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At least 1,639 records · Page 91

Multiplex gas chromatography: an alternative concept for gas chromatographic analysis of planetary atmospheres

Gas chromatography (GC) is a powerful technique for analyzing gaseous mixtures. Applied to the earth's atmosphere, GC can be used to determine the permanent gases--such as carbon dioxide, nitrogen, and oxygen--and to analyze organic pollutants in air. The U.S. National Aeronautics and Space Administration (NASA) has used GC in spacecraft missions to Mars (the Viking Biology Gas Exchange Experiment [GEX] and the Viking Gas Chromatograph-Mass Spectrometer [GC-MS]) and to Venus (the Pioneer Venus Gas Chromatograph [PVGC] on board the Pioneer Venus sounder probe) for determining the atmospheric constituents of these two planets. Even though conventional GC was very useful in the Viking and Pioneer missions, spacecraft constraints and limitations intrinsic to the technique prevented the collection of more samples. With the Venus probe, for instance, each measurement took a relatively long time to complete (10 min), and successive samples could not be introduced until the previous samples had left the column. Therefore, while the probe descended through the Venusian atmosphere, only three samples were acquired at widely separated altitudes. With the Viking mission, the sampling rate was not a serious problem because samples were acquired over a period of one year. However, the detection limit was a major disadvantage. The GC-MS could not detect simple hydrocarbons and simple alcohols below 0.1 ppm, and the GEX could not detect them below 1 ppm. For more complex molecules, the detection limits were at the parts-per-billion level for both instruments. Finally, in both the Viking and Pioneer missions, the relatively slow rate of data acquisition limited the number of analyses, and consequently, the amount of information returned. Similar constraints are expected in future NASA missions. For instance, gas chromatographic instrumentation is being developed to collect and analyze organic gases and aerosols in the atmosphere of Titan (one of Saturn's satellites). The Titan-Cassini entry probe, which is being jointly planned by NASA and the European Space Agency (ESA), might be launched as early as 1994. As in the Pioneer mission, limited time--perhaps only 3-4 h--will be available for the completion of all analyses while the probe descends through the atmosphere. A conventional GC or GC-MS system would be able to analyze no more than two aerosol and two gas samples during the probe's descent. Conventional GC also is limited by the sensitivity of the detector and by the sample volume. For the Titan mission, the sensitivity problems will be worse because the atmospheric pressure at the time of instrument deployment is expected to be < 3 torr. Consequently, the sample volume might not be large enough to satisfy the detector sensitivity requirements. Because of such limitations, alternative GC analysis techniques have been investigated for future NASA missions. Multiplex gas chromatography has been investigated as a possible candidate for chemical analysis within a spacecraft or other restricted environment, and chemical modulators have been developed and used when needed with this technique to reduce the size and weight of the instrumentation. Also, several new multiplex techniques have been developed for use in specific applications.

NASA Center ARC↗

Synthesis of the coenzymes adenosine diphosphate glucose, guanosine diphosphate glucose, and cytidine diphosphoethanolamine under primitive Earth conditions

The nonenzymatic synthesis of the coenzymes adenosine diphosphate glucose (ADPG), guanosine diphosphate glucose (GDPG), and cytidine diphosphoethanolamine (CDP-ethanolamine) has been carried out under conditions considered to have been prevalent on the early Earth. The production of these compounds was performed by allowing simple precursor molecules to react under aqueous solutions, at moderate temperatures and short periods of time, with mediation by cyanamide or urea. These two condensing agents are considered to have been present in significant amounts on the primitive Earth and have been previously used in the nonenzymatic synthesis of several other important biochemical compounds. In our experiments, ADPG was obtained by heating glucose-1-phosphate (G1P) and ATP in the presence of cyanamide for 24 h at 70 degrees C. The reaction of G1P and GTP under the same conditions yielded GDPG. The cyanamide-mediated production of CDP-ethanolamine was carried out by reacting a mixture of ethanolamine phosphate and CTP for 24 h at 70 degrees C. The separation and identification of the reaction products was carried out by paper chromatography, thin-layer chromatography, high performance thin-layer chromatography, high performance liquid chromatography, both normal and reverse-phase, UV spectroscopy, enzymatic assays, and acid hydrolysis. Due to the mild conditions employed, and to the relative ease of these reactions, these studies offer a simple attractive system for the nonenzymatic synthesis of phosphorylated high-energy metabolic intermediates under conditions considered to have been prevalent on the ancient Earth.

