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NASA NTRS1972

The origin and stability of lunar goethite, hematite and magnetite.

Extra-lunar contamination, fumarolic activity, and exposure to oxidizing gases from comet or carbonaceous meteorite impacts have been previously proposed as the causes of magnetite, hematite, and goethite in lunar materials. However, these minerals can occur in the stable low-temperature gas-solid equilibrium assemblages of lunar rocks. Below 600 C magnetite is in equilibrium with C-O-H gases with compositions compatible with high-temperature equilibrium with metallic iron; below 150 C hematite is stable in these same gases. Goethite is not stable in carbonaceous gases at low total pressure, and thus gases from impacting carbonaceous material cannot have produced it. Goethite is stable at low temperatures and pressures in almost pure H2-H2O gases. Its minimum stability against hematite is 2 bars total pressure at 130 C and 0.001 bars at 30 C for H2 to H2O ratios compatible with the high-temperature redox state of lunar materials. Thus the traces of magnetite, hematite, and goethite in lunar materials may be the result of normal low-temperature processes indigenous to the moon and not special processes.

Williams, R. J.↗

NASA NTRS1999

Gas Sensor Evaluations in Polymer Combustion Product Atmospheres

Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.

Delgado, Rafael H.↗

NASA NTRS2001

Buffer Gas Acquisition and Storage

The acquisition and storage of buffer gases (primarily argon and nitrogen) from the Mars atmosphere provides a valuable resource for blanketing and pressurizing fuel tanks and as a buffer gas for breathing air for manned missions. During the acquisition of carbon dioxide (CO2), whether by sorption bed or cryo-freezer, the accompanying buffer gases build up in the carbon dioxide acquisition system, reduce the flow of CO2 to the bed, and lower system efficiency. It is this build up of buffer gases that provide a convenient source, which must be removed, for efficient capture Of CO2 Removal of this buffer gas barrier greatly improves the charging rate of the CO2 acquisition bed and, thereby, maintains the fuel production rates required for a successful mission. Consequently, the acquisition, purification, and storage of these buffer gases are important goals of ISRU plans. Purity of the buffer gases is a concern e.g., if the CO, freezer operates at 140 K, the composition of the inert gas would be approximately 21 percent CO2, 50 percent nitrogen, and 29 percent argon. Although there are several approaches that could be used, this effort focused on a hollow-fiber membrane (HFM) separation method. This study measured the permeation rates of CO2, nitrogen (ND, and argon (Ar) through a multiple-membrane system and the individual membranes from room temperature to 193K and 10 kpa to 300 kPa. Concentrations were measured with a gas chromatograph that used a thermoconductivity (TCD) detector with helium (He) as the carrier gas. The general trend as the temperature was lowered was for the membranes to become more selective, In addition, the relative permeation rates between the three gases changed with temperature. The end result was to provide design parameters that could be used to separate CO2 from N2 and Ar.

Parrish, Clyde F.↗

NASA NTRS2004

Buffer Gas Experiments in Mercury (Hg+) Ion Clock

We describe the results of the frequency shifts measured from various buffer gases that might be used as a buffer gas to increase the loading efficiency and cooling of ions trapped in a small mercury ion clock. The small mass, volume and power requirement of space clock precludes the use of turbo pumps. Hence, a hermetically sealed vacuum system, incorporating a suitable getter material with a fixed amount of inert buffer gas may be a practical alternative to the groundbased system. The collision shifts of 40,507,347.996xx Hz clock transition for helium, neon and argon buffer gases were measured in the ambient earth magnetic field. In addition to the above non-getterable inert gases we also measured the frequency shifts due to getterable, molecular hydrogen and nitrogen gases which may be used as buffer gases when incorporated with a miniature ion pump. We also examined the frequency shift due to the low methane gas partial pressure in a fixed higher pressure neon buffer gas environment. Methane gas interacted with mercury ions in a peculiar way as to preserve the ion number but to relax the population difference in the two hyperfine clock states and thereby reducing the clock resonance signal. The same population relaxation was also observed for other molecular buffer gases (N H ,) but at much reduced rate.

