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At least 181 records · Page 10

The Cosmic Ultraviolet Baryon Survey (CUBS) – III. Physical properties and elemental abundances of Lyman-limit systems at z < 1

ABSTRACT We present a systematic investigation of physical conditions and elemental abundances in four optically thick Lyman-limit systems (LLSs) at z = 0.36–0.6 discovered within the Cosmic Ultraviolet Baryon Survey (CUBS). Because intervening LLSs at z < 1 suppress far-UV (ultraviolet) light from background QSOs, an unbiased search of these absorbers requires a near-UV-selected QSO sample, as achieved by CUBS. CUBS LLSs exhibit multicomponent kinematic structure and a complex mix of multiphase gas, with associated metal transitions from multiple ionization states such as C ii, C iii, N iii, Mg ii, Si ii, Si iii, O ii, O iii, O vi, and Fe ii absorption that span several hundred km s−1 in line-of-sight velocity. Specifically, higher column density components (log N(H i)/cm−2≳ 16) in all four absorbers comprise dynamically cool gas with $\langle T \rangle =(2\pm 1) \times 10^4\,$K and modest non-thermal broadening of $\langle b_\mathrm{nt} \rangle =5\pm 3\,$km s−1. The high quality of the QSO absorption spectra allows us to infer the physical conditions of the gas, using a detailed ionization modelling that takes into account the resolved component structures of H i and metal transitions. The range of inferred gas densities indicates that these absorbers consist of spatially compact clouds with a median line-of-sight thickness of $160^{+140}_{-50}$ pc. While obtaining robust metallicity constraints for the low density, highly ionized phase remains challenging due to the uncertain $N\mathrm{(H\, {\small I})}$, we demonstrate that the cool-phase gas in LLSs has a median metallicity of $\mathrm{[\alpha /H]_{1/2}}=-0.7^{+0.1}_{-0.2}$, with a 16–84 percentile range of [α/H] = (−1.3, −0.1). Furthermore, the wide range of inferred elemental abundance ratios ([C/α], [N/α], and [Fe/α]) indicate a diversity of chemical enrichment histories. Combining the absorption data with deep galaxy survey data characterizing the galaxy environment of these absorbers, we discuss the physical connection between star-forming regions in galaxies and diffuse gas associated with optically thick absorption systems in the z < 1 circumgalactic medium.

Zahedy, Fakhri S. (ORCID:0000000178692551)↗

Internal Active Thermal Control System (IATCS) Sodium Bicarbonate/Carbonate Buffer in an Open Aqueous Carbon Dioxide System and Corollary Electrochemical/Chemical Reactions Relative to System pH Changes

The International Space Station (ISS) Internal Active Thermal Control System (IATCS) experienced a number of chemical changes driven by system absorption of CO2 which altered the coolant’s pH. The natural effects of the decrease in pH from approximately 9.2 to less than 8.4 had immediate consequences on system corrosion rates and corrosion product interactions with specified coolant constituents. The alkalinity of the system was increased through the development and implementation of a carbonate/bicarbonate buffer that would increase coolant pH to 9.0 – 10.0 and maintain pH above 9.0 in the presence of ISS cabin concentrations of CO2 up to twenty times higher than ground concentrations. This paper defines how a carbonate/bicarbonate buffer works in an open carbon dioxide system and summarizes the analyses performed on the buffer for safe and effective application in the on-orbit system. The importance of the relationship between the cabin environment and the IATCS is demonstrated as the dominant factor in understanding the system chemistry and pH trends before and after addition of the carbonate/bicarbonate buffer. The paper also documents the corollary electrochemical and chemical reactions the system has experienced and the rationale for remediation of these effects with the addition of the carbonate/bicarbonate buffer.