NASA Discipline Exobiology↗

Catalyst for Carbon Monoxide Oxidation

In many applications, it is highly desirable to operate a CO2 laser in a sealed condition, for in an open system the laser requires a continuous flow of laser gas to remove the dissociation products that occur in the discharge zone of the laser, in order to maintain a stable power output. This adds to the operating cost of the laser, and in airborne or space applications, it also adds to the weight penalty of the laser. In a sealed CO2 laser, a small amount of CO2 gas is decomposed in the electrical discharge zone into corresponding quantities of CO and O2. As the laser continues to operate, the concentration of CO2 decreases, while the concentrations of CO and O2 correspondingly increase. The increasing concentration of O2 reduces laser power, because O2 scavenges electrons in the electrical discharge, thereby causing arcing in the electric discharge and a loss of the energetic electrons required to boost CO2 molecules to lasing energy levels. As a result, laser power decreases rapidly. The primary object of this invention is to provide a catalyst that, by composition of matter alone, contains chemisorbed water within and upon its structure. Such bound moisture renders the catalyst highly active and very long-lived, such that only a small quantity of it needs to be used with a CO2 laser under ambient operating conditions. This object is achieved by a catalyst that consists essentially of about 1 to 40 percent by weight of one or more platinum group metals (Pt, Pd, Rh, Ir, Ru, Os, Pt being preferred); about 1 to 90 percent by weight of one or more oxides of reducible metals having multiple valence states (such as Sn, Ti, Mn, Cu, and Ce, with SnO2 being preferred); and about 1 to 90 percent by weight of a compound that can bind water to its structure (such as silica gel, calcium chloride, magnesium sulfate, hydrated alumina, and magnesium perchlorate, with silica gel being preferred). Especially beneficial results are obtained when platinum is present in the catalyst composition in an amount of about 5 to 25 (especially 7) percent by weight, SnO2 is present in an amount of about 30 to 40 (especially 40) percent by weight, and silica gel is present in an amount of 45 to 55 (especially 50) percent by weight. The composition of this catalyst was suggested by preliminary experiments in which a Pt/SnO2 catalyst was needed for bound water to enhance its activity. These experimental results suggested that if the water were bound to the surface, this water would enhance and prolong catalyst activity for long time periods. Because the catalyst is to be exposed to a laser gas mixture, and because a CO2 laser can tolerate only a very small amount of moisture, a hygroscopic support for the catalyst would provide the needed H2O into the gas. Silica gel is considered to be superior because of its property to chemisorb water on its surface over a wide range of moisture content.

Davis, Patricia↗

A Phenomenological Thermal Spray Wall Interaction Modeling Framework Applied to a High Temperature Ignition Assistant Device

Airborne compression ignition engines must operate with reliable ignition systems to achieve proper ignition at every cycle, particularly at high altitudes. Glow-plug-based ignition-assistant (IA) devices can provide the necessary energy to preheat the fuel and ensure ignitability of the fuel-air mixture. Ignitability of liquid sprays can be facilitated via direct impingement onto the hot IA surface, however this comes with adverse effects on the IA durability. Therefore, optimizing an IA’s design requires detailed understanding of the physics of fuel spray impingement of superheated surfaces. While spray impingement on relatively low wall temperatures has been extensively studied and appropriate numerical models have been proposed through the years, fundamental understanding of high-speed liquid spray impingement on superheated walls is still elusive. This work aims to formulate a phenomenological thermal spray-wall interaction framework for modeling the film-boiling-induced heat transfer, atomization, and dispersion of fuel spray droplets impinging onto a superheated IA device. A qualitative comparison of the new phenomenological model is performed against optical experiments from the literature of an F-24 fuel spray injected onto an IA device located 12 mm away from the injector tip. The temperature of the IA was set at 1400 K. The fuel injection pressure was 400 bar, while the ambient gas pressure and temperature were 30 bar and 800 K, respectively. The performance of the phenomenological model is evaluated in comparison with two other state-of-art models from the literature. A qualitative analysis of the different spray and fuel-air mixture characteristics is performed to outline the differences in the predictions offered by the new phenomenological model and the two state-of-art spray-wall interaction models.