mercury ion clock↗

NASA NTRS2001

Airbag vent valve and system

An energy absorbing airbag system includes one or more vent valve assemblies for controlling the release of airbag inflation gases to maintain inflation gas pressure within an airbag at a substantially constant pressure during a ride-down of an energy absorbing event. Each vent valve assembly includes a cantilever spring that is flat in an unstressed condition and that has a free end portion. The cantilever spring is secured to an exterior surface of the airbag housing and flexed to cause the second free end portion of the cantilever spring to be pressed, with a preset force, against a vent port or a closure covering the vent port to seal the vent port until inflation gas pressure within the airbag reaches a preselected value determined by the preset force whereupon the free end portion of the cantilever spring is lifted from the vent port by the inflation gases within the airbag to vent the inflation gases from within the airbag. The resilience of the cantilever spring maintains a substantially constant pressure within the airbag during a ride-down portion of an energy absorbing event by causing the cantilever spring to vent gases through the vent port whenever the pressure of the inflation gases reaches the preselected value and by causing the cantilever spring to close the vent port whenever the pressure of the inflation gases falls below the preselected value.

Peterson, Leslie D.↗

NASA NTRS2008

Are Fullerenes Relevant to Cosmochemistry? A New Finding

The abundances of noble gases found in primitive, carbonaceous meteorites are unexpected when compared with our Sun. Known as Q-gases (Q for some unknown carrier dubbed quintessence ), this anomaly has remained a mystery since it was discovered in 1975. Q-gases are characterized by increasing depletions with decreasing atomic number (Z) relative to solar noble gases and normalized to 132Xe (Figure 1). This Q-gas mass fractionation is unexplained, and its investigation is important to understanding the origin of the solar system. However, the subject is fraught with controversy, in part due to the complex nature of Q and in part due to claims of some researchers that cannot be reproduced by other investigators. The topic is discussed in numerous places [e.g., 1-4], with models of Q falling into two basic categories, both involving carbon entrapment of noble gases. First (Group A), there is the conservative two-dimensional view that Q-gases are adsorbed or sorbed onto a "labyrinth" of graphite or carbon grains [5-9], or they undergo active capture onto growing surfaces [6]. Second (Group B), there is the view holding to the remarkable property of carbon discovered in 1985. Carbon can curl up into closed geometries of hexagon- and pentagon-shaped carbon-ring configurations, a property ignored completely by Group A. Group B thinks of Q as a three-dimensional structure of endohedral carbon cages like fullerenes, carbon onions, or some class of carbon nanotubes [3, 4, 10]. Group B does not exclude Group A effects.

