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NASA NTRS2004

Analysis of the Atmospheric Distribution, Sources, and Sinks of Oxygenated Volatile Organic Chemicals Based on Measurements over the Pacific during TRACE-P

Airborne measurements of a large number of oxygenated volatile organic chemicals (OVOC) were carried out in the Pacific troposphere (0.1-12 km) in winter/spring of 2001 (24 February to 10 April). Specifically, these measurements included acetone (CH3COCH3), methylethyl ketone (CH3COC2H5, MEK), methanol (CH3OH), ethanol (C2H5OH), acetaldehyde (CH3CHO), propionaldehyde (C2H5CHO), peroxyacylnitrates (PANs) (C(sub n)H(sub 2n+1)COO2NO2), and organic nitrates (C(sub n)H(sub 2n+1)ONO2). Complementary measurements of formaldehyde (HCHO), methyl hydroperoxide (CH3OOH), and selected tracers were also available. OVOC were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Background mixing ratios were typically highest in the lower troposphere and declined toward the upper troposphere and the lowermost stratosphere. Their total abundance (Summation of OVOC) was nearly twice that of nonmethane hydrocarbons (Summation of C2-C8 NMHC). Throughout the troposphere, the OH reactivity of OVOC is comparable to that of methane and far exceeds that of NMHC. A comparison of these data with western Pacific observations collected some 7 years earlier (February-March 1994) did not reveal significant differences. Mixing ratios of OVOC were strongly correlated with each other as well as with tracers of fossil and biomass/biofuel combustion. Analysis of the relative enhancement of selected OVOC with respect to CH3Cl and CO in 12 plumes originating from fires and sampled in the free troposphere (3-11 km) is used to assess their primary and secondary emissions from biomass combustion. The composition of these plumes also indicates a large shift of reactive nitrogen into the PAN reservoir thereby limiting ozone formation. A three-dimensional global model that uses state of the art chemistry and source information is used to compare measured and simulated mixing ratios of selected OVOC. While there is reasonable agreement in many cases, measured aldehyde concentrations are significantly larger than predicted. At their observed levels, acetaldehyde mixing ratios are shown to be an important source of HCHO (and HO x ) and PAN in the troposphere. On the basis of presently known chemistry, measured mixing ratios of aldehydes and PANs are mutually incompatible. We provide rough estimates of the global sources of several OVOC and conclude that collectively these are extremely large (150-500 Tg C / yr) but remain poorly quantified.

Singh, H. B.↗

NASA NTRS1976

Mariner mission to Encke 1980

Experimental design for the Mariner mission to Comet Encke is considered, examining the following experiments: volatile and nonvolatile chemical analysis, an imaging system for the comet nucleus, the ultraviolet spectrometer, and magnetic field and plasma experiments. Mission design is discussed, emphasizing the mission profile, trajectory and targeting and the spacecraft design.

Yeates, C. M.↗

NASA NTRS2004

Effects of Subsurface Sampling & Processing on Martian Simulant Containing Varying Quantities of Water

The presence of water-ice in the Martian subsurface is a subject of much debate and excited speculation. Recent results from the gammaray spectrometer (GRS) on board NASA's Mars Odyssey spacecraft indicate the presence of large amounts of hydrogen in regions of predicted ice stability. The combination of chemistry, low gravitational field (3.71 m/s(exp 2)) and a surface pressure of about 6.36 mbar at the mean radius, place limits on the stability of H2O on the surface, however, results from the GRS indicate that the hydrogen rich phase may be present at a depth as shallow as one meter in some locations on Mars. The potential for water on Mars leads directly to the speculation that life may once have existed there, since liquid water is the unifying factor for environments known to support life on Earth. Lubricant-free drilling has been considered as a means of obtaining water-rich subsurface samples on Mars, and two recent white papers sponsored by the Mars Program have attempted to identify the problems associated with this goal. The two major issues identified were: the engineering challenges of drilling into a water-soil mixture where phase changes may occur; and the potential to compromise the integrity of in-situ scientific analysis due to contamination, volatilization, and mineralogical or chemical changes as a result of processing. This study is a first attempt to simulate lubricantfree drilling into JSC Mars-1 simulant containing up to 50% water by weight. The goal is to address the following: 1) Does sample processing cause reactions or changes in mineralogy which will compromise the interpretation of scientific measurements conducted on the surface? 2) Does the presence of water-ice in the sample complicate (1)? 3) Do lubricant-free drilling and processing leave trace contaminants which may compromise our understanding of sample composition? 4) How does the torque/power required for drilling change as a function of water content and does this lead to unexpected thermal effects?