droplet dispersion↗

A micro hot test of the Chalmers-GANEX extraction system on used nuclear fuel

In the present study, a 'micro hot test' has been performed using the Chalmers-GANEX (Group Actinide Extraction) system for partitioning of used nuclear fuel. The test included a pre-extraction step using N,N-di-2- ethylhexyl-butyramide (DEHBA) in n-octanol to remove the bulk part of the uranium. This pre-extraction was followed by a group extraction of actinides using the mixture of TBP and CyMe{sub 4}-BTBP in cyclohexanone as suggested in the Chalmers-GANEX process, and a three stage stripping of the extracted actinides. Distribution ratios for the extractions and stripping were determined based on a combination of γ- and α-spectrometry, as well as ICP-MS measurements. Successful extraction of uranium, plutonium and the minor actinides neptunium, americium and curium was achieved. However, measurements also indicated that co-extraction of europium occurs to some extent during the separation. These results were expected based on previous experiments using trace concentrations of actinides and lanthanides. Since this test was only performed in one stage with respect to the group actinide extraction, it is expected that multi stage tests will give even better results. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Multi-omic elucidation of aromatic catabolism in adaptively evolved Rhodococcus opacus

Lignin utilization has been identified as a key factor in biorefinery profitability. However, lignin depolymerization generates heterogeneous aromatic mixtures that inhibit microbial growth and conversion of lignocellulose to biochemicals. Rhodococcus opacus is a promising aromatic-catabolizing, oleaginous bacterium, but mechanisms for its aromatic tolerance and utilization remain undercharacterized. To better understand these mechanisms, we adaptively evolved R. opacus for improved utilization of 32 combinations of diverse aromatic compounds. Evolved R. opacus mutants showed up to 1900% growth improvement in the utilization of phenol, guaiacol, 4-hydroxybenzoate, vanillate, and benzoate compared to the wild-type strain. Whole genome sequencing revealed several redox-related genes with mutations shared across multiple adapted mutants. PVHG6, the mutant with the most improved growth on a mixture of multiple aromatic compounds, showed 56% lower superoxide dismutase activity than the wild-type strain, suggesting that redox reactions are important for aromatic tolerance and utilization. Comparative transcriptomics revealed by-product detoxification pathways and five aromatic funneling pathways that were upregulated in response to specific aromatic compounds. Gene knockout experiments confirmed the two degradation routes of the β-ketoadipate pathway for five aromatic compounds. Finally, these results provide an improved understanding of aromatic bioconversion and facilitate development of R. opacus as a biorefinery host.

09 BIOMASS FUELS↗

First-Principles Petascale Simulations for Predicting Deflagration to Detonation Transition in Hydrogen-Oxygen Mixtures

Hydrogen has emerged as an important fuel across a range of industries as a means of achieving energy independence and to reduce emissions. DDT and the resulting detonation waves in hydrogen-oxygen can have especially catastrophic consequences in a variety of industrial and energy producing settings related to hydrogen. First-principles numerical simulations of flame acceleration and DDT are required for an in-depth understanding of the phenomena and facilitating design of safe hydrogen systems. The goals of this project were (1) to develop first-principles petascale reactive flow Navier-Stokes simulation code for predicting gaseous high-speed combustion and detonation (HSCD) phenomena and (2) demonstrate feasibility of first-principles simulations of rapid flame acceleration and deflagration-to-detonation transition (DDT) in stoichiometric hydrogen-oxygen mixture (2H 2 + O 2 ). The goals of the project have been accomplished. We have developed a novel numerical simulation code, named HSCD, for performing first-principles direct numerical simulations of high-speed hydrogen combustion. We carried out a series of validating numerical simulations of inert and reactive shock reflection experiments in shock tubes. We then performed a pilot numerical simulation of flame acceleration in a long pipe. The simulation showed the transition of the rapidly accelerating flame into a detonation. The DDT simulations were performed using BG/Q Mira at the Argonne National Laboratory, currently the fourth fastest super-computer in the world.

