The Sensitivity of Gas-Phase Chemical Models of Interstellar Clouds to C and O Elemental Abundances and to a New Formation Mechanism for Ammonia

The effects of variations in the gas-phase carbon-to-oxygen elemental abundance ratio (0.42 ≤ C/O ≤ 1.2) and the absolute gas-phase carbon and oxygen elemental abundances on calculated molecular concentrations have been studied for three gas-phase chemical models of dense interstellar clouds. Both the C and O elemental abundances were varied from their "low metal" values, in which C/O = 0.42. The results were compared with observations of the dark interstellar clouds TMC-1 and L134N, the latter being chosen because TMC-1, with its singularly rich component of large hydrocarbons and cyanopolyynes, may not represent dense cores universally. In general, variations in the gas-phase C and O elemental abundances have a large and time-dependent effect on calculated molecular concentrations for all three models. For the "new standard" model, which does not contain many rapid neutral-neutral reactions, excellent "early-time" agreement with TMC-1 occurs for a variety of C/O ratios obtained by depleting the low metal O abundance, but the time of best agreement tends to increase with increasing C/O ratio. At these early times, approx 80% of the calculated abundances are within an order of magnitude of the observed values. Agreement at this level also occurs at steady state if the C and O abundances are first depleted by a factor of 5 and then O is additionally depleted so that C/O ≥ 0.80. In general, a factor of 5 depletion of both C and O increases the production efficiency of large molecules. When the new standard model is applied to L134N, the early-time agreement is not as good as for TMC-1 unless both C and O are first depleted by factors of 5 from their low metal values and the C/O ratio is then maintained at a value less than 0.80. Under these conditions, the steady state results are only slightly worse. The other two models, containing fast neutral-neutral reactions, have their best agreement with TMC-1 when C/O ≥ 1, although the level of agreement is typically worse than with the new standard model, and factor of 5 depletions have little effect. For L134N, on the other hand, the early-time agreement with these latter two models for a wide range of C/O values is almost as good as with the new standard model if factor of 5 depletions in C and O are utilized and is actually superior for most cases when C/O ≥ 1. In general, the negative conclusions concerning models with rapid neutral-neutral reactions may therefore be overly harsh. When the newly studied rapid reaction H+_3+N→NH+_2 + H is included in our model calculations, the abundances of some N-containing species are in better agreement with observed values, but this effect decreases as C/O is increased

Superconducting BSCCO Ceramics as Additive to the Zinc Electrode Mass in the Rechargeable Nickel-Zinc Batteries

The electronic conductivity of the main component of the zinc electrode in the rechargeable zinc-nickel battery – ZnO,  is rather poor and this is the main reason for the electrochemical heterogeneity of the anode mass and the loss of active surface area during charge/discharge cycling with a corresponding negative effect on the electrode characteristics In the present work, the possibility of application of superconductive cuprate Bi-Pb-Sr-Ca-Cu-O (BSCCO) ceramic as a multifunctional conductive additive to the zinc electrode mass is studied. Powder samples of the BSCCO ceramic Bi1,7Pb0,3Sr2Ca2Cu3Ox are produced by two-stage solid-state synthesis and they are physicochemically characterized. The XRD patterns and SEM observation reveal a well crystallized single phase of superconducting 2212 BSCCO system with average crystallite size 5-10 µm. The chemical stability of BSCCO ceramics in highly alkaline medium of the Ni-Zn battery is confirmed by structural and morphological analysis (XRD, SEM and EDX) of the samples before and after prolong exposure (96 h) to 7M KOH. The electrochemical tests are carried out by a specially designed prismatic alkaline Ni-Zn battery cell with conventional sintered type nickel electrodes and pasted zinc electrode with active electrode mass based on ZnO (88 wt.%) and addition of BSCCO powder or acetylene black as conductive additives. The study show that the zinc electrode with BSCCO superconducting ceramic additive exhibits very good cycleability, remarkable capacity stability and much higher discharge capacity at prolong charge/discharge cycling in comparison to the  zinc electrode with the “classic” carbon conductive additive. It is suggested that the addition of BSCCO ceramics improves not only conductivity of the electrode mass and reduces the gas evolution but also stabilizes porosity structure. The results obtained prove the possibility of application of superconducting BSCCO ceramics as a multifunctional additive to the active mass of the zinc electrodes for alkaline battery systems

On the Influence of Uncertainties in Chemical Reaction Rates on Results of the Astrochemical Modelling

With the chemical reaction rate database UMIST95 (Millar et al. 1997) we analyze how uncertainties in rate constants of gas-phase chemical reactions influence the modelling of molecular abundances in the interstellar medium. Random variations are introduced into the rate constants to estimate the scatter in theoretical abundances. Calculations are performed for dark and translucent molecular clouds where gas phase chemistry is adequate. Similar approach was used by Pineau des Forets & Roueff (2000) for the study of chemical bistability. All the species are divided into 6 sensitivity groups according to the value of the scatter in their model abundances computed with varied rate constants. It is shown that the distribution of species within these groups depends on the number of atoms in a molecule and on the adopted physical conditions. The simple method is suggested which allows to single out reactions that are most important for the evolution of a given species.Comment: 4 pages. To appear in the proceedings of the 4th Cologne-Bonn Zermatt Symposiu

Isotopic abundances of carbon and nitrogen in Jupiter-family and Oort Cloud comets

