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At least 37 records · Page 2

Observations of interstellar HOCO(+) - Abundance enhancements toward the Galactic center

The 4(04)-3(03) and 1(01)-0(00) transitions of HOCO(+) toward several molecular clouds have been monitored. Of the molecular clouds considered, the HOCO(+) molecule has been detected only in Sgr B2 and Sgr A. The results suggest that gas phase CO2 is not a major carbon reservoir in typical molecular clouds. For Sgr B2, the column density of HOCO(+) at the northern peak is found to be about 3 x 10 to the 14th/sq cm, and a fractional abundance relative to H2 is obtained which is about 2 orders of magnitude greater than recent theoretical predictions.

Minh, Y. C.↗

Spectroscopic detection of biological NO with a quantum cascade laser

Two configurations of a continuous wave quantum cascade distributed feedback laser-based gas sensor for the detection of NO at a parts per billion (ppb) concentration level, typical of biomedical applications, have been investigated. The laser was operated at liquid nitrogen temperature near lambda = 5.2 microns. In the first configuration, a 100 m optical path length multi-pass cell was employed to enhance the NO absorption. In the second configuration, a technique based on cavity-enhanced spectroscopy (CES) was utilized, with an effective path length of 670 m. Both sensors enabled simultaneous analysis of NO and CO2 concentrations in exhaled air. The minimum detectable NO concentration was found to be 3 ppb with a multi-pass cell and 16 ppb when using CES. The two techniques are compared, and potential future developments are discussed.

NASA Discipline Environmental Health↗

Increasing CO2 Coupled with Other Anthropogenic Perturbations: Effects on Ozone and Other Trace Gases

The GSFC 2D interactive chemistry-radiation-dynamics model has been used to study the effects on stratospheric trace gases of past and future CO2 increases coupled with changes in CFC'S, methane, and nitrous oxide. Previous simulations with the GSFC model showed that the stratospheric cooling calculated to result from doubling atmospheric CO2 would lead, in the absence of a growth of other anthropogenic gases, to a decrease in upper stratospheric NO(y) of roughly 15%. This work has been extended to simulate changes in stratospheric chemistry and dynamics occurring between the years 1960 and 2050. The simulations have been carried out with and without changes in CO2. In the low latitude upper stratosphere ozone is predicted to be 10% greater in 2050 than in 1990 when increased CO2 is included, compared with an increase of only 2% without the inclusion of CO2. In the low latitude lower stratosphere, ozone is predicted to decrease by about 1% between 1990 and 2050 when CO2 changes are taken into account, in contrast to an approximate 3% increase when they are not. The simulated behavior of water vapor is another example of the coupled responses. Between 1990 and 2050 low latitude water vapor is predicted to increase by 4% and 2% in the upper and lower stratosphere, respectively, without the inclusion of CO2 increases. with the inclusion of CO2 changes, the water vapor increases are predicted to be roughly 12% and 8%, for the upper and lower stratosphere, respectively.

Rosenfield, J. E.↗

Application of AVHRR vegetation index to study atmosphere-biosphere exchange of CO2: Results from a 3-D tracer transport model

The 'normalized difference vegetation indices' (NVI) derived from AVHRR radiances are combined with field data of soil respiration and a global map of net primary productivity to prescribe, for the globe, the seasonal exchange of CO2 between the atmosphere and the terrestrial biosphere. The monthly fluxes of CO2 thus obtained are used as inputs to a 3-D tracer transport model which uses winds generated by a 3-D atmospheric general circulation model to advect CO2 as an inert constituent. Analysis of the 3-D model results shows reasonable agreement between the simulated and observed annual cycles of atmospheric CO2 at the locations of the remote monitoring stations. The application is shown of atmospheric CO2 distributions to calibrate the NVI in terms of carbon fluxes. The approach suggests that the NVI may be used to provide quantitative information about long term and global scale variations of photosynthetic activity and of atmospheric CO2 concentrations provided that variations in the atmospheric circulation and in atmospheric composition are known.