08 HYDROGEN↗

Characterization of Oil and Gas Drill Cuttings for Critical Mineral Recovery and Reuse Potential as Soil Supplements

Expansion of unconventional oil and natural gas production over the last decade in the United States has resulted in record production of natural gas and oil in 2024. Millions of tons of drill cuttings generated from shale gas development are currently disposed of in landfills. Converting these cuttings into value product(s) such as critical minerals (CMs) and soil supplements, has the potential of reducing environmental impact of fossil fuel exploration. In this study we characterize the CM distribution and extractability from collected drill cuttings and core samples from major U.S. shale formations. A four-step sequential extraction, consisting of a sonicated soap step, sonicated EDTA step , mildly reducing agent, and a oxidizing agent, was developed to simultaneously extract CMs and convert the drill cuttings into soil supplements. Viability of converted drill cuttings as soil supplement was determined with a seedling growth experiment. Results show high concentrations of vanadium (V) (up to 1575 ppm, barite (up to 5 wt. %), and rare earth elements (REE) concentrations (up to 253 ppm). High extractability of selected critical minerals such as REE (19-50%) and Ba (10-58%) show promising results. Preliminary results show seedling growth in a mixture of converted drill cuttings with soil. These results show the potential for recovery of CMs from drill cuttings as an alternative domestic and the reduction of the environmental impact of fossil fuel production.

Barczok, Maximilian↗

An ERTS multispectral scanner experiment for mapping iron compounds

There are no author-identified significant results in this report. An experimental plan for enhancing spectral features related to the chemical composition of geological targets in ERTS multispectral scanner data is described. The experiment is designed to produce visible-reflective infrared ratio images from ERTS-1 data. Iron compounds are promising remote sensing targets because they display prominent spectral features in the visible-reflective infrared wavelength region and are geologically significant. The region selected for this ERTS experiment is the southern end of the Wind River Range in Wyoming. If this method proves successful it should prove useful for regional geologic mapping, mineralogical exploration, and soil mapping. It may also be helpful to ERTS users in scientific disciplines other than geology, especially to those concerned with targets composed of mixtures of live vegetation and soil or rock.

Vincent, R. K.↗

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

The formation of nitrogen oxides NOx during combustion of methane, propane, and a jet fuel, JP-4, was investigated in a jet stirred combustor. The results of the experiments were interpreted using reaction models in which the nitric oxide (NO) forming reactions were coupled to the appropriate hydrocarbon combustion reaction mechanisms. Comparison between the experimental data and the model predictions reveals that the CH + N2 reaction process has a significant effect on NO formation especially in stoichiometric and fuel rich mixtures. Reaction models were assembled that predicted nitric oxide levels that were in reasonable agreement with the jet stirred combustor data and with data obtained from a high pressure (5.9 atm (0.6 MPa)), prevaporized, premixed, flame tube type combustor. The results also suggested that the behavior of hydrocarbon mixtures, like JP-4, may not be significantly different from that of pure hydrocarbons. Application of the propane combustion and nitric oxide formation model to the analysis of NOx emission data reported for various aircraft gas turbines showed the contribution of the various nitric oxide forming processes to the total NOx formed.

Jachimowski, C. J.↗

Effects of Microsecond Pulse Laser Irradiation on Vis-NIR Reflectance Spectrum of Carbonaceous Chondrite Simulant: Implications for Martian Moons and Primitive Asteroids

Goal of this study is to make a progress in understanding the optical effects of space weathering on small bodies believed to be similar in composition to carbonaceous chondrites: C, G, B, F, T, D, and P asteroids and possibly Martian satellites Phobos and Deimos. The companion work focuses on petrological and mineralogical aspects of this process. One of the main factors of space weathering is meteorite and micrometeorite bombardment leading, in particular, to impact melting of components of the regolith. Studies of lunar regolith and laboratory experiments simulating impact melting show that the melting products differ from the unmelted material in mineralogy and distribution of chemical components among different phases that results in spectral changes. We simulate impact melting of CM chondrite by pulse laser irradiation of an artificial analog of such a meteorite. The analog is a mixture of 46 wt.% non-magnetic fraction of L5 ordinary chondrite Tsarev, 47 wt.% serpentine, 5 wt.% kerite, and 2 wt.% calcite. It simulates rather well bulk chemistry, including volatiles such as H2O and CO2, and only approximately the CM chondrite mineralogy. Thus, we do not expect the mixture to be spectrally similar to CM chondrites, but expect the laser melting products to be similar to those formed by impact melting of natural CM chondrites.