Wilson, T. L.↗

NASA NTRS2003

Calibrating Laser Gas Measurements by Use of Natural CO2

An improved method of calibration has been devised for instruments that utilize tunable lasers to measure the absorption spectra of atmospheric gases in order to determine the relative abundances of the gases. In this method, CO2 in the atmosphere is used as a natural calibration standard. Unlike in one prior calibration method, it is not necessary to perform calibration measurements in advance of use of the instrument and to risk deterioration of accuracy with time during use. Unlike in another prior calibration method, it is not necessary to include a calibration gas standard (and the attendant additional hardware) in the instrument and to interrupt the acquisition of atmospheric data to perform calibration measurements. In the operation of an instrument of this type, the beam from a tunable diode laser or a tunable quantum-cascade laser is directed along a path through the atmosphere, the laser is made to scan in wavelength over an infrared spectral region that contains one or two absorption spectral lines of a gas of interest, and the transmission (and, thereby, the absorption) of the beam is measured. The concentration of the gas of interest can then be calculated from the observed depth of the absorption line(s), given the temperature, pressure, and path length. CO2 is nearly ideal as a natural calibration gas for the following reasons: CO2 has numerous rotation/vibration infrared spectral lines, many of which are near absorption lines of other gases. The concentration of CO2 relative to the concentrations of the major constituents of the atmosphere is well known and varies slowly and by a small enough amount to be considered constant for calibration in the present context. Hence, absorption-spectral measurements of the concentrations of gases of interest can be normalized to the concentrations of CO2. Because at least one CO2 calibration line is present in every spectral scan of the laser during absorption measurements, the atmospheric CO2 serves continuously as a calibration standard for every measurement point. Figure 1 depicts simulated spectral transmission measurements in a wavenumber range that contains two absorption lines of N2O and one of CO2. The simulations were performed for two different upper-atmospheric pressures for an airborne instrument that has a path length of 80 m. The relative abundance of CO2 in air was assumed to be 360 parts per million by volume (approximately its natural level in terrestrial air). In applying the present method to measurements like these, one could average the signals from the two N2O absorption lines and normalize their magnitudes to that of the CO2 absorption line. Other gases with which this calibration method can be used include H2O, CH4, CO, NO, NO2, HOCl, C2H2, NH3, O3, and HCN. One can also take advantage of this method to eliminate an atmospheric-pressure gauge and thereby reduce the mass of the instrument: The atmospheric pressure can be calculated from the temperature, the known relative abundance of CO2, and the concentration of CO2 as measured by spectral absorption. Natural CO2 levels on Mars provide an ideal calibration standard. Figure 2 shows a second example of the application of this method to Mars atmospheric gas measurements. For sticky gases like H2O, the method is particularly powerful, since water is notoriously difficult to handle at low concentrations in pre-flight calibration procedures.

Webster, Chris↗

NASA NTRS2006

Nano Sensors for Gas Detection in Space and Ground Support Applications

Personnel living in a space environment as well as technicians and engineers preparing spacecraft for launch can potentially be exposed to small amounts of hazardous gases. It is therefore important to be able to detect, identify and quantify the presence of a gas especially when its presence could lead to a fatal situation. The use of small and sensitive sensors can allow for the placement of these devices over a large area, thus allowing for a more precise and timely determination of a gas leak. ASRC Aerospace and its research partners are developing nano sensors for detection of various gases, including but not limited to: H2, NH3, N2O4, hydrazine and others. Initial laboratory testing has demonstrated the capability to detect the gases in concentrations lower than parts per million. Testing and development is continuing to improve the response and recovery times, to increase the sensitivity of the devices. Different coatings and electrodes are currently being evaluated to determine the optimum configuration of a variety of gases. The small footprint of the Nano sensors allows for several devices, each responsive in a different way to different gases, to be placed into a single substrate. Multiple devices embedded into a single substrate results in increased reliability and in a decrease for periodic calibrations. The use of different coatings will result in a small electronic nose capable of distinguishing between different gases. A multi-channel signal conditioner amplifier built on a small multi chip module is used to process the output of the sensors and to deliver a signal that can be remotely monitored. All the data is digitized and transmitted over the same cable pair used to power the amplifier. Multiple outputs can be connected to a single cable pair in order to minimize the added weight and expense associated with cabling in a spacecraft. The sensors will be run through a qualification process to evaluate their suitability for space applications we are expecting to have fully functional sensors available for initial field deployment and testing by the end of the year 2006.

