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At least 271 records · Page 15

Meteorological context for fall experiments including distributions of water vapor, ozone, and carbon monoxide

Meteorological contexts for the NASA GTE/CITE 1 fall 1983 flight series are presented and discussed. The large-scale wind, cold cloud, and moisture patterns are illustrated by composite diagrams based on the National Oceanic and Atmospheric Administration 700-, 500-, and 250-mbar analyses and the GOES-West broadband and 6.7-micron (water vapor) infrared photographs. Detailed flight path diagrams are included for seven maritime flights and one continental flight in the free troposphere and boundary layer. For three flights from Hickam Field, in Honolulu, HI, to the Intertropical Convergence Zone, vertical profiles of temperature, dew/frost point departures, wind velocity, and ozone, and carbon monoxide mixing ratios are also presented and discussed. Excellent agreement is demonstrated between the in situ and remote measurements. In particular, the predictive and diagnostic value of the 6.7-micron water vapor photographs is demonstrated.

Danielsen, Edwin F.↗

Toxicological approach to setting spacecraft maximum allowable concentrations for carbon monoxide

The Spacecraft Maximum Allowable Concentrations (SMACs) are exposure limits for airborne chemicals used by NASA in spacecraft. The aim of these SMACs is to protect the spacecrew against adverse health effects and performance decrements that would interfere with mission objectives. Because of the 1 and 24 hr SMACs are set for contingencies, minor reversible toxic effects that do not affect mission objectives are acceptable. The 7, 30, or 180 day SMACs are aimed at nominal operations, so they are established at levels that would not cause noncarcinogenic toxic effects and more than one case of tumor per 1000 exposed individuals over the background. The process used to set the SMACs for carbon monoxide (CO) is described to illustrate the approach used by NASA. After the toxicological literature on CO was reviewed, the data were summarized and separated into acute, subchronic, and chronic toxicity data. CO's toxicity depends on the formation of carboxyhemoglobin (COHb) in the blood, reducing the blood's oxygen carrying capacity. The initial task was to estimate the COHb levels that would not produce toxic effects in the brain and heart.

Wong, K. L.↗

Carbon Monoxide Sensor

The fuel cell is a system which employs an electrochemical process to convert gases- J such as hydrogen and oxygen directly into electricity. Under NASA sponsorship, GE's Aircraft Equipment Division developed fuel cells to supply electrical power for the Gemini and Biosatellite spacecraft of the sixties and is currently working on advanced fuel cell development. This long-term effort has resulted in a series of spinoff applications using the same general technology for a variety of purposes, among them the recently marketed Dosimeter. The Dosimeter is designed to help users meet safety requirements for industrial atmospheres, as specified by the Occupational Safety and Health Administration and other regulatory agencies. The compact, pocket-sized sensor measures personnel exposure to carbon monoxide and provides both a visual and an audible alarm if the concentration of the gas exceeds present levels. The Dosimeter offers substantial improvement in measuring accuracy over earlier warning indicators.

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Poison or Promoter? Investigating the Dual-Role of Carbon Monoxide in Pincer-Iridium-Based Alkane Dehydrogenation Systems via Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy

Pincer-ligated iridium complexes of the form [( R 4 PCP)IrL] ( R 4 PCP = κ 3 -C 6 H 3 -2,6-(XPR 2 ) 2 ; X = CH 2 , O; R = tBu, iPr) have previously been shown competent for acceptorless alkane dehydrogenation when supported on silica. It was observed by postcatalysis solid-state NMR that silica-tethered [(≡SiO- tBu 4 POCOP)Ir(C 2 H 4 )] (3-C 2 H 4 ) was converted fully to [(≡SiO- tBu 4 POCOP)Ir(CO)] (3-CO) at 300 °C. In this work, the characterization of species under dehydrogenation reaction conditions far from equilibrium between butane and butenes (approach to equilibrium Q/K eq = 0.3 at 300 °C) is performed with operando Diffuse Reflectance Infrared Fourier–Transform Spectroscopy (DRIFTS) to show the kinetics of species conversion from 3-C 2 H 4 to 3-CO. It is further found that [(≡SiO- tBu 4 POCOP)IrHCl] (3-HCl), a species considered to be a precatalyst for alkane dehydrogenation, is also fully converted to 3-CO. Here, a mechanism of decomposition is proposed that implicates surface silanol groups, while carbon monoxide acts as a “stabilizer” for the catalyst by promoting their reductive elimination and maintaining the complex in the I oxidation state.

