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Halogens in the atmosphere

Atmospheric halogen measurement data are presented for: (1) inorganic and organic gaseous compounds of chlorine, fluorine, bromine and iodine; and (2) chloride, fluoride, bromide and iodine in particulate form and in precipitation. The roles that these data and other, unavailable data play in the determination of the global cycles of the halogens are discussed. It is found that the speciation of the halogen gases in the troposphere is uncertain, with the only inorganic species detected by species-specific methods being HC1 and SF6. It is shown that heterogeneous reactions, both gas-to-particle and particle-to-gas processes, precipitation removal, and sea-salt aerosol generation and fractionation processes, need quantitative investigation to allow progress in estimating halogen sources and sinks. Where practical, quantitative comparisons are made between measured and predicted concentrations.

Cicerone, R. J.↗

Mathematical Model for Gas Dissolution in Glass

Mathematical model calculates rate of small oxygen-bubble contraction in soda/lime/silicate melts in presence of foreign nondiffusing gas. Process of interest in optical glass fabrication.

Weinberg, M. C.↗

Observations of Far-Infrared Molecular Emission Lines from the Orion Molecular Cloud

The Orion Nebula was the subject of intensive study for over one hundred years. Recently, several far infrared transitions among the low-lying levels of OH were observed toward IRc2. The OH is thought to be abundant, and plays an important role in the chemical evolution of shock and post-shock regions. The OH emission serves as a sensitive probe of the temperature and density for the shock-processed gas. A rigorous treatment of the radiative transfer of these measured transitions was performed using the escape probability formalism. From this analysis, the temperature of the OH-emitting region was determined to be on the order of 40K. This suggests that the gas is part of the post-shock gas that has cooled sufficiently, most likely by way of radiative cooling by CO. Such cooling from shock temperatures of several degrees can be accomplished in 100 years. A molecular hydrogen density of 3 million/cubic cm and an OH column density of 1.0 x 10 to the 17th /sq cm is found. The beam filling factor is determined to be 36%.

Viscuso, P. J.↗

Panel summary of recommendations

The following Space Station internal contamination topics were addressed: past flight experience (Skylab and Spacelab missions); present flight activities (Spacelabs and Soviet Space Station Mir); future activities (materials science and life science experiments); Space Station capabilities (PPMS, FMS, ECLSS, and U.S. Laboratory overview); manned systems/crew safety; internal contamination detection; contamination control - stowage and handling; and contamination control - waste gas processing. Space Station design assumptions are discussed. Issues and concerns are discussed as they relate to (1) policy and management, (2) subsystem design, (3) experiment design, and (4) internal contamination detection and control. The recommendations generated are summarized.

Dunbar, Bonnie J.↗

Pump Effects in Planetary Mass Spectrometers

Mass spectrometers provide a useful tool in solar system exploration since fundamental questions of Solar System formation and evolution may be constrained by models based on the chemical and isotopic data provided by these instruments. For example, comparison of such data between the atmospheres of the terrestrial planets enables an understanding of mechanisms of atmospheric loss to space and production sources such as from planetary outgassing and from infall from objects such as comets. Over the past 25 years, mass spectrometers have been sent to Mars, Venus, Comet Halley, and Jupiter and are presently in transit to the Saturnian system to sample the atmosphere of Saturn's moon Titan. The quality of data derived from a very small, lightweight, and rugged instrument is constrained not only by the mass analyzer itself, but also by the performance of its gas sampling and pumping systems. A comparison of several planetary mass spectrometer experiments is provided with a focus on the demands placed on the gas processing and pumping systems. For example, the figure below is a mass spectrum from deep in the atmosphere of Jupiter obtained from a quadrupole mass spectrometer developed in the early 1980's for the Galileo Probe (Niemann et al., Space Sci. Rev., 60, 111-142 (1992)). Measurements of Jovian noble gases and other species with this system is described.

Mahaffy, Paul↗

Hybrid Modeling for Testing Intelligent Software for Lunar-Mars Closed Life Support

Intelligent software is being developed for closed life support systems with biological components, for human exploration of the Moon and Mars. The intelligent software functions include planning/scheduling, reactive discrete control and sequencing, management of continuous control, and fault detection, diagnosis, and management of failures and errors. Four types of modeling information have been essential to system modeling and simulation to develop and test the software and to provide operational model-based what-if analyses: discrete component operational and failure modes; continuous dynamic performance within component modes, modeled qualitatively or quantitatively; configuration of flows and power among components in the system; and operations activities and scenarios. CONFIG, a multi-purpose discrete event simulation tool that integrates all four types of models for use throughout the engineering and operations life cycle, has been used to model components and systems involved in the production and transfer of oxygen and carbon dioxide in a plant-growth chamber and between that chamber and a habitation chamber with physicochemical systems for gas processing.