Fung, Inez Y.↗

A Preliminary Study of CO2 Flux Measurements by Lidar

A mechanistic understanding of the global carbon cycle requires quantification of terrestrial ecosystem CO2 fluxes at regional scales. In this paper, we analyze the potential of a Doppler DIAL system to make flux measurements of atmospheric CO2 using the eddy-covariance and boundary layer budget methods and present results from a ground based experiment. The goal of this study is to put CO2 flux point measurements in a mesoscale context. In June 2007, a field experiment combining a 2-m Doppler Heterodyne Differential Absorption Lidar (HDIAL) and in-situ sensors of a 447-m tall tower (WLEF) took place in Wisconsin. The HDIAL measures simultaneously: 1) CO2 mixing ratio, 2) atmosphere structure via aerosol backscatter and 3) radial velocity. We demonstrate how to synthesize these data into regional flux estimates. Lidar-inferred fluxes are compared with eddy-covariance fluxes obtained in-situ at 396m AGL from the tower. In cases where the lidar was not yet able to measure the fluxes with acceptable precision, we discuss possible modifications to improve system performance.

Gibert, Fabien↗

Widespread Global Peatland Establishment and Persistence over the Last 130,000 Y

Glacial−interglacial variations in CO2 (exp) and methane in polar ice cores have been attributed, in part, to changes in global wetland extent, but the wetland distribution before the Last Glacial Maximum (LGM, 21 ka to 18 ka) remains virtually unknown. We present a study of global peatland extent and carbon (C) stocks through the last glacial cycle (130 ka to present) using a newly compiled database of 1,063 detailed stratigraphic records of peat deposits buried by mineral sediments, as well as a global peatland model. Quantitative agreement between modeling and observations shows extensive peat accumulation before the LGM in northern latitudes (>40°N), particularly during warmer periods including the last interglacial (130 ka to 116 ka, MIS 5e) and the interstadial (57 ka to 29 ka, MIS 3). During cooling periods of glacial advance and permafrost formation, the burial of northern peatlands by glaciers and mineral sediments decreased active peatland extent, thickness, and modeled C stocks by 70 to 90% from warmer times. Tropical peatland extent and C stocks show little temporal variation throughout the study period. While the increased burial of northern peats was correlated with cooling periods, the burial of tropical peat was predominately driven by changes in sea level and regional hydrology. Peat burial by mineral sediments represents a mechanism for long-term terrestrial C storage in the Earth system. These results show that northern peatlands accumulate significant C stocks during warmer times, indicating their potential for C sequestration during the warming Anthropocene.

Treat, Claire C.↗

Transport Analysis & Optimization in a MW-Scale CO2 Electrolyzer (Final Report)

As Twelve continues to scale up their CO2 electrolyzers, both in the size of a single cell and in the number of cells used in a stack, thermal management becomes a growing concern, since excess heat can affect reaction yield and accelerate degradation. In this project, we aim to computationally explore how the anode flow fields used in Twelve’s CO2 electrolyzers function as heat exchangers. In particular, using a homogenized model of a CO2 electrolyzer, we first estimate the amount of heat generated in a cell. Then, we develop a computational fluid dynamics (CFD) model of the so-called “flow field”, i.e. a flow manifold, based on Twelve’s CAD drawings, to evaluate how these flow fields perform as a heat exchanger for the generated heat. We explore both a single cell and a 3-cell stack operating in parallel, where heat generated in one cell can now be transferred to another cell. We evaluate how performance is affected when environmental heat losses are taken into account. Finally, we leverage topology optimization to explore the types of design features a computational optimization algorithm would suggest to supplement our intuition. Overall, our work aims to provide design recommendations for CO2 electrolyzer flow fields and provides a foundation for future studies of flow field optimization.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Non-Intrusive, Laser-Based Imaging of Jet-A Fuel Injection and Combustion Species in High Pressure, Subsonic Flows