Stegman, Thomas W.↗

Role of nanocellulose in tailoring electroanalytical performance of hybrid nanocellulose/multiwalled carbon nanotube electrodes

Abstract Nanocellulose has emerged as a promising green dispersant for carbon nanotubes (CNTs), and there is an increasing trend in developing nanocellulose/CNT hybrid materials for electrochemical detection of various small molecules. However, there have been very few comprehensive studies investigating the role of nanocellulosic material properties upon the electroanalytical performance of the resultant hybrid electrodes. In this work, we demonstrate the influence of both nanocellulose functionalization and geometry, utilizing sulfated cellulose nanocrystals, sulfated cellulose nanofibers, and TEMPO-oxidized cellulose nanofibers. Transmission electron microscopy tomography enables direct visualization of the effect of nanocellulosic materials on the hybrid architectures. High resolution X-ray absorption spectroscopy verifies that the chemical nature of CNTs in the different hybrids is unmodified. Electroanalytical performances of the different nanocellulose/CNT hybrid electrodes are critically evaluated using physiologically relevant biomolecules with different charge such as, dopamine (cationic), paracetamol (neutral), and uric acid (anionic). The hybrid electrode containing fibrillar nanocellulose geometry with a high degree of sulfate group functionalization provides the highest electroanalytical sensitivity and strongest enrichment towards all studied analytes. These results clearly demonstrate for the first time, the extent of tailorability upon the electroanalytical response of nanocellulose/CNT hybrid electrodes towards different biomolecules, offered simply by the choice of nanocellulosic materials.

Durairaj, Vasuki↗

Building a predictive model for polycyclic aromatic hydrocarbon dosimetry in organotypically cultured human bronchial epithelial cells using benzo[ a ]pyrene

The airway epithelium is a primary route of exposure for inhaled toxicants, and organotypic culture models represent an important advancement for toxicity testing compared to simple in vitro models that may lack metabolic capability and multicellular structure/communication associated with the bronchial epithelium in vivo. A quantitative understanding of chemical dosimetry is key for interpreting and extrapolating study results; however, dosimetry is understudied in organotypic models limiting ability to predict toxicity. We developed a dosimetry model for primary human bronchial epithelial cells (HBECs) cultured at the air-liquid interface (ALI) using benzo[a]pyrene (BAP), a representative polycyclic aromatic hydrocarbon. Dose and time course evaluation of metabolite formation and enzyme activity and expression were utilized to parameterize a cellular dosimetry model to improve the utility of ALI-HBECs for assessing chemical risk. Dosimetry analysis demonstrated absorption of BAP into cells and an increase in Phase 1 and 2 metabolites over time that correlated with regulation of metabolizing enzymes. BAP was cleared from cells by 48 h after exposure, and the primary metabolites generated in ALI-HBECs were BAP-3-phenol, BAP-4,5-dihydrodiol, BAP-7,8-dihydrodiol, BAP-9,10-dihydrodiol, BAP-7,8,9,10-tetrol, BAP-3-phenol-glucuronide, BAP-4,5-dihydrodiol-glucuronide, and BAP-9,10-dihydrodiol-glucuronide. The resulting dosimetry model described BAP and 7,8-dihydrodiol toxicokinetics in ALI-HBECs and suggested active excretion of 7,8-dihydrodiol. Overall, this study demonstrates metabolic competency of ALI-HBECs for BAP metabolism, demonstrates the usefulness of complex in vitro systems for human-relevant toxicity data, and exhibits how in silico models can be utilized for understanding the dosimetry of test compounds to aid in in vitro to human extrapolation of toxicity data for risk assessments.

Benzo[a]pyrene↗

A Membrane Contactor Enabling Energy-Efficient CO 2 Capture from Point Sources with Deep Eutectic Solvents

We demonstrate a scalable and energy-efficient hollow fiber membrane contactor (HFMC)-based process using a green solvent for CO 2 capture. This process uses a deep eutectic solvent (DES) in an HFMC to provide close interfacial interactions and contact between the DES and CO 2 . This approach overcomes disadvantages associated with direct absorption in DES and could potentially be applied to a variety of solvent-based CO 2 capture methods. Commercial low-cost polymer hollow fiber membranes (e.g., microporous polypropylene) were evaluated for CO 2 capture with reline, a prototypical DES. Single-gas measurements showed that the DES-based polypropylene HFMC can capture and separate CO 2 while rejecting N2. From a mixed gas containing 50 mol % N 2 and 50 mol % CO ν , the DES-based HFMC separated CO 2 with a purity of 96.9 mol %. The effect of several process parameters including solvent flow rate, pressure, and temperature on the CO 2 separation performance was studied. The flux of the recovered CO 2 was 67.43 mmole/m 2 /h at a feed pressure of 4 bar. In situ Fourier transform infrared (FTIR) measurements combined with density functional theory (DFT)-based molecular dynamics simulations revealed that reline absorbs CO 2 by physical absorption without forming a new chemical compound, and CO 2 separation by reline occurs via the pressure swing mechanism. This research provides fundamental insights about physical solvent-based separation processes and a pathway toward practical deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery and characterization of an acridine radical photoreductant