02 PETROLEUM↗

Effect of surface acidity modulation on Pt/Al 2 O 3 single atom catalyst for carbon monoxide oxidation and methanol decomposition

With ideal metal utilization efficiency and homogeneous active sites, single atom catalysts (SACs) have attracted extensive attention in heterogeneous catalysis field. The performance of SACs is highly dependent on the local coordination environment of metal single atoms. However, few works reported the effect of surface acidity modification on the performance of SACs such as Pt SACs which have been widely studied nowadays. In this work, a Pt/Al 2 O 3 SAC has been successfully prepared using a bayerite Al(OH) 3 as support through simple IWI method for Pt loading. Through post-modification of Pt/Al 2 O 3 with acidic WO 3 and basic MgO, the surface acidity of Pt/Al 2 O 3 was tuned. Here, activity of CO oxidation and methanol decomposition on the modified catalysts has been evaluated. It was found that the catalytic performance was highly related to the surface acidity of Pt SACs. Basic MgO modified Pt/Al 2 O 3 performed better in CO oxidation under the reaction condition with H 2 O. Acidic WO 3 modified Pt/Al 2 O 3 showed superior activity in methanol decomposition. Detailed characterization and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study suggested that the positive H 2 O effect on CO oxidation was due to the mitigated formation of bicarbonate species on Pt/Al 2 O 3 and WO 3 /Pt/Al 2 O 3 catalysts and the promoted desorption of carbonate species from MgO/Pt/Al 2 O 3 . The superior methanol decomposition performance on WO 3 /Pt/Al 2 O 3 was owing to its abundant oxygen vacancies and high resistance to carbonate accumulation. This study highlights the importance of surface acidity modulation of Pt SACs in heterogeneous catalysis and suggests that fine-tuning the surface acidity can be an effective strategy in new SACs development.

36 MATERIALS SCIENCE↗

Interpreting Space-Based Trends in Carbon Monoxide with Multiple Models

We use a series of chemical transport model and chemistry climate model simulations to investigate the observed negative trends in MOPITT CO over several regions of the world, and to examine the consistency of timedependent emission inventories with observations. We find that simulations driven by the MACCity inventory, used for the Chemistry Climate Modeling Initiative (CCMI), reproduce the negative trends in the CO column observed by MOPITT for 2000-2010 over the eastern United States and Europe. However, the simulations have positive trends over eastern China, in contrast to the negative trends observed by MOPITT. The model bias in CO, after applying MOPITT averaging kernels, contributes to the model-observation discrepancy in the trend over eastern China. This demonstrates that biases in a model's average concentrations can influence the interpretation of the temporal trend compared to satellite observations. The total ozone column plays a role in determining the simulated tropospheric CO trends. A large positive anomaly in the simulated total ozone column in 2010 leads to a negative anomaly in OH and hence a positive anomaly in CO, contributing to the positive trend in simulated CO. These results demonstrate that accurately simulating variability in the ozone column is important for simulating and interpreting trends in CO.

carbon monoxide↗

Carbon Monoxide and the Potential for Prebiotic Chemistry on Habitable Planets Around Main Sequence M Stars

Lifeless planets with CO2 atmospheres produce CO by CO2 photolysis. On planets around M dwarfs, CO is a long-lived atmospheric compound, as long as UV emission due to the stars chromospheric activity lasts, and the sink of CO and O2 in seawater is small compared to its atmospheric production. Atmospheres containing reduced compounds, like CO, may undergo further energetic and chemical processing to give rise to organic compounds of potential importance for the origin of life. We calculated the yield of organic compounds from CO2-rich atmospheres of planets orbiting M dwarf stars, which were previously simulated by Domagal- Goldman et al. (2014) and Harman et al. (2015), by cosmic rays and lightning using results of experiments by Miyakawaet al. (2002) and Schlesinger and Miller (1983a, 1983b). Stellar protons from active stars may be important energy sources for abiotic synthesis and increase production rates of biological compounds by at least 2 orders of magnitude compared to cosmic rays. Simple compounds such as HCN and H2CO are more readily synthesized than more complex ones, such as amino acids and uracil (considered here as an example), resulting in higher yields for the former and lower yields for the latter. Electric discharges are most efficient when a reducing atmosphere is present. Nonetheless, atmospheres with high quantities of CO2 are capable of producing higher amounts of prebiotic compounds, given that CO is constantly produced in the atmosphere. Our results further support planetary systems around M dwarf stars as candidates for supporting life or its origin.