The emphasis of combustion research efforts at NASA Glenn Research Center (GRC) is on collaborating with industry to design and test gas-turbine combustors and subcomponents for both sub- and supersonic applications. These next-generation aircraft combustors are required to meet strict international environmental restrictions limiting emissions. To meet these goals, innovative combustor concepts require operation at temperatures and pressures far exceeding those of current designs. New and innovative diagnostic tools are necessary to characterize these flow streams since existing methods are inadequate. The combustion diagnostics team at GRC has implemented a suite of highly sensitive, nonintrusive optical imaging methods to diagnose the flowfields of these new engine concepts. By using optically accessible combustors and flame-tubes, imaging of fuel and intermediate combustion species via planar laser-induced fluorescence (PLIF) at realistic pressures are now possible. Direct imaging of the fuel injection process through both planar Mie scattering and PLIF methods is also performed. Additionally, a novel combination of planar fuel fluorescence imaging and computational analysis allows a 3-D examination of the flowfield, resulting in spatially and temporally resolved fuel/air volume distribution maps. These maps provide detailed insight into the fuel injection process at actual conditions, thereby greatly enhancing the evaluation of fuel injector performance and other combustion phenomena. Stable species such as CO2, O2, N2, H2O, and hydrocarbons are also investigated by a newly demonstrated 1-D, spontaneous Raman spectroscopic method. This visible wavelength Raman technique allows the acquisition of quantitative, stable species concentration measurements from the flow.

Locke, R. J.↗

The Atmospheres of Saturn and Titan in the Near-Infrared: First Results of Cassini/VIMS

The wide spectral coverage and extensive spatial, temporal, and phase-angle mapping capabilities of the Visual Infrared Mapping Spectrometer (VIMS) onboard the Cassini-Huygens Orbiter are producing fundamental new insights into the nature of the atmospheres of Saturn and Titan. For both bodies, VIMS maps over time and solar phase angles provide information for a multitude of atmospheric constituents and aerosol layers, providing new insights into atmospheric structure and dynamical and chemical processes. For Saturn, salient early results include evidence for phosphine depletion in relatively dark and less cloudy belts at temperate and mid-latitudes compared to the relatively bright and cloudier Equatorial Region, consistent with traditional theories of belts being regions of relative downwelling. Additional Saturn results include (1) the mapping of enhanced trace gas absorptions at the south pole, and (2) the first high phase-angle, high-spatial-resolution imagery of CH4 fluorescence. An additional fundamental new result is the first nighttime near-infrared mapping of Saturn, clearly showing discrete meteorological features relatively deep in the atmosphere beneath the planet's sunlit haze and cloud layers, thus revealing a new dynamical regime at depth where vertical dynamics is relatively more important than zonal dynamics in determining cloud morphology. Zonal wind measurements at deeper levels than previously available are achieved by tracking these features over multiple days, thereby providing measurements of zonal wind shears within Saturn's troposphere when compared to cloudtop movements measured in reflected sunlight. For Titan, initial results include (1) the first detection and mapping of thermal emission spectra of CO, CO2, and CH3D on Titan's nightside limb, (2) the mapping of CH4 fluorescence over the dayside bright limb, extending to approximately 750 km altitude, (3) wind measurements of approximately 0.5 ms(exp -1), favoring prograde, from the movement of a persistent (multiple months) south polar cloud near 88 deg S latitude, and (4) the imaging of two transient mid-southern-latitude cloud features.

Cassini Mission↗

Long-term productivity in the cryptoendolithic microbial community of the Ross Desert, Antarctica

Annual gross productivity of the lichen-dominated cryptoendolithic community was calculated from a computer analysis of photosynthetic response based on laboratory measurements of CO2 exchange and three years (1985-1988) of field nanoclimate data. Photosynthetic optimum increased from -3 to 2 degrees C between irradiance levels of 100 and 1500 micromoles photons m-2 s-1, while the upper compensation point rose from 1 to 17 degrees C. The mean yearly total time available for metabolic activity (temperature above -10 degrees C and moisture present) was 771.3 h for horizontal rock, 421.5 h for northeast-oriented sloped rock, and 1042.2 h for a small depression in horizontal rock (the characteristic site of occasional lichen apothecia). The calculated mean gross productivity value for a horizontal rock was 1215 mg C m-2 y-1, and net photosynthetic gain was 606 mg C m-2 y-1. Net ecosystem productivity (annual accretion of cellular biomass) estimated from long-term events amounted to only about 3 mg C m-2 y-1. The difference between these two values may represent the long-term metabolic costs of the frequent dehydration-rehydration and freezing-thawing cycles or of overwintering, and may account for the leaching of organic substances to the rock. The yearly gross productivity of the cryptoendolithic microbial community of the entire Ross Desert area was estimated at approximately 120,000-180,000 kg C. Of this, 600-900 kg C is in microbial biomass, and much of the rest is soluble compounds that leach into the rocks and possibly percolate to the valleys, providing a source of organic matter for lakes, rivers, and soils.