Malin, Jane T.↗

Modeling Separate and Combined Atmospheres in BIO-Plex

We modeled BIO-Plex designs with separate or combined atmospheres and then simulated controlling the atmosphere composition. The BIO-Plex is the Bioregenerative Planetary Life Support Systems Test Complex, a large regenerative life support test facility under development at NASA Johnson Space Center. Although plants grow better at above-normal carbon dioxide levels, humans can tolerate even higher carbon dioxide levels. Incinerator exhaust has very high levels of carbon dioxide. An elaborate BIO-Plex design would maintain different atmospheres in the crew and plant chambers and isolate the incinerator exhaust in the airlock. This design easily controls the crew and plant carbon dioxide levels but it uses many gas processors, buffers, and controllers. If all the crew's food is grown inside BIO-Plex, all the carbon dioxide required by the plants is supplied by crew respiration and the incineration of plant and food waste. Because the oxygen mass flow must balance in a closed loop, the plants supply all the oxygen required by the crew and the incinerator. Using plants for air revitalization allows using fewer gas processors, buffers, and controllers. In the simplest design, a single combined atmosphere was used for the crew, the plant chamber, and the incinerator. All gas processors, buffers, and controllers were eliminated. The carbon dioxide levels were necessarily similar for the crew and plants. If most of the food is grown, carbon dioxide can be controlled at the desired level by scheduling incineration. An intermediate design uses one atmosphere for the crew and incinerator chambers and a second for the plant chamber. This allows different carbon dioxide levels for the crew and plants. Better control of the atmosphere is obtained by varying the incineration rate. Less gas processing storage and control is needed if more food is grown.

Jones, Harry↗

Modeling Separate and Combined Atmospheres in BIO-Plex

We modeled BIO-Plex designs with separate or combined atmospheres and then simulated controlling the atmosphere composition. The BIO-Plex is the Bioregenerative Planetary Life Support Systems Test Complex, a large regenerative life support test facility under development at NASA Johnson Space Center. Although plants grow better at above-normal carbon dioxide levels, humans can tolerate even higher carbon dioxide levels. incinerator exhaust has very high levels of carbon dioxide. An elaborate BIO-Plex design would maintain different atmospheres in the crew and plant chambers and isolate the incinerator exhaust in the airlock. This design easily controls the crew and plant carbon dioxide levels but it uses many gas processors, buffers, and controllers. If all the crew's food is grown inside BIO-Plex, all the carbon dioxide required by the plants is supplied by crew respiration and the incineration of plant and food waste. Because the oxygen mass flow must balance in a closed loop, the plants supply all the oxygen required by the crew and the incinerator. Using plants for air revitalization allows using fewer gas processors, buffers, and controllers. In the simplest design, a single combined atmosphere was used for the crew, the plant chamber, and the incinerator. All gas processors, buffers, and controllers were eliminated. The carbon dioxide levels were necessarily similar for the crew and plants. If most of the food is grown, carbon dioxide can be controlled at the desired level by scheduling incineration. An intermediate design uses one atmosphere for the crew and incinerator chambers and a second for the plant chamber. This allows different carbon dioxide levels for the crew and plants. Better control of the atmosphere is obtained by varying the incineration rate. Less gas processing, storage, and control is needed if more food is grown.

Jones, Harry↗

Ion Energy and Ion Flux Distributions of CF4/Ar/O2 Inductively Coupled Plasmas in a GEC Cell

Knowledge of ion kinetics in plasma processing gas mixtures, such as CF4:Ar:O2, is important for understanding plasma assisted etching and deposition of materials. Ion energies and ion fluxes were measured in this mixture for 80:10:10, 60:20:20, and 40:30:30 mixture ratios in the pressure range of 10-50 mTorr, and at 200 and 300 W of RF power. Ions from plasma, sampled through a 10 micron orifice in the center of the lower plane electrode, were energy and mass analyzed by a combination of electrostatic energy and quadrupole mass filters. CFx(+) (x = 1 - 3), F2(+), F(+), C(+) from CF4, Ar(+) from Ar, and O2(+) and O(+) from O2, and by-product ions SiFx(+)(x = 1 - 3) from etching of quartz coupling window, COFx(+)(x = 1 - 3), CO(+), CO2(+), and OF(+) were detected. In all conditions ion flux decreases with increase of pressure but increase with increase of RF power. Ar(+) signal decreases with increase of pressure while CF3(+), which is the dominant ion at all conditions, increases with increase in pressure. The loss mechanism for Ar(+) and increase of CF3(+) is due to large cross section for Ar(+) + CF4 yields Ar + CF3(+) + F. Ion energies, which range from 15-25 eV depending on plasma operating conditions, are nearly Gaussian. By-product ion signals are higher at lower pressures indicating stronger plasma interaction with quartz window.

