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At least 1,621 records · Page 90

Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Herz, Richard K.↗

Evidence from the limb infrared monitor of the stratosphere for nonlocal thermodynamic equilibrium in the nu2 mode of mesospheric water vapour and the nu3 mode of stratospheric nitrogen dioxide

Data from the 6.9-micron H2O channel and the 6.2-micron NO2 channel of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) have been used to investigate the daytime enhancement to H2O; the high concentration of H2O sometimes observed in the polar night mesosphere; and the high ratio of daytime to nighttime NO2 in the upper stratosphere. These three phenomena deviate noticeably from the predictions of photochemical theory. The 20 to 30 percent diurnal variation in stratospheric H2O apparent in LIMS data cannot be reconciled with a photochemical lifetime in excess of four months. This is attributed to departure from local thermodynamic equilibrium of daytime emission which had not been accounted for in retrievals. Speculative possibilities of NLTE emission from the H2O nu2 and NO2 nu3 hot bands are discussed. It is found that the nonthermal emission from NO2 significantly affects retrieval of H2O in the polar nighttime and NO2 in the daytime stratosphere at low latitudes.

Kerridge, Brian J.↗

How will changes in carbon dioxide and methane modify the mean structure of the mesosphere and thermosphere?

A global average model of the coupled mesosphere, thermosphere, and ionosphere is used to examine the effect of trace gas variations on the overall structure of these regions. In particular, the variations caused by CO2 and CH4 doublings and halvings from present day mixing ratios are presented. The results indicate that the mesosphere and thermosphere temperatures will cool by about 10 K and 50 K, respectively, as the CO2 and CH4 mixing ratios are doubled. These regions are heated by similar amounts when the trace gas mixing ratios are halved. Compositional redistributions also occur in association with changes in the temperature profile. The results show that global change will occur in the upper atmosphere and ionosphere as well as in the lower atmosphere during the 21st century.

Roble, R. G.↗

Metal oxide regenerable carbon dioxide removal system for an advanced portable life support system

The development of a CO2 removal system for an astronaut portable life support system to meet the EVA requirements for the Space Station is discussed, focusing on the factors important in the selection of the metal oxide absorbent for CO2 removal. Results from laboratory tests on metal oxide absorbent materials are given, including characterization studies and dynamic CO2 uptake and regeneration measurements. The preliminary design of the breadboard system to perform both the absorption and regeneration functions is presented.

Nacheff, Maurena S.↗

Use of vegetation indices to estimate intercepted solar radiation and net carbon dioxide exchange of a grass canopy

Results are presented from field experiments relating spectral reflectance to intercepted photosynthetically active radiation (PAR) and net CO2 exchange in a natural canopy composed of the marsh cordgrass (Spartina alterniflora). Reflectance measurements made by a hand-held radiometer with Landsat TM spectral wavebands are used to compute remote sensing indices such as the normalized difference vegetation index. Consideration is given to the impact of standing dead canopy material on the relationship between intercepted PAR and spectral vegetation indices and the impact of changes in photosynthetic efficiency on the relationship between vegetation indices and CO2 exchange rates. The results suggest that quantitative remote assessment of photosynthesis and net gas exchange in natural vegetation is feasible, especially if the analysis incorporates information on biological responses to environmental variables.

Bartlett, David S.↗

Operational overview of NASA GTE/CITE 2 airborne instrument intercomparisons - Nitrogen dioxide, nitric acid, and peroxyacetyl nitrate

This paper provides the rationale, objectives, approach, and a brief description of the instrumentation included in the second airborne Chemical Instrumentation Test and Evaluation (CITE 2) mission conducted on NASA's Electra aircraft. CITE 2 intercompared data from instruments measuring NO2, HNO3, and PAN in the troposphere. This study, conducted in August 1986, encountered marine and continental air with free tropospheric mixing ratios of NO2, HNO3, and PAN typically less than 120, 150, and 200 parts per trillion by volume, respectively.

Hoell, James M., Jr.↗

An intercomparison of airborne nitrogen dioxide instruments

Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).

Gregory, G. L.↗

Sensitivity of the equilibrium surface temperature of a GCM to systematic changes in atmospheric carbon dioxide

The equilibrium response of surface temperature to atmospheric CO2 concentration, for six values between 100 and 1000 ppm, is calculated from a series of GCM experiments. This response is nonlinear, showing greater sensitivity for lower values of CO2 than for the higher values. It is suggested that changes in CO2 concentration of a given magnitude (e.g., 100 ppm) played a larger role in the Pleistocene ice-age-type temperature variations than in causing global temperature changes due to anthropogenic increases.