Menard, J.↗

NASA NTRS2004

Performance Assessment of ISS Water Processor Assembly Reactor

Due to modifications to the ISS waste water composition, the concentration of volatile organics has significantly increased in the feed to the Water Processor Assembly (WPA). In parallel, the oxygen supply pressure increased, resulting in a higher flow rate of oxygen to the WPA. Preliminary testing at Hamilton Sund strand indicated that the higher oxygen flow rate would increase the WPA capacity for volatile organics. Following an analysis of the expected waste water composition, personnel at NASA MSFC and Hamilton Sundstrand conducted a test of a flight-like reactor to assess its capacity for the higher organic loads. The results of this test indicate the WPA can accommodate the expected organic load in the ISS waste water with margin.

Carter, Layne↗

NASA NTRS2016

Advanced Laser Architecture for Two-Step Laser Tandem Mass Spectrometer

Future astrobiology missions will focus on planets with significant astrochemical or potential astrobiological features, such as small, primitive bodies and the icy moons of the outer planets that may host diverse organic compounds. These missions require advanced instrument techniques to fully and unambiguously characterize the composition of surface and dust materials. Laser desorptionionization mass spectrometry (LDMS) is an emerging instrument technology for in situ mass analysis of non-volatile sample composition. A recent Goddard LDMS advancement is the two-step laser tandem mass spectrometer (L2MS) instrument to address the need for future flight instrumentation to deconvolve complex organic signatures. The L2MS prototype uses a resonance enhanced multi-photon laser ionization mechanism to selectively detect aromatic species from a more complex sample. By neglecting the aliphatic and inorganic mineral signatures in the two-step mass spectrum, the L2MS approach can provide both mass assignments and clues to structural information for an in situ investigation of non-volatile sample composition. In this paper we will describe our development effort on a new laser architecture that is based on the previously flown Lunar Orbiter Laser Altimeter (LOLA) laser transmitter for the L2MS instrument. The laser provides two discrete midinfrared wavelengths (2.8 m and 3.4 m) using monolithic optical parametric oscillators and ultraviolet (UV) wavelength (266 nm) on a single laser bench with a straightforward development path toward flight readiness.

Laser↗

NASA NTRSDate not supplied

Numerical Study of Water Ice and Molecular Contamination Build Up during JWST Deployment

This paper summarizes a recent numerical analysis of water vapor and volatile condensible material deposition on the James Webb Space Telescope from the initial orbit insertion up to 180 days post launch. The analysis utilized 17 distinct geometry files capturing observatory configuration changes during the deployment. Surface temperature was set from a time-dependent thermal analysis solution. A vapor pressure model was used to calculate the net water ice adsorption. Molecular contamination included a contribution from UV photopolymerization. The analysis predicted levels of ice and molecular accumulation were found to be within the allowable limits specified by the observatory contamination control plan.

James Webb Space Telescope↗

NASA NTRSDate not supplied

Numerical Study of Water Ice and Molecular Contamination Build Up during JWST Deployment

James Webb Space Telescope↗

NASA NTRS2016

Perchlorate and Volatiles of the Brine of Lake Vida (Antarctica): Implication for the in Situ Analysis of Mars Sediments

The cold (-13.4 C), cryoencapsulated, anoxic, interstitial brine of the 27 m-thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 microgram L-1 of perchlorate and 11 microgram L-1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 microgram L-1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

Mars analog experiment↗

NASA NTRS1980

A meteoritic component rich in volatile elements - Its characterization and implications

An analysis of a study of minerals unique to enstatite chondrites, an unusual group of meteorites characterized by highly reduced mineral assemblages, is presented. Various samples of crushed fragments of the Abee meteorite were studied and the normal procedures for identifying the minerals in sections and then extracting them were reversed. An unusual carbon-rich material was found that is highly enriched in volatile elements by factors of 10000 relative to the case for nonvolatile elements. It is believed that this volatile-rich material forms in the solar nebula toward the end of accretion, when small amounts of residual dust acquire all the uncondensed volatile elements.