Not provided.Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. Finally, we demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interstellar matter.

Interstellar material, emphasizing chemical characterization of dust by absorption spectroscopy

COSMIC DUST↗

Selenium in soils of the Lower Wasatch Formation, Campbell County, Wyoming: Geochemistry, distribution, and environmental hazards

The author has identified the following significant results. Seleniferous Shingle series soils and sandstone outcrops of section 27, T 48 N, R 71 W, Wyoming are mapped on aerial photography by their association with Astragalus bisulcatus. Chemical leachate analyses and atomic absorption methods reveal all studied Samsil and Shingle soils to contain acid, base, and water soluble selenium compounds, and that water extractions showed varied concentration behavior due to soil pH. Acid-soluble selenium is found to be associated with smectite. Statistical analyses confirm that A. bisulcatus presence has a weak influence on soil-lens organic selenium concentration, and determine the importance of other geobotanical factors for convertor presence. Environmental procedures of high selenium lens burial, convertor plant eradication, and revegetated site monitoring are recommended. Usage of density analysis and photographic enlargement are used to successfully produce both a control area and a Campbell County, Wyoming regional map of A. bisulcatus supportive soils and outcrops using Skylab photography.

Kolm, K. E.↗

Advanced sensors for spaceborne measurements of the earth's atmosphere

Concepts involved in remote sensing from space are reviewed, together with performance requirements of proposed and planned equipment. Attention is focused on measurements of the troposphere, particularly meteorological variables and chemical species. The principles of absorption, using either passive or active sensors, emission detection, fluorescence measurements, and EM radiation scattering are outlined. The proposed NASA Windsat, using a CO2 laser from the Orbiter or from an 800 km orbit spacecraft to measure low-level wind speeds is described, as are the uses of the AMTS atmospheric sounder instrument for IR atmospheric temperature sensing and a 20-channel microwave radiometer to detect moisture profiles in the water vapor bands. Additionally, a microwave pressure sounder to detect backscattered signals at 60 GHz is outlined, along with lidar pressure and wind speed measurement methods.

Hinkley, E. D.↗

Photovoltaic module encapsulation design and materials section, volume 2

Tests for chemical structure, material properties, water absorption, aging and curing agent of Ethylene Vinyl Acetate (EVA) and UV absorption studies are carried out. A computer model was developed for thermal optical modeling, to investigate dependence between module operating temperature and solar insolation, and heat dissapation behavior. Structural analyses were performed in order to determine the stress distribution under wind and heat conditions. Curves are shown for thermal loading conditions. An electrical isolation was carried out to investigate electrical stress aging of non-metallic encapsulation materials and limiting material flaws, and to develop a computer model of electrical fields and stresses in encapsulation materials. In addition, a mathematical model was developed and tests were conducted to predict hygroscopic and thermal expansion and contraction on a plastic coated wooden substrate. Thermal cycle and humidity freezing cycle tests, partial discharge tests, and hail impact tests were also carried out. Finally, the effects of soiling on the surface of photovoltaic modules were investigated. Two antisoiling coatings, a fluorinated silane and perflourodecanoic acid were considered.