Medelius, Pedro J.↗

NASA NTRS2013

Lunar Sulfur Capture System

The Lunar Sulfur Capture System (LSCS) protects in situ resource utilization (ISRU) hardware from corrosion, and reduces contaminant levels in water condensed for electrolysis. The LSCS uses a lunar soil sorbent to trap over 98 percent of sulfur gases and about two-thirds of halide gases evolved during hydrogen reduction of lunar soils. LSCS soil sorbent is based on lunar minerals containing iron and calcium compounds that trap sulfur and halide gas contaminants in a fixed-bed reactor held at temperatures between 250 and 400 C, allowing moisture produced during reduction to pass through in vapor phase. Small amounts of Earth-based polishing sorbents consisting of zinc oxide and sodium aluminate are used to reduce contaminant concentrations to one ppm or less. The preferred LSCS configuration employs lunar soil beneficiation to boost concentrations of reactive sorbent minerals. Lunar soils contain sulfur in concentrations of about 0.1 percent, and halogen compounds including chlorine and fluorine in concentrations of about 0.01 percent. These contaminants are released as gases such as H2S, COS, CS2,HCl, and HF during thermal ISRU processing with hydrogen or other reducing gases. Removal of contaminant gases is required during ISRU processing to prevent hardware corrosion, electrolyzer damage, and catalyst poisoning. The use of Earth-supplied, single-use consumables to entirely remove contaminants at the levels existing in lunar soils would make many ISRU processes unattractive due to the large mass of consumables relative to the mass of oxygen produced. The LSCS concept of using a primary sorbent prepared from lunar soil was identified as a method by which the majority of contaminants could be removed from process gas streams, thereby substantially reducing the required mass of Earth-supplied consumables. The LSCS takes advantage of minerals containing iron and calcium compounds that are present in lunar soil to trap sulfur and halide gases in a fixedbed reactor downstream of an in-ISRU process such as hydrogen reduction. The lunar-soil-sorbent trap is held at a temperature significantly lower than the operating temperature of the hydrogen reduction or other ISRU process in order to maximize capture of contaminants, but is held at a high enough temperature to allow moisture to pass through without condensing. The lunar soil benefits from physical beneficiation to remove ultrafine particles (to reduce pressure drop through a fixed bed reactor) and to upgrade concentrations of iron and/or calcium compounds (to improve reactivity with gaseous contaminants).

Berggren, Mark↗

DOE OSTI2020

Improved sampling technique to collect natural gas from hydrate-bearing pressure cores

High quality gas compositional data are an important factor in interpreting the genetic source of natural gas hosted in hydrate-bearing sediments and other subsurface systems. In order to accurately characterize the composition of gas samples degassed from hydrate-bearing pressure cores, one must use a reproducible sampling technique that minimizes artifacts of the sampling process. Herein, we review sediment core degassing techniques and compare data obtained from a commonly used degassing approach, which we term the standard quantitative degassing (SQD) technique, to our newly developed modified quantitative degassing (MQD) method designed to minimize atmospheric contamination and gas-water interactions. The SQD method allows sample gas to interact with water in a bubbling chamber, which we hypothesize could alter the gas composition following mixing with water or dissolved gases in the bubbling chamber. Whereas, the MQD method allows for the collection of sample gas prior to the bubbling chamber. To compare the SQD and MQD methods, we performed a side-by-side comparison of noble (He, Ne, Ar, Kr, and Xe), major (H 2 , N 2 , O 2 , and CO 2 ), and hydrocarbon (CH 4 , C 2 H 6 , C 3 H 8 , i-C 4 H 10 , C 4 H 10 , i-C 5 H 12 , C 5 H 12 ) gas concentrations and select isotopic compositions obtained using both sample collection techniques. Gas samples were collected from hydrate-bearing pressure cores recovered and maintained under hydrate stable conditions from the northern Gulf of Mexico during the UT-GOM 2 -1 Expedition. The MQD method displayed significantly lower concentrations of atmospheric gases, higher proportions of hydrocarbon gases, lower ratios of C 1 /C 2 + , and heavier stable carbon and hydrogen isotopes of methane than the SQD method. These results demonstrate that the MQD method reduced air contamination and minimized alteration of the hydrocarbon gases. Finally, we conclude this method may be important for future work that seeks to determine the composition of natural gas from pressure cores using quantitative degassing experiments, especially those seeking to measure major (e.g., N 2 ) and noble gases.