Oglesby, Robert J.↗

Characterization of metal oxide absorbents for regenerative carbon dioxide and water vapor removal for advanced portable life support systems

Characterization of the performance of a silver-oxide-based absorbent in terms of its ability to remove both gaseous CO2 and water vapor in an astronaut portable life support systems (PLSS) is discussed. Attention is focused on regeneration of the absorbent from the carbonite state of the oxide state, preconditioning of the absorbent using a humidified gas stream, and absorption breakthrough testing. Based on the results of bench-scale experiments, a test plan is carried out to further characterize the silver-oxide-based absorbent on a larger scale; it calls for examination of the absorbent in both an adiabatic packed bed and a near-isothermal cooled bed configuration. It is demonstrated that the tested absorbent can be utilized in a way that removes substantial amounts of CO2 and water vapor during an 8-hour extravehicular activity mission, and that applying the absorbent to PLSS applications can simplify the ventilation loop.

Kast, Timothy P.↗

Three-Man Solid Electrolyte Carbon Dioxide Electrolysis Breadboard

The development of the Three-Man (2.2 lb CO2/man-day) Solid Electrolyte CO2 Electrolysis Breadboard consisted of a Phase 1 and 2 effort. The Phase 1 effort constituted fabrication of three electrolysis cell types and performing parametric testing, off-design testing, and cell life testing. The Phase 2 consisted of the preliminary design, incorporation of palladium (Pd) tubes for hydrogen separation from the electrolyzer cathode feed gases, design support testing, final design, fabrication, and performance testing of the breadboard system. The results of performance tests demonstrated that CO2 electrolysis in an oxygen reclamation system for long duration space-based habitats is feasible. Closure of the oxygen system loop, therefore, can be achieved by CO2 electrolysis. In a two step process the metabolic CO2 and H2O vapor are electrolyzed into O2, H2, and CO. The CO can subsequently be disproportionated into carbon and CO2 in a carbon deposition reactor and the CO2 in turn be recycled and electrolyzed for total O2 recovery. The development effort demonstrated electrolyzer system can be designed and built to operate safely and reliably and the incorporation of Pd tubes for hydrogen diffusion can be integrated safely with predictable performance.

Isenberg, Arnold O.↗

Chemical approaches to carbon dioxide utilization for manned Mars missions

Use of resources available in situ is a critical enabling technology for a permanent human presence in space. A permanent presence on Mars, e.g., requires a large infrastructure to sustain life under hostile conditions. As a resource on Mars, atmospheric CO2 is as follows: abundant; available at all points on the surface; of known presence; chemically simple; and can be obtained by simple compression. Many studies focus on obtaining O2 and the various uses for O2 including life support and fuel; discussion of CO, the coproduct from CO2 fixation revolves around its uses as a fuel, being oxidized back to CO2. Several new proposals are studied for CO2 fixation through chemical, photochemical, and photoelectrochemical means. For example, the reduction of CO2 to hydrocarbons such as acetylene (C2H2) can be accomplished with H2. C2H2 has a theoretical vacuum specific impulse of approx. 375 secs. Potential uses were also studied of CO2, as obtained or further reduced to carbon, as a reducing agent in metal oxide processing to form metals or metal carbides for use as structural or power materials; the CO2 can be recycled to generate O2 and CO.

Hepp, Aloysius F.↗

Monolith catalysts for closed-cycle carbon dioxide lasers

The objective was to explore ways of making a monolithic form of catalyst for CO2 lasers. The approach chosen was to pelletize the catalyst material, Au/MnO2 powder, and epoxy the pellets to stainless steel sheets as structural supports. The CO oxidation reaction over Au/MnO2 powder was found to be first overall, and the reaction rate constant at room temperature was 4.4 +/- 0.3 cc/(g x sec). The activation energy was 5.7 kcal/mol. The BET surface area of the pellets was found to vary from 125 to 140 sq m/g between different batches of catalyst. Pellets epoxied to stainless steel strips showed no sign of fracture or dusting when subjected to thermal tests. Pellets can be dropped onto hard surfaces with chipping of edges but no breakage of the pellets. Mechanical strength tests performed on the pellets showed that the crush strength is roughly one-fourth of the pelletizing force. The apparent activity and activation energy over the pellets were found to be less than over the powdered form of the catalyst. The lower apparent activity and activation energy of the pellets are due to the fact that the internal surface area of a pellet is not exposed to the reactant concentration present in the flowing gas as a result of intrapellet diffusion resistance. Effectiveness factors varied from 0.44, for pellets having thickness of 2 mm and attached with epoxy to a stainless steel strip. The epoxy and the stainless steel strip were found to simply block off one of the circular faces of the pellets. The epoxy did not penetrate the pellets and block the active sites. The values of the effective diffusivities were estimated to be between 2.3 x 10(exp -3) and 4.9 x 10(exp -3) sq cm/s. With measurements performed on one powder sample and one pellet configuration, reasonable accurate predictions can be made of conversions that would be obtained with other pellet thickness and configurations.