NASA Program Exobiology↗

On the Assessment and Uncertainty of Atmospheric Trace Gas Burden Measurements with High Resolution Infrared Solar Occultation Spectra from Space by the ATMOS Experiment

The Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument is a high resolution Fourier transform spectrometer that measures atmospheric composition from low Earth orbit with infrared solar occultation sounding in the limb geometry. Following an initial flight in 1985, ATMOS participated in the Atmospheric Laboratory for Applications and Science (ATLAS) 1, 2, and 3 Space Shuttle missions in 1992, 1993, and 1994 yielding a total of 440 occultation measurements over a nine year period. The suite of more than thirty atmospheric trace gases profiled includes CO2, O3, N2O, CH4, H2O, NO, NO2, HNO3, HCl, HF, ClONO2, CCl3F, CCl2F2, CHF2Cl, and N2O5. The analysis method has been revised throughout the mission years culminating in the 'version 2' data set. The spectroscopic error analysis is described in the context of supporting the precision estimates reported with the profiles; in addition, systematic uncertainties assessed from the quality of the spectroscopic database are described and tabulated for comparisons with other experiments.

Abrams, M. C.↗

A computer program for thermal radiation from gaseous rocket exhuast plumes (GASRAD)

A computer code is presented for predicting incident thermal radiation from defined plume gas properties in either axisymmetric or cylindrical coordinate systems. The radiation model is a statistical band model for exponential line strength distribution with Lorentz/Doppler line shapes for 5 gaseous species (H2O, CO2, CO, HCl and HF) and an appoximate (non-scattering) treatment of carbon particles. The Curtis-Godson approximation is used for inhomogeneous gases, but a subroutine is available for using Young's intuitive derivative method for H2O with Lorentz line shape and exponentially-tailed-inverse line strength distribution. The geometry model provides integration over a hemisphere with up to 6 individually oriented identical axisymmetric plumes, a single 3-D plume, Shading surfaces may be used in any of 7 shapes, and a conical limit may be defined for the plume to set individual line-of-signt limits. Intermediate coordinate systems may specified to simplify input of plumes and shading surfaces.

Reardon, J. E.↗

Earth's partial pressure of CO2 over the past 120 Ma; evidence from Ce anomalies in the deep (greater than 600 m) Pacific Ocean, 1

It was found that Ce serves as a chemical tracer of paleo-oceanic redox conditions. It was shown that the unoxidized and soluble Ce(3+) in modern seawater exhibits a negative anomaly relative to the other soluble REE(3+). An expression of soluble Ce(3+) in seawater that was approximately 1900X greater than the average observed in Ce in 600-5000 m Pacific seawater was derived. Since Ce(CO3)(+) and Ce(CO3)2(-) complexes greatly exceed the Ce(PO4) complexes in seawater, the formulations of using carbonate complexes were followed and it was found that the calculated Ce and observed concentrations in the deep 600-5000 m Pacific Ocean agree within the uncertainties of the thermodynamic data. As expected, the calculated Ce concentrations are a strong function of pH and found to be lesser functions of CO3(2-) activities.