58 GEOSCIENCES↗

DOE OSTI2025

Using Radiogenic Noble Gas Nuclides to Identify and Characterize Rock Fracturing

Abstract Fracture‐released radiogenic noble gas nuclides are used to identify locations and constrain the volume of new fracture creation during subsurface detonations. Real‐time, in situ noble gases and reactive gases were monitored using a field‐deployed mass spectrometer and automated sampling system in a multilevel borehole array. Released gases were measured after two different detonations having distinct energy, pressure, and gas volume characteristics. Explosive‐derived gases (N 2 O, CO 2 ) and excess radiogenic 4 He and 40 Ar above atmospheric background are used to identify locations of gas transport and new fracture creation after each detonation. Fracture‐released radiogenic 4 He is used to constrain the volume of newly created fractures with a model of helium release from fracturing. Explosive by‐product gas was observed in multiple locations both near and distal to the shot locations for both detonations. Radiogenic 4 He and 40 Ar release from rock damage was observed in locations near the detonation after the second, more powerful detonation. Observed 4 He response is consistent with a model of diffusive release from newly created fractures. Volume of new fractures estimated from the 4 He release ranges from 1 to 5 m 2 with apertures ranging from 0.1 to 1 m. Our results provide evidence that radiogenic noble gases released during fracture creation can be identified at the field scale in real time and used to identify timing and location of fracture creation during deformation events. This technique could be useful in subsurface science and engineering problems where the location and amount of newly created rock fracturing is of interest including fault rupture, mine safety, subsurface detonation monitoring and reservoir stimulation.

58 GEOSCIENCES↗

NASA NTRS1949

Experimental Study of Gas-Flow Separation in Overexpanded Exhaust Nozzles for Rocket Motors

In a rocket motor having a de Laval nozzle with a fixed expansion ratio, there is only one pressure ratio (p(sub c)/p(sub o)) for which this expansion ratio is correct. At any other pressure ratio the gases will be either underexpanded or overexpanded, depending on whether the pressure ratio is higher or lower than the correct value. Rocket motor flame patterns illustrating the four possible regimes are shown in Figures 1 to 4, inclusive. In Figure 1, the pressure ratio is higher than the correct one for the fixed expansion ratio of the nozzle, resulting in underexpansion of the gases. in Figure 2, the pressure ratio is the correct one. In Figure 3, the pressure ratio is only slightly lower than the correct one, resulting in overexpansion without separation of the gases from the wall. In Figure 4, the pressure ratio is considerably below the correct one, resulting in overexpansion with separation of the gases from the nozzle wall. The present report is concerned primarily with this fourth type of flow, that is, overexpansion of the gases with separation of the flow from the wall. Such a situation exists in a rocket motor operating at a considerably lower altitude than that for which its exhaust nozzle was designed.

Cowles, Frederick B.↗

NASA NTRS1973

Atmospheric composition

The earth's atmosphere is made up of a number of gases in different relative amounts. Near sea level and up to about 90 km, the amount of these atmospheric gases in clean, relatively dry air is practically constant. Four of these gases, nitrogen, oxygen, argon, and carbon dioxide, make up 99.99 percent by volume of the atmosphere. Two gases, ozone and water vapor, change in relative amounts, but the total amount of these two is very small compared to the amount of the other gases. The atmospheric composition shown in a table can be considered valid up to 90 km geometric altitude. Above 90 km, mainly because of molecular dissociation and diffusive separation, the composition changes.

Daniels, G. E.↗

NASA NTRS1981

Noble-gas-rich separates from the Allende meteorite

Predominantly carbonaceous HF/HCl-resistant residues from the Allende meteorite are studied. Samples are characterized by SEM/EDXA, X-ray diffraction, INAA, C, S, H, N, and noble gas analyses. Isotopic data for carbon show variations no greater than 5%, while isotopic data from noble gases confirm previously established systematics. Noble gas abundances correlate with those of C and N, and concomitant partial loss of C and normal trapped gas occur during treatments with oxidizing acids. HF/HCl demineralization of bulk meteorite results in similar fractional losses of C and trapped noble gases, which leads to the conclusion that various macromolecular carbonaceous substances serve as the main host phase for normal trapped noble gases and anomalous gases in acid-resistant residues, and as the carrier of the major part of trapped noble gases lost during HF/HCl demineralization. Limits on the possible abundances of dense mineralic host phases in the residues are obtained, and considerations of the nucleogenetic origin for CCF-XE indicate that carbonaceous host phases and various forms of organic matter in carbonaceous meteorites may have a presolar origin.