Rao, M. V. V. S.↗

Plasma Processing of Lunar Regolith Simulant for Diverse Applications

Versatile manufacturing technologies for extracting resources from the moon are needed to support future space missions. Of particular interest is the production of gases and metals from lunar resources for life support, propulsion, and in-space fabrication. Deposits made from lunar regolith could yield highly emissive coatings and near-net shaped parts for replacement or repair of critical components. Equally important is development of high fidelity lunar simulants for ground based validation of potential lunar surface operations. Described herein is an innovative plasma processing technique for insitu production of gases, metals, coatings, and deposits from lunar regolith, and synthesis of high fidelity lunar simulant from NASA issued lunar simulant JSC-1. Initial plasma reduction trials of JSC-1 lunar simulant have indicated production of metallic iron and magnesium. Evolution of carbon monoxide has been detected subsequent to reduction of the simulant using the plasma process. Plasma processing of the simulant has also resulted in glassy phases resembling the volcanic glass and agglutinates found in lunar regolith. Complete and partial glassy phase deposits have been obtained by varying the plasma process variables. Experimental techniques, product characterization, and process gas analysis will be discussed.

Schofield, Elizabeth C.↗

Design and Development of a Miniaturized Double Latching Solenoid Valve for the Sample Analysis at Mars Instrument Suite

The development of the in-house Miniaturized Double Latching Solenoid Valve, or Microvalve, for the Gas Processing System (GPS) of the Sample Analysis at Mars (SAM) instrument suite is described. The Microvalve is a double latching solenoid valve that actuates a pintle shaft axially to hermetically seal an orifice. The key requirements and the design innovations implemented to meet them are described.

Smith, James T.↗

Miniature Mass Spectrometers on Space and Planetary Missions

Space flight mass spectrometers contribute our understanding of the origin and evolution of our solar system and even of life itself. This fundamental role has motivated increasing interest in miniature mass spectrometry for planetary missions. Several remarkable new instruments are en route or under development to investigate the composition of planetary bodies such as Mars and comets. For instance, the Sample Analysis at Mars (SAM) suite on the 2009 Mars Science Laboratory (MSL) mission includes a quadrupole mass spectrometer with a sophisticated gas processing system as well as pyrolysis and chemical derivatization protocols for solid samples. Future missions will require even lighter, lower power, and yet more capable mass spectrometers, particularly to analyze samples in situ on planetary surfaces. We have been developing laser-based mass spectrometers for elemental and organic/molecular analysis of rock, ice, or fine particle samples. These typically use time-of-flight (TOF) mass analyzers, which are readily miniaturized and can detect both atomic species and complex organics that occur in a variety of planetary materials. For example, nonvolatile polycyclic aromatic hydrocarbons and kerogen-like macromolecular carbon are found in some carbonaceous meteorites, which derived from asteroid parent bodies. A single focused laser pulse is able to volatilize and ionize some of these compounds for direct TOF analysis. While this is possible without any sample preparation or contact, sensitivity and quantitative performance can improve significantly with some sample handling. As such we have also been examining robotic mechanisms and protocols to accompany space flight mass spectrometers. In addition, sensors in early development may significantly improve these capabilities, via use of techniques such as switchable polarity, ambient pressure, or resonant ionization; tandem mass spectrometry (TOF or ion trap); and chemical imaging.

Brinckerhoff, William↗

Methods for producing silicon carbide architectural preforms

Methods are disclosed for producing architectural preforms and high-temperature composite structures containing high-strength ceramic fibers with reduced preforming stresses within each fiber, with an in-situ grown coating on each fiber surface, with reduced boron within the bulk of each fiber, and with improved tensile creep and rupture resistance properties for each fiber. The methods include the steps of preparing an original sample of a preform formed from a pre-selected high-strength silicon carbide ceramic fiber type, placing the original sample in a processing furnace under a pre-selected preforming stress state and thermally treating the sample in the processing furnace at a pre-selected processing temperature and hold time in a processing gas having a pre-selected composition, pressure, and flow rate. For the high-temperature composite structures, the method includes additional steps of depositing a thin interphase coating on the surface of each fiber and forming a ceramic or carbon-based matrix within the sample.