Herz, Richard K.↗

Effects of elevated atmospheric carbon dioxide concentrations on water and acid requirements of soybeans grown in a recirculating hydroponic system

Establishing mass budgets of various crop needs, i.e. water and nutrients, in different environments is essential for the Controlled Ecological Life Support System (CELSS). The effects of CO2 (500 and 1000 umol mol (exp -1)) on water and acid use (for pH control) by soybeans in a recirculating hydroponic system were examined. Plants of cvs. McCall and Pixie were grown for 90 days using the nutrient film technique (NFT) and a nitrate based nutrient solution. System acid use for both CO2 levels peaked near 4 weeks during a phase of rapid vegetative growth, but acid use decreased more rapidly under 500 compared to 1000 umol mol (exp GR) CO2. Total system water use by 500 and 1000 umol mol (exp -1) plants was similar, leaving off at 5 weeks and declining as plants senesced (ca. 9 weeks). However, single leaf transpiration rates were consistently lower at 1000 umol mol (exp -1). The data suggest that high CO2 concentrations increase system acid (and nutrient) use because of increased vegetative growth, which in turn negates the benefit of reduced water use (lower transpiration rates) per unit leaf area.

Mackowiak, C. L.↗

Isotopic exchange between carbon dioxide and ozone via O(1D) in the stratosphere

A novel mechanism for isotropic exchange between CO2 and O3 via O(1D) + CO2 - CO3(asterisk) followed by CO3(asterisk) - CO2 + O(3P). A one-dimensional model calculation shows that this mechanism can account for the enrichment in O-18 in the stratospheric CO2 observed by Gamo et al. (1989), using the heavy O3 profile observed by Mauersberger (1981). The implications of this mechanism for other stratospheric species and as a source of isotopically heavy CO2 in the troposphere are briefly discussed.

Yung, Yuk L.↗

A study of the radiative effects of the 9.4- and 10.4-micron bands of carbon dioxide

The potential radiative impact of the relatively weak 9.4- and 10.4-micron bands of CO2 is investigated. A comparison of line-by-line calculations to laboratory data demonstrates that the line-by-line procedure and laboratory data typically yield comparable results; however, there are cases of substantial disagreement between the line-by-line results and the laboratory data. It is observed that the Goody narrow-band model yields band absorptances in good agreement with the reference line-by-line calculations. For application to climate models, new broadband parameterizations, are presented for the 9.4- and 10.4-micron bands of CO2. Clear-sky flux calculations demonstrate that for projected increases of CO2 the impact of the 9.4- and 10.4-micron bands is comparable to that attributed to projected increases of tropospheric ozone.

Kratz, D. P.↗

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Freund, Friedemann↗

Automated carbon dioxide cleaning system

Solidified CO2 pellets are an effective blast media for the cleaning of a variety of materials. CO2 is obtained from the waste gas streams generated from other manufacturing processes and therefore does not contribute to the greenhouse effect, depletion of the ozone layer, or the environmental burden of hazardous waste disposal. The system is capable of removing as much as 90 percent of the contamination from a surface in one pass or to a high cleanliness level after multiple passes. Although the system is packaged and designed for manual hand held cleaning processes, the nozzle can easily be attached to the end effector of a robot for automated cleaning of predefined and known geometries. Specific tailoring of cleaning parameters are required to optimize the process for each individual geometry. Using optimum cleaning parameters the CO2 systems were shown to be capable of cleaning to molecular levels below 0.7 mg/sq ft. The systems were effective for removing a variety of contaminants such as lubricating oils, cutting oils, grease, alcohol residue, biological films, and silicone. The system was effective on steel, aluminum, and carbon phenolic substrates.

Hoppe, David T.↗