Ganapathy, R.↗

NASA NTRS2012

Chromatographic, Spectroscopic and Mass Spectrometric Approaches for Exploring the Habitability of Mars in 2012 and Beyond with the Curiosity Rover

The Sample Analysis at Mars (SAM) suite of instruments on the Curiosity Rover of Mars Science Laboratory Mission is designed to provide chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples. The goals of the science investigation enabled by the gas chromatograph mass spectrometer and tunable laser spectrometer instruments of SAM are to work together with the other MSL investigations is to quantitatively assess habitability through a series of chemical and geological measurements. We describe the multi-column gas chromatograph system employed on SAM and the approach to extraction and analysis of organic compounds that might be preserved in ancient martian rocks.

Mahaffy, Paul↗

NASA NTRS2012

Calibration and Sequence Development Status for the Sample Analysis at Mars Investigation on the Mars Science Laboratory

The measurement goals of the Sample Analysis at Mars (SAM) instrument suite on the "Curiosity" Rover of the Mars Science Laboratory (MSL) include chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples [1,2]. SAM directly supports the ambitious goals of the MSL mission to provide a quantitative assessment of habitability and preservation in Gale crater by means of a range of chemical and geological measurements [3]. The SAM FM combined calibration and environmental testing took place primarily in 2010 with a limited set of tests implemented after integration into the rover in January 2011. The scope of SAM FM testing was limited both to preserve SAM consumables such as life time of its electromechanical elements and to minimize the level of terrestrial contamination in the SAM instrument. A more comprehensive calibration of a SAM-like suite of instruments will be implemented in 2012 with calibration runs planned for the SAM testbed. The SAM Testbed is nearly identical to the SAM FM and operates in a ambient pressure chamber. The SAM Instrument Suite: SAM's instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). Gas Chromatography Mass Spectrometry is designed for identification of even trace organic compounds. The TLS [5] secures the C, H, and O isotopic composition in carbon dioxide, water, and methane. Sieved materials are delivered from the MSL sample acquisition and processing system to one of68 cups of the Sample Manipulation System (SMS). 59 of these cups are fabricated from inert quartz. After sample delivery, a cup is inserted into one of 2 ovens for evolved gas analysis (EGA ambient to >9500C) by the QMS and TLS. A portion of the gas released can be trapped and subsequently analyzed by GCMS. Nine sealed cups contain liquid solvents and chemical derivatization or thermochemolysis agents to extract and transform polar molecules such as amino acids, nucleobases, and carboxylic acids into compounds that are sufficiently volatile to transmit through the GC columns. The remaining 6 cups contain calibrants. SAM FM Calibration Overview: The SAM FM calibration in the Mars chamber employed a variety of pure gases, gas mixtures, and solid materials. Isotope calibration runs for the TLS utilized 13C enriched C02 standards and 0 enriched CH4. A variety of fluorocarbon compounds that spanned the entire mass range of the QMS as well as C3-C6 hydrocarbons were utilized for calibration of the GCMS. Solid samples consisting of a mixture of calcite, melanterite, and inert silica glass either doped or not with fluorocarbons were introduced into the SAM FM cups through the SAM inlet funnel/tube system.

Mahaffy, Paul R.↗

NASA NTRS2010

Stability of Materials in High Temperature Water Vapor: SOFC Applications

Solid oxide fuel cell material systems require long term stability in environments containing high-temperature water vapor. Many materials in fuel cell systems react with high-temperature water vapor to form volatile hydroxides which can degrade cell performance. In this paper, experimental methods to characterize these volatility reactions including the transpiration technique, thermogravimetric analysis, and high pressure mass spectrometry are reviewed. Experimentally determined data for chromia, silica, and alumina volatility are presented. In addition, data from the literature for the stability of other materials important in fuel cell systems are reviewed. Finally, methods for predicting material recession due to volatilization reactions are described.