Hiroi, T.↗

Buoyancy Effects in Strongly-Pulsed, Turbulent Diffusion Flames

The objective of this experiment is to better understand the combustion behavior of pulsed, turbulent diffusion flames by conducting experiments in microgravity. The fuel jet is fully-modulated (i.e., completely shut off between pulses) by an externally controlled valve system leading to enhanced fuel/air mixing compared to acoustically excited or partially-modulated jets. Experiments are conducted both in laboratories at UW and WPI and in the GRC 2.2s Drop Tower. A single fuel nozzle with diameter d = 2 mm is centered in a combustor 20 20 cm in cross section and 67 cm in height. The gaseous fuel flow (ethylene or a 50/50 ethylene/nitrogen mixture by volume) is fully-modulated by a fast-response solenoid valve with injection times from tau = 4 to tau = 300 ms. The nominal Reynolds number based on the fuel velocity during injection, U(sub jet), is 5,000. A slow oxidizer co-flow properly ventilates the flame and an electrically heated wire loop serves as a continuous ignition source. Diagnostic techniques include video imaging, fine-wire thermocouples and thermopile radiometers, and gas sampling and standard emissions instruments (the last in the laboratory only).

Hermanson, J. C.↗

Mixing and Recovery Performance of Triplet Impinging Injectors with Varying Flow Areas for Detonative Combustion

Detonation combustion devices such as rotating detonation rocket engines (RDREs) have been proposed as an alternative to traditional deflagration engines as detonative combustion has a higher theoretical thermodynamic efficiency. Improved performance of an RDRE depends heavily on the propellant injection and mixing. Impingement type injectors have been shown to achieve higher characteristic velocity or combustion efficiency for both detonative and deflagrative engines. This work is exploratory in nature and focuses on unlike triplet impinging injectors to study how the flow area of the injector affects the mixing of propellants and recovery under the transient, high-peak pressure conditions unique to RDREs. A ratio of fuel flow area to oxidizer flow area is set to achieve a given mass flow rate and thus propellant mixture ratio. Four different fluid flow areas are studies while keeping the fuel/oxidizer ratio constant. This work has found that, while maintaining a fixed ratio fuel to oxidizer flow area, the injectors with smaller orifice areas show better resistance to backflow in steady state tests and have shorter recovery times in backflow experiments. Even with the shorter recovery times, it is found that the shortest recovery time is still an order of magnitude slower than the frequency of a single detonation wave traversing a 3” RDRE.

Michaela R. Hemming↗

The Impact of Fullerene Structure on Its Miscibility with P3HT and Its Correlation of Performance in Organic Photovoltaics

Neutron reflectivity experiments are utilized to obtain the miscibility limit of four different fullerenes, bis-PCBM, ICBA, thio-PCBM, and PC70BM, in poly(3-hexylthiophene) (P3HT). The intermixing of P3HT and fullerene bilayers is monitored by neutron reflectivity before and after thermal annealing, providing quantification of the miscibility and interdiffusion of the fullerene within P3HT. These results indicate that the miscibility limit of these fullerenes in P3HT ranges from 11% to 26%, where the bis-adduct fullerenes exhibit lower miscibility in P3HT, which is also verified by small angle neutron scatting (SANS). The in-plane morphology of the P3HT:fullerene mixtures was also examined by SANS, which shows a decrease in domain size and an increase in the specific interfacial area between the fullerene and the polymer with the bis-fullerenes. Correlation of miscibility and morphology to device performance indicates that polymer/ fullerene miscibility is crucial to rationally optimize the design of fullerenes for use in organic photovoltaics. Bis-PCBM has a higher open circuit voltage (Voc) than PC60BM with P3HT; however, device performance of bis-PCBM based devices is lower than that of PC60BM based devices. This decrease in performance is attributed to the lower miscibility of bis-PCBM in P3HT, which decreases the probability of exciton dissociation and enhances the recombination of free charge carriers in the miscible region. Moreover, the minimum distance between fullerenes in the miscible region to facilitate intermolecular transport is identified as 11 .