M stars↗

Rationalizing Burned Carbon with Carbon Monoxide Exported from South America

We present several estimates cross-checking the fluxes of carbon to the atmosphere from burning, comparing models that are based on simple land-surface parameterizations and atmospheric transport dynamics. Both estimates made by NASA Ames and USP modeling techniques are quite high compared to some detailed satellite/land-use studies of emissions. The flux of carbon liberated to the atmosphere via biomass burning is important for several reasons. This flux is a fundamental statistic for the parameterization of the large-scale flux of gases controlling the reactive greenhouse gases methane and ozone. Similarly, it is central to the estimation of the translocation of nitrogen and pyrodenitrification in the tropics. Thirdly, CO2 emitted from rainforest clearing contributes directly to carbon lost from the rainforest system as it contributes to greenhouse gas forcing. While CO2 from pasturage, agriculture, etc, is considered to be reabsorbed seasonally, and so "off budget" for the carbon cycle, it must also be accounted. CO2 anomalies related to daily weather and interannual climatic variation are strong enough to perturb our scientific perception of long-term carbon storage trends. We compare fluxes deduced from land-use statistics (originally, W.M. Hao) and from satellite hot pixels (A. Setzer) with atmospheric fluxes determined by the mesoscale/continental scale models RAMS and MM5, and point to some new work with highly resolved global models (the NASA Data Assimilation Office's GEOS4). Our simulations are tied to events, so that measured tracers like CO tie the models directly to the burning and meteorology of a specific period. We point out a particular sensitivity in estimates based on CO, and indicate how analysis of CO2 along with other biomass-burning tracers may lead to an improved multi-species estimator of carbon burned.

Chatfield, R.↗

Gas-phase production of single-walled carbon nanotubes from carbon monoxide: a review of the hipco process

The latest process for producing large quantities of single-walled carbon nanotubes (SWNTs) to emerge from the Rice University, dubbed HiPco, is living up to its promise. The current production rates approach 450 mg/h (or 10 g/day), and nanotubes typically have no more than 7 mol % of iron impurities. Second-generation HiPco apparatus can run continuously for 7-10 days at a time. In the HiPco process nanotubes grow in high-pressure, high-temperature flowing CO on catalytic clusters of iron. Catalyst is formed in situ by thermal decomposition of iron pentacarbonyl, which is delivered intact within a cold CO flow and then rapidly mixed with hot CO in the reaction zone. Upon heating, the Fe(CO)5 decomposes into atoms that condense into larger clusters. SWNTs nucleate and grow on these particles in the gas phase via CO disproportionation: CO + CO --> CO2 + C (SWNT), catalyzed by the Fe surface. The concentration of CO2 produced in this reaction is equal to that of carbon and can therefore serve as a useful real-time feedback parameter. It was used to study and optimize SWNT production as a function of temperature, pressure, and Fe(CO)5 concentration. The results of the parametric study are in agreement with current understanding of the nanotube formation mechanism.

