Incorporation of Nitrogen into Organics Produced by Fischer-Tropsch Type Chemistry

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feed-stock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydro-carbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases; and a separate suite of studies included sulfur as sulfide minerals or H2S, which yielded products such as thiols and amino acids. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. As a consequence, it is difficult to extrapolate these results to geologic systems or to evaluate how variations in reactant compositions would affect the distribution of products over time. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N

The Bell Laboratories (13)CO Survey: Longitude-Velocity Maps

A survey is presented of the Galactic plane in the J=1-0 transition of (13)CO. About 73,000 spectra were obtained with the 7 m telescope at Bell Laboratories over a ten-year period. The coverage of survey is (l, b) = (-5 to 117, -1 to +1), or 244 square degrees, with a grid spacing of 3' for |b| < 0.5, and a grid spacing of 6' for |b| > 0.5. The data presented here have been resampled onto a 3' grid. For 0.68 km/s channels, the rms noise level of the survey is 0.1 K on the $T_R^*$ scale. The raw data have been transformed into FITS format, and all the reduction processes, such as correcting for emission in the reference positions, baseline removal and interpolation were conducted within IRAF using the FCRAO task package and additional programs. The reduced data are presented here in the form of longitude-velocity color maps at each latitude. These data allow identification and classification of molecular clouds with masses in excess of ~ 1,000 solar masses throughout the first quadrant of the Galaxy. Spiral structure is manifested by the locations of the largest and brightest molecular clouds.Comment: 23 pages, 7 figures, ApJS submitted (out of 41 frames of Figure4, only one is included becaue of size limit

An ASCA Study of the W51 Complex

We present the analysis of ASCA archival data from the Galactic source W51. The ASCA spectra show that the soft (kT<= 2.5 keV) X-rays are of thermal origin and are compatible with W51C being a single, isothermal (kT~0.3 keV) supernova remnant at the far-side of the Sagittarius arm. The ASCA images reveal hard (kT>=2.5 keV) X-ray sources which were not seen in previous X-ray observations. Some of these sources are coincident with massive star-forming regions and the spectra are used to derive X-ray parameters. By comparing the X-ray absorbing column density with atomic hydrogen column density, we infer the location of star-forming regions relative to molecular clouds. There are unidentified hard X-ray sources superposed on the supernova remnant and we discuss the possibility of their association.Comment: 13 pages, 11 figures, to be published in Astronomical Journa

Giant Molecular Clouds are More Concentrated to Spiral Arms than Smaller Clouds

From our catalog of Milky Way molecular clouds, created using a temperature thresholding algorithm on the Bell Laboratories 13CO Survey, we have extracted two subsets:(1) Giant Molecular Clouds (GMCs), clouds that are definitely larger than 10^5 solar masses, even if they are at their `near distance', and (2) clouds that are definitely smaller than 10^5 solar masses, even if they are at their `far distance'. The positions and velocities of these clouds are compared to the loci of spiral arms in (l, v) space. The velocity separation of each cloud from the nearest spiral arm is introduced as a `concentration statistic'. Almost all of the GMCs are found near spiral arms. The density of smaller clouds is enhanced near spiral arms, but some clouds (~10%) are unassociated with any spiral arm. The median velocity separation between a GMC and the nearest spiral arm is 3.4+-0.6 km/s, whereas the median separation between smaller clouds and the nearest spiral arm is 5.5+-0.2 km/s.Comment: 11 pages, 3 figure

[Fe II] and H2 filaments in the Supernova Remnant G11.2-0.3: Supernova Ejecta and Presupernova Circumstellar Wind

We present the results of near-infrared imaging and spectroscopic observations of the young, core-collapse supernova remnant (SNR) G11.2-0.3. In the [Fe II] 1.644 um image, we first discover long, clumpy [Fe II] filaments within the radio shell of the SNR, together with some faint, knotty features in the interior of the remnant. We have detected several [Fe II] lines and HI Br-G line toward the peak position of the bright southeastern [Fe II] filament. The derived extinction is large (Av=13 mag) and it is the brightest [Fe II] filament detected toward SNRs to date. By analyzing two [Fe II] 1.644 um images obtained in 2.2 yrs apart, we detect a proper motion corresponding to an expansion rate of 0.''035 (0.''013) /yr [or 830 (310) km/s]. We also discover two small H2 filaments. One is bright and along the SE boundary of the radio shell, while the other is faint and just outside of its NE boundary. We have detected H2 (2-1) S(3) line toward the former filament and derive an excitation temperature of 2,100 K. We suggest that the H2 filaments are dense clumps in a presupernova circumstellar wind swept up by the SNR shock while the [Fe II] filaments are probably composed of both shocked wind material and shocked supernova (SN) ejecta. The distribution of [Fe II] filaments may indicate that the SN explosion in G11.2-0.3 was asymmetric as in Cassiopeia A. Our results support the suggestion that G11.2-0.3 is a remnant of a SN IIL/b interacting with a dense red supergiant wind.Comment: 30 pages with 10 figures, To appear in the Astrophysical Journa

Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

Portlandite [Ca(OH)2] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH)2] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO2(OH)n]2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility

Statistical Communication Theory

Contains research objectives and reports on three research projects

The chemistry of vibrationally excited H2 in the interstellar medium

The internal energy available in vibrationally excited H2 molecules can be used to overcome or diminish the activation barrier of various chemical reactions of interest for molecular astrophysics. In this article we investigate in detail the impact on the chemical composition of interstellar clouds of the reactions of vibrationally excited H2 with C+, He+, O, OH, and CN, based on the available chemical kinetics data. It is found that the reaction of H2 (v>0) and C+ has a profound impact on the abundances of some molecules, especially CH+, which is a direct product and is readily formed in astronomical regions with fractional abundances of vibrationally excited H2, relative to ground state H2, in excess of 10^(-6), independently of whether the gas is hot or not. The effects of these reactions on the chemical composition of the diffuse clouds zeta Oph and HD 34078, the dense PDR Orion Bar, the planetary nebula NGC 7027, and the circumstellar disk around the B9 star HD 176386 are investigated through PDR models. We find that formation of CH+ is especially favored in dense and highly FUV illuminated regions such as the Orion Bar and the planetary nebula NGC 7027, where column densities in excess of 10^(13) cm^(-2) are predicted. In diffuse clouds, however, this mechanism is found to be not efficient enough to form CH+ with a column density close to the values derived from astronomical observations.Comment: accepted for publication in the Astrophysical Journal; 9 pages, 7 figure