The 12C14N/12C15N and 12C14N/13C14N isotopic ratios are determined for the first time in a Jupiter-family comet, 88P/1981 Q1 Howell, and in the chemically peculiar Oort Cloud comet C/1999 S4 (LINEAR). By comparing these measurements to previous ones derived for six other Oort Cloud comets (including one of Halley-type), we find that both the carbon and nitrogen isotopic ratios are constant within the uncertainties. The mean values are 12C/13C ~ 90 and 14N/15N \~ 145 for the eight comets. These results strengthen the view that CN radicals originate from refractory organics formed in the protosolar molecular cloud and subsequently incorporated in comets.Comment: Accepted for publication in A&A letter

A low fraction of nitrogen in molecular form in a dark cloud

Nitrogen is the fifth most abundant element in the Universe. In the interstellar medium, it has been thought to be mostly molecular (N-2)(1). However, N-2 has no observable rotational or vibrational transitions, so its abundance in the interstellar medium remains poorly known. In comets, the N-2 abundance is very low(2,3), while the elemental nitrogen abundance is deficient with respect to the solar value. Moreover, large nitrogen isotopic anomalies are observed in meteorites and interstellar dust particles(4). Here we report the N2H+ (and by inference the N-2) abundance inside a cold dark molecular cloud. We find that only a small fraction of nitrogen in the gas phase is molecular, with most of it being atomic. Because the compositions of comets probably reflect those of dark clouds(5), this result explains the low N-2 abundance in comets. We argue that the elemental nitrogen abundance deficiency in comets can be understood if the atomic oxygen abundance is lower than predicted by present chemical models. Furthermore, the lack of molecular nitrogen in molecular clouds explains the nitrogen anomalies in meteorites and interstellar dust particles, as nitrogen fractionation is enhanced if gaseous nitrogen is atomic(6).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62670/1/nature04919.pd

Axi-symmetric models of ultraviolet radiative transfer with applications to circumstellar disk chemistry

A new two-dimensional axi-symmetric ultraviolet radiative transfer code is presented, which is used to calculate photodissociation and ionization rates for use in chemistry models of flaring circumstellar disks. Scattering and absorption of photons from the central star and from the interstellar radiation field are taken into account. The molecules are effectively photodissociated in the surface layer of the disk, but can exist in the intermediate, moderately warm layers. A comparison has been made with an approximate 2D ray-tracing method and it was found that the latter underestimates the ultraviolet field and thus the molecular photodissociation rates below the disk surface. The full 2D results show significantly higher abundances of radicals such as CN and C2H than previous work, partly due to the fact that CO is dissociated to greater depths. Results for different stellar radiation fields are also presented. The CN/HCN ratio shows a strong dependence on the stellar spectrum, whereas other ratios such as HCO+/CO show only little variation.Comment: 15 pages, 14 figures, 2 tables. Accepted for publication in A&

AC loss in ReBCO pancake coils and stacks of them: modelling and measurement

Many applications of ReBCO coated conductors contain stacks of pancake coils. In order to reduce their high AC loss, it is necessary to understand the loss mechanisms. In this article, we measure and simulate the AC loss and the critical current, I_c, in stacks of pancake coils ("pancakes"). We construct stacks of up to 4 pancakes and we measure them by electrical means. We also obtain the anisotropic field dependence of J_c from I_c measurements of the tape. This J_c is the only input to the simulations, together with the coil dimensions. After validating our computations with the measurements, we simulate stacks of many pancakes, up to 32. We found that the AC loss in a stack of (four) pancakes is very high, two orders of magnitude larger than for a single tape. A double pancake behaves as a single one with double width but a stack of more pancakes is very different. Finally, we found that a 2-strand Roebel cable reduces the AC loss in a stack of pancakes but not in a single pancake. In conclusion, the AC loss in stacks of pancakes is too high. However, our simulations are useful to predict the AC loss and optimise the coil design, reducing the AC loss.Comment: 34 pages, 18 figures. All figures are modified; figures 3, 7 and 10 are new. Text thoroughly revised and extende

SURVIVAL, INDUCTION AND RESUSCITATION OF Vibrio cholerae FROM THE VIABLE BUT NON-CULTURABLE STATE IN THE SOUTHERN CARIBBEAN SEA

The causative agent of cholera, Vibrio cholerae, can enter into a viable but non-culturable (VBNC) state in response to unfavorable conditions. The aim of this study was to evaluate the in situ survival of V. cholerae in an aquatic environment of the Southern Caribbean Sea, and its induction and resuscitation from the VBNC state. V. cholerae non-O1, non-O139 was inoculated into diffusion chambers placed at the Cuare Wildlife Refuge, Venezuela, and monitored for plate, total and viable cells counts. At 119 days of exposure to the environment, the colony count was < 10 CFU/mL and a portion of the bacterial population entered the VBNC state. Additionally, the viability decreased two orders of magnitude and morphological changes occurred from rod to coccoid cells. Among the aquatic environmental variables, the salinity had negative correlation with the colony counts in the dry season. Resuscitation studies showed significant recovery of cell cultivability with spent media addition (p < 0.05). These results suggest that V. cholerae can persist in the VBNC state in this Caribbean environment and revert to a cultivable form under favorable conditions. The VBNC state might represent a critical step in cholera transmission in susceptible areas