Cuddihy, E. F.↗

The nitrogen cycle: Atmosphere interactions

Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

Levine, J. S.↗

Thermal control paints on LDEF: Results of M0003 sub-experiment 18

Several thermal control paints were flown on the Long Duration Exposure Facility (LDEF), including the white paints Chemglaze A276, S13GLO, and YB-71, and the black paint D-111. The effects of low earth orbit, which includes those induced by UV radiation and atomic oxygen, varied significantly with each paint and its location on LDEF. For example, samples of Chemglaze A276 located on the trailing edge of LDEF darkened significantly due to UV-induced degradation of the paint's binder, while leading edge samples remained white but exhibited severe atomic oxygen erosion of the binder. Although the response of S13GLO to low earth orbit is much more complicated, it also exhibited greater darkening on trailing edge samples as compared to leading edge samples. In contrast, YB-71 and D-111 remained relatively stable and showed minimal degradation. The performance of these paints as determined by changes in their optical and physical properties, including solar absorptance as well as surface chemical changes and changes in surface morphology is examined. It will also provide a correlation of these optical and physical property changes to the physical phenomena that occurred in these materials during the LDEF mission.

Jaggers, C. H.↗

Adding intelligent services to an object oriented system

As today's software becomes increasingly complex, the need grows for intelligence of one sort or another to becomes part of the application, often an intelligence that does not readily fit the paradigm of one's software development. There are many methods of developing software, but at this time, the most promising is the object oriented (OO) method. This method involves an analysis to abstract the problem into separate 'objects' that are unique in the data that describe them and the behavior that they exhibit, and eventually to convert this analysis into computer code using a programming language that was designed (or retrofitted) for OO implementation. This paper discusses the creation of three different applications that are analyzed, designed, and programmed using the Shlaer/Mellor method of OO development and C++ as the programming language. All three, however, require the use of an expert system to provide an intelligence that C++ (or any other 'traditional' language) is not directly suited to supply. The flexibility of CLIPS permitted us to make modifications to it that allow seamless integration with any of our applications that require an expert system. We illustrate this integration with the following applications: (1) an after action review (AAR) station that assists a reviewer in watching a simulated tank battle and developing an AAR to critique the performance of the participants in the battle; (2) an embedded training system and over-the-shoulder coach for howitzer crewmen; and (3) a system to identify various chemical compounds from their infrared absorption spectra.

Robideaux, Bret R.↗

Volume Ice Radiolysis in the Outer Solar System

The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that highly reducing environment. The red colors of low-inclination classical Kuiper Belt Objects at 40-50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

Cooper, John F.↗

TPSAS-NF1676L-11084-DND

The solar radiation must be considered as the primary factor when we study the climatic system because it provides almost all energy that drives the climatic system and most atmospheric phenomena. The solar radiation at the TOA is partially transferred, transformed into other forms of energy that are eventually dissipated by the general circulation of the atmosphere and oceans, and partially used in chemical and biological processes. The absorption of solar energy in the atmosphere (Acol) plays a key role in the climate system, not only because it affects the amount of solar energy absorbed by the Earth system, but also because it changes the vertical distribution of absorbed energy, which in turn impacts surface evaporation, atmospheric convection and precipitation. To investigate Acol, we have collected the collocated satellite-surface observations over the 35 selected BSRN surface sites during the period 2000-2004. The surface radiation budgets are averaged from the BSRN Shortwave (SW) observations over a 1-hour interval centered at the time of the NASA Terra and Aqua satellites overpass, and the TOA radiation budgets are averaged from the closest FOV satellite data to the BSRN stations. Then the atmospheric column SW absorption will be inferred from the satellite TOA albedo and BSRN surface absorption (through the estimated surface albedo). Monthly means of Acol, TOA albedo, and surface absorption have been calculated under both clear- and all-sky conditions over the 35 selected BSRN sites which represent different climate regimes. To evaluate the GCM simulations, we have collected the ECHAM5-HAM simulated surface, TOA and atmospheric radiation budgets by researchers at ETH Zurich and compared those simulations with observations. The preliminary comparisons have shown that the ECHAM5 simulated clear-sky surface absorption, TOA albedo, and ACOL agree very well (1-3%) with observations. Under all-sky conditions, they have strong correlations with CERES-derived cloud fraction. The simulated surface absorption is lower and TOA albedo is higher than those under clear skies, but ACOL does not increase too much. However, there are relatively large differences over some regions and months. A further study is needed.

X. Dong↗