Chen, Huipeng↗

Spatial electron density and electric field strength measurements in microwave cavity experiments

Measurements of electron density and electric field strength have been made in an argon plasma contained in a resonant microwave cavity at 2.45 GHz. Spatial measurements of electron density, n sub e, are correlated with fluorescence observations of the discharge. Measurements of n sub e were made with Stark broadening and compared with n sub 3 calculated from measured plasma conductivity. Additional measurements of n sub 3 as a function of pressure and in mixtures of argon and oxygen are presented for pressures from 10 Torr to 1 atm. Measurements in flowing gases and in static systems are presented. In addition, limitations of these measurements are identified.

Peters, M.↗

Spatial electron density and electric field strength measurements in microwave cavity experiments

Measurements of electron density and electric field strength have been made in an argon plasma contained in a resonant microwave cavity at 2.45 GHz. Spatial measurements of electron density, n sub e, are correlated with fluorescence observations of the discharge. Measurements of n sub e were made with Stark broadening and compared with n sub e calculated from measured plasma conductivity. Additional measurements of n sub e as a function of pressure and in mixtures of argon and oxygen are presented for pressures from 10 Torr to 1 atm. Measurements in flowing gases and in static systems are presented. In addition, limitations of these measurements are identified.

Peters, M.↗

Investigation of Frozen Chemistry for Molten Salt Reactors (MSRs)

Understanding accident progression and the potential/conditions for fission product release from fuel is necessary to evaluate safety for any nuclear reactor system. Molten Salt Reactors (MSRs) under development need such analysis to support safety evaluations. Fission product chemistry specific to MSR concepts is a critical area that introduces distinct considerations relative to the current state-of-knowledge in reactor safety, primarily developed for water-moderated nuclear reactor systems. In Light Water Reactor (LWR) systems, it is necessary to capture the chemical interaction of fission products with the reactor evironment, containment and confinement systems. The overall effects at this point are relatively well understood for the purposes of performing safety evaluations. A key insight from LWR studies is that fission product chemical behavior can be reasonably captured by modeling approaches where the chemistry is "frozen". These modeling approaches assume that radionuclide reaction and speciation can be represented by chemical classes, each with characteristic transport behavior that is invariant under a broad range of thermochemical conditions. However, radionuclides can exhibit a range of behavior in the liquid salt-melt phase of the coolant used in MSRs. Radionuclides, salt, and the metal containment surfaces (i.e. pipes) can co-exist in dynamic equilibrium that could evolve with small system mass changes. A detailed investigation to the degree the equilibrium state can dynamically evolve with changes in the conditions of the molten salt mixture has not been previously conducted. It is currently not well understood where frozen chemistry assumptions are valid. Expanding the state-of-knowledge in this regard is relevant to better assessing the range of chemical effects that should be incorporated as part of MSR safety assessments. This investigation used the Oak Ridge Isotope GENeration (ORIGEN) module of the Standardized Computer-Analysis for Licensing Evaluation (SCALE) code to generate simulated radionuclide inventories for the MSR Experiment (MSRE) and then modeled reactor chemical speciation using the Molten Salt Thermodynamic Database – Thermochemical (MSTDB-TC) coupled with Thermochimica. The effect of composition variation during decay of fission product inventory in a molten salt over a period of 500 days prolonged post- at multiple temperatures was studied. Mass fractions for fluorine and berilium were varied in order to probe the effects of free fluorine control. Finally, speciation of fluoride reactors were showed by comparing MSRE readionuclide inventories with a FLiBe based molten salt breeder reactor (MSBR). The results showed that fission product mass change has little effect on phase mass changes and vapor pressures for fluoride species, but differ with varying carrier and fuel salt compositions. However, iodine species were found to have a vapor pressure not only dependent on temperature, but also the free fluorine potential, releasing iodine when the free fluorine potential is equal to the iodine inventory. This observation, however, arose under free fluorine potentials that are very unlikely to be realized in typical molten salt mixtures. Despite this observation, temperature was found to be the dominant parameter that drove phase change and fission product species vapor pressure. The results indicate that the current frozen chemistry approach is adequate for MSR analysis.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