Opila, E. J.↗

NASA NTRS2012

The Role of (Delta)C-13 in the Search for Reduced Organics on the Surface of Mars

The capabilities of the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to detect trace amounts of organic carbon compounds are unprecedented, and MSL may be the first mission to reveal the presence of organic carbon on Mars. The search for reduced organic carbon on Mars is inextricably tied to: a) the preservation potential of the environment from which we take a solid sample, and b) the evolved gas analysis (EGA) techniques used by SAM to release volatiles from this solid sample. Several prospective targets have been identified for sample analysis at Gale Crater. Stratigraphic sequences of phyllosilicates and sulfates at Gale are thought to represent a period of global climate transition from a moderate pH lacustrine environment to an evaporitic environment, both of which could sequester organic carbon (Thomson et al. 2011). The sediment mound in Gale Crater contains a range of lithologies suggesting changes in redox conditions, and evidence of both lacustrine and fluvial depositional processes, which may have transported organic carbon from the layer in which it formed and resulted in its preservation elsewhere within the crater (Anderson and Bell, 2010). Inverted channel fills suggest erosion resistant material that could serve to preserve organics originally deposited in a low energy aqueous environment. The lithology sampled will affect not only the preservation of organics, but also our ability to detect organics during our evolved gas analysis, based on the sample matrix. For example, reduced organics may be trapped in the mineral structure, and thermal evolution of these organics will occur during thermal decomposition of the host mineral. If organics are occluded in minerals that have very high thermal decomposition temperatures, they may be, in effect, "too well preserved," and difficult to detect during EGA. Alternatively, the possible presence of perchlorate, or other strong oxidants in surface regolith, may result in destruction of structural information identifying organic molecules before reaching the QMS on SAM via oxidation to C02 during heating. If this is the case, the stable carbon isotopic composition (delta 13C) of the C02 evolved and measured by the Tunable Laser Spectrometer (TLS) on SAM may help identify the presence of organics. On Earth, biological activity can cause large fractionations of 13C/12C, which can preserved in sedimentary deposits and distinguish the organic products of biotic processes from inorganic atmospheric and geological reservoirs. It is plausible that similar fractionations could occur on Mars and be preserved in reduced organic matter in sediments. Bulk delta 13C measurements alone may not reveal a signature of trace organic carbon that may be present along with inorganic carbon. If both organic and inorganic carbon compounds are present, it may be possible to detect the organic carbon by comparing the 013C of pyrolysis and combustion experiments. The TLS on SAM is capable of obtaining high precision measurements of delta13C from C02 evolved during pyrolysis and combustion of solid regolith samples. Because carbonates are expected to be present at abundances of 0.1-1 % in Martian soil, and organics in the ppb range (Webster and Mahaffy, 2011), analog samples must represent this mix of reduced organic carbon and carbonate. The work presented here will examine the use of delta13C of C02 produced during combustion of bulk Mars analog samples as a proxy for detection of reduced organic carbon.

Stern, J. C.↗

NASA NTRS1976

A composite system approach to aircraft cabin fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of one of the baremaleimide composites are detailed.

Kourtides, D. A.↗

NASA NTRS1976

Flammability characteristics of aircraft interior composites

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of pyrolysis. The performance of foam filled honeycomb laminated panels consisting of high-temperature laminating bismaleimide resins is compared with the performance of empty honeycomb laminated panels consisting of laminating epoxy or phenolic resins at similar densities. Processing parameters of one of the bismaleimide composites is detailed.

Kourtides, D. A.↗

NASA NTRS1976

Materials research for aircraft fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of the state-of-the-art and the advanced bismaleimide composites are detailed.

Kourtides, D. A.↗

NASA NTRS1976

A composite system approach to aircraft cabin fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of one of the bismaleimide composites is detailed.

Kourtides, D. A.↗

NASA NTRS1979

Thermal response of composite panels

The thermochemical and flammability characteristics of laminating resins and composites currently in use and others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as modified phenolics, polyimides and bismaleimides is compared with the performance of epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of the state-of-the-art epoxy resin and the advanced resin composites are detailed.

Kourtides, D. A.↗