Review↗

Diagnostics Adapted for Heat-Treating Furnace Environment

Diagnostics developed for the in situ monitoring of rocket combustion environments were adapted for use in heat-treating furnaces. Simultaneous, in situ monitoring of the carbon monoxide, carbon dioxide, methane, water, and hydrogen concentrations in the endothermic gas of a heat-treating furnace were demonstrated under a Space Act Agreement between the NASA Lewis Research Center, the Heat Treating Network, and Akron Steel Treating Company. This endothermic gas, or "endogas," is produced in a catalytic process, where natural gas is "cracked" in the presence of air. Variations in the composition of the natural gas supplied lead to variations in the composition of the endothermic gas. These variations could lead to an unacceptable quality of steel products that are hardened through the carborization process that uses this gas. Conventional methods of monitoring the endogas include measuring the dew point of the gas and the oxygen concentration. From these data, the carbon monoxide content of the gas can be calculated. This carbon monoxide concentration creates the carbon potential needed for carburization. Several weak links are present in this approach. The oxygen monitor deteriorates over time, and the measurement might be inaccurate by 50 percent. Also, the chemistry equations, which are based on several assumptions, such as secondary species concentrations, provide only an approximate estimate of the carbon monoxide concentration. To address these weaknesses, we investigated a new method based on ordinary Raman spectroscopy, in which the carbon monoxide concentration is measured directly and in situ. This method measures the laser light scattered from the molecules. Each species interacts with the light and scatters the light at a different frequency. Spectral monitoring of the scattered light intensity at each molecular frequency of interest provides the species concentrations. One advantage over the conventional method is that several species can be monitored simultaneously. A second advantage is that the measurement is direct; there is no need to make assumptions, to filter the gas, or to calibrate the instrument. An instrument was designed consisting of a laser and a detection system within an enclosure, connected to an optical probe by fibers. For determining carbon monoxide concentration, the probe is mounted on the endothermic gas line, close to the generator. Optical fibers with a length of 150 ft have been used to transmit laser light from the instrument to the probe. There, the light is focused into the gas, and the scattered light is collected and transmitted back to the instrument where it is analyzed with a photomultiplier and lock-in amplifier. Laboratory tests have shown that with the current system the concentration of carbon monoxide, water, nitrogen, oxygen, and hydrogen in the air can be monitored with an accuracy of 1 percent. The concentration of carbon dioxide in the air can be monitored with an accuracy of 0.5 percent, and the concentration of methane with an accuracy of 0.2 percent. This instrument was taken to the Akron Steel Treating Plant, where field tests are in progress to verify the system capabilities. Planned developments are improving the accuracy, monitoring multiple locations, and reducing instrument size and cost.

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The GeoCarb Mission: One Tool in the Evolving Understanding of Methane and Carbon Monoxide Budgets

NASA plans to operate an instrument in geostationary orbit over the Americas beginning in 2022. This mission allows a coordinated study of climate-determining carbon species. Prime focus is on CO2 fluxes, but the reactive species CO and CH4 are particularly relevant to IGAC. Measurements of solar-induced fluorescence will describe plant photosynthesis contemporaneous with emissions. To outline the technology: Grating mapping spectrometery, using a single slit and four focal planes set at 0.76, 1.60, 2.07, and 2.32 microns and ~17000 resolving power. Retrieval profiting from the rich heritage of OCO-2, GOSAT, TropOMI, and GOME/SCIAMACHY. Column concentrations of CO2, CH4, and CO, with finest resolution at 3 km x 6 km. A selection of scans allowing appreciable refinement in fluxes of CO2 and CH4. Rapid re-pointing allowing at least one synoptic observation of all North and South America daily, and 3 observations through the day for selected areas.This presentation is an appeal to IGAC community to use GeoCarb to help improve the attribution of fluxes by sector and by geography. Cost constraints allow GeoCarb only limited listed goals. For example, GeoCarb aspires to constrain CH4 emissions for the whole US, closing the ~60% gap between US EPA estimation and 3-d models. Detailed CO measurements should also aid photochemical and aerosol studies. NASA's TEMPO (UV-Vis geostationary) instrument will overlap GeoCarb. Consequently, HCHO, NO2, aerosol, and CO may be intercompared, allowing elucidation of chemical sources and also transformation timescales. We expect that Sentinel-5P's TropOMI will lead the way here; geostationary imaging will allow diurnal views and reduced cloud obscuration of interesting areas. Analysis of current data suggests interesting questions: (a) puzzling XCH4 diel variations in the Amazonian rainforest; (b) time-varying CO/NO2 relationships in urban plumes. We also urge the suite of airborne and small-sat measurements needed to complete the story at fine scales.