Liu, Y.-G↗

Cyanobacterial mats: Microanalysis of community metabolism

The microbial communities in two sites were studied using several approaches: (1) light microscopy; (2) the measurement of microprofiles of oxygen and sulfide at the surface of the microbial mat; (3) the study of diurnal variation of oxygen and sulfides; (4) in situ measurement of photosynthesis and sulfate reduction and study of the coupling of these two processes; (5) measurement of glutathione in the upper layers of the microbial mat as a possible oxygen quencher; (6) measurement of reduced iron as a possible intermediate electron donor along the established redoxcline in the mats; (7) measurement of dissolved phosphate as an indicator of processes of break down of organic matter in these systems; and (8) measurement of carbon dioxide in the interstitial water and its delta C-13 in an attempt to understand the flow of CO2 through the systems. Microbial processes of primary production and initial degradation at the most active zone of the microbial mat were analyzed.

Cohen, Y.↗

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photon counting with intensified charge coupled device (ICCD) – I. In-depth detector characterization

While the adsorption properties of transition metal catalysts have been widely studied, leading to the discovery of various scaling relations, descriptors of catalytic activity, and well-established computational models, a similar understanding of semiconductor catalysts has not yet been achieved. In this work, we present a high-throughput density functional theory investigation into the adsorption properties of 5 oxides of interest to the photocatalytic CO 2 reduction reaction: TiO 2 (rutile and anatase), SrTiO 3 , NaTaO 3 , and CeO 2 . Using a systematic approach, we exhaustively identify unique surfaces and construct adsorption structures to undergo geometry optimizations. We then perform a data-driven analysis, which reveals the presence of weak adsorption energy scaling relations, the propensity of adsorbates of interest to interact with oxygen surface sites, and the importance of slab deformation upon adsorption. Our findings are presented in the context of experimental observations and in comparison to previously studied classes of catalysts, such as pure metals and tellurium-containing semiconductors, and reinforce the need for a comprehensive approach to the study of site-specific surface phenomena on semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Joint Theoretical and Experimental Study of the Electronic, Magnetic, and Lattice Phonon Dynamics Properties of Ca x Fe y O z Compounds Applied to CO 2 Capture

Unleashing energy innovation ensures a resilient and reliable energy supply. There is a critical need for the development of new carbon dioxide (CO 2 ) captors that have improved energy efficiency accompanied by lower capital and operational costs to ensure abundant, affordable, and secure energy. Among solid materials, CaO is a good CO 2 sorbent for capture technology due to its wide availability and low cost. However, CaO also suffers from some disadvantages, such as high calcination temperature, decreasing capability due to sintering, attrition, and reaction with SO x and NO x . In this study, we employed an ab initio thermodynamic approach and experimental measurements to improve its CO 2 capture performance during the cycles. To do so, we explored the electronic, magnetic, and lattice dynamic properties of a series of calcium ferrites (Ca x Fe y O z ) and applied them for CO 2 capture. Our results showed that all of them can thermodynamically react with CO 2 to form CaCO 3 and iron oxides. Compared to pure CaO capturing CO 2 , CaFe 3 O 4 , CaFe 2 O 4 , and Ca 2 Fe 2 O 5 could shift the CO 2 regeneration temperature to a lower range. The experimental measurements showed that CaFeO 2 is a good CO 2 captor with or without the presence of an O 2 presence. The calculated thermodynamic properties of Ca x Fe y O z capturing the CO 2 reactions can be used to find their operational temperature ranges for different CO 2 capture technologies.

CO2 capture↗

A review of laser-pumped infrared lasers

The lasing mechanisms are reviewed of molecules that have demonstrated laser action in the laboratories with laser emissions in the spectral range from 3 to 35 microns. A list of lasants and laser mechanisms are defined. The pumping sources for these lasers are mainly infrared lasers; however, the case in which excitation of bromine atoms at 2.71 microns by a flashlamp as energy input is also included in the review. A conceptual drawing of lasing mechanisms is shown. Three pumping mechanisms are shown, the first being the direct-pumped system in which the lasant molecule absorbs the infrared radiation from pump laser directly, and it is excited into the upper laser level from the ground state. The second system is the indirect-pumped system where the infrared-pump laser first excites an absorbing molecule which stores its vibrational energy. Through collision this energy is transferred to the lasant molecule, populating the upper laser level. In the third system, i.e., in a Br2-CO2 mixture, a flashlamp replaces the infrared laser as the pump source for the absorbing molecule.

Chen, K. Y.↗