DiCarlo, James A.↗

Architectures and Evaluation for Adjustable Control Autonomy for Space-Based Life Support Systems

In the past five years, a number of automation applications for control of crew life support systems have been developed and evaluated in the Adjustable Autonomy Testbed at NASA's Johnson Space Center. This paper surveys progress on an adjustable autonomous control architecture for situations where software and human operators work together to manage anomalies and other system problems. When problems occur, the level of control autonomy can be adjusted, so that operators and software agents can work together on diagnosis and recovery. In 1997 adjustable autonomy software was developed to manage gas transfer and storage in a closed life support test. Four crewmembers lived and worked in a chamber for 91 days, with both air and water recycling. CO2 was converted to O2 by gas processing systems and wheat crops. With the automation software, significantly fewer hours were spent monitoring operations. System-level validation testing of the software by interactive hybrid simulation revealed problems both in software requirements and implementation. Since that time, we have been developing multi-agent approaches for automation software and human operators, to cooperatively control systems and manage problems. Each new capability has been tested and demonstrated in realistic dynamic anomaly scenarios, using the hybrid simulation tool.

Malin, Jane T.↗

The Sample Analysis at Mars Investigation and Instrument Suite

The Sample Analysis at Mars (SAM) investigation of the Mars Science Laboratory (MSL) addresses the chemical and isotopic composition of the atmosphere and volatiles extracted from solid samples. The SAM investigation is designed to contribute substantially to the mission goal of quantitatively assessing the habitability of Mars as an essential step in the search for past or present life on Mars. SAM is a 40 kg instrument suite located in the interior of MSL's Curiosity rover. The SAM instruments are a quadrupole mass spectrometer, a tunable laser spectrometer, and a 6-column gas chromatograph all coupled through solid and gas processing systems to provide complementary information on the same samples. The SAM suite is able to measure a suite of light isotopes and to analyze volatiles directly from the atmosphere or thermally released from solid samples. In addition to measurements of simple inorganic compounds and noble gases SAM will conduct a sensitive search for organic compounds with either thermal or chemical extraction from sieved samples delivered by the sample processing system on the Curiosity rover's robotic arm,

Mahaffy, Paul↗

Detection of Organic Constituents Including Chloromethylpropene in the Analyses of the ROCKNEST Drift by Sample Analysis at Mars (SAM)

key challenge in assessing the habitability of martian environments is the detection of organic matter - a requirement of all life as we know it. The Curiosity rover, which landed on August 6, 2012 in Gale Crater of Mars, includes the Sample Analysis at Mars (SAM) instrument suite capable of in situ analysis of gaseous organic components thermally evolved from sediment samples collected, sieved, and delivered by the MSL rover. On Sol 94, SAM received its first solid sample: scooped sediment from Rocknest that was sieved to <150 m particle size. Multiple 10-40 mg portions of the scoop #5 sample were delivered to SAM for analyses. Prior to their introduction, a blank (empty cup) analysis was performed. This blank served 1) to clean the analytical instrument of SAMinternal materials that accumulated in the gas processing system since integration into the rover, and 2) to characterize the background signatures of SAM. Both the blank and the Rocknest samples showed the presence of hydrocarbon components.

Eigenbrode, J. L.↗

Methods for Producing High-Performance Silicon Carbide Fibers, Architectural Preforms, and High-Temperature Composite Structures

Methods are disclosed for producing architectural preforms and high-temperature composite structures containing high-strength ceramic fibers with reduced preforming stresses within each fiber, with an in-situ grown coating on each fiber surface, with reduced boron within the bulk of each fiber, and with improved tensile creep and rupture resistance properties tier each fiber. The methods include the steps of preparing an original sample of a preform formed from a pre-selected high-strength silicon carbide ceramic fiber type, placing the original sample in a processing furnace under a pre-selected preforming stress state and thermally treating the sample in the processing furnace at a pre-selected processing temperature and hold time in a processing gas having a pre-selected composition, pressure, and flow rate. For the high-temperature composite structures, the method includes additional steps of depositing a thin interphase coating on the surface of each fiber and forming a ceramic or carbon-based matrix within the sample.

DiCarlo, James A.↗

Effect of the Presence of Chlorates and Perchlorates on the Pyrolysis of Organic Compounds: Implications for Measurements Done with the SAM Experiment Onboard the Curiosity Rover

The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

Millan, M.↗