completing one or more of the following activities: brainstorming, sorting, and rating. Brainstorming required participants to generate ideas in response to the focus prompt, “One way I would like to use information and communication technologies to address the hearing and communication needs of adults with hearing loss and their family and friends is to….” The sorting task required participants to sort all statements into groups that made sense to them. Finally, the rating task required participants to rate each of the statements according to “How helpful would this idea be to you?” using a 5-point Likert scale. Hierarchical cluster analysis was applied to the “sorting” data to develop a cluster map using the Concept Systems software. The “rating” data were subsequently analyzed at a cluster level and an individual-item level using descriptive statistics. Differences in cluster ratings between stakeholder groups were examined using Kruskal-Wallis tests. / Results: Overall, 123 statements were generated by participants in response to the focus prompt and were included in subsequent analyses. Based on the “sorting” data and hierarchical cluster analysis, a seven-cluster map was deemed to be the best representation of the data. Three key themes emerged from the data, including using eHealth to (1) Educate and Involve Others; (2) Support Aural Rehabilitation; and (3) Educate About and Demonstrate the Impacts of Hearing Impairment and Benefits of Hearing Rehabilitation. Overall median rating scores for each cluster ranged from 3.97 (educate and involve significant others) to 3.44 (empower adults with hearing impairment to manage their hearing impairment from home). / Conclusions: These research findings demonstrate the broad range of clinical applications of eHealth that have the capacity to support the implementation of patient- and family-centered hearing care, with self-directed educational tools and resources typically being rated as most helpful. Therefore, eHealth appears to be a viable option for enabling a more biopsychosocial approach to hearing healthcare and educating and involving significant others in the hearing rehabilitation process without adding more pressure on clinical time. More research is needed to inform the subsequent development of eHealth interventions, and it is recommended that health behavior change theory be adhered to for such interventions