Ott, U.↗

NASA NTRS1989

Introduction and data summary, chapter 5

A subset of data representing most of the participating model groups was discussed and reviewed. The results are presented for intercomparisons of that subset of data. Subsequent to the workshop, the various modeling groups had the opportunity to either update or add to the data sets discussed at the workshop. The overall revised data sets as of December 1988 are presented. Data from all the models (where available) are grouped according to: (1) photochemistry and radiation (photodissociation coefficients, and ultraviolet heating and infrared cooling); (2) transport (net radiative heating, tropospheric source tracer experiment, time-dependent source conserved tracer experiment, stratospheric source tracer experiment, and O3 column); (3) current atmosphere (integrated columns of trace gases, Cl(y) and NO(y), nitrogen gases, chlorine gases, O(x) and HO(x) gases, and source gases); and (4) perturbed circulations and temperatures. The data presented provide a detailed summary of the two-dimensional picture of the atmosphere as seen by current atmospheric models.

Source record↗

NASA NTRS1989

Measurements of CH4, N2O, CO, H2O and O3 in the middle atmosphere by the ATMOS experiment on Spacelab 3

The volume mixing ratios of five minor gases (CH4, N2O, CO, H2O, and O3) were retrieved through the middle atmosphere from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 28 N and 48 S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, flown on board Spacelab 3. The results, which constitute the first simultaneous observations of continuous profiles through the middle atmosphere for these gases, are in general agreement with reported measurements from ground, balloon and satellite-based instruments for the same seasons. In detail, the vertical profiles of these gases show the effects of the upper and middle atmospheric transport patterns dominant during the season of these observations. The profiles inferred at different longitudes around 28 N suggest a near-uniform zonal distribution of these gases. Although based on fewer observations, the sunrise occultation measurements point to a larger variability in the vertical distribution of these gases at 48 S.

Gunson, M. R.↗

NASA NTRS1991

Effect of pressure on electrostatic processes on Mars

Paschen's Law as illustrated by Paschen curves for various gases shows that the minimum breakdown voltage for gases for breakdown distances of interest, i.e., 1 to 1000 mm is at or near the surface pressure on Mars. This means that the physics of many electrostatic processes is markedly different on Mars than on Earth. The primary effect is that voltage potentials above 100 volts are subject to breakdown in the Martian atmosphere. Sharp electrodes, dusty atmospheric conditions, or other anomalies modify the breakdown voltage, usually causing lower breakdown voltages. Paschen's curves for most common pure gases were experimentally determined. A very small amount of mixing of different gases radically changes the curve as shown in the curve for neon plus 0.1 percent argon compared to either neon or argon. Paschen's curve for the exact composition of gases for Mars was not determined; thus, the breakdown voltages are not known. A second important effect is that the breakdown for most Martian cases is a glow discharge rather than a spark discharge. It would seem that simple measurements of breakdown manner and voltage should be included on a Mars lander vehicle.

Leach, Rodman N.↗

NASA NTRS1992

Implications for volcanogenic volatile release on the weathering of Mars

Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the similarities are such that the suite of gases emitted from martian volcanic activity surely includes gases such as H2O, CO2, S-containing gases (H2S, SO3, or SO2), and Cl-containing gases (e.g. Cl or HCl). Both H2O and CO2 are present in the atmosphere of Mars; both are also present as surface condensates. Spectroscopic observations of the martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted. Likewise, there is no evidence of surface condensates of compounds of these elements. Within the soil, there is direct evidence of incorporation of H2O and some compounds of sulfur and chlorine. None of the resultant weathering products have been directly identified, but both clays and salts have been indirectly implicated. Other aspects of the implications for volcanogenic volatile release on the weathering of Mars are discussed.

Clark, Benton C.↗