Chatfield, Robert B.↗

Model Analysis of the Factors Regulating Trends and Variability of Methane, Carbon Monoxide and OH: 1. Model Validation

Methane (CH4) is the second most important anthropogenic greenhouse gas (GHG). Its 100-year global warming potential (GWP) is 25 times larger than that for carbon dioxide. The 100-yr integrated GWP of CH4 is sensitive to changes in OH levels. Methane's atmospheric growth rate was estimated to be more than 10 ppb yr(exp -1) in 1998 but less than zero in 2001, 2004 and 2005 (Kirschke et al., 2013). Since 2006, the CH4 is increasing again. This phenomena is yet not well understood. Oxidation of CH4 by OH is the main loss process, thus affecting the oxidizing capacity of the atmosphere and contributing to the global ozone background. Current models typically use an annual cycle of offline OH fields to simulate CH4. The implemented OH fields in these models are typically tuned so that simulated CH4 growth rates match that measured. For future and climate simulations, the OH tuning technique may not be suitable. In addition, running full chemistry, multi-decadal CH4 simulations is a serious challenge and currently, due to computational intensity, almost impossible.

OH↗

The origin of carbon monoxide in Neptunes's atmosphere

The CO abundance in the observable atmosphere of Neptune can be plausibly explained by rapid vertical mixing from the deeper atmosphere if Neptune has a greater complement of water than Uranus. Thermochemical equilibrium and kinetic calculations reveal that Neptune must and Uranus may have about 10 times more oxygen than carbon, whereas for Jupiter and Saturn equal enrichments of carbon and oxygen are satifactory to explain the observed CO abundances by deep vertical mixing. Relative to hydrogen and solar composition, the respective enrichment factors for carbon and oxygen are 41, 440 (Neptune); 32, less than or equal 260 (Uranus); 6.6, 6.6 (Saturn); and 2.8, 2.8 (Jupiter). Because water ice is the most refractory ice among the ices assumed to be present in the outer solar nebula, the most massive H2O enrichment is expected for the outermost planet of this group. Thus, Neptune can indeed be regarded as the 'god of the seas.'

Lodders, K.↗

Photochemical reactions of water and carbon monoxide in earth's primitive atmosphere

The gas-phase photolysis of H2O at 1849 A in the presence of CO yields mainly CO2 and H2 and a variety of organic compounds, including C1-C3 hydrocarbons, alcohols, aldehydes, acetone, and acetic acid. The overall quantum yield for conversion of CO to organic compounds varies between 0.23 and 0.03 as a function of the CO abundance. These results indicate that even if primitive earth's atmosphere initially contained no molecular hydrogen and contained carbon only in the form of CO or a mixture of CO and CO2, the prebiotic environment would have become enriched with a variety of organic compounds produced by photochemical processes.

Bar-Nun, A.↗

Advanced nanoscale characterization of aluminum nanoparticles with modified surface morphology via atmospheric helium and carbon monoxide plasmas

Aluminum nanoparticles (nAl) have the potential as energetic additives in explosive/propellant formulations. Scalable methodologies must be pursued to mitigate the inactive amorphous alumina shell surrounding the active aluminum (Al) core with modified surface morphology and chemistry for increased combustion effects. This work explores the feasibility of making reactive core/shell nAl with thinned oxide shells and modified surface coatings via a two-step atmospheric plasma surface treatment process in a custom dielectric barrier discharge plasma reactor. The commercial nAl of nominal average size similar to 40-60nm was first treated with helium (He) followed by He/carbon monoxide (CO) plasmas for different durations. The resultant samples were characterized via high-resolution transmission electron microscopy (HRTEM) and Fourier transform IR (FTIR) spectra. HRTEM images revealed sporadic patchy gamma -alumina deposits on particle surfaces and in gaps among particles for all samples, suggesting the non-uniform plasma effects of the He/CO glow. Nanoscale chemical analyses via scanning transmission electron microscopy elemental mapping and x-ray energy dispersive spectroscopy were further performed. Although no carbon-associated structure appeared in electron energy loss spectroscopy (EELS) spectra, the presence of carbonaceous materials was confirmed as a thin dispersive layer evenly distributed on the nAl surface suggesting either its amorphous nature or is present at a level insufficient to generate satisfactory EELS spectra. The trend of intensity profiles for key elements acquired by drawing lines across a single particle on the elemental maps confirmed that carbonaceous materials only existed on the surface and they were most likely carboxylates that increased with increased He/CO treatment duration, as evident by FTIR results. Finally, this work demonstrated the success of atmospheric plasma-treated reactive nAl with comprehensively characterized surface features via advanced microscopy and spectroscopy.

36 MATERIALS SCIENCE↗